Molecules having pesticidal utility, and intermediates, compositions, and processes, related thereto

Abstract

This disclosure relates to the field of molecules having pesticidal utility against pests in Phyla Arthropoda, Mollusca, and Nematoda, processes to produce such molecules, intermediates used in such processes, compositions containing such molecules, and processes of using such molecules and compositions against such pests. These molecules and compositions may be used, for example, as acaricides, insecticides, miticides, molluscicides, and nematicides. This document discloses molecules having the following formula (Formula One). ##STR00001##

Claims

1. A molecule having the following formula ##STR01045## wherein: (A) R.sup.1, R.sup.5, R.sup.6, R.sup.11, and R.sup.12 are each independently selected from the group consisting of H, F, Cl, Br, I, CN, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.4)haloalkoxy; (B) R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of H, F, Cl, Br, I, CN, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (C) R.sup.7 is (C.sub.1-C.sub.6)haloalkyl; (D) R.sup.9 is selected from the group consisting of (F), H, F, Cl, Br, I, CN, (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.1-C.sub.4)alkoxy, and (C.sub.1-C.sub.4)haloalkoxy; (E) R.sup.10 is selected from the group consisting of (F), F, Cl, Br, I, CN, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (F) R.sup.9 and R.sup.10 together can optionally form a 3- to 5-membered saturated or unsaturated, hydrocarbyl link, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, OH, and oxo; (G) Q.sup.1 and Q.sup.2 are each independently O or S; (H) R.sup.13 is selected from the group consisting of H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (I) R.sup.14 is selected from the group consisting of (K), (O), H, (C.sub.1-C.sub.4)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (J) R.sup.15 is selected from the group consisting of (K), H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (K) R.sup.14 and R.sup.15 together can optionally form a 2- to 5-membered saturated, hydrocarbyl link, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, and CN; (L) L is selected from the group consisting of (1) a bond connecting C(R.sup.14)(R.sup.15) to C(=Q.sup.2), and (2) a (C.sub.1-C.sub.6)alkyl wherein said alkyl is optionally substituted with one or more substituents independently selected from the group consisting of F, Cl, CN, OH, and oxo; (M) X is selected from the group consisting of (1) a bond connecting C(=Q.sup.2) to R.sup.17, and (2) a N, O, and S connecting C(=Q.sup.2) to R.sup.17; (N) R.sup.16 is selected from the group consisting of (O), H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.2-C.sub.6)alkenyloxy, (C.sub.1-C.sub.6)haloalkoxy, amino, and NHC(O)O(C.sub.1-C.sub.6)alkyl; (O) R.sup.14 and R.sup.16 together can optionally form a 2- to 4-membered saturated, hydrocarbyl link, which may contain one or more heteroatoms selected from the group consisting of nitrogen, sulfur, and oxygen, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, OH, and oxo; (P) R.sup.17 is selected from the group consisting of H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.3-C.sub.6)halocycloalkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.2-C.sub.6)alkenyloxy, (C.sub.1-C.sub.6)haloalkoxy, and (C.sub.1-C.sub.6)alkyl(C.sub.3-C.sub.6)cycloalkyl; (Q) R.sup.16 and R.sup.17 together can optionally form a 2- to 6-membered saturated, hydrocarbyl link, which may contain one or more heteroatoms selected from the group consisting of nitrogen, sulfur, and oxygen, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, OH, and oxo; and agriculturally acceptable acid addition salts, salt derivatives, solvates, ester derivatives, crystal polymorphs, isotopes, resolved stereoisomers, and tautomers, of the molecules of Formula One.

2. A molecule according to claim 1 wherein R.sup.1, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 are H.

3. A molecule according to claim 1 wherein R.sup.2 is F, Cl, Br, or CH.sub.3.

4. A molecule according to claim 1 wherein R.sup.3 is F, Cl, Br, or CHCH.sub.2.

5. A molecule according to claim 1 wherein R.sup.4 is Cl, Br, or CH.sub.3.

6. A molecule according to claim 1 wherein R.sup.2, R.sup.3, and R.sup.4 are C.sub.1.

7. A molecule according to claim 1 wherein R.sup.7 is (C.sub.1-C.sub.6)haloalkyl.

8. A molecule according to claim 1 wherein R.sup.7 is CF.sub.3, CF.sub.2CH.sub.3, or CF.sub.2CH.sub.2CH.sub.3.

9. A molecule according to claim 1 wherein R.sup.10 is Cl, Br, I, CH.sub.3, or CF.sub.3.

10. A molecule according to claim 1 wherein Q.sup.1 and Q.sup.2 are O.

11. A molecule according to claim 1 wherein R.sup.13, R.sup.14, and R.sup.15 are CH.sub.3 or CH.sub.2CH.sub.3.

12. A molecule according to claim 1 wherein R.sup.14 and R.sup.15 together form a 2-membered saturated, hydrocarbyl link.

13. A molecule according to claim 1 wherein L is a bond connecting C(R.sup.14)(R.sup.15) to C(=Q.sup.2).

14. A molecule according to claim 1 wherein X is a bond connecting C(=Q.sup.2) to R.sup.17.

15. A molecule according to claim 1 wherein X is N connecting C(=Q.sup.2) to R.sup.17.

16. A molecule according to claim 1 wherein R.sup.16 is CH.sub.3, CH.sub.2CH.sub.3, OCH.sub.3, OCH.sub.2CHCH.sub.2, NH.sub.2, or NHC(O)OC(CH.sub.3).sub.3.

17. A molecule according to claim 1 wherein R.sup.14 and R.sup.16 together form a 2- to 4-membered saturated, hydrocarbyl link, which may contain one or more oxygen heteroatoms.

18. A molecule according to claim 1 wherein R.sup.17 is CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH(CH.sub.3).sub.2, CH.sub.2CHCH.sub.2, CH.sub.2CCH, CH.sub.2CHF.sub.2, CH.sub.2CF.sub.3, CH.sub.2CH.sub.2CF.sub.3, CH.sub.2CF.sub.2CH.sub.3, CH(CH.sub.3)CF.sub.3, CH.sub.2CH.sub.2CH.sub.2CF.sub.3, CHCHCH.sub.2CF.sub.3, 3,3-difluorocyclobutyl, CH.sub.2CH.sub.2cyclopropyl, and CH.sub.2cyclobutyl.

19. A molecule according to claim 1 wherein (A) R.sup.1, R.sup.5, R.sup.6, R.sup.11, and R.sup.12 are H; (B) R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of H, F, Cl, Br, (C.sub.1-C.sub.6)alkyl, and (C.sub.2-C.sub.6)alkenyl; (C) R.sup.7 is (C.sub.1-C.sub.6)haloalkyl; (D) R.sup.9 is H; (E) R.sup.10 is selected from the group consisting of Cl, Br, I, (C.sub.1-C.sub.6)alkyl, and (C.sub.1-C.sub.6)haloalkyl; (G) Q.sup.1 and Q.sup.2 are O; (H) R.sup.13 is selected from the group consisting of H and (C.sub.1-C.sub.6)alkyl; (I) R.sup.14 is selected from the group consisting of (K), (O), H, and (C.sub.1-C.sub.4)alkyl; (J) R.sup.15 is selected from the group consisting of (K), H, and (C.sub.1-C.sub.6)alkyl; (K) R.sup.14 and R.sup.15 together can optionally form a 2- to 5-membered saturated, hydrocarbyl link; (L) L is a bond connecting C(R.sup.14)(R.sup.15) to C=Q.sup.2; (M) X is selected from the group consisting of (1) a bond connecting C(=Q.sup.2) to R.sup.17, and (2) a N, O, and S connecting C(=Q.sup.2) to R.sup.17; (N) R.sup.16 is selected from the group consisting of (O), H, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.2-C.sub.6)alkenyloxy, amino, and NHC(O)O(C.sub.1-C.sub.6)alkyl; (O) R.sup.14 and R.sup.16 together can optionally form a 2- to 4-membered saturated, hydrocarbyl link, which may contain one or more oxygen heteroatoms; (P) R.sup.17 is selected from the group consisting of H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)haloalkenyl, (C.sub.3-C.sub.6)halocycloalkyl, and (C.sub.1-C.sub.6)alkyl(C.sub.3-C.sub.6)cycloalkyl.

20. A pesticidal composition comprising a molecule according to claim 1 further comprising one or more active ingredients.

21. A pesticidal composition according to claim 20 wherein said active ingredient is from AIGA.

22. A pesticidal composition comprising a molecule according to claim 1 further comprising one or more MoA Materials.

23. A pesticidal composition according to claim 22 wherein said MoA Material is from MoAMGA.

24. A pesticidal composition comprising a molecule according to claim 1 and a seed.

25. A process to control a pest said process comprising applying to a locus, a pesticidally effective amount of a pesticidal composition wherein said pesticidal composition comprises a molecule according to claim 1.

26. A molecule according to claim 1 wherein said molecule is selected from one of the following molecules TABLE-US-00019 No. Structure F1 F2 F3 F4 F5 F6 F7 F8 F9 F10 F11 F12 F13 F14 F15 F16 F17 F18 F19 F20 F21 F22 F23 F24 F25 F26 F27 F28 F29 F30 F31 F32 F33 F34 F35 F36 F37 F38 F39 F40 F41 F42 F43 F44 F45 F46 F47 F48 F49 F50 F51 F52 F53 F54 F55 F56 F57 F58 F59 F60 F61 F62 F63 F64 F65 F66 F67 F68 F69 F70 F71 F72 F73 F74 F75 F76 F77 F78 F79 F80 F81 F82 F83 F84 F85 F86 F87 F88 F89 F90 F91 F92 F93 F94 F95 F96 F97 F98 F99 F100 F101 F102 F103 F104 F105 F106 F107 F108 F109 F110 F111 F112 F113 F114 F115 F116 F117 F118 F119 F120 F121 F122 F123 F124 F125 F126 F127 F128 F129 F130 F131 F132 F133 F134 F135 F136 F137 F138 F139 F140 F141 F142 F143 F144 F145 F146 F147 F148 F150 F153 F154 F155 F157 F158 F159 F160 F161 F162 F163 F164 F165 F166 F167 F168 F169 F170 F171 F172 F173 F174 F175 F176 F177 F178 F180 F181 F182 F183 F184 F185 F186 F187 F188 F189 F190 F191 F192 F193 F194 F195 F196 F197 F198 F199 F200 F201 F202 F203 F204 F205 F206 F207 F208 F209 F210 F211 F212 F213 F214 F215 F216 F217

27. A molecule according to claim 1 wherein said molecule is selected from one of the following molecules TABLE-US-00020 No. Structure P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 P11 P12 P13 P14 P15 P16 P17 P18 P19 P20 P21 P22 P23 P24 P25 P26 P27 P28 P29 P30 P31 P32 P33 P34 P35 P37 P39 P40 P41 P42 P43 P44 P45 P46 P47 P48 P49 P50 P51 P52 P53 P54 P55 P56 P57 P58 P59 P60 P61 P62 P63 P64 P65 P66 P67 P68 P69 P70 P71 P72 P73 P74 P75 P76 P77 P78 P79 P80 P81 P82 P83 P84 P85 P86 P87 P88 P89 P90 P91 P92 P93 P94 P95 P96 P97 P98 P99 P100 P101 P102 P103 P104

28. A pesticidal composition according to claim 20 wherein said active ingredient is selected from the group consisting of chlorpyrifos, chlorpyrifos-methyl, methoxyfenozide, spinetoram, spinosad, and sulfoxaflor.

Description

DETAILED DESCRIPTION OF THE DISCLOSURE

(1) This document discloses molecules of Formula One

(2) ##STR00012##
wherein: (A) R.sup.1, R.sup.5, R.sup.6, R.sup.11, and R.sup.12 are each independently selected from the group consisting of H, F, Cl, Br, I, CN, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.4)haloalkoxy; (B) R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of H, F, Cl, Br, I, CN, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (C) R.sup.7 is (C.sub.1-C.sub.6)haloalkyl; (D) R.sup.9 is selected from the group consisting of (F), H, F, Cl, Br, I, CN, (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.1-C.sub.4)alkoxy, and (C.sub.1-C.sub.4)haloalkoxy; (E) R.sup.10 is selected from the group consisting of (F), F, Cl, Br, I, CN, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (F) R.sup.9 and R.sup.10 together can optionally form a 3- to 5-membered saturated or unsaturated, hydrocarbyl link, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, OH, and oxo; (G) Q.sup.1 and Q.sup.2 are each independently O or S; (H) R.sup.13 is selected from the group consisting of H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (I) R.sup.14 is selected from the group consisting of (K), (O), H, (C.sub.1-C.sub.4)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (J) R.sup.15 is selected from the group consisting of (K), H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy; (K) R.sup.14 and R.sup.15 together can optionally form a 2- to 5-membered saturated, hydrocarbyl link, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, and CN; (L) L is selected from the group consisting of (1) a bond, and (2) a (C.sub.1-C.sub.6)alkyl wherein said alkyl is optionally substituted with one or more substituents independently selected from the group consisting of F, Cl, CN, OH, and oxo; (M) X is selected from the group consisting of (1) R.sup.17, and (2) a NR.sup.16R.sup.17, (3) OR.sup.17, and (4) SR.sup.17; (N) R.sup.6 is selected from the group consisting of (O), (Q), H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.2-C.sub.6)alkenyloxy, (C.sub.1-C.sub.6)haloalkoxy, amino, and NHC(O)O(C.sub.1-C.sub.6)alkyl; (O) R.sup.14 and R.sup.16 together can optionally form a 2- to 4-membered saturated link that is either (1) a hydrocarbyl link or (2) a heterohydrocarbyl link that contains one or more heteroatoms selected from the group consisting of nitrogen, sulfur, and oxygen, wherein said link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, OH, and oxo; (P) R.sup.17 is selected from the group consisting of (Q), H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.3-C.sub.6)halocycloalkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.2-C.sub.6)alkenyloxy, (C.sub.1-C.sub.6)haloalkoxy, and (C.sub.1-C.sub.6)alkyl(C.sub.3-C.sub.6)cycloalkyl; (Q) R.sup.16 and R.sup.17 together can optionally form a 2- to 6-membered saturated link that is either (1) a hydrocarbyl link or (2) a heterohydrocarbyl link that contains one or more heteroatoms selected from the group consisting of nitrogen, sulfur, and oxygen, wherein said link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, OH, and oxo; and agriculturally acceptable add addition salts, salt derivatives, solvates, ester derivatives, crystal polymorphs, isotopes, resolved stereoisomers, and tautomers, of the molecules of Formula One.

(3) In another embodiment R.sup.1, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.11, R.sup.12, R.sup.13, R.sup.14 R.sup.15, R.sup.16, and R.sup.17 are H. This embodiment may be used in combination with the other embodiments of R.sup.2, R.sup.7, R.sup.10, Q.sup.1, L, Q.sup.2, and X.

(4) In another embodiment R.sup.2 is F, Cl, Br, or CH.sub.3. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, R.sup.15, L, Q.sup.2, X, R.sup.16, and R.sup.17.

(5) In another embodiment R.sup.3 is F, Cl, Br, or CHCH.sub.2. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.14, L, Q.sup.2, X, R.sup.16, and R.sup.17.

(6) In another embodiment R.sup.4 is Cl, Br, or CH.sub.3. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, R.sup.15, L, Q.sup.2, X, R.sup.16, and R.sup.17.

(7) In another embodiment R.sup.2, R.sup.3, and R.sup.4 are Cl. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, L, Q.sup.2, X, R.sup.16, and R.sup.17.

(8) In another embodiment R.sup.7 is (C.sub.1-C.sub.6)haloalkyl. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, R.sup.15, L, Q.sup.2, X, R.sup.16, and R.sup.17.

(9) In another embodiment R.sup.7 is CF.sub.3, CF.sub.2CH.sub.3, or CF.sub.2CH.sub.2CH.sub.3. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.10, R.sup.11, Q.sup.1, R.sup.13, R.sup.14, L, Q.sup.2, X, and R.sup.17.

(10) In another embodiment R.sup.10 is Cl, Br, I, CH.sub.3, or CF.sub.3. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, R.sup.16, L, Q.sup.2, X, R.sup.16, and R.sup.17.

(11) In another embodiment Q.sup.1 and Q.sup.2 are O. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, L, X, R.sup.16, and R.sup.17.

(12) In another embodiment R.sup.13, R.sup.14, and R.sup.15 are CH.sub.3 or CH.sub.2CH.sub.3. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, L, Q.sup.2, X, R.sup.16, and R.sup.17.

(13) In another embodiment R.sup.14 and R.sup.15 together form a 2-membered saturated, hydrocarbyl link. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, L, Q.sup.2, X, R.sup.16, and R.sup.17.

(14) In another embodiment L is a bond. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.11, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, R.sup.15, Q.sup.2, X, R.sup.1, and R.sup.17.

(15) In another embodiment X is R.sup.17. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.11, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, R.sup.15, L, and Q.sup.2.

(16) In another embodiment X is NR.sup.16R.sup.17. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, R.sup.15, L, and Q.sup.2.

(17) In another embodiment R.sup.16 is CH.sub.3, CH.sub.2CH.sub.3, OCH.sub.3, OCH.sub.2CHCH.sub.2, NH.sub.2, or NHC(O)OC(CH.sub.3).sub.3. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, R.sup.15, L, Q.sup.2, X, and R.sup.17.

(18) In another embodiment R.sup.14 and R.sup.15 together form a 2- to 4-membered saturated link that is either (1) a hydrocarbyl link or (2) a heterohydrocarbyl link that contains one or more oxygen atoms. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.1, R.sup.12, Q.sup.1, R.sup.13, R.sup.15, L, Q.sup.2, X, and R.sup.17.

(19) In another embodiment R.sup.17 is CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH(CH.sub.3).sub.2, CH.sub.2CHCH.sub.2, CH.sub.2CCH, CH.sub.2CHF.sub.2, CH.sub.2CF.sub.3, CH.sub.2CH.sub.2CF.sub.3, CH.sub.2CF.sub.2CH.sub.3, CH(CH.sub.3)CF.sub.3, CH.sub.2CH.sub.2CH.sub.2CF.sub.3, CHCHCH.sub.2CF.sub.3, 3,3-difluorocyclobutyl, CH.sub.2CH.sub.2 cyclopropyl, and CH.sub.2 cyclobutyl. This embodiment may be used in combination with the other embodiments of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, Q.sup.1, R.sup.13, R.sup.14, R.sup.15, L, Q.sup.2, X, and R.sup.16.

(20) In another embodiment: (A) R.sup.1, R.sup.5, R.sup.6, R.sup.11, and R.sup.12 are H; (B) R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of H, F, Cl, Br, (C.sub.1-C.sub.6)alkyl, and (C.sub.2-C.sub.6)alkenyl; (C) R.sup.7 is (C.sub.1-C.sub.6)haloalkyl; (D) R.sup.9 is H; (E) R.sup.10 is selected from the group consisting of Cl, Br, I, (C.sub.1-C.sub.6)alkyl, and (C.sub.1-C.sub.6)haloalkyl; (G) Q.sup.1 and Q.sup.2 are O; (H) R.sup.13 is selected from the group consisting of H and (C.sub.1-C.sub.6)alkyl; (I) R.sup.14 is selected from the group consisting of (K), (O), H, and (C.sub.1-C.sub.4)alkyl; (J) R.sup.15 is selected from the group consisting of (K), H, and (C.sub.1-C.sub.6)alkyl; (K) R.sup.14 and R.sup.15 together can optionally form a 2- to 5-membered saturated, hydrocarbyl link; (L) L is a bond; (M) X is selected from the group consisting of (1) R.sup.17, and (2) a NR.sup.16R.sup.17; (N) R.sup.16 is selected from the group consisting of (O), H, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.2-C.sub.6)alkenyloxy, amino, and NHC(O)O(C.sub.1-C.sub.6)alkyl; (O) R.sup.14 and R.sup.16 together can optionally form a 2- to 4-membered saturated, link that is either (1) a hydrocarbyl link or (2) a heterohydrocarbyl link that contains one or more oxygen atoms; (P) R.sup.17 is selected from the group consisting of H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.3-C.sub.6)halocycloalkyl, and (C.sub.1-C.sub.6)alkyl(C.sub.3-C.sub.6)cycloalkyl.
Preparation of Benzyl Halides

(21) Benzyl alcohol 1-3, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 are as previously disclosed, may be prepared in several ways. Ketones 1-1 may be prepared by treating bromobenzenes with a lithium base such as n-butyllithium in a polar, aprotic solvent preferably diethyl ether at temperatures from about 78 C. to about 0 C. followed by treatment with esters R.sup.7C(O)O(C.sub.1-C.sub.4)alkyl, wherein R.sup.7 is as previously disclosed, such as ethyl 2,2-difluoropropanoate (not shown). Treatment of ketones 1-1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.7 are as previously disclosed, with a reducing agent such as sodium borohydride, in the presence of a base, such as aqueous sodium hydroxide, in a polar, protic solvent preferably methanol at about 10 C. to about 10 C. may provide benzyl alcohols 1-3 (Scheme 1, step a). Alternatively, aldehydes 1-2, wherein R.sup.6 is H and R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are as previously disclosed, may be allowed to react with trifluorotrimethylsilane in the presence of a catalytic amount of tetrabutylammonium fluoride in a polar, aprotic solvent preferably tetrahydrofuran (Scheme 1, step b) to provide benzyl alcohols 1-3, wherein R.sup.7 is CF.sub.3. Subsequently, benzyl alcohols 1-3 may be converted into benzyl halides 1-4, wherein E is Br, Cl, or I, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 are as previously disclosed, by treatment with a halogenating reagent, such as N-bromosuccinimide, and triethylphosphite in a solvent that does not react with the reagents preferably dichloromethane at about 40 C. to provide benzyl halides 1-4, E is Br (Scheme 1, step c). Alternatively, benzyl alcohols 1-3 may be converted into benzyl halides 1-4, where E is Br by treatment with a sulfonyl chloride such as methanesulfonyl chloride in the presence of a base such as triethylamine and subsequent treatment of the resultant sulfonate with a transition metal bromide such as iron(III) bromide. Additionally, treatment with chlorinating reagents such as thionyl chloride in the presence of a base such as pyridine in a hydrocarbon solvent such as toluene at about 110 C. may provide benzyl halides 1-4, where E is Cl (Scheme 1, step c).

(22) ##STR00013##
Preparation of Fluorinated Vinylbenzoic Esters and Acids

(23) Halobenzoic acids 2-1, wherein R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are as previously disclosed may be converted to halobenzoic acid esters 2-2, wherein R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are as previously disclosed. Halobenzoic acids 2-1, may be treated with an acid, such as sulfuric acid, in the presence of a (C.sub.1-C.sub.8)alcohol such as ethanol, to provide halobenzoic acid ethyl esters 2-2 (Scheme 2, step a). Fluorinated vinylbenzoic acid esters 2-3 may be accessed via reaction of 2-2 with a fluorinated vinyl silane in the presence of a palladium catalyst such as tetrakis(triphenylphospine)palladium(0), a copper additive such as copper(I) iodide, and a fluoride source, such as cesium fluoride in a polar, aprotic solvent preferably 1,3-dimethyl-2-imidazolidinone at temperatures ranging from about ambient temperature to about 45 C., to provide fluorinated vinyl benzoic acid esters 2-3 (Scheme 2, step b). Fluorinated vinyl benzoic acid esters 2-3 may be treated with a metal hydroxide source such as lithium hydroxide in a mixed solvent system comprising a polar, aprotic solvent preferably tetrahydrofuran and polar, protic solvents preferably methanol and water at about ambient temperature to provide fluorinated vinyl benzoic acids 2-4 (Scheme 2, step c).

(24) ##STR00014##

(25) Alternatively, halobenzoic acids 2-1 may be directly treated with a vinyl borane source such as vinyltrifluoroborate or 3-hydroxy-2,3-dimethylbutan-2-yl hydrogen vinylboronate in the presence of a palladium catalyst such as 1,1-bis(diphenylphosphino)ferrocene palladium(II) dichloride, and a base such as potassium carbonate, in a polar, aprotic solvent preferably dimethylsulfoxide at temperatures ranging from about 80 C. to about 140 C., to provide vinyl benzoic acids 3-1, wherein R.sup.1, R.sup.10, R.sup.11, and R.sup.12 are as previously disclosed (Scheme 3, step a). Vinyl benzoic acids 3-1 may be treated with bromine source such as N-bromosuccinimide, and a fluorine source such as triethylamine trihydrofluoride, in a polar, aprotic solvent preferably dichloromethane at about 0 C., to provide bromofluoroalkyl benzoic acids 3-2, wherein R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are as previously disclosed (Scheme 3, step b). Bromofluoroalkyl benzoic acids 3-2 may be treated with a base such as potassium tert-butoxide, in a polar, protic solvent preferably methanol, at temperatures ranging from about 0 C. to about ambient temperature, to provide fluorinated vinyl benzoic acids 2-4 (Scheme 3, step c).

(26) ##STR00015##
Preparation of Fluorinated Phenyl Allylbenzoic Acids

(27) Benzyl halides 1-4 and fluorinated vinylbenzoic acids 2-4 may be treated with a copper(I) source such as copper(I) chloride or copper(I) bromide and a pyridine ligand such as 2,2-bipyridyl in a polar, aprotic solvent preferably N-methyl-2-pyrrolidone, at a temperature between about 100 C. to about 180 C. to provide fluorinated phenyl allylbenzoic acids 4-1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are as previously disclosed (Scheme 4, step a).

(28) ##STR00016##
Preparation of Fluorinated Phenyl Allylbenzoic Amides

(29) Fluorinated phenyl allylbenzoic amides 5-3, wherein Q.sup.1 is O and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.1, L, Q.sup.2, and X are as previously disclosed may be prepared by treatment with amines or amine salts 5-2, wherein R.sup.13, R.sup.14, R.sup.15, L, Q.sup.2, and X are as previously disclosed, and activated carboxylic acids 5-1, wherein A is an activating group, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are as previously disclosed, with a base such as triethylamine, diisopropylethylamine, or 4-methylmorpholine in a polar, aprotic solvent such as dichloromethane, tetrahydrofuran, 1,2-dichloroethane, N,N-dimethylformamide, or any combination thereof, at temperatures between about 0 C. and about 120 C. (Scheme 5, step a).

(30) ##STR00017##
Activated carboxylic acids 5-1 may be an acid halide such as an acid chloride, an acid bromide, or an acid fluoride; a carboxylic ester such as a para-nitrophenyl ester, a pentafluorophenyl ester, an ethyl (hydroxyiminio)cyanoacetate ester, a methyl ester, an ethyl ester, a benzyl ester, an N-hydroxysuccinimidyl ester, a hydroxybenzotriazol-1-yl ester, or a hydroxypyridyltriazol-1-yl ester; an O-acylisourea; an acid anhydride; or a thioester. Acid chlorides may be prepared from the corresponding carboxylic acids by treatment with a dehydrating, chlorinating reagent such as oxalyl chloride or thionyl chloride. Activated carboxylic acids 5-1 may be prepared from carboxylic acids in situ with a uronium salt such as 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate (HATU), O-(benzotriazol-1-yl)-N,N,N,N-tetramethyluronium hexafluorophosphate (HBTU), or (1-cyano-2-ethoxy-2-oxoethylidenaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (COMU). Activated carboxylic acids 5-1 may also be prepared from carboxylic acids in situ with a phosphonium salt such as benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBop). Activated carboxylic acids 5-1 may also be prepared from carboxylic acids in situ with a coupling reagent such as 1-(3-dimethylamino propyl)-3-ethylcarbodiimide, or dicyclohexylcarbodiimide in the presence of a triazole such as hydroxybenzotriazole-monohydrate (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt). O-Acylisoureas may be prepared with a dehydrating carbodimide such as 1-(3-dimethylamino propyl)-3-ethylcarbodiimide or dicyclohexylcarbodiimide. Activated carboxylic acids 5-1 may also be prepared from carboxylic acids in situ with a coupling reagent such as 2-chloro-1,3-dimethylimidazolidinium hexafluorophosphate (CIP) in the presence of a triazole such as 1-hydroxy-7-azabenzotriazole (HOAt).

(31) Amines or amine salts 5-2 may be generated in situ from the corresponding N-tert-butoxycarbonyl amines by treatment with an acid such as hydrogen chloride. Optionally, the amine salts 5-2 may be neutralized in the presence of a base such as sodium bicarbonate or triethylamine prior to reaction with activated carboxylic acids 5-1 or in situ during reaction with activated carboxylic acids 5-1 to provide fluorinated phenyl allylbenzoic amides 5-3.

(32) Fluorinated phenyl allylbenzoic amides 6-1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, Q.sup.1, L, Q.sup.2, and X are as previously disclosed may be exposed to ultraviolet irradiation in deuterated or non-deuterated polar, aprotic solvents such as acetone to provide (E)-fluorinated phenyl allylbenzoic amides 6-2, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, Q.sup.1, L, Q.sup.2, and X are as previously disclosed (Scheme 6, step a).

(33) ##STR00018##

(34) Activated carboxylic acids 5-1 may be treated with amino acids 7-1, wherein R.sup.13 is H, L is a bond, and R.sup.14 and R.sup.15 are as previously disclosed, and a base such as triethylamine, diisopropylethylamine, or 4-methylmorpholine (Scheme 7, step 7a), followed by treatment with a dehydration reagent such as trifluoroacetic anhydride, in a polar, aprotic solvent such as dichloromethane, tetrahydrofuran, 1,2-dichloroethane, N,N-dimethylformamide, or any combination thereof, at temperatures between about 0 C. and about 120 C., to provide azlactone 7-2, wherein L is a bond, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, and R.sup.15 are as previously disclosed (Scheme 7, step b).

(35) ##STR00019##
Azlactone 7-2 may be treated with a nucleophile 7-3, wherein X is as previously disclosed, and a base such as triethylamine, diisopropylethylamine, or 4-methylmorpholine, in a polar, aprotic solvent such as dichloromethane, at temperatures between about 0 C. and about 120 C., to give fluorinated phenyl allylbenzoic amides 7-4, wherein R.sup.13 is H, L is a bond, Q.sup.1 and Q.sup.2 are O, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, and X are as previously disclosed (Scheme 7, step c).

(36) Alternatively, activated carboxylic acids 5-1 may be treated with amino acids 8-1, wherein R.sup.13 is H, and L, R.sup.14, and R.sup.15 are as previously disclosed, and a base such as triethylamine, diisopropylethylamine, or 4-methylmorpholine (Scheme 8, step a), followed with a thionating agent such as Lawesson's reagent to provide thioamide 8-2, wherein Q.sup.1 is S, R.sup.13 is H, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.1, R.sup.12, R.sup.14, R.sup.15, L, and Q.sup.2 are as previously disclosed (Scheme 8, step b).

(37) ##STR00020##
Thioamide 8-2 may be treated with a nucleophile 7-3, wherein X is as previously disclosed, and a base such as triethylamine, diisopropylethylamine, or 4-methylmorpholine, in a polar, aprotic solvent such as dichloromethane, at temperatures between about 0 C. and about 120 C., to give fluorinated phenyl allylbenzoic amides 8-3, wherein Q.sup.1 is S, R.sup.13 is H, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, L, Q.sup.2, and X are as previously disclosed (Scheme 8, step c).
Preparation of Amines and Amine Salts 5-2

(38) Amino acids 8-1 may be treated with di-tert-butyl dicarbonate and a base, such as triethylamine, in a polar, aprotic solvent preferably dichloromethane, at temperatures between about 0 C. and about 120 C., to give carbamate acids 9-2, wherein R.sup.13 is H and L, R.sup.14, and R.sup.15 are as previously disclosed (Scheme 9, step a). Activated carbamate acids 9-2 may be treated with a nucleophile 7-3 and a base such as triethylamine, diisopropylethylamine, or 4-methylmorpholine, in a polar, aprotic solvent preferably dichloromethane, at temperatures between about 0 C. and about 120 C., to give carbamates 9-3 (Scheme 9, step b). Activated carbamate acids 9-2 may be a carbamate ester prepared in situ with a coupling reagent such as 1-(3-dimethylamino propyl)-3-ethylcarbodiimide, or dicyclohexylcarbodiimide in the presence of a triazole such as hydroxybenzotriazole-monohydrate (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt). O-Acylisoureas may be prepared with a dehydrating carbodimide such as 1-(3-dimethylamino propyl)-3-ethylcarbodiimide or dicyclohexylcarbodiimide. Carbamate esters may also be prepared from carboxylic acids in situ with a coupling reagent such as 2-chloro-1,3-dimethylimidazolidinium hexafluorophosphate (CIP) in the presence of a triazole such as 1-hydroxy-7-azabenzotriazole (HOAt). Carbamates 9-3 may be treated with an alkylating agent 9-4, wherein LG is a leaving group selected from mesylate, tosylate, triflate, halide, and carboxylate, and R.sup.13 is as previously disclosed, and a base such as sodium hydride or cesium carbonate, in a polar, aprotic solvent such as diethyl ether, tetrahydrofuran, or dioxane, at temperatures between about 0 C. and about 120 C., to give carbamates 9-5, wherein R.sup.13 is not H, and R.sup.13, R.sup.14 and R.sup.15 are as previously disclosed (Scheme 9, step e).

(39) ##STR00021##
Carbamates 9-3 and 9-5 may be treated with an acid such as hydrochloric acid, in a polar, aprotic solvent preferably dichloromethane, at temperatures between about 0 C. and about 120 C., to give amine salts 5-2, wherein Q.sup.2 is O (Scheme 9, step c). Amine salts 5-2 may be neutralized in the presence of a base such as sodium bicarbonate or triethylamine. Alternatively, carbamates 9-3 and 9-5 may be treated with a thionating agent such as Lawesson's reagent (Scheme 9, step d), prior to the acid promoted deprotection, to give amine salts 5-2, wherein Q.sup.2 is S (Scheme 9, step c).

EXAMPLES

(40) These examples are for illustration purposes and are not to be construed as limiting this disclosure to only the embodiments disclosed in these examples.

(41) Starting materials, reagents, and solvents that were obtained from commercial sources were used without further purification. Anhydrous solvents were purchased as Sure/Seal from Aldrich and were used as received. Melting points were obtained on a Thomas Hoover Unimelt capillary melting point apparatus or an OptiMelt Automated Melting Point System from Stanford Research Systems and are uncorrected. Examples using room temperature were conducted in climate controlled laboratories with temperatures ranging from about 20 C. to about 24 C. Molecules are given their known names, named according to naming programs within ISIS Draw, ChemDraw, or ACD Name Pro. If such programs are unable to name a molecule, such molecule is named using conventional naming rules. .sup.1H NMR spectral data are in ppm () and were recorded at 300, 400, 500, or 600 MHz; .sup.13C NMR spectral data are in ppm () and were recorded at 75, 100, or 150 MHz, and .sup.19F NMR spectral data are in ppm () and were recorded at 376 MHz, unless otherwise stated.

Example 1: Preparation of (Z)-2-bromo-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoic acid (C1)

(42) ##STR00022##

(43) To a 25 mL round-bottomed flask were added 2,2-bipyridine (0.255 g, 1.63 mmol), 2-bromo-4-(1-fluorovinyl)benzoic acid (C24) (1.00 g, 4.08 mmol), and 5-(1-bromo-2,2,2-trifluoroethyl)-1,2,3-trichlorobenzene (2.79 g, 8.16 mmol) in N-methylpyrrolidone (2.0 mL) to give a yellow solution. Copper(I) bromide (0.117 g, 0.816 mmol) was added and the reaction mixture was purged with nitrogen for 5 minutes. The reaction was then heated to 150 C. for 3 hours. The reaction mixture was poured into ice water (100 mL). The water was filtered and the resultant black gum was dissolved in ethyl acetate (800 mL), washed with brine (2200 mL), and water (2200 mL), dried over magnesium sulfate, filtered, and concentrated to provide the title compound as a brown oil (1.40 g, 64%):

(44) .sup.1H NMR (400 MHz, CDCl.sub.3) 8.03 (d, J=8.2 Hz, 1H), 7.89 (d, J=1.8 Hz, 1H), 7.59 (dd, J=8.3, 1.8 Hz, 1H), 7.43 (s, 2H), 5.83 (dd, J=32.4, 9.6 Hz, 1H), 4.60 (p, J=8.8 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 69.32 (d, J=2.3 Hz), 108.70-119.01 (m); ESIMS m/z 505 ([MH].sup.).

(45) The following compounds were prepared in like manner to the procedure outlined in Example 1:

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C2)

(46) ##STR00023##

(47) Isolated as a yellow oil (7.6 g, 68%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.04 (d, J=8.2 Hz, 1H), 7.99-7.94 (m, 1H), 7.84 (dd, J=8.2, 1.8 Hz, 1H), 7.44 (s, 2H), 5.90 (dd, J=32.4, 9.6 Hz, 1H), 4.62 (p, J=8.9 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.60, 69.28 (d, J=2.3 Hz), 112.11; ESIMS m/z 493 ([MH].sup.).

(Z)-4-(1,4,4-Trifluoro-3-(3,4,5-trichlorophenyl)pent-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C3)

(48) ##STR00024##

(49) Isolated as a yellow foam (0.628 g, 60%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.00 (d, J=8.2 Hz, 1H), 7.95 (d, J=8.8 Hz, 1H), 7.81 (d, J=8.3 Hz, 1H), 7.42 (s, 2H), 5.96 (dd, J=33.6, 9.8 Hz, 1H), 4.29 (td, J=14.3, 9.8 Hz, 1H), 1.65 (t, J=18.4 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.61, 92.97-97.35 (m), 114.82; ESIMS m/z 491 ([MH].sup.).

(Z)-2-Chloro-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoic acid (C4)

(50) ##STR00025##

(51) Isolated as a white solid (4.27 g, 88%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.07 (d, J=8.2 Hz, 1H), 7.68 (d, J=1.7 Hz, 1H), 7.54 (dd, J=8.3, 1.8 Hz, 1H), 7.43 (s, 2H), 5.85 (dd, J=32.4, 9.6 Hz, 1H), 4.60 (p, J=8.8 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 69.33 (d, J=2.2 Hz), 112.18 (d, J=2.4 Hz); ESIMS m/z 461 ([MH].sup.).

(Z)-4-(3-(3,5-Dibromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C5)

(52) ##STR00026##

(53) Isolated as a brown gum (2.00 g, 37%): ESIMS m/z 583 ([MH].sup.).

(Z)-4-(3-(3,5-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C6)

(54) ##STR00027##

(55) Isolated as a brown gum (0.50 g, 43%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 13.9 (br s, 1H), 8.16 (s, 1H), 8.09 (d, J=8.0 Hz, 1H), 7.92 (d, J=8.0 Hz, 1H), 7.82 (s, 2H), 7.64 (t, J=6.0 Hz, 1H), 6.90 (dd, J=36.0, 10.4 Hz, 1H), 5.26-5.17 (m, 1H); IR (thin film) 3416, 2926, 1716, 1119 cm.sup.1; ESIMS m/z 449 ([M+H].sup.+).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C7)

(56) ##STR00028##

(57) Isolated as a brown gum (2.50 g, 56%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.9 (br s, 1H), 8.16 (s, 1H), 8.09 (d, J=10.8 Hz, 1H), 8.08 (s, 1H), 7.92 (d, J=8.1 Hz, 1H), 7.75-7.65 (m, 2H), 6.90 (dd, J=36.0, 10.4 Hz, 1H), 5.22-5.16 (m, 1H); IR (thin film) 3440, 2927, 1716, 1175 cm.sup.1; ESIMS m/z 459 ([MH].sup.).

(Z)-4-(3-(3,5-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C8)

(58) ##STR00029##

(59) Isolated as a brown gum (2.20 g, 39%): .sup.1H NMR (300 MHz, CDCl.sub.3) 8.05-7.95 (m, 2H), 7.84 (d, J=7.2 Hz, 1H), 7.69-7.68 (m, 1H), 7.49 (s, 2H), 5.95 (dd, J=32.7, 9.6 Hz, 1H), 4.64-4.58 (p, 1H); IR (thin film) 3439, 2925, 1714, 1118, 746 cm.sup.1; ESIMS m/z 549 ([MH].sup.).

(Z)-4-(3-(3,5-Dichloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C9)

(60) ##STR00030##

(61) Isolated as a brown gum (1.20 g, 54%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.88 (s, 2H), 7.76-7.75 (m, 1H), 7.37 (d, J=6.0 Hz, 2H), 5.90 (dd, J=32.1, 9.0 Hz, 1H), 4.62-4.56 (p, 1H); IR (thin film) 3445, 2926, 1698, 1260, 750 cm.sup.1; ESIMS m/z 477 ([MH].sup.).

(Z)-4-(3-(4-Chloro-3,5-dimethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C10)

(62) ##STR00031##

(63) Isolated as a yellow gum (2.20 g, 53%): .sup.1H NMR (300 MHz, CDCl.sub.3) 8.01 (d, J=8.1 Hz, 1H), 7.94 (s, 1H), 7.83 (d, J=8.1 Hz, 1H), 7.11 (s, 2H), 6.00 (dd, J=33.0, 9.9 Hz, 1H), 4.58-4.55 (m, 1H), 2.40 (s, 6H); IR (thin film) 3445, 1713, 852 cm.sup.1; ESIMS m/z 453 ([MH].sup.).

(Z)-4-(3-(4-Bromo-3,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C11)

(64) ##STR00032##

(65) Isolated as a brown solid (1.50 g, 65%): mp 78-81 C.; .sup.1H NMR (300 MHz, CDCl.sub.3) 8.09-7.99 (m, 2H), 7.83-7.81 (m, 1H), 7.42 (s, 2H), 5.95 (dd, J=32.4 Hz, 9.6 Hz, 1H), 4.63-4.57 (m, 1H); IR (thin film) 3445, 1713, 852 cm.sup.1; ESIMS m/z 538 ([M+H].sup.+).

(Z)-4-(3-(3-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C12)

(66) ##STR00033##

(67) Isolated as a brown gum (2.0 g, 62%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.80 (br s, 1H), 8.15 (s, 1H), 8.09 (d, J=8.1 Hz, 1H), 7.93-7.78 (m, 4H), 6.91 (dd, J=35.7, 10.2 Hz, 1H), 5.27-5.14 (m, 1H); IR (thin film) 3081, 2927, 1714, 776 cm.sup.1; ESIMS m/z 503 ([MH].sup.).

(Z)-4-(3-(3,4-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C13)

(68) ##STR00034##

(69) Isolated as a yellow gum (2.1 g, 78%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.02 (d, J=8.4 Hz, 1H), 7.94 (s, 1H), 7.83 (d, J=8.4 Hz, 1H), 7.66 (d, J=8.4 Hz, 2H), 7.26-7.21 (m, 1H), 5.96 (dd, J=32.4, 9.2 Hz, 1H), 4.67-4.58 (p, 1H); IR (thin film) 3426, 2925, 1714, 1115 cm.sup.1; ESIMS m/z 547 ([MH].sup.).

(Z)-2-Methyl-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoic acid (C14)

(70) ##STR00035##

(71) Isolated as an orange oil (0.94 g, 61%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.09 (d, J=8.8 Hz, 1H), 7.49-7.45 (m, 2H), 7.44 (s, 2H), 5.80 (dd, J=32.7, 9.6 Hz, 1H), 4.60 (p, J=8.9 Hz, 1H), 2.69 (s, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 69.40 (d, J=2.3 Hz), 108.40-115.65 (m); ESIMS m/z 441 ([MH].sup.).

(Z)-2-Methyl-4-(1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)pent-1-en-1-yl)benzoic acid (C15)

(72) ##STR00036##

(73) Isolated as an orange foam (0.204 g, 51%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.07 (d, J=8.8 Hz, 1H), 7.49-7.40 (m, 4H), 5.86 (dd, J=33.9, 9.9 Hz, 1H), 4.27 (td, J=14.3, 9.7 Hz, 1H), 2.68 (s, 3H), 1.65 (t, J=18.4 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 95.11, 95.18, 114.57; ESIMS m/z 437 ([MH].sup.).

(Z)-4-(1,4,4-Trifluoro-3-(3,4,5-trichlorophenyl)hex-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C16)

(74) ##STR00037##

(75) Isolated as an orange foam (0.136 g, 63%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.99 (dd, J=8.4, 4.0 Hz, 1H), 7.93 (s, 1H), 7.80 (d, J=7.9 Hz, 1H), 7.42 (d, J=2.6 Hz, 2H), 6.08-5.87 (m, 1H), 4.32 (td, J=14.6, 9.8 Hz, 1H), 1.87 (ddt, 1=21.6, 15.4, 8.0 Hz, 2H), 1.07 (t, J=7.4 Hz, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 170.72, 156.96 (d, J.sub.CF=253.0 Hz), 136.85, 135.06, 134.53, 133.75, 131.90, 131.19, 130.18, 129.17, 128.60, 128.05, 127.29, 124.11, 123.36-122.67 (m), 121.39, 104.66 (d, J.sub.CF=18.0 Hz), 46.46, 29.70-27.14 (m), 6.40-5.44 (m); ESIMS m/z 503 ([MH].sup.).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4-trifluoropent-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C17)

(76) ##STR00038##

(77) Isolated as an orange glass (0.495 g, 51%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.01 (d, J=8.2 Hz, 1H), 7.94 (d, J=1.6 Hz, 1H), 7.80 (dd, J=8.2, 1.8 Hz, 1H), 7.49 (d, J=2.1 Hz, 1H), 7.45 (d, J=8.3 Hz, 1H), 7.26 7.22 (m, 1H), 6.00 (dd, J=33.9, 9.8 Hz, 1H), 4.32 (ddd, J=15.8, 13.0, 9.8 Hz, 1H), 1.62 (t, J=18.4 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.58, 89.79-99.81 (m) 115.63; IR (thin film) 3008, 1711 cm.sup.1; ESIMS m/z 455 ([MH].sup.).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4-trifluoropent-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C18)

(78) ##STR00039##

(79) Isolated as a brown gum (2.5 g, 46%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.79 (br s, 1H), 8.15-8.06 (m, 3H), 7.91 (d, J=8.1 Hz, 1H), 7.71 (s, 2H), 6.90 (dd, J=36.0, 10.2 Hz, 1H), 5.21-5.15 (m, 1H); IR (thin film) 3431, 2924, 1623, 597 cm.sup.1; ESIMS m/z 503 ([MH].sup.).

(Z)-4-(3-(3-Chloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C19)

(80) ##STR00040##

(81) Isolated as a yellow gum (1.50 g, 57%): .sup.1H NMR (300 MHz, CDCl.sub.3) 8.01 (d, J=8.1 Hz, 2H) 7.94 (s, 2H), 7.76-7.75 (m, 1H), 7.37 (d, J=6.0 Hz, 2H), 5.90 (dd, J=32.1, 9.0 Hz, 1H); IR (thin film) 3445, 2926, 1698, 1260, 750 cm.sup.1; ESIMS m/z 443 ([MH].sup.).

(Z)-4-(3-(4-Chloro-3-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C20)

(82) ##STR00041##

(83) Isolated as a brown gum (0.50 g, 48%): .sup.1H NMR (300 MHz, CDCl.sub.3) 8.03 (d, J=8.1 Hz, 1H), 7.94 (s, 1H), 7.83 (d, J=7.8 Hz, 1H), 7.46-7.44 (m, 1H), 7.23-7.13 (m, 2H), 5.98 (dd, J=34.2, 9.9 Hz, 1H), 4.69-4.63 (m, 1H); IR (thin film) 3092, 1751, 750 cm.sup.1; ESIMS m/z 443 ([MH].sup.).

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoic acid (CC1)

(84) ##STR00042##

(85) Isolated as a yellow gum (1.1 g, 56%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.15 (d, J=8.2 Hz, 2H), 7.67 (d, J=8.3 Hz, 2H), 7.44 (s, 2H), 5.84 (dd, J=32.6, 9.6 Hz, 1H), 4.61 (p, J=8.9 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 69.38 (d, J=2.2 Hz), 109.75-116.47 (m); ESIMS m/z 427 ([MH].sup.).

Example 2: Preparation of (Z)-2-iodo-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoic acid (C21)

(86) ##STR00043##

(87) To a 25 mL vial were added (Z)-2-bromo-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoic acid (C1) (0.500 g, 0.987 mmol), copper(I) iodide (0.0094 g, 0.049 mmol), and 1,4-dioxane (4.9 mL) to form a yellow suspension. Sodium iodide (0.296 g, 1.97 mmol) and trans-N,N-dimethylcyclohexane-1,2-diamine (0.014 g, 0.099 mmol) were added, and the reaction mixture was stirred at 110 C. for 3.5 hours. The reaction mixture was concentrated and purified by flash column chromatography to provide the title compound as a brown oil (0.247 g, 43%): .sup.1H NMR (300 MHz, CDCl.sub.3) 8.21 (d, J=1.7 Hz, 1H), 8.02 (d, J=8.2 Hz, 1H), 7.62 (dd, J=8.3, 1.7 Hz, 1H), 7.43 (s, 2H), 5.82 (dd, J=32.5, 9.6 Hz, 1H), 4.59 (p, J=8.9 Hz, 1H); .sup.19F NMR (471 MHz, CDCl.sub.3) 69.32, 112.14 (d, J=20.8 Hz); ESIMS m/z 553 ([MH].sup.).

Example 3: Preparation of (Z)-2-iodo-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzoic acid (C22)

(88) ##STR00044##

(89) Tetrakis(triphenylphosphine)palladium(0) (0.30 g, 0.26 mmol) was added to a solution of (Z)-4-(3-(4-bromo-3,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C11) (1.4 g, 2.6 mmol) in toluene (10 mL) at room temperature. The reaction mixture was degassed by purging with nitrogen (310 minutes). Tributyl vinyl stannane (0.82 g, 2.6 mmol) was added to the reaction mixture. The reaction mixture was again degassed by purging with nitrogen (310 minutes) and stirred at 120 C. for 3 hours. The reaction mixture was quenched with water and then extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using 30% ethyl acetate/hexanes provided the title compound as a pale yellow gum (0.80 g, 63%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.85 (s, 1H), 7.82 (d, J=8.4 Hz, 1H), 7.74 (d, J=8.4 Hz, 1H), 7.42 (s, 1H), 7.37 (s, 1H), 6.72-6.65 (dd, J=17.6 Hz, 11.6 Hz, 1H), 5.86-5.73 (m, 3H), 4.61-4.56 (m, 1H); IR (thin film) 3445, 2925, 1646, 1275, 749 cm.sup.1; ESIMS m/z 488 ([M+H].sup.+).

Example 4: Preparation of (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoyl chloride (C23)

(90) ##STR00045##

(91) To a 25 mL vial was added (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C2) (0.200 g, 0.404 mmol), oxalyl chloride (0.095 mL, 1.09 mmol), and N,N-dimethylformamide (catalytic amount) in dichloromethane (1.3 mL) to give a yellow solution. The reaction was stirred for 15 hours at room temperature. The solvent was removed under vacuum providing the title compound as a yellow gum (0.220 g, 95%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.99 (d, J=8.2 Hz, 1H), 7.92 (d, J=1.7 Hz, 1H), 7.81 (dd, J=8.2, 1.8 Hz, 1H), 7.44 (s, 2H), 5.88 (dd, J=32.5, 9.6 Hz, 1H), 4.73-4.50 (m, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.58, 69.32, 109.75-113.19 (m); IR (thin film) 3445, 2925, 1646, 1275, 749 cm.sup.1; ESIMS m/z 476 ([MCl].sup.+).

Example 5: Preparation of 2-bromo-4-(1-fluorovinyl)benzoic acid (C24)

(92) ##STR00046##

(93) To a 250 mL round-bottomed flask were added methyl 2-bromo-4-(1-fluorovinyl)benzoate (C29) (1.8 g, 7.0 mmol), lithium hydroxide hydrate (0.88 g, 21 mmol), methanol (7.0 mL), tetrahydrofuran (21 mL), and water (7.0 mL), and the reaction mixture was stirred overnight at room temperature. The mixture was concentrated, quenched with a pH 4 buffer, and extracted with ethyl acetate to provide the title compound as a white solid (1.0 g, 56%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.01 (d, J=8.2 Hz, 1H), 7.89 (d, J=1.8 Hz, 1H), 7.57 (dd, J=8.3, 1.8 Hz, 1H), 5.21 (dd, J=48.6, 4.0 Hz, 1H), 5.06 (dd, J=17.3, 3.9 Hz, 1H); .sup.19F NMR (471 MHz, CDCl.sub.3) 108.71 (d, J=1.4 Hz); ESIMS m/z 244 ([MH].sup.).

(94) The following compounds were prepared in like manner to the procedure outlined in Example 5:

4-(1-Fluorovinyl)-2-(trifluoromethyl)benzoic acid (C25)

(95) ##STR00047##

(96) Isolated as a white solid (1.9 g, 93%): .sup.1H NMR (400 MHz, methanol-d.sub.4) 7.95 (d, J=1.5 Hz, 1H), 7.95-7.91 (m, 1H), 7.90-7.86 (m, 1H), 5.46 (dd, J=50.0, 4.1 Hz, 1H), 5.09 (dd, J=18.0, 4.1 Hz, 1H); .sup.19F NMR (376 MHz, methanol-d.sub.4) 61.04 (d, J=1.1 Hz), 110.93; ESIMS m/z 233 ([MH].sup.).

2-Chloro-4-(1-fluorovinyl)benzoic acid (C26)

(97) ##STR00048##

(98) Isolated as a white solid (3.5 g, 75%): .sup.1H NMR (400 MHz, acetone-d.sub.6) 7.97 (dd, J=8.2, 0.9 Hz, 1H), 7.76 (d, J=1.7 Hz, 1H), 7.70 (dd, J=8.2, 1.7 Hz, 1H), 5.68-5.45 (m, 1H), 5.11 (dd, J=18.2, 4.1 Hz, 1H); .sup.19F NMR (376 MHz, acetone-d.sub.6) 108.71; ESIMS m/z 200 ([MH].sup.).

4-(1-fluorovinyl)-2-methylbenzoic acid (C27)

(99) ##STR00049##

(100) Isolated as a white solid (0.550 g, 89%): .sup.1H NMR (400 MHz, methanol-d.sub.4) 7.92 (d, J=8.1 Hz, 1H), 7.59-7.52 (m, 1H), 7.52-7.44 (m, 1H), 5.29 (dd, J=50.1, 3.7 Hz, 1H), 4.93 (dd, J=18.1, 3.7 Hz, 1H), 2.60 (s, 3H); .sup.19F NMR (376 MHz, methanol-d.sub.4) 110.32 (d, J=2.1 Hz); ESIMS m/z 181 ([M+H].sup.+).

Example 6: Preparation of methyl 4-(1-fluorovinyl)-2-(trifluoromethyl)benzoate (C28)

(101) ##STR00050##

(102) To a 100 mL round-bottomed flask was added methyl 4-bromo-2-(trifluoromethyl)benzoate (2.25 g, 8.00 mmol), (1-fluorovinyl)(methyl)diphenylsilane (3.58 g, 14.8 mmol), and 1,3-dimethylimidazolidin-2-one (40 mL). Tetrakis(triphenylphosphine)palladium(0) (0.459 g, 0.400 mmol), copper(I) iodide (0.0760 mg, 0.400 mmol), and cesium fluoride (3.62 g, 23.9 mmol) were added and the reaction was stirred at room temperature for 24 hours under a nitrogen atmosphere. Water was added to the mixture and the mixture was diluted with 3:1 hexanes/diethyl ether. The layer was separated, and the organic layer was dried over sodium sulfate, concentrated, and the residue was purified by flash column chromatography provided the title compound as a colorless oil (2.00 g, 96%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.96-7.87 (m, 1H), 7.83 (dq, J=8.1, 0.7 Hz, 1H), 7.77 (dd, J=8.2, 1.7 Hz, 1H), 5.23 (dd, J=48.6, 4.0 Hz, 1H), 5.07 (dd, J=17.4, 4.0 Hz, 1H), 3.95 (s, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.92, 108.73 (d, J=1.4 Hz); EIMS m/z 248 ([M].sup.+).

(103) The following compounds were prepared in like manner to the procedure outlined in Example 6:

Methyl 2-bromo-4-(1-fluorovinyl)benzoate (C29)

(104) ##STR00051##

(105) Isolated as a colorless oil (1.8 g, 93%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.84 (d, J=1.7 Hz, 1H), 7.82 (dd, J=8.2, 0.9 Hz, 1H), 7.50 (d, J=1.5 Hz, 1H), 5.16 (dd, J=48.7, 3.9 Hz, 1H), 5.01 (dd, J=17.3, 3.9 Hz, 1H), 3.94 (d, J=2.2 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 108.61 (d, J=1.5 Hz); ESIMS m/z 258 ([MH].sup.).

Methyl 2-chloro-4-(1-fluorovinyl)benzoate (C30)

(106) ##STR00052##

(107) Isolated as a colorless oil (2.1 g, 99%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (dd, J=8.2, 0.9 Hz, 1H), 7.64 (d, J=1.7 Hz, 1H), 7.48 (dd, J=8.3, 1.8 Hz, 1H), 5.17 (dd, J=48.7, 3.8 Hz, 1H), 5.02 (dd, J=17.3, 3.9 Hz, 1H), 3.94 (s, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 108.63 (d, J=1.4 Hz); ESIMS m/z 214 ([MH].sup.).

Methyl 2-chloro-4-(1-fluorovinyl)benzoate (C31)

(108) ##STR00053##

(109) Isolated as a colorless oil (0.5 g, 85%): .sup.1H NMR (400 MHz, methanol-d.sub.4) 7.90 (d, J=8.2 Hz, 1H), 7.51 (s, 1H), 7.49 (dd, J=8.0, 1.6 Hz, 1H), 5.30 (dd, J=50.1, 3.7 Hz, 1H), 4.95 (dd, J=18.0, 3.7 Hz, 1H), 3.88 (d, J=5.9 Hz, 3H), 2.59 (s, 3H); .sup.19F NMR (376 MHz, methanol-d.sub.4) 110.41 (d, J=1.3 Hz); ESIMS m/z 195 ([M+H].sup.+).

Example 7: Preparation of 4-(1-fluorovinyl)-2-(trifluoromethyl)benzoic acid (C25)

(110) ##STR00054##

Step 1: 4-(2-bromo-1-fluoroethyl)-2-(trifluoromethyl)benzoic acid (C32)

(111) 2-(Trifluoromethyl)-4-vinylbenzoic acid (5.3 g, 24 mmol) was dissolved in dichloromethane (123 mL) at 0 C., triethylamine trihydrofluoride was added (8.0 mL, 49 mmol) followed by N-bromosuccinimide (8.7 g, 49 mmol). The reaction mixture was stirred for 16 hours while warming to room temperature. Water was then added to the mixture, washed with dichloromethane, dried over sodium sulfate, filtered, and concentrated providing the title compound as a yellow oil which was used without further purification (5.0 g, 65%).

Step 2: 4-(1-fluorovinyl)-2-(trifluoromethyl)benzoic acid (C25)

(112) 4-(2-Bromo-1-fluoroethyl)-2-(trifluoromethyl)benzoic acid (4.3 g, 14 mmol) was dissolved in methanol (68 mL) at 0 C. and potassium tert-butoxide (4.6 g, 41 mmol) was added as a solid while stirring. The reaction mixture was allowed to slowly warm to 23 C. and then stirred for 4 hours. Hydrochloric acid (1 N) was slowly added, and the mixture was extracted with ethyl acetate. Purification by flash column chromatography using 0-40% acetone/hexanes provided the title compound as an off-white solid (1.7 g, 53%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.02 (d, J=8.2 Hz, 1H), 8.00-7.93 (m, 1H), 7.82 (dd, J=8.2, 1.8 Hz, 1H), 5.27 (dd, J=48.5, 4.1 Hz, 1H), 5.11 (dd, J=17.3, 4.1 Hz, 1H).

(113) The following compounds were prepared in like manner to the procedure outlined in Example 7:

4-(1-Fluorovinyl)benzoic acid (C33)

(114) ##STR00055##

(115) Isolated as a white solid (6.5 g, 86%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.13 (d, J=8.2 Hz, 2H), 7.69-7.62 (m, 2H), 5.21 (dd, J=49.0, 3.7 Hz, 1H), 5.02 (dd, J=17.5, 3.7 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 108.35; ESIMS m/z 165 ([MH].sup.).

4-(1-Fluorovinyl)-2-methylbenzoic acid (C27)

(116) ##STR00056##

(117) Isolated as a colorless oil (0.165 g, 89%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.12-8.03 (m, 1H), 7.46 (dd, J=5.8, 2.1 Hz, 2H), 5.17 (dd, J=49.1, 3.7 Hz, 1H), 4.98 (dd, J=17.5, 3.7 Hz, 1H), 2.68 (s, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 5-108.50.

Example 8: Preparation of 5-(1-bromo-2,2-difluoropropyl)-1,2,3-trichlorobenzene (C34)

(118) ##STR00057##

(119) N-Bromosuccinimide (12.0 g, 67.5 mmol) was added to a solution of 2,2-difluoro-1-(3,4,5-trichlorophenyl)propan-1-ol (C43) (6.00 g, 21.8 mmol) in dichloromethane (72.6 mL). To this stirred solution was added triphenyl phosphite (17.1 mL, 65.3 mmol) slowly, dropwise, and the reaction mixture became dark brown. The reaction mixture was then heated at reflux for 3 hours. The solvent was concentrated, and the residue was triturated with diethyl ether. The solid was filtered, the filtrate was concentrated and the resultant oil was purified by flash column chromatography using hexanes as eluent to provide the title compound as a clear and colorless oil (2.20 g, 25%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.52 (s, 2H), 4.85 (dd, J=12.3, 10.4 Hz, 1H), 1.77 (t, J=18.2 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 92.14-95.01 (m); EIMS m/z 338 ([M].sup.+).

(120) The following compounds were prepared in like manner to the procedure outlined in Example 8:

1,3-Dibromo-5-(1-bromo-2,2,2-trifluoroethyl)-2-chlorobenzene (C35)

(121) ##STR00058##

(122) Isolated as a clear oil (28 g, 56%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.01-7.97 (m, 2H), 6.26-6.20 (m, 1H); IR (thin film) 1168, 736, 557 cm.sup.1; ESIMS m/z 428 ([M+H].sup.+).

5-(1-Bromo-2,2,2-trifluoroethyl)-2-chloro-1,3-dimethylbenzene (C36)

(123) ##STR00059##

(124) Isolated as a clear oil (6.32 g, 89%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 7.39 (s, 2H), 6.17-6.09 (m, 1H), 2.35 (s, 6H); IR (thin film) 1114, 754 cm.sup.1; ESIMS m/z 302 ([M+H].sup.+).

2-Bromo-5-(1-bromo-2,2,2-trifluoroethyl)-1,3-dichlorobenzene (C37)

(125) ##STR00060##

(126) Isolated as a clear oil (19 g, 46%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.54-7.51 (m, 2H), 5.03-4.98 (m, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 10-70.38.

4-(1-Bromo-2,2-difluoropropyl)-1,2-dichlorobenzene (C38)

(127) ##STR00061##

(128) Isolated as a colorless liquid (1.40 g, 65%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 7.76-7.70 (m, 2H), 7.54 (dd, J=8.4, 1.8 Hz, 1H), 5.81-5.73 (m, 1H), 1.67 (d, 1=18.9 Hz, 3H); IR (thin film) 1118, 800, 499 cm.sup.1; EIMS m/z 304 ([M].sup.+).

2-Bromo-4-(1-bromo-2,2,2-trifluoroethyl)-1-chlorobenzene (C39)

(129) ##STR00062##

(130) Isolated as a colorless liquid (10.5 g, 54%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.76 (d, J=1.2 Hz, 1H), 7.49-7.47 (m, 1H), 7.41-7.39 (m, 1H), 5.07-5.02 (m, 1H); IR (thin film) 3437, 2924, 1631, 1114 cm.sup.1; EIMS m/z 350 ([M].sup.+).

4-(1-Bromo-2,2,2-trifluoroethyl)-2-chloro-1-fluorobenzene (C40)

(131) ##STR00063##

(132) Isolated as a colorless oil (8.0 g, 73%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.59-7.57 (m, 1H), 7.42-7.33 (m, 1H), 7.20-7.14 (m, 1H), 5.10-5.03 (m, 1H); IR (thin film) 3429, 2926, 1502, 750 cm.sup.1; ESIMS m/z 292 ([M+H].sup.+).

4-(1-Bromo-2,2,2-trifluoroethyl)-1-chloro-2-fluorobenzene (C41)

(133) ##STR00064##

(134) Isolated as a yellow oil (1.1 g, 45%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.44 (dd, J=8.3, 7.5 Hz, 2H), 7.34 (dd, J=9.5, 1.9 Hz, 1H), 7.26-7.22 (m, 1H), 5.08 (q, J=7.1 Hz, 1H); EIMS m/z 291 ([M].sup.+).

Example 9: Preparation of 5-(1-bromo-2,2-difluorobutyl)-1,2,3-trichlorobenzene (C42)

(135) ##STR00065##

(136) Triethylamine (2.46 mL, 17.6 mmol) and methanesulfonyl chloride (1.10 mL, 14.1 mmol) were added to a solution of 2,2-difluoro-1-(3,4,5-trichlorophenyl)butan-1-ol (C44) (3.40 g, 11.7 mmol) in dichloromethane (58.7 mL). The reaction mixture was stirred for 1 hour, and then pentane was added. Filtration followed by concentration of the filtrate under vacuum provided a white solid. The solid was dissolved in dichloromethane (58.7 mL) to which iron(III) bromide (6.94 g, 23.5 mmol) was added. The reaction mixture was stirred overnight. The mixture was poured into water and then extracted with dichloromethane. The organics were washed with brine, dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using hexanes as eluent provided the title compound as a white solid (3.52 g, 72%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.51 (s, 2H), 4.85 (t, J=12.1 Hz, 1H), 2.14-1.91 (m, 2H), 1.06 (t, J=7.5 Hz, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 135.55, 134.39, 132.52, 129.48, 120.25 (t, J=249.0 Hz), 49.76 (t, J=30.3 Hz), 28.03 (t, J=25.2 Hz), 6.06 (t, J=5.1 Hz); ESIMS m/z 351 ([MH].sup.).

Example 10: Preparation of 2,2-difluoro-1-(3,4,5-trichlorophenyl)propan-1-ol (C43)

(137) ##STR00066##

(138) 2,2-Difluoro-1-(3,4,5-trichlorophenyl)propan-1-one (C52) (1.75 g, 6.40 mmol) was dissolved in methanol (64.0 mL) at room temperature and sodium borohydride (0.290 g, 7.68 mmol) was added. The reaction stirred at room temperature for 1 hour, until gas evolution ceased. The reaction mixture was poured into water and extracted with diethyl ether. The organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using 0-30% acetone/hexanes as eluent provided the title compound as a clear, colorless oil (1.60 g, 91%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.50 (d, J=0.9 Hz, 2H), 4.81 (td, J=8.7, 3.8 Hz, 1H), 1.65-1.41 (m, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 98.54-101.73 (m); IR (thin film) 3405, 1555, 1389 cm.sup.1.

(139) The following compounds were prepared in like manner to the procedure outlined in Example 10:

2,2-Difluoro-1-(3,4,5-trichlorophenyl)butan-1-ol (C44)

(140) ##STR00067##

(141) Isolated as a clear and colorless oil (3.4 g, 48%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.48 (d, J=0.9 Hz, 2H), 4.87-4.70 (m, 1H), 2.54 (dt, J=4.0, 1.0 Hz, 1H), 2.06-1.82 (m, 1H), 1.82-1.63 (m, 1H), 1.02 (t, J=7.5 Hz, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 136.85, 134.20, 131.60, 127.54, 123.19 (t, J=248.0 Hz), 73.71 (t, J=30.0 Hz), 25.05 (t, J=24.6 Hz), 5.35 (t, J=5.2 Hz); EIMS m/z 287 ([M].sup.+).

1-(3,4-Dichlorophenyl)-2,2-difluoropropan-1-ol (C45)

(142) ##STR00068##

(143) Isolated as a clear and colorless oil (2.78 g, 89%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.57 (dd, J=2.0, 0.9 Hz, 1H), 7.46 (d, J=8.3 Hz, 1H), 7.33-7.27 (m, 1H), 4.83 (td, J=8.9, 3.7 Hz, 1H), 2.55 (dt, =3.8, 1.1 Hz, 1H), 1.50 (t, J=18.9 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 99.52 (d, J=249.6 Hz), 101.09 (d, J=249.4 Hz); IR (thin film) 3417 cm.sup.1.

Example 11: Preparation of 1-(3-bromo-4-chlorophenyl)-2,2,2-trifluoroethanol (C46)

(144) ##STR00069##

(145) Trimethyl(trifluoromethyl)silane (10.1 mL, 68.4 mmol) and tetrabutylammonium fluoride (1.44 g, 4.56 mmol) were added to a stirred solution of 3-bromo-4-chloro-benzaldehyde (10.0 g, 45.6 mmol) in tetrahydrofuran (150 mL) at room temperature and the reaction mixture was stirred for 2 hours. The reaction mixture was diluted with dichloromethane and washed with hydrochloric acid (2 N). The separated organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated to afford the title compound as a brown liquid that was used without further purification (13.2 g, 94%):

(146) .sup.1H NMR (300 MHz, CDCl.sub.3) 7.76 (s, 1H), 7.50-7.48 (m, 1H), 7.38-7.35 (m, 1H), 5.03-4.97 (m, 1H), 2.95 (br s, 1H); IR (thin film) 3406, 2881, 1469, 814 cm.sup.1; EIMS m/z 288 ([M].sup.+).

(147) The following compounds were prepared in like manner to the procedure outlined in Example 11:

1-(3,5-Dibromo-4-chlorophenyl)-2,2,2-trifluoroethanol (C47)

(148) ##STR00070##

(149) Isolated as a pale yellow liquid (7.4 g, 85%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.90 (s, 2H), 7.24 (d, J=5.2 Hz, 1H), 5.33 (d, J=6.4 Hz, 1H); IR (thin film) 3370, 1175, 735, 541 cm.sup.1; EIMS m/z 366 ([M].sup.+).

1-(4-Chloro-3,5-dimethylphenyl)-2,2,2-trifluoroethanol (C48)

(150) ##STR00071##

(151) Isolated as a clear liquid (5.0 g, 70%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.18 (s, 2H), 4.95-4.92 (m, 1H), 2.40 (s, 6H); IR (thin film) 3378, 1124, 833 cm.sup.1; EIMS m/z 238 ([M].sup.+).

1-(4-Bromo-3,5-dichlorophenyl)-2,2,2-trifluoroethanol (C49)

(152) ##STR00072##

(153) Isolated as a clear oil (33 g, 86%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.51 (s, 2H), 5.01-4.96 (m, 1H), 4.14-4.09 (m, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 78.32.

1-(3-Chloro-4-fluorophenyl)-2,2,2-trifluoroethanol (C50)

(154) ##STR00073##

(155) Isolated as a clear and brown gum (7.0 g, 97%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.58-7.55 (m, 1H), 7.38-7.33 (m, 1H), 7.20-7.15 (m, 1H), 5.03-4.97 (m, 1H); EIMS m/z 228 ([M].sup.+).

1-(4-Chloro-3-fluorophenyl)-2,2,2-trifluoroethanol (C51)

(156) ##STR00074##

(157) Isolated as a clear and colorless oil (1.97 g, 75%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.52-7.37 (m, 1H), 7.32 (d, J=9.6 Hz, 1H), 7.21 (d, J=8.3 Hz, 1H), 5.03 (dd, J=6.3, 3.6 Hz, 1H), 2.62 (d, J=4.0 Hz, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) 158.06 (J.sub.CF=250.4), 134.40 (d, J.sub.CF=6.6 Hz), 130.79, 123.83 (d, J.sub.CF=3.5 Hz), 122.4 (q, J.sub.CF=188.9 Hz), 115.8 (d, J=25.3 Hz), 71.65 (q, J.sub.CF=31.6 Hz); EIMS m/z 228 ([M].sup.+).

Example 12: Preparation of 2,2-difluoro-1-(3,4,5-trichlorophenyl) propan-1-one (C52)

(158) ##STR00075##

(159) To 5-bromo-1,2,3-trichlorobenzene (2.28 g, 8.76 mmol) dissolved in diethyl ether (39.8 mL) at 78 C. under nitrogen was added n-butyllithium (3.50 mL, 8.76 mmol). The solution was stirred for 30 minutes. To this was added ethyl 2,2-difluoropropanoate (1.10 g, 7.96 mmol, as a 20% w/w solution in toluene) dropwise over 10 minutes, and the reaction mixture was stirred for an additional hour. Saturated aqueous ammonium chloride solution was added to the mixture and stirring was continued as the reaction flask warmed to room temperature. The reaction mixture was then extracted with diethyl ether, washed with water and brine, dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography provided the title compound as a pale yellow oil (1.76 g, 73%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.11 (d, J=0.9 Hz, 2H), 1.89 (t, 1=19.6 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 92.66; ESIMS m/z 271 ([MH].sup.).

(160) The following compounds were prepared in like manner to the procedure outlined in Example 12:

2,2-Difluoro-1-(3,4,5-trichlorophenyl)butan-1-one (C53)

(161) ##STR00076##

(162) Isolated as an oil (2.3 g, 68%) and used without further purification or characterization.

1-(3,4-Dichlorophenyl)-2,2-difluoropropan-1-one (C54)

(163) ##STR00077##

(164) Isolated as a colorless oil (3.89 g, 71%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.21-8.18 (m, 1H), 7.99-7.93 (m, 1H), 7.59 (dd, J=8.4, 4.2 Hz, 1H), 1.89 (t, J=19.6 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 92.08-93.21 (m); EIMS m/z 238/240 ([M].sup.+).

Example 13: Preparation of (Z)N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F1)

(165) ##STR00078##

(166) To a 25 mL vial was added (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C2) (0.105 g, 0.210 mmol) and dichloromethane (4 mL) to give a yellow solution. 2-Amino-N-(2,2,2-trifluoroethyl)acetamide hydrochloride (0.0610 g, 0.320 mmol) and benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (0.165 g, 0.320 mmol) were then added. Triethylamine (0.120 mL, 0.850 mmol) was added and the reaction mixture was stirred at room temperature overnight. The reaction mixture was then concentrated and purified by flash column chromatography providing the title compound as a yellow gum (0.105 g, 74%).

(167) The following compounds were prepared according to the procedures disclosed in Example 13:

N((R)-1-Oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F2)

(168) ##STR00079##

(169) Isolated as a yellow gum (0.120 g, 83%).

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F3)

(170) ##STR00080##

(171) Isolated as a colorless oil (0.022 g, 48%).

(Z)-2-Methyl-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F6)

(172) ##STR00081##

(173) Isolated as an off-white gum (0.090 g, 86%).

2-Methyl-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F7)

(174) ##STR00082##

(175) Isolated as an off-white gum (0.088 g, 78%).

N((R)-1-(Allylamino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F11)

(176) ##STR00083##

(177) Isolated as a yellow gum (0.069 g, 76%).

N((R)-1-((2-Cyclopropylethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F12)

(178) ##STR00084##

(179) Isolated as a yellow gum (0.09 g, 77%).

N((R)-1-(Methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F13)

(180) ##STR00085##

(181) Isolated as a yellow gum (0.032 g, 46%).

N((R)-1-(Allylamino)-1-oxopropan-2-yl)-2-methyl-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F14)

(182) ##STR00086##

(183) Isolated as a yellow gum (0.031 g, 52%).

N((R)-1-((2-Cyclopropylethyl)amino)-1-oxopropan-2-yl)-2-methyl-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F15)

(184) ##STR00087##

(185) Isolated as a yellow gum (0.026 g, 42%).

N((R)-1-(Butylamino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F16)

(186) ##STR00088##

(187) Isolated as a colorless oil (0.032 g, 39%).

2-Bromo-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F18)

(188) ##STR00089##

(189) Isolated as a colorless oil (0.065 g, 77%).

(Z)-2-Bromo-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F19)

(190) ##STR00090##

(191) Isolated as a colorless oil (0.051 g, 62%).

N((R)-1-(Ethyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F20)

(192) ##STR00091##

(193) Isolated as a colorless oil (0.025 g, 55%).

(Z)-2-Chloro-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4, 5-trichlorophenyl)but-1-en-1-yl)benzamide (F22)

(194) ##STR00092##

(195) Isolated as a colorless oil (0.116 g, 85%).

2-Chloro-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F23)

(196) ##STR00093##

(197) Isolated as a colorless oil (0.090 g, 64%).

2-Bromo-N((R)-1-(ethyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4, 5-trichlorophenyl)but-1-en-1-yl)benzamide (F25)

(198) ##STR00094##

(199) Isolated as a yellow oil (0.096 g, 84%).

2-Methyl-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)pent-1-en-1-yl)benzamide (F26)

(200) ##STR00095##

(201) Isolated as a yellow foam (0.035 g, 66%).

N((R)-1-Oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)pent-1-en-1-yl)-2-(trifluoromethyl)benzamide (F29)

(202) ##STR00096##

(203) Isolated as a white foam (0.058 g, 80%).

N((R)-1-((2,2-Difluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F30)

(204) ##STR00097##

(205) Isolated as a yellow oil (0.132 g, 89%).

2-Bromo-N((R)-1-((2,2-difluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F31)

(206) ##STR00098##

(207) Isolated as a yellow oil (0.079 g, 74%).

2-Chloro-N((R)-1-((2,2-difluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F32)

(208) ##STR00099##

(209) Isolated as a white solid (0.103 g, 76%).

4-((Z)-3-(3,5-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F33)

(210) ##STR00100##

(211) Isolated as a pale yellow solid (0.140 g, 57%).

(Z)-4-(3-(3,5-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F35)

(212) ##STR00101##

(213) Isolated as a pale yellow solid (0.145 g, 62%).

4-((Z)-3-(3,5-Dichloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F36)

(214) ##STR00102##

(215) Isolated as a pale yellow solid (0.170 g, 61%).

(Z)-4-(3-(3,5-Dichloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F38)

(216) ##STR00103##

(217) Isolated as a pale yellow solid (0.105 g, 52%).

(Z)-4-(3-(3,5-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F39)

(218) ##STR00104##

(219) Isolated as a brown gum (0.110 g, 38%).

(Z)-4-(3-(3,5-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F40)

(220) ##STR00105##

(221) Isolated as a brown gum (0.120 g, 40%).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F41)

(222) ##STR00106##

(223) Isolated as a pale yellow solid (0.110 g, 32%).

4-((Z)-3-(3,4-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F42)

(224) ##STR00107##

(225) Isolated as a brown solid (0.180 g, 65%).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F43)

(226) ##STR00108##

(227) Isolated as a brown solid (0.130 g, 40%).

(Z)-2-Chloro-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F47)

(228) ##STR00109##

(229) Isolated as a colorless gum (0.099 g, 83%).

(Z)-2-Bromo-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F48)

(230) ##STR00110##

(231) Isolated as a colorless gum (0.094 g, 81%).

2-Chloro-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F49)

(232) ##STR00111##

(233) Isolated as a colorless gum (0.107 g, 88%).

2-Bromo-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F50)

(234) ##STR00112##

(235) Isolated as a colorless gum (0.082 g, 69%).

(Z)N-(2-(Methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F51)

(236) ##STR00113##

(237) Isolated as a yellow gum (0.107 g, 92%).

N((R)-2-Ethyl-3-oxoisoxazolidin-4-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F53)

(238) ##STR00114##

(239) Isolated as a brown gum (0.100 g, 41%).

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(1-(4,4,4-trifluorobutanoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F56)

(240) ##STR00115##

(241) Isolated as a yellow oil (0.092 g, 66%).

(Z)-4-(1,4,4-Trifluoro-3-(3,4,5-trichlorophenyl)pent-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F58)

(242) ##STR00116##

(243) Isolated as a white gum (0.070 g, 85%).

(Z)N-(2-Oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)pent-1-en-1-yl)-2-(trifluoromethyl)benzamide (F62)

(244) ##STR00117##

(245) Isolated as a white foam (0.049 g, 64%).

N((R)-1-(Ethylamino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F63)

(246) ##STR00118##

(247) Isolated as a yellow oil (0.089 g, 88%).

2-Chloro-N((R)-1-(ethylamino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F64)

(248) ##STR00119##

(249) Isolated as a white gum (0.035 g, 45%).

(Z)N-(2-Oxo-2-((1,1,1-trifluoropropan-2-yl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F65)

(250) ##STR00120##

(251) Isolated as a yellow gum (0.108 g, 98%).

(Z)-2-Chloro-N-(2-oxo-2-((1,1,1-trifluoropropan-2-yl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F66)

(252) ##STR00121##

(253) Isolated as a colorless gum (0.048 g, 98%).

2-Iodo-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F67)

(254) ##STR00122##

(255) Isolated as a brown oil (0.162 g, 64%).

4-((Z)-3-(3,4-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F79)

(256) ##STR00123##

(257) Isolated as a pale yellow solid (0.140 g, 55%).

4-((Z)-3-(3,5-Dichloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (F81)

(258) ##STR00124##

(259) Isolated as a yellow gum (0.152 g, 60%).

(Z)-4-(3-(3,5-Dichloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (F82)

(260) ##STR00125##

(261) Isolated as a yellow gum (0.182 g, 64%).

4-((Z)-3-(3,5-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (F83)

(262) ##STR00126##

(263) Isolated as a yellow gum (0.155 g, 56%).

(Z)-4-(3-(3,5-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (F84)

(264) ##STR00127##

(265) Isolated as a yellow gum (0.180 g, 67%).

(Z)N-(2-Oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)hex-1-en-1-yl)-2-(trifluoromethyl)benzamide (F87)

(266) ##STR00128##

(267) Isolated as a white gum (0.052 g, 68%).

(Z)-4-(1,4,4-Trifluoro-3-(3,4,5-trichlorophenyl)hex-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F88)

(268) ##STR00129##

(269) Isolated as a white foam (0.048 g, 60%).

(Z)N-(1-(Methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F96)

(270) ##STR00130##

(271) Isolated as a yellow gum (0.073 g, 64%).

(Z)-2-Chloro-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F97)

(272) ##STR00131##

(273) Isolated as a yellow oil (0.021 g, 18%).

N((R)-1-Oxo-1-((2,2,2-trifluoroethyl)amino)butan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F98)

(274) ##STR00132##

(275) Isolated as a yellow gum (0.145 g, 98%).

2-Chloro-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)butan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F100)

(276) ##STR00133##

(277) Isolated as a colorless gum (0.035 g, 40%).

N((R)-3-Oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F106)

(278) ##STR00134##

(279) Isolated as a yellow gum (0.100 g, 31%).

(Z)-4-(3-(3,4-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F107)

(280) ##STR00135##

(281) Isolated as a pale yellow solid (0.126 g, 48%).

4-((Z)-3-(3,4-Dichlorophenyl)-1,4,4-trifluoropent-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F112)

(282) ##STR00136##

(283) Isolated as a white foam (0.052 g, 58%).

2-Bromo-4-((Z)-3-(3,4-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)benzamide (F123)

(284) ##STR00137##

(285) Isolated as a yellow gum (0.073 g, 63%).

(Z)-2-Bromo-4-(3-(3,4-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2, 2,2-trifluoroethyl)amino)ethyl)benzamide (F124)

(286) ##STR00138##

(287) Isolated as a yellow gum (0.065 g, 60%).

(Z)-2-Bromo-4-(3-(3,4-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)benzamide (F125)

(288) ##STR00139##

(289) Isolated as a yellow gum (0.094 g, 77%).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4-trifluoropent-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F128)

(290) ##STR00140##

(291) Isolated as a white gum (0.045 g, 55%).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4-trifluoropent-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F129)

(292) ##STR00141##

(293) Isolated as a white gum (0.070 g, 90%).

4-((Z)-3-(3-Chloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F132)

(294) ##STR00142##

(295) Isolated as a yellow gum (0.121 g, 43%).

(Z)N-(2-Oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (FC1)

(296) ##STR00143##

(297) Isolated as a white glass (0.043 g, 54%).

N((R)-1-Oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (FC2)

(298) ##STR00144##

(299) Isolated as a white foam (0.067 g, 82%).

Example 14: Preparation of (Z)N-(1-((2-cyclopropylethyl)carbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F4)

(300) ##STR00145##

(301) To a 25 mL round-bottomed flask was added (Z)-5-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)phenyl)-6-oxa-4-azaspiro[2.4]hept-4-en-7-one (C56) (0.040 g, 0.071 mmol) and 2-cyclopropylethanamine (0.010 g, 0.11 mmol) in dichloromethane (1 mL) to give a colorless solution. The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated. Purification by flash column chromatography provided the title compound as a colorless oil (0.046 g, 95%).

(302) The following compounds were prepared according to the procedures disclosed in Example 14:

(Z)N-(1-(Allylcarbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F5)

(303) ##STR00146##

(304) Isolated as a colorless oil (0.045 g, 97%).

(Z)N-(1-(Allylcarbamoyl)cyclopropyl)-2-methyl-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F9)

(305) ##STR00147##

(306) Isolated as a colorless oil (0.033 g, 36%).

(Z)N-(1-((2-Cyclopropylethyl)carbamoyl)cyclopropyl)-2-methyl-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F10)

(307) ##STR00148##

(308) Isolated as a colorless oil (0.028 g, 92%).

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(1-((4,4,4-trifluorobutyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F89)

(309) ##STR00149##

(310) Isolated as a colorless oil (0.055 g, 99%).

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)-N-(1-((3,3,3-trifluoropropyl)carbamoyl)cyclopropyl)benzamide (F90)

(311) ##STR00150##

(312) Isolated as a colorless oil (0.052 g, 99%).

(Z)N-(1-(Isopentylcarbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F91)

(313) ##STR00151##

(314) Isolated as a colorless gum (0.039 g, 80%).

(Z)N-(1-((2,2-Difluoropropyl)carbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F92)

(315) ##STR00152##

(316) Isolated as a colorless gum (0.051 g, 99%).

(Z)N-(1-((Cyclobutylmethyl)carbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F93)

(317) ##STR00153##

(318) Isolated as a colorless gum (0.051 g, 99%).

(Z)N-(1-(Prop-2-yn-1-ylcarbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F94)

(319) ##STR00154##

(320) Isolated as a colorless gum (0.039 g, 84%).

(Z)N-(1-((2,2-Difluoroethyl)carbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F95)

(321) ##STR00155##

(322) Isolated as a colorless oil (0.035 g, 73%).

(Z)N-(1-((3,3-Difluorocyclobutyl)carbamoyl)cyclopropyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F101)

(323) ##STR00156##

(324) Isolated as a white gum (0.015 g, 30%).

Example 15: Preparation of (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F3)

(325) ##STR00157##

(326) To a 20 mL vial was added 1-amino-N-(2,2,2-trifluoroethyl)cyclopropanecarboxamide hydrochloride (0.255 g, 1.17 mmol), (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoyl chloride (C24) (0.150 g, 0.290 mmol), and 1,2-dichloroethane (3 mL) to give a brown suspension. 4-Methylmorpholine (0.239 g, 2.33 mmol) was added and the reaction mixture was agitated twice by vortex and stirred at room temperature in a closed vessel overnight. The mixture was diluted with ethyl acetate and washed with citric acid (5%). The organic phase was concentrated. Purification by flash column chromatography using 0-30% ethyl acetate/hexanes as eluent provided the title compound as a colorless oil (0.101 g, 50%).

(327) The following compounds were prepared according to the procedures disclosed in Example 15:

(Z)-2-Methyl-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)benzamide (F8)

(328) ##STR00158##

(329) Isolated as an off-white gum (0.215 g, 68%).

(Z)-2-Bromo-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)benzamide (F21)

(330) ##STR00159##

(331) Isolated as a colorless oil (0.047 g, 39%).

N((R)-1-(Methoxy(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F24)

(332) ##STR00160##

(333) Isolated as a brown foam (0.118 g, 86%).

N((R)-1-((Allyloxy)(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F27)

(334) ##STR00161##

(335) Isolated as a brown foam (0.118 g, 83%).

(Z)-2-Chloro-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)benzamide (F28)

(336) ##STR00162##

(337) Isolated as a yellow oil (0.116 g, 82%).

(Z)N-(2-Methyl-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F54)

(338) ##STR00163##

(339) Isolated as a yellow oil (0.050 g, 37%).

tert-Butyl 2-((2R)-2-(4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamido) propanoyl)-2-(2,2,2-trifluoroethyl)hydrazinecarboxylate (F55)

(340) ##STR00164##

(341) Isolated as a brown foam (0.180 g, 97%).

(Z)N-Methyl-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F68)

(342) ##STR00165##

(343) Isolated as a brown/glass foam (0.180 g, 64%).

(Z)N-Methyl-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F99)

(344) ##STR00166##

(345) Isolated as a brown/glass foam (0.163 g, 57%).

(Z)N-(2-Oxo-1-(2,2,2-trifluoroethyl)piperidin-3-yl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F104)

(346) ##STR00167##

(347) Isolated as a beige foam (0.066 g, 57%).

N((R)-1-Amino-1-oxobutan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F126)

(348) ##STR00168##

(349) Isolated as an orange solid (0.820 g, 60%).

(Z)N-(2-Amino-2-oxoethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F127)

(350) ##STR00169##

(351) Isolated as an orange solid (0.850 g, 65%).

Example 16: Preparation of (Z)-4-(3-(3,5-dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F34)

(352) ##STR00170##

(353) Diisopropylethylamine (0.17 mL, 0.98 mmol), 2-chloro-1,3-dimethylimidazolidinium hexafluorophosphate (0.091 g, 0.32 mmol), 1-hydroxy-7-azabenzotriazole (0.044 g, 0.32 mmol), and 1-amino-N-(2,2,2-trifluoroethyl)cyclopropanecarboxamide (0.086 g, 0.39 mmol) were added to a solution of (Z)-4-(3-(3,5-dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (0.18 g, 0.33 mmol) in dichloromethane at room temperature, and the mixture was stirred for 6 hours. The reaction mixture was diluted with dichloromethane and washed with water. The separated organic layer was dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using 25% ethyl acetate/petroleum ether as eluent provided the title compound as a pale yellow solid (0.13 g, 48%).

(354) The following compounds were prepared according to the procedures disclosed in Example 16:

(Z)-4-(3-(3,5-Dichloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F37)

(355) ##STR00171##

(356) Isolated as a pale yellow solid (0.155 g, 55%).

4-((Z)-3-(3,5-Dibromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F44)

(357) ##STR00172##

(358) Isolated as a pale yellow solid (0.125 g, 27%).

(Z)-4-(3-(3,5-Dibromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F45)

(359) ##STR00173##

(360) Isolated as a yellow solid (0.107 g, 25%).

(Z)-4-(3-(3,5-Dibromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F46)

(361) ##STR00174##

(362) Isolated as a yellow solid (0.105 g, 29%).

4-((Z)-3-(3,5-Dichloro-4-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F52)

(363) ##STR00175##

(364) Isolated as a pale yellow gum (0.080 g, 34%).

4-((Z)-3-(4-Bromo-3,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F59)

(365) ##STR00176##

(366) Isolated as a yellow gum (0.100 g, 41%).

(Z)-4-(3-(4-Bromo-3,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F60)

(367) ##STR00177##

(368) Isolated as a yellow gum (0.110 g, 39%).

(Z)-4-(3-(3,5-Dichloro-4-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F61)

(369) ##STR00178##

(370) Isolated as an off-white solid (0.089 g, 38%).

4-((Z)-3-(4-Chloro-3,5-dimethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F69)

(371) ##STR00179##

(372) Isolated as a pale yellow solid (0.120 g, 44%).

(Z)-4-(3-(4-Chloro-3,5-dimethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F70)

(373) ##STR00180##

(374) Isolated as a pale yellow solid (0.110 g, 36%).

(Z)-4-(3-(4-Chloro-3,5-dimethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F71)

(375) ##STR00181##

(376) Isolated as a white solid (0.150 g, 51%).

4-((Z)-3-(3,5-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (F72)

(377) ##STR00182##

(378) Isolated as a yellow gum (0.110 g, 40%).

4-((Z)-3-(3,4-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (F73)

(379) ##STR00183##

(380) Isolated as a yellow gum (0.130 g, 47%).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (F74)

(381) ##STR00184##

(382) Isolated as a yellow gum (0.170 g, 63%).

(Z)-4-(3-(4-Bromo-3,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (F75)

(383) ##STR00185##

(384) Isolated as a yellow gum (0.130 g, 53%).

4-((Z)-3-(4-Bromo-3,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (F76)

(385) ##STR00186##

(386) Isolated as a brown gum (0.115 g, 44%).

(Z)-4-(3-(3,5-Dibromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (F77)

(387) ##STR00187##

(388) Isolated as a yellow gum (0.112 g, 3%).

4-((Z)-3-(3,5-Dibromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (F78)

(389) ##STR00188##

(390) Isolated as a yellow gum (0.135 g, 37%).

(Z)-4-(3-(3,4-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F80)

(391) ##STR00189##

(392) Isolated as a pale yellow solid (0.127 g, 47%).

(Z)-4-(3-(3,5-Dichloro-4-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (F85)

(393) ##STR00190##

(394) Isolated as an off-white solid (0.110 g, 46%).

4-((Z)-3-(3,5-Dichloro-4-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (F86)

(395) ##STR00191##

(396) Isolated as an off-white solid (0.140 g, 57%).

4-((Z)-3-(4-Chloro-3,5-dimethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (F102)

(397) ##STR00192##

(398) Isolated as a white solid (0.130 g, 39%).

(Z)-4-(3-(4-Chloro-3,5-dimethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (F103)

(399) ##STR00193##

(400) Isolated as a white solid (0.170 g, 52%).

4-((Z)-3-(3,5-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F105)

(401) ##STR00194##

(402) Isolated as a yellow gum (0.115 g, 55%).

(Z)-4-(3-(3,5-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F108)

(403) ##STR00195##

(404) Isolated as a pale yellow gum (0.103 g, 39%).

4-((Z)-3-(3-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan)-2-yl)-2-(trifluoromethyl)benzamide (F109)

(405) ##STR00196##

(406) Isolated as a yellow gum (0.115 g, 55%).

(Z)-4-(3-(4-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F110)

(407) ##STR00197##

(408) Isolated as a brown solid (0.115 g, 53%).

(Z)-4-(3-(3,5-Dichloro-4-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F111)

(409) ##STR00198##

(410) Isolated as a yellow gummy solid (0.075 g, 30%).

(Z)-4-(3-(3,5-Dichloro-4-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F113)

(411) ##STR00199##

(412) Isolated as a pale yellow gum (0.085 g, 35%).

(Z)-4-(3-(3,5-Dichloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F114)

(413) ##STR00200##

(414) Isolated as a pale yellow gum (0.100 g, 32%).

(Z)-4-(3-(3,5-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F115)

(415) ##STR00201##

(416) Isolated as an orange gum (0.085 g, 26%).

(Z)-4-(3-(3-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F116)

(417) ##STR00202##

(418) Isolated as a brown gum (0.120 g, 56%).

(Z)-4-(3-(4-Bromo-3,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F117)

(419) ##STR00203##

(420) Isolated as a yellow gum (0.085 g, 36%).

(Z)-4-(3-(4-Dibromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F118)

(421) ##STR00204##

(422) Isolated as a yellow gum (0.092 g, 30%).

(Z)-4-(3-(4-Chloro-3,5-dimethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F119)

(423) ##STR00205##

(424) Isolated as a yellow solid (0.085 g, 20%).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F120)

(425) ##STR00206##

(426) Isolated as a yellow solid (0.110 g, 34%).

4-((Z)-3-(3-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F121)

(427) ##STR00207##

(428) Isolated as a yellow gum (0.115 g, 55%).

(Z)-4-(3-(3-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F122)

(429) ##STR00208##

(430) Isolated as a yellow gum (0.110 g, 52%).

(Z)-4-(3-(3,4-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F130)

(431) ##STR00209##

(432) Isolated as a yellow gum (0.157 g, 60%).

(Z)-4-(3-(3-Chloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F131)

(433) ##STR00210##

(434) Isolated as a yellow gum (0.120 g, 41%).

(Z)-4-(3-(3,5-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F133)

(435) ##STR00211##

(436) Isolated as an orange gum (0.080 g, 26%).

(Z)-4-(3-(4-Chloro-3,5-dimethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F134)

(437) ##STR00212##

(438) Isolated as a yellow solid (0.085 g, 27%).

(Z)-4-(3-(3,4-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F135)

(439) ##STR00213##

(440) Isolated as a yellow solid (0.110 g, 38%).

(Z)-4-(3-(4-Chloro-3-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F136)

(441) ##STR00214##

(442) Isolated as a yellow solid (0.160 g, 53%).

(Z)-4-(3-(3-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2, 2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (F137)

(443) ##STR00215##

(444) Isolated as a brown gum (0.120 g, 52%).

4-((Z)-3-(3-Bromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F138)

(445) ##STR00216##

(446) Isolated as an off-white solid (0.112 g, 51%).

(Z)-4-(3-(3-Bromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F139)

(447) ##STR00217##

(448) Isolated as an off-white solid (0.110 g, 51%).

Example 17: Preparation of N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((E)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F17)

(449) ##STR00218##

(450) In an NMR tube, N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F2) (0.05 g, 0.077 mmol) was dissolved into acetone-d.sub.6. The reaction vessel was set up in a UV chamber and irradiated for 7 days. The reaction mixture was concentrated. Purification by flash column chromatography provided the title compound as a colorless oil (0.015 g, 30%).

Example 18: Preparation of N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((E)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F57)

(451) ##STR00219##

(452) tert-Butyl 2-((2R)-2-(4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamido) propanoyl)-2-(2,2,2-trifluoroethyl)hydrazinecarboxylate (F55) (0.150 g, 0.197 mmol) was dissolved in dichloromethane (5 mL). Hydrogen chloride (2 M in diethyl ether, 1-2 mL) was added and the reaction mixture was stirred at room temperature for 3 days. The reaction mixture was concentrated and the residue was taken up in diethyl ether and washed with aqueous sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated. Purification by flash column chromatography using 2% acetone/dichloromethane as eluent provided the title compound as a white foam (0.0620 g, 48%).

Example 19: Preparation of (Z)-5-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)phenyl)-6-oxa-4-azaspiro[2.4]hept-4-en-7-one (C55)

(453) ##STR00220##

(454) To a 25 mL round-bottomed flask was added (Z)-1-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamido)cyclopropanecarboxylic acid (C57) (0.250 g, 0.432 mmol) in dichloromethane (4 mL) to give a yellow solution. 2,2,2-Trifluoroacetic anhydride (0.120 mL, 0.864 mmol) was then added and the reaction mixture was stirred at room temperature overnight. Following concentration, the mixture was purified by flash column chromatography to provide the title compound as a yellow oil (0.0780 g, 30%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.04-7.96 (m, 2H), 7.85 (dd, J=8.1, 1.9 Hz, 1H), 7.44 (s, 2H), 5.90 (dd, J=32.5, 9.6 Hz, 1H), 4.62 (p, J=8.8 Hz, 1H), 2.00-1.94 (m, 2H), 1.89-1.85 (m, 2H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.53, 69.26 (d, J=2.4 Hz), 112.22; ESIMS m/z 560 ([MH].sup.).

(455) The following compounds were prepared according to the procedures disclosed in Example 19:

(Z)-5-(2-Methyl-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)phenyl)-6-oxa-4-azaspiro[2.4]hept-4-en-7-one (C56)

(456) ##STR00221##

(457) Isolated as a yellow foam (0.100 g, 53%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.98-7.88 (m, 1H), 7.51-7.45 (m, 2H), 7.44 (s, 2H), 5.79 (dd, J=32.8, 9.6 Hz, 1H), 4.60 (p, J=8.9 Hz, 1H), 2.67 (s, 3H), 1.96-1.87 (m, 2H), 1.87-1.78 (m, 2H); .sup.19F NMR (376 MHz, CDCl.sub.3) 69.39 (d, J=2.4 Hz), 112.11; ESIMS m/z 506 ([MH].sup.).

Example 20: Preparation of (Z)-1-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamido)cyclopropanecarboxylic acid (C57)

(458) ##STR00222##

(459) To a 250 mL round-bottomed flask was added (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoyl chloride (C23) (0.037 g, 0.072 mmol) and tetrahydrofuran (53 mL). N,N,N-Trimethyl-1-dodecanaminium bromide (0.0022 mg, 0.0072 mmol), sodium carbonate (0.012 g, 0.011 mmol), and 1-aminocyclopropanecarboxylic acid hydrochloride (0.020 g, 0.144 mmol) were all added and the reaction mixture was stirred overnight at reflux. The reaction mixture was cooled to room temperature and the solid residue filtered. The filtrate was concentrated to provide the title compound as a colorless oil which was used directly in the next step (0.038 g, 83%): .sup.1H NMR (300 MHz, Methanol-d.sub.4) 8.01 (d, J=9.5 Hz, 2H), 7.85 (d, J=8.0 Hz, 1H), 7.78 (s, 2H), 6.45 (dd, J=34.1, 9.8 Hz, 1H), 4.97 (s, 1H), 1.49 (q, J=4.5 Hz, 2H), 1.08 (q, J=4.4 Hz, 2H); 19F NMR (376 MHz, CDCl.sub.3) 60.81, 69.45, 111.92; ESIMS m/z 576 ([MH].sup.).

(460) The following compounds were prepared according to the procedures disclosed in Example 20:

(Z)-1-(2-Methyl-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamido)cyclopropanecarboxylic acid (C58)

(461) ##STR00223##

(462) Isolated (0.140 g, 67%): ESIMS m/z 524 ([MH].sup.).

Example 21: Preparation of (R)N-allyl-2-aminopropanamide hydrochloride (C59)

(463) ##STR00224##

(464) (R)-tert-Butyl (1-(allylamino)-1-oxopropan-2-yl)carbamate (C65) (3.30 g, 14.5 mmol) was taken up in dichloromethane (15 mL) and treated with hydrogen chloride (4 M in dioxane, 15.0 mL, 60.0 mmol). The reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was concentrated and the residue was suspended in dichloromethane. Concentration in vacuo provided the title compound as a white solid (2.42 g, quant): mp 143-153 C.; .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.71 (t, J=5.9 Hz, 1H), 8.37-8.18 (m, 3H), 5.80 (ddd, J=15.7, 10.7, 5.1 Hz, 1H), 5.13 (dd, J=32.1, 13.8 Hz, 2H), 3.85 (t, J=6.2 Hz, 1H), 3.75 (d, J=4.8 Hz, 2H), 1.38 (d, J=6.9 Hz, 3H); .sup.13C NMR (101 MHz, DMSO-d.sub.6) 169.21, 134.48, 115.30, 48.08, 40.74, 17.24; IR (thin film) 3213, 3073, 3026, 2855, 1649, 1609 cm.sup.1.

(465) The following compounds were prepared according to the procedures disclosed in Example 21:

(R)-2-Amino-N-(2-cyclopropylethyl)propanamide hydrochloride (C60)

(466) ##STR00225##

(467) Isolated as a gum (3.39 g, 100%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.56 (t, J=5.6 Hz, 1H), 8.25 (s, 3H), 3.79 (m, 1H), 3.24-3.08 (m, 2H), 1.34 (d, J=7.0 Hz, 3H), 1.33-1.28 (m, 2H), 0.68 (q, J=6.8, 6.3 Hz, 1H), 0.38 (d, J=8.0 Hz, 2H), 0.02 (d, J=5.5 Hz, 2H); .sup.13C NMR (101 MHz, DMSO-d.sub.6) 169.06, 48.11, 38.94, 33.72, 17.19, 8.45, 4.07; IR (thin film) 2916, 1661, 1560, 1490, 1255, 1117 cm.sup.1.

(R)-2-Amino-N-(2-cyclopropylethyl)propanamide hydrochloride (C61)

(468) ##STR00226##

(469) Isolated as an off-white solid (0.624 g, quant): .sup.1H NMR (400 MHz, Methanol-d.sub.4) rotamers 4.40 (q, J=7.0 Hz, 1H), 4.29-4.12 (m, 1H), 3.97 (dq, J=15.2, 9.1 Hz, 1H), major, 3.12 (s, 3H), minor 2.99 (s, 3H), major 1.40 (d, J=7.0 Hz, 3H), minor 1.38 (d, J=7.2 Hz, 3H).

(R)-2-Amino-N-ethyl-N-(2,2,2-trifluoroethyl)propanamide hydrochloride (C62)

(470) ##STR00227##

(471) Isolated as a gum (0.194 g, 92%): mp 148-151 C.; .sup.1H NMR (400 MHz, DMSO-d.sub.6) rotamers 8.59 (s, 2H), 4.46-4.37 (m, 1H), 4.32-4.27 (m, 1H), 4.16-3.93 (m, 1H), 3.62-3.53 (m, 1H), 3.45-3.33 (m, 2H), major 1.38 (d, J=6.8 Hz, 3H), minor 1.32 (d, J=6.7 Hz, 3H), major 1.19 (t, J=7.0 Hz, 3H), minor 1.06 (t, J=7.0 Hz, 3H); .sup.13C NMR (101 MHz, DMSO-d.sub.6) rotamers major 171.03, minor 170.59, 124.76 (q, J.sub.CF=281.1 Hz), 54.91, minor 47.23 (q, J.sub.CF=32.3 Hz), 45.82, 45.48, major 44.60 (q, J.sub.CF=32.3 Hz), 42.62, 16.66, 13.70, 11.83; .sup.19F NMR (376 MHz, DMSO-d.sub.6) 68.42, 69.10.

(R)-2-Amino-N-(2,2-difluoroethyl)propanamide hydrochloride (C63)

(472) ##STR00228##

(473) Isolated as a gum (0.194 g, 92%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.98 (t, J=6.0 Hz, 1H), 8.36 (s, 3H), 6.06 (tt, J=55.6, 3.6 Hz, 1H), 3.88 (q, J=6.9 Hz, 1H), 3.71-3.39 (m, 2H), 1.38 (d, J=7.0 Hz, 3H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) 122.15.

(R)-2-Amino-N-(2,2,2-trifluoroethyl)butanamide hydrochloride (C64)

(474) ##STR00229##

(475) Isolated as a white solid (2.17 g, quant): mp 162-173 C.; .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.33 (t, J=6.3 Hz, 1H), 8.40 (s, 3H), 4.19-4.01 (m, 1H), 3.93 (dt, J=10.7, 5.5 Hz, 1H), 3.87-3.76 (m, 1H), 1.79 (ddt, J=21.3, 14.1, 7.1 Hz, 2H), 0.88 (t, J=7.5 Hz, 3H); .sup.19F NMR (471 MHz, DMSO-d.sub.6) 5-70.64 (t, J=9.8 Hz); IR (thin film) 3348, 2887, 1674, 1601, 1157 cm.sup.1.

1-(1-Aminocyclopropyl)-4,4,4-trifluoro-butan-1-one hydrochloride (C65)

(476) ##STR00230##

(477) Isolated as a tan solid (0.296 g, 93%): mp 119-140 C.; .sup.1H NMR (400 MHz, Methanol-d.sub.4) 2.71-2.37 (m, 4H), 1.84 (d, J=6.8 Hz, 2H), 1.55 (d, J=7.3 Hz, 2H); .sup.13C NMR (101 MHz, Methanol-d.sub.4) 203.26, 129.13 (q, J.sub.CF=275.5 Hz), 43.93, 29.45 (q, J.sub.CF=29.8 Hz), 29.02, 15.24; .sup.19F NMR (376 MHz, Acetone-d.sub.6) 108.19.

1-Amino-N-methyl-N-(2,2,2-trifluoroethyl)cyclopropanecarboxamide hydrochloride (C66)

(478) ##STR00231##

(479) Isolated as an off white solid (2.83 g, 90%): mp 145-155 C.; .sup.1H NMR (500 MHz, DMSO-d.sub.6) 9.29 (s, 3H), 4.22 (q, J=9.5 Hz, 2H), 3.25 (s, 3H), 1.50-1.40 (m, 2H), 1.23-1.14 (m, 2H); .sup.13C NMR (126 MHz, DMSO-d.sub.6) 166.62, 124.20 (q, J.sub.CF=281.1 Hz), 47.73 (q, J.sub.CF=32.8 Hz), 36.27, 33.89, 10.36; .sup.19F NMR (471 MHz, DMSO-d.sub.6) 68.16 (t, J=9.5 Hz).

(R)N-(Allyloxy)-2-amino-N-(2,2,2-trifluoroethyl)propanamide hydrochloride (C67)

(480) ##STR00232##

(481) Isolated as a glassy oil (0.120 g, 87%).

Example 22: Preparation of (R)-tert-butyl (1-(allylamino)-1-oxopropan-2-yl)carbamate (C68)

(482) ##STR00233##

(483) (R)-2-((tert-Butoxycarbonyl)amino)propanoic acid (5.26 g, 27.8 mmol) in dichloromethane (40 mL) in a round-bottomed flask was placed in a room temperature water bath. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide (5.91 g, 30.3 mmol) was added followed by allyl amine (4.00 mL, 53.5 mmol) in 0.5 mL portions. 4-Dimethylaminopyridine (3.70 g, 30.3 mmol) was added, and the reaction mixture was stirred for 18 hours at room temperature while under a drying tube charged with calcium sulfate. The reaction mixture was washed with hydrochloric acid (10%, 3). The organic layer was diluted with a dichloromethane (100 mL) and ethyl acetate (250 mL), washed with saturated sodium bicarbonate and saturated sodium chloride, dried over magnesium sulfate, filtered, and concentrated providing the title compound as a white solid (3.51 g, 55%): [a].sup.3+30.6 (c 0.00620, dichloromethane); mp 87-94 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) 6.40 (s, 1H), 5.91-5.75 (m, 1H), 5.25-5.09 (m, 2H), 5.07 (s, 1H), 4.19 (d, J=10.6 Hz, 1H), 3.88 (t, J=5.8 Hz, 2H), 1.44 (s, 9H), 1.37 (d, J=7.1 Hz, 3H); EIMS m/z 228 ([M].sup.+).

(484) The following compounds were prepared according to the procedures disclosed in Example 22:

(R)-tert-Butyl (1-((2-cyclopropylethyl)amino)-1-oxopropan-2-yl)carbamate (C69)

(485) ##STR00234##

(486) Isolated (4.7 g, 71%): mp 67-69 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) 6.35 (s, 1H), 5.05 (s, 1H), 4.14 (m, 1H), 3.34 (m, 2H), 1.44 (s, 9H), 1.40 (m, 2H), 1.35 (d, J=7.1 Hz, 3H), 0.74-0.59 (m, 1H), 0.53-0.37 (m, 2H), 0.14-0.03 (m, 2H); EIMS m/z 256 ([M].sup.+).

(R)-tert-Butyl (1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)carbamate (C70)

(487) ##STR00235##

(488) Isolated as a white solid using 2,2,2-trifluoro-N-methylethanamine hydrochloride (0.388 g, 22%): [a].sub.D.sup.231.1 (c 0.00540, dichloromethane); mp 52-54 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) rotamers 5.38 (d, J=8.4 Hz, 1H), 4.76-4.59 (m, 1H), 4.30 (dd, J=15.0, 9.1 Hz, 1H), 3.89-3.65 (m, 1H), 3.20 (s, 3H), 1.43 (m, 9H), 1.33 (d, J=6.8 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) rotamers 69.85, 70.62.

(R)-tert-Butyl (1-((2,2-difluoroethyl)amino)-1-oxopropan-2-yl)carbamate (C71)

(489) ##STR00236##

(490) Isolated as a white solid (3.30 g, 60%): mp 69-72 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) 6.78 (s, 1H), 5.83 (tt, J=56.0, 4.1 Hz, 1H), 5.00 (d, J=7.5 Hz, 1H), 4.36-4.11 (m, 1H), 3.74-3.40 (m, 2H), 1.45 (s, 9H), 1.37 (d, J=7.1 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 123.02 (d, J=3.5 Hz); IR (thin film) 3334, 2924, 2853, 1670, 1598 cm.sup.1; EIMS m/z 179 ([M-Otert-butyl].sup.+).

(R)-tert-Butyl (1-oxo-1-((2,2,2-trifluoroethyl)amino)butan-2-yl)carbamate (C72)

(491) ##STR00237##

(492) Isolated as a white solid (2.77 g, 83%): mp 110-114 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.50-7.29 (m, 1H), 5.32 (d, J=8.4 Hz, 1H), 4.16 (d, J=7.6 Hz, 1H), 3.96 (m, 1H), 3.88-3.69 (m, 1H), 1.89-1.73 (m, 1H), 1.66 (m, 1H), 1.44 (s, 9H), 0.95 (t, J=7.4 Hz, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 173.43, 156.09, 124.05 (q, J.sub.CF=278.6 Hz), 80.10, 55.54, 40.39 (q, J.sub.CF=34.7 Hz), 28.15, 25.90, 9.74; .sup.19F NMR (471 MHz, CDCl.sub.3) 5 rotamers 72.52, 73.29; EIMS m/z 229 ([M].sup.+).

Example 23: Preparation of (R)-tert-butyl (1-(ethyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)carbamate (C73)

(493) ##STR00238##

(494) To a 20 mL vial containing a solution of (R)-2-((tert-butoxycarbonyl)amino)propanoic acid (0.489 g, 2.58 mmol) in dichloromethane (5 mL) cooled to 0 C. was added 2,2,2-trifluoro-N-ethylethanamine hydrochloride (0.384 g, 2.35 mmol), 1H-benzo[d][1,2,3]triazol-1-ol hydrate (0.360 g, 2.35 mmol), diisopropylethylamine (1.00 mL, 5.16 mmol), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (0.495 g, 2.58 mmol). The reaction was stirred for 2 days at room temperature. The reaction mixture was diluted with diethyl ether, washed with hydrochloric acid (0.1 N), sodium bicarbonate (15%), and saturated sodium chloride, dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using 0-100% ethyl acetate/hexanes as eluent provided the title compound as a white solid (0.092 g, 12%): .sup.1H NMR (400 MHz, CDCl.sub.3) 5.34 (d, J=8.7 Hz, 1H), 4.73-4.60 (m, 1H), 4.39 (dq, J=15.0, 9.2 Hz, 1H), 3.80-3.43 (m, 3H), 1.43 (d, J=5.2 Hz, 9H), 1.34 (d, J=6.8 Hz, 3H), 1.29 (q, J=6.9 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 69.65, 70.65; ESIMS m/z 242 ([M-tert-butyl].sup.).

Example 24: Preparation of tert-butyl 2-(2,2,2-trifluoroethyl)hydrazinecarboxylate (C74)

(495) ##STR00239##

(496) A 100 mL round-bottomed flask was charged with (2,2,2-trifluoroethyl)hydrazine (2.0 g, 12 mmol) and methanol (15 mL) and stirred at room temperature. Di-tert butyl dicarbonate (2.7 g, 12 mmol) was added in several portions. The reaction mixture was stirred at room temperature for 18 hours. The reaction mixture was concentrated providing the title compound as a white solid (2.3 g, 87%): .sup.1H NMR (300 MHz, CDCl.sub.3) 6.24 (s, 1H), 4.23 (s, 1H), 3.41 (qd, J=9.3, 4.6 Hz, 2H), 1.47 (s, 9H).

Example 25: Preparation of (R)-tert-butyl 2-(2-(((benzyloxy)carbonyl)amino)propanoyl)-2-(2,2,2-trifluoroethyl)hydrazinecarboxylate (C75)

(497) ##STR00240##

(498) To a solution of (R)-2-((benzyloxy)carbonyl)amino)propanoic acid (0.500 g, 2.24 mmol) in dry dichloromethane (10 mL) was added 1-chloro-N,N,2-trimethyl-1-propenylamine (0.359 g, 2.69 mmol) in dichloromethane via pipette at 0 C. The reaction mixture was stirred for 10 minutes. A pre-mixed solution of pyridine (0.213 g, 2.69 mmol) and tert-butyl 2-(2,2,2-trifluoroethyl)hydrazinecarboxylate (C71) (0.480 g, 2.24 mmol) was added via pipette. The reaction mixture was stirred at 0 C. to room temperature overnight. The reaction mixture was diluted with dichloromethane and added to dilute aqueous hydrochloric acid. The layers were separated and the aqueous layer was extracted with dichloromethane (2) and discarded. The combined organic layers were washed with saturated aqueous sodium bicarbonate (2), dried over magnesium sulfate, filtered, and concentrated. Purification by flash column chromatography using 15-20% ethyl acetate/hexanes as eluent provided the title compound as a pale thick oil (0.820 g, 87%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.34 (s, 5H), 6.77 (s, 1H), 5.42 (s, 1H), 5.09 (s, 2H), 4.83 (m, 2H), 3.55 (d, J=33.0 Hz, 1H), 1.50 (s, 9H), 1.32 (d, J=6.8 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) rotamers 69.70, 70.12.

Example 26: Preparation of (R)-tert-butyl 2-(2-aminopropanoyl)-2-(2,2,2-trifluoroethyl)hydrazinecarboxylate (C76)

(499) ##STR00241##

(500) (R)-tert-Butyl 2-(2-(((benzyloxy)carbonyl)amino)propanoyl)-2-(2,2,2-trifluoroethyl)hydrazinecarboxylate (C72) (0.820 g, 1.96 mmol) was dissolved in ethanol (10 mL) and palladium on carbon (5%, catalytic amount) was added. The reaction was shaken under a hydrogen atmosphere at room temperature for 18 hours. The reaction mixture was filtered through a pad of Celite and the pad was washed several times with ethanol. The combined ethanol was concentrated. The residue was taken up in dichloromethane, washed repeatedly with saturated sodium chloride, dried over magnesium sulfate, filtered, and concentrated to provide the title compound as a glassy oil (0.400 g, 72%): ESIMS m/z 286 ([M+H].sup.+).

Example 27: Preparation of tert-butyl N-[1-(4,4,4-trifluorobutanoyl)cyclopropyl]carbamate (C77)

(501) ##STR00242##

(502) To a solution of 3,3,3-trifluoropropyl magnesium bromide (0.5 M, 30.0 mL, 15.0 mmol) in tetrahydrofuran in an oven-dried round-bottomed flask under a nitrogen atmosphere was added tert-butyl (1-(methoxy(methyl)carbamoyl)cyclopropyl)carbamate (1.01 g, 4.12 mmol) in tetrahydrofuran (5.00 mL). The mixture was stirred at room temperature for 20 hours and then quenched with aqueous sodium bisulfate (5%). The mixture was extracted ethyl acetate and the organic phase washed with saturated sodium chloride, dried over magnesium sulfate, filtered, and concentrated. Purification by flash column chromatography using ethyl acetate/hexanes as eluent provided the title compound as a white solid (0.826 g, 71%): mp 71-93 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) 5.20 (s, 1H), 2.95 (t, J=7.8 Hz, 2H), 2.50-2.20 (m, 2H), 1.63-1.57 (m, 2H), 1.47 (s, 9H), 1.22-1.14 (m, 2H); .sup.19F NMR (376 MHz, CDCl.sub.3) 66.64; EIMS m/z 225 ([(M+H)-(tert-butyl)].sup.+).

Example 28: Preparation of tert-butyl (1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)carbamate (C78)

(503) ##STR00243##

(504) To a mixture of 1-((tert-butoxycarbonyl)amino)cyclopropanecarboxylic acid (3.00 g, 14.9 mmol) and 2,2,2-trifluoro-N-methylethanamine hydrochloride (2.23 g, 14.9 mmol) in dichloromethane (40 mL) was added diisopropylethylamine (6.51 mL, 37.3 mmol) followed by ((1H-benzo[d][1, 2, 3]triazol-1-yl)oxy)tri(pyrrolidin-1-yl)phosphonium hexafluorophosphate(V) (7.76 g, 14.9 mmol). The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with ethyl acetate and washed with aqueous hydrochloric acid (0.5 M) followed by a saturated aqueous sodium bicarbonate wash. The organic layer was dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography provided the title compound as an off-white solid (3.60 g, 73%): 109-112 C.; .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.73 (s, 1H), 4.31-4.03 (m, 2H), 3.22-3.01 (m, 3H), 1.35 (d, J=13.0 Hz, 9H), 1.15 (t, J=4.0 Hz, 2H), 0.87 (q, J=4.7 Hz, 2H); .sup.13C NMR (126 MHz, CDCl.sub.3) 171.72, 154.93, 124.79 (q, J.sub.CF=280 Hz), 80.32, 49.73 (q, J.sub.CF=34.00 Hz), 37.00, 35.47, 28.15, 15.43; .sup.19F NMR (471 MHz, CDCl.sub.3) rotamers 69.41, 69.73.

Example 29: Preparation of (R)-benzyl (1-(methoxyamino)-1-oxopropan-2-yl)carbamate (C79)

(505) ##STR00244##

(506) (R)-2-(((Benzyloxy)carbonyl)amino)propanoic acid (0.500 g, 2.24 mmol) in tetrahydrofuran/water (2:1, 15 mL) was treated with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (0.472 g, 2.46 mmol), O-methylhydroxylamine hydrochloride (0.224 g, 2.69 mmol), and triethylamine (0.272 g, 2.69 mmol). The reaction mixture was stirred for 18 hours, then concentrated. The residue was partitioned between dichloromethane and dilute aqueous hydrochloric acid. The aqueous phase was extracted with dichloromethane. The combined organic layers were washed with aqueous sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated providing the title compound as a white solid (0.250 g, 44%): mp 109-110 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) 9.01 (s, 1H), 7.35 (m, 5H), 5.10 (m, 3H), 4.12 (s, 1H), 3.75 (s, 3H), 1.39 (d, J=7.0 Hz, 3H); ESIMS m/z 253 ([M+H].sup.+).

Example 30: Preparation of (R)-benzyl (1-(methoxy(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)carbamate (C80)

(507) ##STR00245##

(508) A mixture of (R)-benzyl (1-(methoxyamino)-1-oxopropan-2-yl)carbamate (C79) (0.300 g, 1.19 mmol), potassium carbonate (0.329 g, 2.38 mmol), and anhydrous tetrahydrofuran (15 mL) was treated with 2,2,2-trifluoroethyl trifluoromethanesulfonate (0.552 g, 2.38 mmol). The resulting mixture was stirred at room temperature for 18 hours, then partitioned between water and diethyl ether. The aqueous phase was extracted with diethyl ether (2). The combined organic layers were washed with saturated sodium chloride, dried over magnesium sulfate, filtered, and concentrated. Purification by flash column chromatography using 1% acetone/dichloromethane as eluent provided the title compound as a clear oil (0.150 g, 38%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.36 (d, J=3.7 Hz, 5H), 5.43 (d, J=8.5 Hz, 1H), 5.11 (q, J=12.2 Hz, 2H), 4.78 (t, J=7.5 Hz, 1H), 4.44 (dd, J=16.0, 8.4 Hz, 1H), 4.10-3.92 (m, 1H), 3.86 (s, 3H), 1.38 (d, J=7.0 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 20-69.31; ESIMS m/z 335 ([M+H].sup.+).

(509) The following compound was prepared according to the procedure disclosed in Example 30:

(R)-tert-Butyl (1-((allyloxy)(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)carbamate (C81)

(510) ##STR00246##

(511) Isolated as a white solid (0.200 g, 30%): .sup.1H NMR (400 MHz, CDCl.sub.3) 6.08-5.89 (m, 1H), 5.49-5.31 (m, 2H), 5.14 (d, J=8.5 Hz, 1H), 4.71 (t, J=7.7 Hz, 1H), 4.52 (m, 3H), 4.03 (m, 1H), 1.44 (s, 9H), 1.35 (d, J=7.0 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 69.09.

Example 31: Preparation of (R)-2-amino-N-methoxy-N-(2,2,2-trifluoroethyl)propanamide hydrochloride (C82)

(512) ##STR00247##

(513) A solution of (R)-benzyl (1-(methoxy(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)carbamate (C80) (0.300 g, 0.897 mmol) in ethanol (10 mL) and hydrochloric acid (1 N, 1 mL) in ethanol was treated with palladium on carbon (5%, catalytic amount). The reaction was shaken under hydrogen at room temperature for 18 hours. The reaction mixture was filtered through a pad of Celite and the pad was washed several times with ethanol. The combined ethanol washes were concentrated to provide the title compound as a beige foam (0.210 g, 99%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.43 (s, 3H), 4.71 (dq, J=16.1, 9.3 Hz, 1H), 4.55 (dq, J=17.2, 8.8 Hz, 1H), 4.26 (q, J=7.2 Hz, 1H), 3.82 (s, 3H), 1.38 (d, J=6.9 Hz, 3H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) 68.12.

Example 32: Preparation of N-methyl-2-(methylamino)-N-(2,2,2-trifluoroethyl)acetamide hydrochloride (C83)

(514) ##STR00248##

(515) To a mixture of (1-cyano-2-ethoxy-2-oxoethylidenaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (0.754 g, 1.76 mmol) and 2-((tert-butoxycarbonyl)(methyl)amino)acetic acid (0.333 g, 1.76 mmol) dissolved in N,N-dimethylformamide (2 mL) was added diisopropylethylamine (1.40 mL, 8.02 mmol). The solution was stirred for 15 minutes at room temperature then treated with 2,2,2-trifluoro-N-methylethanamine hydrochloride (0.342 g, 2.29 mmol). After stirring overnight at room temperature, the mixture was partitioned between water and ethyl acetate. The organic phase was dried over magnesium sulfate, concentrated, and purified by flash column chromatography to afford a foam which was dissolved in dichloromethane and treated with hydrogen chloride (4 M in dioxane, 0.750 mL, 3.00 mmol). After standing overnight under a nitrogen atmosphere the solution was then concentrated to provide the title compound as a colorless foam (0.164 g, 38%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.86 (s, 2H), 4.29 (dq, J=28.7, 9.3 Hz, 2H), 4.16 (s, 2H), 3.07 (s, 3H), 2.56 (s, 3H); .sup.13C NMR (126 MHz, DMSO-d.sub.6) 167.45, 125.23 (q, J.sub.CF=281.2 Hz), 48.73, 47.59 (q, J.sub.CF=32.7 Hz), 35.72, 33.09; .sup.19F NMR (376 MHz, Methanol-d.sub.4) rotamers 71.67, 71.68, 71.70.

Example 33: Preparation of (R)-tert-butyl (1-((allyloxy)amino)-1-oxopropan-2-yl)carbamate (C84)

(516) ##STR00249##

(517) To (R)-2-((tert-butoxycarbonyl)amino)propanoic acid (2.00 g, 10.6 mmol) in tetrahydrofuran (35 mL) was added 2-chloro-4,6-dimethoxy-1,3,5-triazine (2.21 g, 12.6 mmol) and 4-methylmorpholine (3.21 g, 31.7 mmol). The reaction mixture was stirred at room temperature for 1 hour then O-allylhydroxylamine hydrochloride (1.16 g, 10.6 mmol) was added. After stirring 18 hours water was added and the mixture extracted with diethyl ether (3). The combined ether layer was washed with saturated aqueous carbonate (2), aqueous hydrochloric acid (1 N), saturated sodium chloride, dried over magnesium sulfate, filtered, and concentrated to provide the title compound as a white solid (1.83 g, 71%): .sup.1H NMR (400 MHz, CDCl.sub.3) 9.15 (s, 1H), 5.97 (ddt, J=16.9, 10.3, 6.4 Hz, 1H), 5.33 (m, 2H), 5.00 (d, J=13.5 Hz, 1H), 4.39 (m, 2H), 4.05 (d, J=12.8 Hz, 1H), 1.44 (s, 9H), 1.36 (d, J=7.0 Hz, 3H).

Example 34: Preparation of 3-amino-1-(2,2,2-trifluoroethyl)-piperidin-2-one hydrochloride (C85)

(518) ##STR00250##

(519) To a solution of tert-butyl (2-oxopiperidin-3-yl)carbamate (0.250 g, 1.17 mmol) in 10 mL of anhydrous tetrahydrofuran, cooled in an ice-water bath, was added sodium hydride (60% oil immersion, 0.0470 g, 1.17 mmol). After stirring 1 hour at ambient temperature 2,2,2-trifluoroethyl trifluoromethanesulfonate (0.284 g, 1.23 mmol) was added and the resulting mixture was stirred at room temperature for 20 hours. The mixture was partitioned between water and diethyl ether. The aqueous phase was extracted with diethyl ether (3). The combined organic layer was dried with magnesium sulfate, concentrated, and purified by flash column chromatography using 2% acetone/dichloromethane as eluent to provide a clear oil. The oil was taken up in dichloromethane (5 mL) and hydrogen chloride (2 N in diethyl ether, 1 mL). After stirring for 18 hours, the mixture was concentrated to provide the title compound as a white foam (0.0600 g, 26%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.29 (s, 3H), 4.47-4.14 (m, 2H), 4.00 (dd, J=11.6, 6.2 Hz, 1H), 3.64-3.41 (m, 2H), 2.17 (m, 1H), 1.92 (m, 2H), 1.85-1.58 (m, 1H).

(520) The following molecules in Table 1 may be prepared according to the procedures disclosed: P1, P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P26, P27, P28, P29, P30, P31, P32, P33, P34, P35, P37, P39, P40, P41, P42, P43, P44, P45, P46, P47, P48, P49, P50, P51, P52, P53, P54, P55, P56, P57, P58, P59, P60, P61, P62, P63, P64, P65, P66, P67, P68, P69, P70, P71, P72, P73, P74, P75, P76, P77, P78, P79, P80, P81, P82, P83, P84, P85, P86, P87, P88, P89, P90, P91, P92, P93, P94, P95, P96, P97, P98, P99, P100, P101, P102, P103, and P104.

(521) TABLE-US-00002 TABLE 1 Structure and Preparation Method for Prophetic Molecules No. Structure P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 0 P11 P12 P13 P14 P15 P16 P17 P18 P19 P20 0 P21 P22 P23 P24 P25 P26 P27 P28 P29 P30 0 P31 P32 P33 P34 P35 P37 P39 P40 P41 P42 0 P43 P44 P45 P46 P47 P48 P49 P50 P51 P52 00 P53 01 P54 02 P55 03 P56 04 P57 05 P58 06 P59 07 P60 08 P61 09 P62 0 P63 P64 P65 P66 P67 P68 P69 P70 P71 P72 0 P73 P74 P75 P76 P77 P78 P79 P80 P81 P82 0 P83 P84 P85 P86 P87 P88 P89 P90 P91 P92 0 P93 P94 P95 P96 P97 P98 P99 P100 P101 P102 0 P103 P104

(522) The following compounds were prepared in like manner to the procedure outlined in Example 1:

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-1-naphthoic acid (C86)

(523) ##STR00353##

(524) Isolated as a yellow solid (0.85 g, 53%): .sup.1H NMR (300 MHz, CDCl.sub.3) 8.30 (d, J=7.5 Hz, 1H), 8.07-8.05 (m, 1H), 7.70-7.61 (m, 4H), 7.49 (s, 2H), 5.69 (dd, J=9.9, 31.2 Hz, 1H), 4.75-4.69 (m, 1H); IR (thin film) 3445, 1684, 1260, 750 cm.sup.1; ESIMS m/z 475.23 ([M].sup.).

(Z)-4-(3-(3-Chloro-5-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C87)

(525) ##STR00354##

(526) Isolated as a brown solid (1.0 g, 47%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.80 (s, 1H), 8.17-8.12 (m, 3H), 7.91-7.86 (m, 3H), 6.87 (dd, J=9.9, 36.0 Hz, 1H), 5.39-5.32 (m, 1H); ESIMS m/z 493.14 ([MH].sup.).

(Z)-4-(3-(3,4-Dichloro-5-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C88)

(527) ##STR00355##

(528) Isolated as a brown gum (1.7 g, 42%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.80 (s, 1H), 8.14 (s, 1H), 8.09 (d, J=8.1 Hz, 1H), 7.91 (d, J=8.1 Hz, 1H), 7.83 (s, 1H), 7.65 (s, 1H), 6.87 (dd, J=9.9, 36.0 Hz, 1H), 5.13-5.07 (m, 1H), 2.42 (s, 3H); IR (thin film) 3446, 2928, 1716 cm.sup.1; ESIMS m/z 473.10 ([MH].sup.).

(Z)-4-(3-(4-Bromo-3-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C89)

(529) ##STR00356##

(530) Isolated as a brown gum (2.5 g, 68%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.02 (d, J=8.4 Hz, 1H), 7.94 (s, 1H), 7.83 (d, J=7.2 Hz, 1H), 7.66 (d, J=8.4 Hz, 1H), 7.50 (s, 1H), 7.17 (dd, J=2.0, 8.4 Hz, 1H), 5.96 (dd, J=9.2, 32.0 Hz, 1H), 4.65-4.61 (m, 1H); IR (thin film) 3447, 2927, 1715, 750 cm.sup.1; ESIMS m/z 504.4 ([MH].sup.).

(Z)-4-(3-(3-Bromo-4,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C90)

(531) ##STR00357##

(532) Isolated as a yellow gum (2.6 g, 27%): .sup.1H NMR (400 MHz, CDCl.sub.3) 11.66 (s, 1H), 8.04 (d, J=7.3 Hz, 1H), 7.97 (d, J=1.7 Hz, 1H), 7.84 (dd, J=8.2, 1.8 Hz, 1H), 7.60 (d, J=2.0 Hz, 1H), 7.49 (d, J=2.1 Hz, 1H), 5.91 (dd, J=32.4, 9.6 Hz, 1H), 4.62 (p, J=8.8 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 57.06, 66.85, 110.35; ESIMS m/z 540 ([MH].sup.).

(Z)-4-(3-(4-Chloro-3-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C91)

(533) ##STR00358##

(534) Isolated as a brown gummy oil (0.45 g, 75%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.60 (br s, 1H), 7.98 (s, 1H) 7.92 (d, J=8.1 Hz, 1H), 7.90 (d, J=8.1 Hz, 1H), 7.53-7.38 (m, 2H), 7.04 (dd, J=8.4, 15.6 Hz, 1H), 6.89 (d, J=15.9 Hz, 1H), 4.76-4.63 (m, 1H), 2.35 (s, 3H); IR (thin film) 3436, 1727, 1150, 765 cm.sup.1; ESIMS m/z 420.79 ([MH].sup.).

(Z)-2-Chloro-4-(1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)pent-1-en-1-yl)benzoic acid (C92)

(535) ##STR00359##

(536) Isolated as a brown gum (1.5 g, 39%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, J=7.2 Hz, 1H), 7.66 (d, J=8.0 Hz, 1H), 7.41-7.35 (m, 3H), 5.96 (dd, J=10.0, 33.6 Hz, 1H), 4.98-4.96 (m, 1H), 1.67 (t, 1=19.2 Hz, 3H).

(Z)-4-(3-(3,5-Dichloro-4-(difluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C94)

(537) ##STR00360##

(538) Isolated as a yellow gum (0.45 g, 25%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 13.80 (s, 1H), 8.15 (s, 1H), 8.09 (dd, J=8.0 Hz, 1H), 8.00 (s, 2H), 7.92 (d, J=8.4 Hz, 1H), 7.45 (t, J=12.9 Hz, 1H), 6.90 (dd, J=10.0, 35.6 Hz, 1H), 5.33-5.31 (m, 1H); ESIMS m/z 509.11 ([MH].sup.).

(Z)-4-(3-(3-Chloro-4-methoxyphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C95)

(539) ##STR00361##

(540) Isolated as a yellow gum (0.46 g, 66%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.98 (d, J=8.4 Hz, 1H), 7.93 (s, 1H), 7.81 (d, J=8.0 Hz, 1H), 7.42 (s, 1H), 7.26 (s, 1H), 6.95 (d, J=8.8 Hz, 1H), 5.96 (dd, J=10.0, 32.8 Hz, 1H), 4.62-4.57 (m, 1H), 3.91 (s, 3H); ESIMS m/z 455.36 ([MH].sup.).

(Z)-4-(3-(3-Chloro-4-ethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C96)

(541) ##STR00362##

(542) Isolated as a yellow gum (0.60 g, 53%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 13.75 (br s, 1H), 8.15 (s, 1H), 8.01 (d, J=8.4 Hz, 1H), 7.90 (d, J=8.4 Hz, 1H), 7.78 (d, J=8.4 Hz, 1H), 7.55 (d, J=8.4 Hz, 1H), 7.41 (d, J=8.0 Hz, 1H), 6.87 (dd, J=9.6, 35.6 Hz, 1H), 5.08-5.04 (m, 1H), 2.73-2.67 (m, 2H), 1.17 (t, J=6.0 Hz, 3H); ESIMS m/z 453.38 ([MH].sup.).

(Z)-4-(3-(3-Chloro-4-(2,2,2-trifluoroethoxy)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C97)

(543) ##STR00363##

(544) Isolated as a brown solid (0.30 g, 53%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.90 (br s, 1H), 8.05-7.99 (m, 2H), 7.83-7.75 (m, 2H), 7.64-7.61 (m, 1H), 7.34 (d, J=8.4 Hz, 1H), 6.81 (dd, J=9.9, 36.3 Hz, 1H), 5.08-4.82 (m, 3H); IR (thin film) 3433, 2924, 1712, 749 cm.sup.1; ESIMS m/z 523.20 ([MH].sup.).

(Z)-4-(1,4,4,4-Tetrafluoro-3-(4-fluoro-3-(trifluoromethyl)phenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C98)

(545) ##STR00364##

(546) Isolated as a brown gum (1.0 g, 42%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.80 (br s, 1H), 8.16 (s, 1H), 8.12-8.07 (m, 3H), 7.92 (d, J=8.7 Hz, 1H), 7.66 (d, J=10.2 Hz, 1H), 6.96 (dd, J=9.9, 35.4 Hz, 1H), 5.36-5.29 (m, 1H); IR (thin film) 2926, 1715, 765 cm.sup.1; ESIMS m/z 477.2 ([MH].sup.).

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trifluorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C99)

(547) ##STR00365##

(548) Isolated as a brown gum (0.8 g, 56%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.98 (br s, 1H), 8.14 (br s, 1H), 8.08-8.05 (m, 1H), 7.92-7.89 (m, 1H), 7.77-7.72 (m, 2H), 6.85 (dd, J=9.9, 35.4 Hz, 1H), 5.23-5.16 (m, 1H); IR (thin film) 3100, 1715 cm.sup.1; ESIMS m/z 444.79 ([MH].sup.).

(Z)-4-(3-(3-Chloro-4,5-difluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C100)

(549) ##STR00366##

(550) Isolated as a brown gum (0.55 g, 56%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 13.92 (br s, 1H), 8.14 (s, 1H), 8.08 (d, J=8.1 Hz, 1H), 7.92-7.85 (s, 3H), 6.87 (dd, J=9.9, 35.4 Hz, 1H), 5.24-5.18 (m, 1H); IR (thin film) 3085, 1715, 659 cm.sup.1; ESIMS m/z 461.24 ([MH].sup.).

(Z)-4-(3-(3-Chloro-5-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C101)

(551) ##STR00367##

(552) Isolated as a brown gum (0.40 g, 63%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 13.89 (br s, 1H), 8.16 (s, 1H), 8.09 (d, J=8.4 Hz, 1H), 7.93-7.86 (m, 1H), 7.69 (s, 1H), 7.63 (d, J=9.6 Hz, 1H), 7.52-7.49 (m, 1H), 6.87 (dd, J=10.4, 35.6 Hz, 1H), 5.23-5.18 (m, 1H); IR (thin film) 2924, 1698, 1258 cm.sup.1; ESIMS m/z 442.80 ([MH].sup.).

(Z)-4-(3-(4-Bromo-3-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C102)

(553) ##STR00368##

(554) Isolated as a dark brown oil (0.130 g, 28%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.87 (m, 2H), 7.74 (d, J=8.1 Hz, 1H), 7.58 (dd, J=8.3, 7.1 Hz, 1H), 7.18 (dd, J=9.2, 2.0 Hz, 1H), 7.08 (d, J=8.6 Hz, 1H), 5.86 (dd, J=32.7, 9.6 Hz, 1H), 4.64 (p, J=8.9 Hz, 1H); ESIMS m/z 486.9 ([MH].sup.).

(Z)-4-(3-(3,4-Dichloro-5-(1,1-difluoroethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C103)

(555) ##STR00369##

(556) Isolated as a yellow foam (0.05 g, 23%): .sup.1H NMR (400 MHz, CDCl.sub.3) 11.66 (s, 1H), 7.85 (dd, J=9.3, 1.8 Hz, 1H), 7.80-7.71 (m, 1H), 7.61 (d, J=2.2 Hz, 1H), 7.56 (d, J=8.1 Hz, 1H), 7.26 (s, 1H), 5.86 (dd, J=32.6, 9.6 Hz, 1H), 4.86 (p, J=7.0 Hz, 1H), 4.01-3.81 (m, 1H), 2.18-1.93 (m, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 57.66, 69.34 (d, J=2.3 Hz), 72.58, 87.48, 106.98; ESIMS m/z 525 ([MH].sup.).

(Z)-4-(3-(4-Chloro-3-fluoro-5-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C104)

(557) ##STR00370##

(558) Isolated as a yellow gum (1.1 g, 54%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.03 (d, J=8.2 Hz, 1H), 7.98-7.93 (m, 2H), 7.84 (dd, J=8.1, 1.8 Hz, 1H), 7.54 (s, 1H), 7.44 (d, J=8.7 Hz, 1H), 5.91 (dd, J=32.4, 9.5 Hz, 1H), 4.72 (p, J=8.8 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.64, 62.52, 69.35 (d, J=2.1 Hz), 109.31, 111.51 (d, J=2.3 Hz); ESIMS m/z 512 ([MH].sup.).

(Z)-4-(3-(3-Bromo-4,5-difluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C105)

(559) ##STR00371##

(560) Isolated as a yellow gum (1.3 g, 54%): .sup.1H NMR (400 MHz, CDCl.sub.3) 9.76 (s, 1H), 8.05 (d, J=8.2 Hz, 1H), 8.01-7.91 (m, 1H), 7.84 (dd, J=8.2, 1.8 Hz, 1H), 7.39 (dt, J=4.9, 2.1 Hz, 1H), 7.22 (ddd, J=10.1, 6.6, 2.2 Hz, 1H), 5.90 (dd, J=32.5, 9.6 Hz, 1H), 4.62 (q, J=8.9 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.58, 69.53 (d, J=2.3 Hz), 110.42, 129.11 (d, J=21.5 Hz), 132.15 (d, J=21.4 Hz).; ESIMS m/z 505 ([MH].sup.).

(Z)-4-(3-(3-Chloro-5-(1, 1-difluoroethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C106)

(561) ##STR00372##

(562) Isolated as a brown foam (0.190 g, 62.1%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.99 (d, J=8.1 Hz, 1H), 7.78 (s, 1H), 7.66 (d, J=8.2 Hz, 1H), 7.52 (s, 1H), 7.46 (s, 1H), 7.40 (s, 1H), 6.67 (d, J=15.9 Hz, 1H), 6.56 (dd, J=15.9, 7.7 Hz, 1H), 4.23 (p, J=8.7 Hz, 1H), 1.93 (t, J=18.2 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.51, 68.50, 88.16 (d, J=9.2 Hz); IR (thin film) 3006, 1706 cm.sup.1; ESIMS m/z 470.9 ([MH].sup.).

(Z)-4-(3-(3-Chloro-5-(2,2,2-trifluoroethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C107)

(563) ##STR00373##

(564) Isolated as an orange oil (0.513 g, 59%); .sup.1H NMR (400 MHz, CDCl.sub.3) 8.03 (d, J=8.2 Hz, 1H), 7.96 (s, 1H), 7.83 (dd, J=8.2, 1.3 Hz, 1H), 7.40 (s, 1H), 7.33 (s, 1H), 7.22 (s, 1H), 5.93 (dd, J=32.6, 9.7 Hz, 1H), 4.67 (p, J=8.9 Hz, 1H), 3.39 (q, J=10.5 Hz, 2H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.60, 65.69, 69.25 (d, J=2.3 Hz), 112.97; IR (thin film) 3018, 1710 cm.sup.1; ESIMS m/z 507.0 ((MH].sup.).

(Z)-4-(1,4,4-Trifluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C108)

(565) ##STR00374##

(566) Isolated as a brown foam (1.8 g, 49%); .sup.1H NMR (400 MHz, CDCl.sub.3) 8.04 (d, J=8.1 Hz, 1H), 7.97 (s, 1H), 7.84 (d, J=8.2 Hz, 1H), 7.42 (s, 2H), 6.25-5.80 (m, 2H), 4.55-4.23 (m, 1H); IR (thin film) 2979, 1706, 1615, 1573, 1404 cm.sup.1; ESIMS m/z 474.9 ([MH].sup.).

(Z)-4-(3-(3-Chloro-4-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C109)

(567) ##STR00375##

(568) Isolated as an orange oil (1.22 g, 58%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.04 (d, J=8.2 Hz, 1H), 7.96 (d, J=1.7 Hz, 1H), 7.84 (dd, J=8.3, 1.8 Hz, 1H), 7.74 (d, J=8.2 Hz, 1H), 7.57 (d, J=1.6 Hz, 1H), 7.43 (d, J=8.2 Hz, 1H), 5.94 (dd, J=32.5, 9.6 Hz, 1H), 4.73 (p, J=8.9 Hz, 1H); IR (thin film) 3022, 1710 cm.sup.1; ESIMS m/z 493.0 ([MH].sup.).

(Z)-4-(3-(3-Chloro-5-(trifluoromethoxy)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C110)

(569) ##STR00376##

(570) Isolated as an orange oil (0.744 g, 68%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.04 (d, J=8.2 Hz, 1H), 8.01-7.94 (m, 1H), 7.84 (dd, J=8.2, 1.7 Hz, 1H), 7.36 (d, J=1.6 Hz, 1H), 7.27 (dt, J=2.3, 1.1 Hz, 1H), 7.17 (s, 1H), 5.91 (dd, J=32.4, 9.6 Hz, 1H), 4.68 (p, J=8.8 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 57.93, 59.60, 69.24 (d, J=2.5 Hz), 112.31 (d, J=2.6 Hz); IR (thin film) 3005, 1712, 1605, 1507, 1408 cm.sup.1; ESIMS m/z 508.8 ([MH].sup.).

(Z)-4-(3-(3-Chloro-4-(trifluoromethoxy)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C111)

(571) ##STR00377##

(572) Isolated as an orange oil (0.428 g, 56%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.04 (d, J=8.2 Hz, 1H), 7.99-7.94 (m, 1H), 7.84 (dd, J=8.2, 1.8 Hz, 1H), 7.54 (s, 1H), 7.36 (q, J=1.0 Hz, 2H), 5.93 (dd, J=32.5, 9.7 Hz, 1H), 4.68 (p, J=8.9 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 57.82, 59.60, 69.36 (d, J=2.2 Hz), 112.78 (d, J=2.7 Hz); IR (thin film) 3010, 1711, 1497, 1412 cm.sup.1; ESIMS m/z 508.8 ([MH].sup.).

(Z)-4-(3-(4-Chloro-3-(trifluoromethoxy)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C112)

(573) ##STR00378##

(574) Isolated as an orange oil (0.712 g, 65%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.03 (d, J=8.1 Hz, 1H), 7.95 (d, J=1.6 Hz, 1H), 7.83 (dd, J=8.2, 1.8 Hz, 1H), 7.53 (d, J=8.3 Hz, 1H), 7.37 (s, 1H), 7.32 (dd, J=8.5, 2.1 Hz, 1H), 5.92 (dd, J=32.5, 9.6 Hz, 1H), 4.69 (p, J=8.9 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 57.85, 59.63, 69.49 (d, J=2.2 Hz), 112.48 (t, J=2.7 Hz); IR (thin film) 3089, 1713, 1490 cm.sup.1; ESIMS m/z 508.8 ([MH].sup.).

(Z)-4-(3-(3-Bromo-4-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C113)

(575) ##STR00379##

(576) Isolated as an orange oil (0.749 g, 65%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.03 (d, J=8.2 Hz, 1H), 7.96 (d, J=1.6 Hz, 1H), 7.86-7.80 (m, 1H), 7.77 (d, J=1.7 Hz, 1H), 7.73 (d, J=8.2 Hz, 1H), 7.51-7.44 (m, 1H), 5.94 (dd, J=32.5, 9.6 Hz, 1H), 4.72 (p, J=8.9 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.64 (d, J=21.5 Hz), 62.85, 69.05 (d, J=2.3 Hz), 112.23 (d, J=2.7 Hz); IR (thin film) 3084, 1709 cm.sup.1; ESIMS m/z 539.0 ([MH].sup.).

(Z)-4-(3-(3-chloro-5-hydroxyphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C114)

(577) ##STR00380##

(578) Isolated as an orange oil (0.090 g, 29.4%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.01 (d, J=8.2 Hz, 1H), 7.95 (t, J=1.2 Hz, 1H), 7.82 (dd, J=8.2, 1.7 Hz, 1H), 6.97 (d, J=1.8 Hz, 1H), 6.87 (t, J=2.0 Hz, 1H), 6.80 (d, J=1.8 Hz, 1H), 5.90 (dd, J=32.7, 9.8 Hz, 1H), 4.59 (p, J=9.0 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.60, 69.15 (d, J=2.4 Hz), 113.71 (d, J=3.0 Hz); ESIMS m/z 441.0 ([MH].sup.).

(579) The following compounds were prepared in like manner to the procedure outlined in Example 3:

(Z)-4-(3-(3,4-Dichloro-5-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C115)

(580) ##STR00381##

(581) Isolated as a yellow wax (0.19 g, 65%): .sup.1H NMR (400 MHz, CDCl.sub.3) 9.76 (s, 1H), 8.02 (d, J=8.2 Hz, 1H), 7.95 (s, 1H), 7.82 (d, J=8.2 Hz, 1H), 7.52-7.39 (m, 2H), 7.09 (dd, J=17.5, 11.0 Hz, 1H), 6.04-5.85 (m, 1H), 5.76 (dd, J=17.5, 13.8 Hz, 1H), 5.55-5.45 (m, 1H), 4.65 (p, J=8.9 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.56, 67.15, 113.15; ESIMS m/z 487 ([MH].sup.).

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-vinylbenzoic acid (C116)

(582) ##STR00382##

(583) Isolated as a yellow gum (0.3 g, 86%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.06 (d, J=8.4 Hz, 1H), 7.81-7.64 (m, 2H), 7.61-7.49 (m, 2H), 7.44 (s, 2H), 5.95-5.67 (m, 2H), 5.47 (dd, J=15.5, 11.0 Hz, 1H), 4.63 (dp, J=13.9, 8.9 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 69.35, 112.10; ESIMS m/z 451 ([MH].sup.).

(Z)-4-(3-(3-Chloro-5-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C117)

(584) ##STR00383##

(585) Isolated as a yellow gum (0.065 g, 58%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.95-7.92 (m, 2H), 7.81 (dd, J=8.2, 1.8 Hz, 1H), 7.57 (dd, J=7.5, 1.7 Hz, 1H), 7.41 (t, J=1.8 Hz, 1H), 7.30 (s, 1H), 7.30 (s, 1H), 6.67 (dd, J=17.6, 10.9 Hz, 1H), 5.94 (s, 1H), 5.80 (d, J=17.5 Hz, 1H), 5.37 (d, J=10.9 Hz, 1H), 4.77-4.55 (m, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.66, 69.30, 112.51; ESIMS m/z 452 ([MH].sup.).

(586) The following compound was prepared in like manner to the procedure outlined in Example 7:

(4-(1-Fluorovinyl)-1-naphthoic acid (C118)

(587) ##STR00384##

(588) Isolated as an off-white solid (0.70 g, 52%): mp 154-156 C.; .sup.1H NMR (400 MHz, DMSO-d.sub.6) 13.40 (br s, 1H), 8.88-8.84 (m, 1H), 8.17-8.10 (m, 2H), 7.75-7.66 (m, 3H), 5.39 (dd, J=3.6, 17.2 Hz, 1H), 5.23 (dd, J=36.0, 50.4 Hz, 1H); ESIMS m/z 215.20 ([MH].sup.).

(589) The following compounds were prepared in like manner to the procedure outlined in Example 8:

5-(1-Bromo-2,2,2-trifluoroethyl)-2-chloro-1-fluoro-3-(trifluoromethyl)benzene (C119)

(590) ##STR00385##

(591) Isolated as a yellow gum (2.5 g, 49%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.62 (t, J=1.6 Hz, 1H), 7.57 (dd, J=8.7, 2.1 Hz, 1H), 5.12 (q, J=7.0 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 62.69, 70.52, 108.76; ESIMS m/z 359 ([MH].sup.).

5-(1-Bromo-2, 2,2-trifluoroethyl)-1,2-dichloro-3-(1,1-difluoroethyl)benzene (C120)

(592) ##STR00386##

(593) Isolated as a yellow oil (2 g, 39%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.91 (dd, J=9.3, 1.8 Hz, 1H), 7.80-7.71 (m, 1H), 5.16 (q, J=7.0 Hz, 1H), 2.22-1.99 (m, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.68, 69.32, 112.07; ESIMS m/z 371 ([MH].sup.).

1-Bromo-5-(1-bromo-2,2,2-trifluoroethyl)-2,3-dichlorobenzene (C121)

(594) ##STR00387##

(595) Isolated as a yellow oil (4.5 g, 46%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.58 (d, J=2.1 Hz, 1H), 7.46 (d, J=2.1 Hz, 1H), 4.35 (s, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 70.40; ESIMS m/z 386 ([MH].sup.).

1-Bromo-5-(1-bromo-2,2,2-trifluoroethyl)-2,3-difluorobenzene (C122)

(596) ##STR00388##

(597) Isolated as a pale yellow oil (1.8 g, 64%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.52-7.44 (m, 1H), 7.36 (td, J=7.4, 7.0, 3.4 Hz, 1H), 5.03 (q, J=7.0 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 70.63, 126.49 (d, J=21.3 Hz), 131.58 (dd, J=21.3, 0.9 Hz); ESIMS m/z 336 ([MH].sup.).

1-(1-Bromo-2,2,2-trifluoroethyl)-3-chloro-5-(1,1-difluoroethyl)benzene (C123)

(598) ##STR00389##

(599) Isolated as a clear oil (0.665 g, 68%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.59 (s, 1H), 7.53 (s, 1H), 7.50 (s, 1H), 5.10 (q, J=7.2 Hz, 1H), 1.92 (t, J=18.2 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 70.39, 88.36 (d, J=1.6 Hz); IR (thin film) 1588 cm.sup.1; ESIMS m/z 336.4 ([M+H].sup.+).

1-(1-Bromo-2,2,2-trifluoroethyl)-3-chloro-5-(2,2,2-trifluoroethyl)benzene (C124)

(600) ##STR00390##

(601) Isolated as a pale yellow oil (0.930 g, 73%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.51 (s, 1H), 7.35 (s, 1H), 7.32 (s, 1H), 5.07 (q, J=7.2 Hz, 1H), 3.38 (q, J=10.5 Hz, 2H); .sup.19F NMR (376 MHz, CDCl.sub.3) 65.71, 70.43; IR (thin film) 1113 cm.sup.1; EIMS m/z 356 ([M].sup.+).

5-(1-Bromo-2,2-difluoroethyl)-1,2,3-trichlorobenzene (C125)

(602) ##STR00391##

(603) Isolated as a clear oil (8.3 g, 66.9%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.49 (s, 2H), 6.00 (td, J=55.4, 3.8 Hz, 1H), 4.85 (ddd, J=13.7, 10.4, 3.8 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 116.16 (ddd, J=278.0, 55.2, 10.4 Hz), 119.84 (ddd, J=278.1, 55.6, 13.4 Hz); IR (thin film) 1552, 1431 cm.sup.1; ESIMS m/z 323.9 ([M+H].sup.+).

4-(1-Bromo-2,2,2-trifluoroethyl)-2-chloro-1-(trifluoromethyl)benzene (C126)

(604) ##STR00392##

(605) Isolated as a colorless oil (3.33 g, 46%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.73 (d, J=8.2 Hz, 1H), 7.68 (s, 1H), 7.52 (d, J=8.2 Hz, 1H), 5.11 (q, J=7.1 Hz, 1H); .sup.13C NMR (75 MHz, CDCl.sub.3) 137.94, 133.06 (d, J=1.9 Hz), 132.10, 129.93 (q, J=32.0 Hz), 128.10 (q, J=5.3 Hz), 127.47, 124.46 (d, J=48.7 Hz), 120.81 (d, J=43.9 Hz), 44.84 (q, J=34.8 Hz); ESIMS m/z 342.0 ([M+H].sup.+).

1-(1-Bromo-2,2,2-trifluoroethyl)-3-chloro-5-(trifluoromethoxy)benzene (C127)

(606) ##STR00393##

(607) Isolated as a colorless oil (2.27 g, 60%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.45 (d, J=1.7 Hz, 1H), 7.30 (s, 1H), 7.28 (s, 1H), 5.07 (q, J=7.1 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 58.02, 70.44; IR (thin film) 1588, 1450 cm.sup.1; EIMS m/z 358 ([M].sup.+).

4-(1-Bromo-2,2,2-trifluoroethyl)-2-chloro-1-(trifluoromethoxy)benzene (C128)

(608) ##STR00394##

(609) Isolated as a colorless oil (2.83 g, 62%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.65 (d, J=2.2 Hz, 1H), 7.45 (dd, J=8.6, 2.3 Hz, 1H), 7.36 (dd, J=8.6, 1.5 Hz, 1H), 5.09 (q, J=7.1 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 57.75, 70.52; IR (thin film) 1497 cm.sup.1; EIMS m/z 356 ([M].sup.+).

4-(1-Bromo-2,2,2-trifluoroethyl)-1-chloro-2-(trifluoromethoxy)benzene (C129)

(610) ##STR00395##

(611) Isolated as a clear oil (2.50 g, 56%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.52 (d, J=8.4 Hz, 1H), 7.48 (s, 1H), 7.41 (dd, J=8.4, 2.1 Hz, 1H), 5.10 (q, J=7.1 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 57.94, 70.63; IR (thin film) 1492, 1423 cm.sup.1; EIMS m/z 356 ([M].sup.+).

2-Bromo-4-(1-bromo-2,2,2-trifluoroethyl)-1-(trifluoromethyl)benzene (C130)

(612) ##STR00396##

(613) Isolated as a pale yellow oil (3.88 g, 61%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, J=1.6 Hz, 1H), 7.74 (d, J=8.2 Hz, 1H), 7.59-7.50 (m, 1H), 5.09 (qd, J=6.4, 3.8 Hz, 1H), 2.88 (d, J=4.3 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 62.86, 78.24; IR (thin film) 3392 cm.sup.1; ESIMS m/z 322.0 ([MH].sup.).

3-(1-Bromo-2,2,2-trifluoroethyl)-5-chlorophenol (C131)

(614) ##STR00397##

(615) Isolated as a brown oil (2.29 g, 38%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.03 (d, J=1.7 Hz, 1H), 6.88 (d, J=1.7 Hz, 2H), 6.32 (s, 1H), 4.98 (q, J=7.2 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 70.32; ESIMS m/z 288.9 ([MH].sup.).

1-Bromo-4-(1-bromo-2,2,2-trifluoroethyl)-2-chlorobenzene (C132)

(616) ##STR00398##

(617) Isolated as a light yellow oil (7.0 g, 51%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.65-7.62 (m, 1H), 7.61-7.59 (m, 1H), 7.29-7.25 (m, 1H), 5.08-5.02 (m, 1H); ESIMS m/z 351.9 ([M].sup.+).

4-(1-Bromo-2,2,2-trifluoroethyl)-1-chloro-2-methylbenzene (C133)

(618) ##STR00399##

(619) Isolated as a colorless oil (5.0 g, 44%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 7.55-7.50 (m, 2H), 7.44 (d, J=8.4 Hz, 1H), 6.24-6.16 (m, 1H), 2.36 (s, 3H); IR (thin film) 1112, 749, 564 cm.sup.1; ESIMS m/z 286.1 ([M].sup.+).

5-(1-Bromo-2,2,2-trifluoroethyl)-1,3-dichloro-2-(difluoromethyl)benzene (C134)

(620) ##STR00400##

(621) Isolated as a brown solid (2.2 g, 60%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.71 (s, 2H), 7.46 (t, J=51.6 Hz, 1H), 6.32-6.26 (m, 1H); ESIMS m/z 335.91 ([M].sup.+).

4-(1-Bromo-2,2,2-trifluoroethyl)-2-chloro-1-methoxybenzene (C135)

(622) ##STR00401##

(623) Isolated as a pale yellow oil (2.5 g, 33%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 7.61 (s, 1H), 7.55 (d, J=8.7 Hz, 1H), 7.26 (d, J=8.7 Hz, 1H), 6.22-6.14 (m, 1H), 3.89 (s, 3H); ESIMS m/z 302.0 ([M].sup.+).

4-(1-Bromo-2,2,2-trifluoroethyl)-2-chloro-1-ethylbenzene (C136)

(624) ##STR00402##

(625) Isolated as a yellow oil (3.5 g, 57%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.59 (s, 1H), 7.53-7.45 (m, 2H), 6.25-6.17 (m, 1H), 2.75-2.69 (m, 2H), 1.19 (t, J=7.6 Hz, 3H); IR (thin film) 3444, 2926, 1627, 750 cm.sup.1; ESIMS m/z 300.00 ([M].sup.+).

4-(1-Bromo-2,2,2-trifluoroethyl)-2-chloro-1-(2,2,2-trifluoroethoxy)benzene (C137)

(626) ##STR00403##

(627) Isolated as a colorless oil (1.50 g, 55%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 7.68 (m, 1H), 7.59-7.55 (m, 1H), 7.38-7.35 (m, 1H), 6.24-6.16 (m, 1H), 4.98-4.90 (m, 2H); IR (thin film) 3437, 2929, 1503, 1166 cm.sup.1; ESIMS m/z 370.00 ([M].sup.+).

5-(1-Bromo-2,2,2-trifluoroethyl)-1-chloro-2,3-difluorobenzene (C138)

(628) ##STR00404##

(629) Isolated as a colorless oil (2.5 g, 31%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.35-7.28 (m, 2H), 5.05-4.99 (m, 1H); IR (thin film) 2965, 1508, 758 cm.sup.1; ESIMS m/z 308.00 ([M].sup.+).

1-(1-Bromo-2,2,2-trifluoroethyl)-3-chloro-5-fluorobenzene (C139)

(630) ##STR00405##

(631) Isolated as a colorless oil (1.3 g, 32%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.29 (s, 1H), 7.17-7.13 (m, 2H), 5.07-5.01 (m, 1H); IR (thin film) 3419, 1265, 746 cm.sup.1; ESIMS m/z 290.01 ([M].sup.+).

1-Bromo-4-(1-bromo-2,2,2-trifluoroethyl)-2-fluorobenzene (C140)

(632) ##STR00406##

(633) Isolated as a dark brown oil (0.390 g, 64%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.59 (dd, J=8.3, 7.0 Hz, 1H), 7.31 (dd, J=9.0, 2.2 Hz, 1H), 7.17 (ddt, J=8.2, 2.0, 0.7 Hz, 1H), 5.07 (q, J=7.2 Hz, 1H); IR (thin film) 1684, 1257, 1167, 1117 cm.sup.1; ESIMS m/z 336 ([M].sup.+).

5-(1-Bromo-2,2,2-trifluoroethyl)-1,2-dichloro-3-methylbenzene (C199)

(634) ##STR00407##

(635) Isolated as a clear oil (6.7 g, 67%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.46 (s, 1H), 7.28 (s, 1H), 5.02 (q, J=7.2 Hz, 1H), 2.45 (s, 3H); IR (thin film) 1260, 1113, 750 cm.sup.1; EIMS m/z 322 ([M].sup.+).

(636) The following compounds were prepared in like manner to the procedure outlined in Example 10:

1-(4-Chloro-3-fluoro-5-(trifluoromethyl)phenyl)-2,2,2-trifluoroethan-1-ol (C141)

(637) ##STR00408##

(638) Isolated as a yellow gum (5.0 g, 73%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.63 (s, 1H), 7.54 (dd, J=8.9, 1.7 Hz, 1H), 5.16-5.02 (m, 1H), 2.95-2.74 (m, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 62.56, 78.52, 110.00; ESIMS m/z 296 ([MH].sup.).

1-(3,4-Dichloro-5-(1,1-difluoroethyl)phenyl)-2,2,2-trifluoroethan-1-ol (C142)

(639) ##STR00409##

(640) Isolated as a yellow oil (0.75 g, 87%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (dd, J=9.3, 1.8 Hz, 1H), 7.82-7.69 (m, 1H), 5.04-4.99 (m, 1H), 3.75-3.64 (m, 1H), 2.25-2.11 (m, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 113.14, 139.92 (d, J=20.8 Hz); ESIMS m/z 307 ([MH].sup.).

1-(3-Bromo-4,5-dichlorophenyl)-2,2,2-trifluoroethan-1-ol (C143)

(641) ##STR00410##

(642) Isolated as a yellow oil (5.5 g, 86%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.68 (s, 1H), 7.57 (s, 1H), 5.00 (d, J=11.5 Hz, 1H), 4.75 (s, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 78.32; ESIMS m/z 323 ([MH].sup.).

1-(3-Bromo-4,5-difluorophenyl)-2,2,2-trifluoroethan-1-ol (C144)

(643) ##STR00411##

(644) Isolated as a yellow oil (5.5 g, 90%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.44 (dd, J=17.9, 5.5 Hz, 2H), 5.02 (q, J=6.5 Hz, 1H), 1.55 (br, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 78.63, 128.47 (d, J=21.3 Hz), 135.58 (dd, J=21.3, 0.9 Hz); ESIMS m/z 291 ([MH].sup.).

2,2-Difluoro-1-(3,4,5-trichlorophenyl)ethan-1-ol (C145)

(645) ##STR00412##

(646) Isolated as a pale yellow solid (9.4 g, 98%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.48 (s, 2H), 5.72 (td, J=55.7, 4.7 Hz, 1H), 4.80 (tt, 1=9.3, 4.2 Hz, 1H), 2.65 (s, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 127.41 (m); IR (thin film) 3381 cm.sup.1; ESIMS m/z 260.0 ([M+H].sup.+).

1-(3-Chloro-5-fluorophenyl)-2,2,2-trifluoroethan-1-ol (C146)

(647) ##STR00413##

(648) Isolated as an off-white solid (3.0 g, 83%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.28-7.26 (m, 1H), 7.15-7.12 (m, 2H), 5.04-4.97 (m, 1H), 3.64-3.58 (m, 1H); IR (thin film) 3421, 1266, 742 cm.sup.1; ESIMS m/z 228.01 ([M].sup.+).

1-(3,4-Dichloro-5-methylphenyl)-2,2,2-trifluoroethan-1-ol (C200)

(649) ##STR00414##

(650) Isolated as a pale yellow oil (4.6 g, 79%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.44 (s, 1H), 7.26 (s, 1H), 4.97 (q, J=6.6 Hz, 1H), 2.44 (s, 3H); IR (thin film) 3428, 1275, 1262, 750 cm.sup.1; EIMS m/z 258 ([M].sup.+).

(651) The following compounds were prepared in like manner to the procedure outlined in Example 11:

1-(3-Chloro-5-(1,1-difluoroethyl)phenyl)-2,2,2-trifluoroethan-1-ol (C147)

(652) ##STR00415##

(653) Isolated as a clear oil (0.800 g, 90%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.56 (s, 1H), 7.54 (s, 1H), 7.51 (s, 1H), 5.14-5.01 (m, 1H), 2.77 (s, 1H), 1.92 (t, J=18.2 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 78.37, 88.20 (d, J=9.9 Hz); IR (thin film) 3422 cm.sup.1; EIMS m/z 274 ([M].sup.+).

1-(3-Chloro-5-(2,2,2-trifluoroethyl)phenyl)-2,2,2-trifluoroethan-1-ol (C148)

(654) ##STR00416##

(655) Isolated as a pale yellow oil (1.05 g, 61%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.49 (s, 1H), 7.35 (s, 1H), 7.31 (s, 1H), 5.07-5.00 (m, 1H), 3.38 (q, J=10.5 Hz, 2H), 2.64 (d, J=4.4 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 65.75, 78.39; IR (thin film) 3562 cm.sup.1; EIMS m/z 292 ([M].sup.+).

1-(3-Chloro-4-(trifluoromethyl)phenyl)-2,2,2-trifluoroethan-1-ol (C149)

(656) ##STR00417##

(657) Isolated as a colorless oil (5.90 g, 88%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.74 (d, J=8.2 Hz, 1H), 7.68 (s, 1H), 7.50 (d, J=8.1, 2.0, 0.9 Hz, 1H), 5.25-4.95 (m, 1H), 3.14 (s, 1H); .sup.13C NMR (75 MHz, CDCl.sub.3) 139.39, 132.66, 130.35, 129.22 (q, J=31.5 Hz), 127.67 (q, J=5.3 Hz), 129.69-116.91 (m), 117.16, 71.40 (q, J=32.4 Hz); ESIMS m/z 278.1 ([M+H].sup.+).

1-(3-Chloro-4-(trifluoromethoxy)phenyl)-2,2,2-trifluoroethan-1-ol (C150)

(658) ##STR00418##

(659) Isolated as a clear oil (3.4 g, 86%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.64 (dq, J=1.9, 0.6 Hz, 1H), 7.47-7.33 (m, 2H), 5.04 (qd, J=6.5, 4.4 Hz, 1H), 2.98 (d, J=4.1 Hz, 1H); IR (thin film) 3392, 1496 cm.sup.1; EIMS m/z 294 ([M].sup.+).

1-(3-Chloro-5-(trifluoromethoxy)phenyl)-2,2,2-trifluoroethan-1-ol (C151)

(660) ##STR00419##

(661) Isolated as a clear oil (3.15 g, 80%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.45 (s, 1H), 7.30-7.26 (m, 2H), 5.04 (q, J=6.4 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 58.01, 78.40; IR (thin film) 3305, 1587, 1442 cm.sup.1; EIMS m/z 294 ([M].sup.+).

1-(4-Chloro-3-(trifluoromethoxy)phenyl)-2,2,2-trifluoroethan-1-ol (C152)

(662) ##STR00420##

(663) Isolated as a clear oil (3.72 g, 95%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.53 (d, J=8.3 Hz, 1H), 7.49 (s, 1H), 7.38 (d, J=8.4 Hz, 1H), 5.06 (dd, J=6.6, 3.4 Hz, 1H), 3.80-3.70 (m, 1H), 2.92 (s, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 57.90, 78.59; IR (thin film) 3396, 1489 cm.sup.1; EIMS m/z 294 ([M].sup.+).

1-(3-Bromo-4-(trifluoromethyl)phenyl)-2,2,2-trifluoroethan-1-ol (C153)

(664) ##STR00421##

(665) Isolated as a pale yellow oil (3.88 g, 61%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, J=1.6 Hz, 1H), 7.74 (d, J=8.2 Hz, 1H), 7.59-7.50 (m, 1H), 5.09 (qd, J=6.4, 3.8 Hz, 1H), 2.88 (d, J=4.3 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 62.86, 78.24; IR (thin film) 3392 cm.sup.1; ESIMS m/z 322.0 ([MH].sup.).

3-Chloro-5-(2,2,2-trifluoro-1-hydroxyethyl)phenol (C154)

(666) ##STR00422##

(667) Isolated as a yellow solid (5.373 g, 85%): .sup.1H NMR (400 MHz, CDCl.sub.3) 6.97 (s, 1H), 6.88 (s, 1H), 6.82 (dq, J=5.1, 2.0 Hz, 1H), 4.95 (qd, J=6.7, 1.6 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 78.28-82.47 (m); ESIMS m/z 228.1 ([M+H].sup.+).

1-(4-Bromo-3-chlorophenyl)-2,2,2-trifluoroethan-1-ol (C155)

(668) ##STR00423##

(669) Isolated as a brown gum (12 g, 77%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.65-7.60 (m, 1H), 7.59 (s, 1H), 7.23-7.19 (m, 1H), 5.09-5.01 (m, 1H), 2.86 (br s, 1H); ESIMS m/z 289.90 ([M].sup.+).

1-(4-Chloro-3-methylphenyl)-2,2,2-trifluoroethan-1-ol (C156)

(670) ##STR00424##

(671) Isolated as a brown oil (7.2 g, 95%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 7.46 (m, 2H), 7.34 (d, J=8.4 Hz, 1H), 5.19-5.10 (m, 1H), 3.62-3.58 (m, 1H), 2.34 (s, 3H); IR (thin film) 3400, 1128, 720 cm.sup.1; ESIMS m/z 242.2 ([M].sup.+).

1-(3,5-Dichloro-4-(difluoromethyl)phenyl)-2,2,2-trifluoroethan-1-ol (C157)

(672) ##STR00425##

(673) Isolated as a pale yellow gum (2.6 g, 62%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.73 (s, 2H), 7.45 (t, J=52.0 Hz, 1H), 7.30 (d, J=6.4 Hz, 1H), 5.39 (t, J=6.8 Hz, 1H); IR (thin film) 3418, 1562, 1135 cm.sup.1; ESIMS m/z 293.9 ([M].sup.+).

1-(3-Chloro-4-methoxyphenyl)-2,2, 2-trifluoroethan-1-ol (C158)

(674) ##STR00426##

(675) Isolated as a brown viscous oil (4.0 g, 79%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.51 (s, 1H), 7.43 (d, J=8.1 Hz, 1H), 7.19 (d, J=8.4 Hz, 1H), 6.85 (d, J=5.2 Hz, 1H), 5.16-5.12 (m, 1H), 3.86 (s, 3H); IR (thin film) 3445, 2952, 1606, 1262 cm.sup.1; ESIMS m/z 240.0 ([M].sup.+).

1-(3-Chloro-4-ethylphenyl)-2,2,2-trifluoroethan-1-ol (C159)

(676) ##STR00427##

(677) Isolated as a yellow gum (5.0 g, 36%): .sup.1H NMR 400 MHz, CDCl.sub.3) 7.42 (s, 1H), 7.38-7.31 (m, 2H), 5.02-4.95 (m, 1H), 2.81-2.74 (m, 2H), 2.61 (br s, 1H), 1.24 (t, J=8.0 Hz, 3H); IR (thin film) 3420, 2973, 1565, 1131 cm.sup.1; ESIMS m/z 238.10 ([M].sup.+).

1-(3-Chloro-4-(2,2,2-trifluoroethoxy)phenyl)-2,2,2-trifluoroethan-1-ol (C160)

(678) ##STR00428##

(679) Isolated as a pale yellow oil (2.0 g, 59%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.58 (s, 1H), 7.49-7.44 (m, 1H), 7.33-7.30 (m, 1H), 6.93-6.92 (m, 1H), 5.19 (br s, 1H), 4.91-4.86 (m, 2H); IR (thin film) 3428, 2962, 1501, 1254 cm.sup.1; ESIMS m/z 308.10 ([M].sup.+).

1-(3-Chloro-4,5-difluorophenyl)-2,2,2-trifluoroethan-1-ol (C161)

(680) ##STR00429##

(681) Isolated as a colorless oil (4.6 g, 33%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.34-7.30 (m, 2H), 5.01-4.95 (m, 1H), 3.21 (br s, 1H); IR (thin film) 3302, 1709, 750 cm.sup.1; ESIMS m/z 246.00 ([M].sup.+).

(682) The following compound was prepared in like manner to the procedure outlined in Example 12:

2,2-Difluoro-1-(3,4,5-trichlorophenyl)ethan-1-one (C162)

(683) ##STR00430##

(684) Isolated as an off-white solid (9.25 g, 88%): mp 45-48 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) 7.71 (s, 2H), 6.21 (t, J=53.5 Hz, 1H); .sup.19F NMR (376 MHz, CDCl.sub.3) 126.71 (d, J=53.4 Hz); IR (thin film) 1743, 1559 cm.sup.1; ESIMS m/z 260.0 ([M+H].sup.+).

(685) The following compounds were prepared in like manner to the procedure outlined in Example 13:

N((R)-1-Oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-1-naphthamide (PF1)

(686) ##STR00431##

(687) Isolated as a yellow solid (0.110 g, 44%).

(Z)-4-(3-(3,4-Dibromophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino]-2-oxoethyl)-2-(trifluoromethyl)benzamide (PF4)

(688) ##STR00432##

(689) Isolated as a yellow gum (0.154 g, 62%).

(Z)-4-(3-(3-Chloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino]-2-oxoethyl)-2-(trifluoromethyl)benzamide (PF6)

(690) ##STR00433##

(691) Isolated as a yellow gum (0.160 g, 61%).

4-((Z)-3-(3-Chloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (PF7)

(692) ##STR00434##

(693) Isolated as a yellow gum (0.121 g, 43%).

4-((Z)-3-(3-Chloro-4-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (PF8)

(694) ##STR00435##

(695) Isolated as a yellow gum (0.195 g, 74%).

4-((2)-1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N((R)-1-thioxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (PF96)

(696) ##STR00436##

(697) Isolated as a yellow oil (0.097 g, 69%).

(Z)-4-(1,4,4,4-Tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamothioyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF98)

(698) ##STR00437##

(699) Isolated as a yellow gum (0.047 g, 33%).

4-((Z)-3-(3,5-Dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F144)

(700) ##STR00438##

(701) Isolated as a brown gum (0.100 g, 35%).

(Z)-4-(3-(3-Chloro-4-methoxyphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F158)

(702) ##STR00439##

(703) Isolated as a yellow solid (0.105 g, 42%).

4-((Z)-3-(3-Chloro-4-methoxyphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F161)

(704) ##STR00440##

(705) Isolated as a yellow solid (0.150 g, 58%).

4-((Z)-3-(3-Chloro-4-ethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F164)

(706) ##STR00441##

(707) Isolated as a yellow gum (0.120 g, 48%).

(Z)-4-(3-(3-Chloro-4-ethylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F165)

(708) ##STR00442##

(709) Isolated as a pale yellow solid (0.120 g, 51%).

N((R)-1-Oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)hex-1-en-1-yl)-2-(trifluoromethyl)benzamide (F174)

(710) ##STR00443##

(711) Isolated as a white foamy glass (0.047 g, 60%).

4-((Z)-3-(3-Chloro-5-(1, 1-difluoroethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F175)

(712) ##STR00444##

(713) Isolated as a pale yellow foam (0.061 g, 55%).

4-((Z)-3-(3-Chloro-5-(2,2,2-trifluoroethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F176)

(714) ##STR00445##

(715) Isolated as a white foamy wax (0.079 g, 60.8%).

N((R)-3-Oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-4-((Z)-1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F177)

(716) ##STR00446##

(717) Isolated as an off-white solid (0.144 g, 52%).

4-((Z)-3-(3-Chloro-5-(2,2,2-trifluoroethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-3-oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-2-(trifluoromethyl)benzamide (F178)

(718) ##STR00447##

(719) Isolated as a white foamy glass (0.052 g, 56%).

4-((Z)-3-(3-Chloro-4-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-3-oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-2-(trifluoromethyl)benzamide (F180)

(720) ##STR00448##

(721) Isolated as a white foam (0.103 g, 74.8%).

4-((Z)-3-(3-Chloro-5-(trifluoromethoxy)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F181)

(722) ##STR00449##

(723) Isolated as a clear orange oil (0.077 g, 74.2%).

4-((Z)-3-(3-Chloro-4-(trifluoromethoxy)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F182)

(724) ##STR00450##

(725) Isolated as a yellow glass (0.073 g, 89%).

4-((Z)-3-(4-Chloro-3-(trifluoromethoxy)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F183)

(726) ##STR00451##

(727) Isolated as a pale yellow glass (0.102 g, 77%).

4-((Z)-3-(3-Bromo-4,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F185)

(728) ##STR00452##

(729) Isolated as a white gum (0.0721 g, 60%).

4-((Z)-3-(3,4-Dichloro-5-(1,1-difluoroethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F193)

(730) ##STR00453##

(731) Isolated as a yellow gum (0.044 g, 32%).

4-((Z)-3-(3,4-Dichloro-5-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-3-oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-2-(trifluoromethyl)benzamide (F196)

(732) ##STR00454##

(733) Isolated as a colorless gum (0.030 g, 82%).

4-((Z)-3-(3-Bromo-4,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-3-oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-2-(trifluoromethyl)benzamide (F197)

(734) ##STR00455##

(735) Isolated as a white wax (0.091 g, 94%).

2-Bromo-N((R)-3-oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)benzamide (F198)

(736) ##STR00456##

(737) Isolated as a white wax (0.045 g, 46%).

(Z)N-(2-Oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-vinylbenzamide (F200)

(738) ##STR00457##

(739) Isolated as a yellow gum (0.026 g, 46%).

N((R)-1-Oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl]-2-vinylbenzamide (F201)

(740) ##STR00458##

(741) Isolated as a colorless gum (0.052 g, 40%).

4-((Z)-3-(4-Chloro-3-fluoro-5-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F202)

(742) ##STR00459##

(743) Isolated as a pale yellow gum (0.052 g, 86%).

(Z)-4-(3-(4-Chloro-3-fluoro-5-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluoro-but-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F203)

(744) ##STR00460##

(745) Isolated as a yellow oil (0.141 g, 76%).

N((R)-3-Oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-vinylbenzamide (F204)

(746) ##STR00461##

(747) Isolated as a yellow gum (0.101 g, 21%).

4-((Z)-3-(3-Chloro-4-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F205)

(748) ##STR00462##

(749) Isolated as an orange oil (0.081 g, 44.6%).

(Z)-4-(3-(3-Chloro-4-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2, 2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F206)

(750) ##STR00463##

(751) Isolated as an off-white foam (0.074 g, 41%).

4-((Z)-3-(3-Bromo-4,5-difluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F214)

(752) ##STR00464##

(753) Isolated as an orange oil (0.048 g, 72%).

(Z)-4-(3-(3-Bromo-4,5-difluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F217)

(754) ##STR00465##

(755) Isolated as an orange oil (0.062 g, 81%).

4-((Z)-3-(3-Chloro-5-hydroxyphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (C163)

(756) ##STR00466##

(757) Isolated as an orange oil (0.23 g, 10%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (s, 1H), 7.76 (d, J=8.1 Hz, 1H), 7.56 (d, J=8.1 Hz, 1H), 6.96 (s, 1H), 6.85 (t, J=2.1 Hz, 1H), 6.78 (d, J=10.5 Hz, 2H), 6.44 (d, J=7.5 Hz, 1H), 5.83 (dd, J=32.8, 9.8 Hz, 1H), 5.63 (s, 1H), 4.74 (p, J=7.1 Hz, 1H), 4.56 (p, J=9.0 Hz, 1H), 3.94 (dq, J=9.3, 7.1 Hz, 2H), 1.51 (dd, J=7.0, 5.1 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.11, 69.19 (d, J=2.6 Hz), 72.56, 113.58; IR (thin film) 3303, 1692, 1531 cm.sup.1; ESIMS m/z 595.3 ([M+H].sup.+).

(758) The following compounds were prepared in like manner to the procedure outlined in Example 15:

N((R)-1-(Dimethylamino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F172)

(759) ##STR00467##

(760) Isolated as a white foam (0.134 g, 55%).

N((R)-1-(Methylamino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F173)

(761) ##STR00468##

(762) Isolated as a white foam (0.0120 g, 51%).

Methyl (Z)-4,4,4-trifluoro-3-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamido)butanoate (F166)

(763) ##STR00469##

(764) Isolated as a yellow/orange gum (0.059 g, 76%).

N((R)-1-(Hydroxy(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F169)

(765) ##STR00470##

(766) Isolated as a white foam (0.117 g, 44%).

4-((Z)-3-(4-Bromo-3-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F170)

(767) ##STR00471##

(768) Isolated as a white foam (0.093 g, 55%).

N((R)-2-Oxo-1-(2,2,2-trifluoroethyl)pyrrolidin-3-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F171)

(769) ##STR00472##

(770) Isolated as a white foam (0.114 g, 57%).

(771) The following compounds were prepared in like manner to the procedure outlined in Example 16:

4-((Z)-3-(3,4-Dibromophenyl)-1,4,4,4-tetrafluoro-but-1-en-1-yl)-N((R)-1-(methyl(2,2, 2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (PF2)

(772) ##STR00473##

(773) Isolated as a yellow gum (0.169 g, 68%).

(Z)-4-(3-(3,4-Dibromophenyl)-1,4,4,4-tetrafluoro-but-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF3)

(774) ##STR00474##

(775) Isolated as a yellow solid (0.157 g, 60%).

(Z)-4-(3-(3-Chloro-4-fluorophenyl)-1,4,4,4-tetrafluoro-but-1-en-1-yl)]-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF10)

(776) ##STR00475##

(777) Isolated as a brown gum (0.142 g, 53%).

(Z)-4-(3-(3,4-Dichloro-5-methylphenyl)-1,4,4,4-tetrafluoro-but-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (PF12)

(778) ##STR00476##

(779) Isolated as a pale yellow solid (0.176 g, 57%).

4-((Z)-3-(3,4-Dichloro-5-methylphenyl)-1,4,4,4-tetrafluoro-but-1-en-1-yl)-N((R)-1-oxo-1-(2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (PF13)

(780) ##STR00477##

(781) Isolated as a pale yellow solid (0.155 g, 54%).

4-((Z)-3-(3,4-Dichloro-5-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (PF14)

(782) ##STR00478##

(783) Isolated as a yellow gum (0.165 g, 60%).

(Z)-4-(3-(3,4-Dichloro-5-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(2,2, 2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF15)

(784) ##STR00479##

(785) Isolated as a pale yellow solid (0.140 g, 51%).

(Z)-4-(3-(3,4-Dichloro-5-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF16)

(786) ##STR00480##

(787) Isolated as a yellow solid (0.175 g, 64%).

(Z)-4-(3-(4-Chloro-3-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (PF18)

(788) ##STR00481##

(789) Isolated as a white solid (0.153 g, 48%).

4-((Z)-3-(4-Chloro-3-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (PF19)

(790) ##STR00482##

(791) Isolated as a yellow solid (0.088 g, 41%).

4-((Z)-3-(4-Chloro-3-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (PF20)

(792) ##STR00483##

(793) Isolated as a yellow gum (0.150 g, 47%).

(Z)-4-(3-(4-Chloro-3-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF22)

(794) ##STR00484##

(795) Isolated as a yellow gum (0.090 g, 33%).

(Z)-4-(3-(4-Bromo-3-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (PF24)

(796) ##STR00485##

(797) Isolated as a yellow gum (0.101 g, 43%).

4-((Z)-3-(4-Bromo-3-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-(2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (PF25)

(798) ##STR00486##

(799) Isolated as a pale brown solid (0.168 g, 65%).

4-((Z)-3-(4-Bromo-3-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl]-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (PF26)

(800) ##STR00487##

(801) Isolated as a pale yellow solid (0.076 g, 32%).

(Z)-4-(3-(4-Bromo-3-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF27)

(802) ##STR00488##

(803) Isolated as an off-white solid (0.149 g, 57%).

(Z)-4-(3-(4-Bromo-3-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl]-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF28)

(804) ##STR00489##

(805) Isolated as an off-white solid (0.055 g, 23%).

4-((Z)-3-(3-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (PF31)

(806) ##STR00490##

(807) Isolated as a yellow gum (0.124 g, 54%).

(Z)-4-(3-(3-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF32)

(808) ##STR00491##

(809) Isolated as a brown gum (0.115 g, 56%).

(Z)-4-(3-(3-Bromo-5-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF33)

(810) ##STR00492##

(811) Isolated as a yellow gum (0.136 g, 51%).

(Z)-4-(3-(3-Bromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (PF35)

(812) ##STR00493##

(813) Isolated as a yellow gum (0.111 g, 56%).

4-((Z)-3-(3-Bromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (PF37)

(814) ##STR00494##

(815) Isolated as a yellow gum (0.131 g, 67%).

(Z)-4-(3-(3-Bromo-4-chlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF39)

(816) ##STR00495##

(817) Isolated as a yellow gum (0.107 g, 47%).

(Z)-4-(3-(3-Chloro-5-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-2-(trifluoromethyl)benzamide (PF41)

(818) ##STR00496##

(819) Isolated as a pale yellow solid (0.077 g, 32%).

4-((Z)-3-(3-Chloro-5-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-((1R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (PF42)

(820) ##STR00497##

(821) Isolated as a yellow solid (0.076 g, 32%).

4-((Z)-3-(3-Chloro-5-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (PF43)

(822) ##STR00498##

(823) Isolated as a brown gum (0.051 g, 21%).

(Z)-4-(3-(3-Chloro-5-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)]-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF44)

(824) ##STR00499##

(825) Isolated as a pale brown solid (0.088 g, 37%).

(Z)-4-(3-(3-Chloro-5-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF45)

(826) ##STR00500##

(827) Isolated as a brown solid (0.045 g, 18%).

(Z)-4-(3-(4-Chloro-3-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-(methyl(2,2, 2-trifluoroethyl)amino]-2-oxoethyl)-2-(trifluoromethyl)benzamide (PF47)

(828) ##STR00501##

(829) Isolated as a pale yellow solid (0.100 g, 41%).

4-((Z)-3-(4-Chloro-3-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-(2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (PF48)

(830) ##STR00502##

(831) Isolated as a pale yellow solid (0.080 g, 33%).

4-((Z)-3-(4-Chloro-3-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-(methyl(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)-2-(trifluoromethyl)benzamide (PF49)

(832) ##STR00503##

(833) Isolated as an off-white solid (0.058 g, 28%).

(Z)-4-(3-(4-Chloro-3-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF50)

(834) ##STR00504##

(835) Isolated as a pale yellow solid (0.106 g, 39%).

(Z)-4-(3-(4-Chloro-3-methylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (PF51)

(836) ##STR00505##

(837) Isolated as a pale yellow solid (0.098 g, 39%).

2-Chloro-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)pent-1-en-1-yl)benzamide (PF60)

(838) ##STR00506##

(839) Isolated as a pale brown solid (0.100 g, 32%).

(Z)-2-Chloro-4-(1,4,4-trifluoro-3-(3,4,5-trichlorophenyl)pent-1-en-1-yl)-N-(1-((2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)benzamide (PF62)

(840) ##STR00507##

(841) Isolated as a pale yellow gum (0.101 g, 33%).

N((R)-1-Oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(4-fluoro-3-(trifluoromethyl)phenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F141)

(842) ##STR00508##

(843) Isolated as a pale yellow solid (0.190 g, 51%).

4-((Z)-3-(3,5-Dichloro-4-(difluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F142)

(844) ##STR00509##

(845) Isolated as a pale yellow solid (0.130 g, 50%).

4-((2)-3-(3,5-Dichloro-4-(difluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-3-oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-2-(trifluoromethyl)benzamide (F143)

(846) ##STR00510##

(847) Isolated as a pale yellow gum (0.112 g, 52%).

(Z)-4-(3-(4-Bromo-3,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(1-(methyl(2,2,2-trifluoroethyl)carbamoyl)cyclopropyl)-2-(trifluoromethyl)benzamide (F145)

(848) ##STR00511##

(849) Isolated as a yellow gum (0.085 g, 37%).

N((R)-3-Oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-4-((2)-1,4,4,4-tetrafluoro-3-(4-fluoro-3-(trifluoromethyl)phenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F150)

(850) ##STR00512##

(851) Isolated as a brown gum (0.100 g, 37%).

(Z)-4-(3-(3-Chloro-4,5-difluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F153)

(852) ##STR00513##

(853) Isolated as a brown gum (0.110 g, 47%).

4-((Z)-3-(3-Chloro-4,5-difluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F154)

(854) ##STR00514##

(855) Isolated as a pale yellow gum (0.119 g, 50%).

N((R)-3-Oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trifluorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F155)

(856) ##STR00515##

(857) Isolated as a pale yellow gum (0.110 g, 56%).

(Z)-4-(3-(3-Chloro-5-fluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F157)

(858) ##STR00516##

(859) Isolated as a pale yellow gum (0.085 g, 51%).

N((R)-1-Oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trifluorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F159)

(860) ##STR00517##

(861) Isolated as a pale yellow gum (0.120 g, 44%).

(Z)N-(2-Oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trifluorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F160)

(862) ##STR00518##

(863) Isolated as an off-white solid (0.115 g, 41%).

4-((Z)-3-(3-Chloro-4-(2,2,2-trifluoroethoxy)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F162)

(864) ##STR00519##

(865) Isolated as a yellow gum (0.115 g, 44%).

(Z)N-(2-Oxo-2-((2-oxopropyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F163)

(866) ##STR00520##

(867) Isolated as a pale brown gum (0.112 g, 49%).

(868) The following compounds were prepared in like manner to the procedure outlined in Example 21:

2-Amino-N-(2-hydroxy-2-methylpropyl)acetamide hydrochloride (C164)

(869) ##STR00521##

(870) Isolated as a colorless gum (0.45 g, 31%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.56 (br s, 2H), 8.16 (br s, 3H), 3.61-3.15 (m, 2H), 3.09-3.07 (m, 2H), 1.53 (s, 3H), 1.07 (s, 3H); ESIMS m/z 147.35 ([M+H].sup.+).

(R)-2-Amino-N-(2,2,2-trifluoroethyl)propanehydrazide hydrochloride (C165)

(871) ##STR00522##

(872) Isolated as an off-white solid (0.15 g, 68%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 10.06 (s, 1H), 8.30 (br s, 3H), 3.76-3.72 (m, 1H), 3.56 (s, 1H), 3.48-3.38 (m, 2H), 1.34 (d, J=6.8 Hz, 3H); IR (thin film) 3425, 1683, 1145 cm.sup.1; ESIMS m/z 186.30 ([M+H].sup.+).

(R)-2-Amino-N-methyl-N-(2,2,2-trifluoroethyl)propanehydrazide hydrochloride (C166)

(873) ##STR00523##

(874) Isolated as a pale yellow solid (0.50 g, 91%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.26 (br s, 3H), 6.08 (br s, 1H), 4.36-4.28 (m, 1H), 3.68-3.64 (m, 2H), 3.03 (s, 3H), 1.34 (d, J=6.9 Hz, 3H); IR (thin film) 3452, 1667, 764 cm.sup.1; ESIMS m/z 200.30 ([M+H].sup.+).

1-Methyl-2-(2,2,2-trifluoroethyl)hydrazine hydrochloride (C167)

(875) ##STR00524##

(876) Isolated as an off white solid (0.70 g, 97%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 10.82 (br s, 2H), 6.68 (br s, 1H), 3.90-3.74 (m, 2H), 2.66 (s, 3H); ESIMS m/z 129.10 ([M+H].sup.+).

(R)-2-Amino-N,N-dimethyl-N-(2,2,2-trifluoroethyl)propanehydrazide hydrochloride (C168)

(877) ##STR00525##

(878) Isolated as an off-white solid (0.30 g, 75%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.17 (br s, 3H), 4.14-4.07 (m, 1H), 3.71-3.56 (m, 2H), 2.92 (s, 3H), 2.69 (s, 3H), 1.36 (d, J=7.2 Hz, 3H); ESIMS m/z 214.00 ([M+H].sup.+).

1,2-Dimethyl-1-(2,2,2-trifluoroethyl)hydrazine hydrochloride (C169)

(879) ##STR00526##

(880) Isolated as an off-white solid (0.50 g, 68%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 10.90 (s, 2H), 3.86-3.77 (m, 2H), 2.78 (s, 3H), 2.59 (m, 3H); IR (thin film) 2464, 1634, 790 cm.sup.1.

2-Amino-N-(2-oxopropyl)acetamide hydrochloride (C170)

(881) ##STR00527##

(882) Isolated as a brown gum (0.40 g, 60%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.72 (br s, 1H), 8.20 (br s, 3H), 4.05-4.03 (m, 2H), 3.61-3.60 (m, 2H), 2.10 (s, 3H); IR (thin film) 3421, 1261 cm.sup.1.

2-Amino-N-ethyl-N-(2,2,2-trifluoroethyl)acetamide hydrochloride (C171)

(883) ##STR00528##

(884) Isolated as a pink solid (2.33 g, 93%): mp 158-162 C.: .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.30 (s, 3H), minor rotamer 4.35 (q, J=9.2 Hz, 2H), major rotamer 4.23 (q, J=9.5 Hz, 2H), minor rotamer 3.98 (s, 2H), 3.43 (d, 1=7.0 Hz, 2H), 2.53 (m, 2H), minor rotamer 1.17 (m, 3H), minor rotamer 1.09 (m, 3H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) major rotamer 68.20, minor rotamer 69.03; IR (thin film) 1665, 1156, 1109 cm.sup.1.

(R)-2-Amino-N-(3,3-difluorocyclobutyl)propanamide hydrochloride (C172)

(885) ##STR00529##

(886) Isolated and carried on without further purification as a brown viscous oil: .sup.19F NMR (376 MHz, Methanol-d.sub.4) 85.81 (d, J=199.0 Hz), 99.35 (d, J=199.1 Hz); IR (thin film) 1669, 1299 cm.sup.1.

(887) The following compound was prepared in like manner to the procedure outlined in Example 22:

tert-Butyl (R)-(1-((3,3-difluorocyclobutyl)amino)-1-oxopropan-2-yl)carbamate (C173)

(888) ##STR00530##

(889) Isolated as a white solid (1.57 g, 51%): mp 149-153 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) 6.75 (br s, 1H), 4.96 (br s, 1H), 4.30-4.19 (m, 1H), 4.18-4.07 (m, 1H), 3.04-2.94 (m, 2H), 2.54-2.39 (m, 2H), 1.45 (s, 9H), 1.34 (d, J=7.1 Hz, 3H); .sup.19F NMR (376 MHz, Methanol-d.sub.4) 84.89 (d, J=198.9 Hz), 97.22 (d, J=199.1 Hz); IR (thin film) 1680, 1652, 1522, 1157 cm.sup.1; ESIMS m/z 222 ([M-C.sub.4H.sub.9].sup.+).

(890) The following compound was prepared in like manner to the procedure outlined in Example 30:

Benzyl (R)-(1-((benzyloxy)(2,2,2-trifluoroethyl)amino)-1-oxopropan-2-yl)carbamate (C174)

(891) ##STR00531##

(892) Isolated as a colorless oil (0.350 g, 40%): .sup.1H NMR (300 MHz, CDCl.sub.3) 7.39 (m, 10H), 5.42 (d, J=8.6 Hz, 1H), 5.14 (m, 2H), 5.03 (s, 2H), 4.87 (m, 1H), 4.56 (m, 1H), 3.82 (dd, J=15.9, 8.0 Hz, 1H), 1.36 (d, J=7.0 Hz, 3H); IR (thin film) 1684, 1256, 1188, 1154, 696 cm.sup.1; ESIMS m/z 411.2 ([M+H].sup.+).

(893) The following compound was prepared in like manner to the procedure outlined in Example 31:

(R)-2-Amino-N-hydroxy-N-(2,2,2-trifluoroethyl)propanamide hydrochloride (C175)

(894) ##STR00532##

(895) Isolated and carried on without further purification as a brown viscous oil: .sup.1H NMR (300 MHz, DMSO-d.sub.6) 11.14 (s, 1H), 8.37 (s, 3H), 4.62-4.27 (m, 2H), 3.49-3.38 (m, 1H), 1.43 (d, J=6.9 Hz, 3H); ESIMS m/z 184.9 ([MH].sup.).

(896) The following compound was prepared in like manner to the procedure outlined in Example 34:

(R)-3-Amino-1-(2,2,2-trifluoroethyl)pyrrolidin-2-one hydrochloride (C176)

(897) ##STR00533##

(898) Isolated as a white solid (0.320 g, 59%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.55 (s, 3H), 4.16 (dddd, J=24.0, 14.3, 9.7, 5.1 Hz, 3H), 3.55-3.47 (m, 2H), 2.42 (ddd, J=13.0, 6.5, 3.4 Hz, 1H), 1.99 (dq, J=12.5, 9.5 Hz, 1H).

Example 35: Preparation of (Z)-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)phenylcarbonothioyl)glycine (C177)

(899) ##STR00534##

(900) To tert-butyl (Z)-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)phenylcarbonothioyl)glycinate (C178) (0.236 g, 0.378 mmol) in dichloromethane (5 mL) was added trifluoroacetic acid (0.116 mL, 1.51 mmol). After stirring 20 hours at room temperature and 1 hour at reflux, the mixture was cooled to room temperature and additional trifluoroacetic acid (0.233 mL, 3.02 mmol) was added. After 30 minutes the mixture was concentrated under reduced pressure. Purification of the residue by column chromatography (SiO.sub.2, eluting with 0-100% ethyl acetate gradient in hexanes) afforded the title compound as a yellow foam (0.066 g, 29%): .sup.1H NMR (400 MHz, CDCl.sub.3) 9.06 (s, 1H), 7.84 (s, 1H), 7.82 (d, J=1.7 Hz, 1H), 7.74 (dd, J=8.3, 1.7 Hz, 1H), 7.63 (d, J=8.1 Hz, 1H), 7.43 (s, 2H), 5.81 (dd, J=32.6, 9.6 Hz, 1H), 4.65-4.56 (m, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 58.34, 69.35, 111.88; ESIMS m/z 567 [(MH).sup.].

Example 36: Preparation of tert-butyl (Z)-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)phenylcarbonothioyl)glycinate (C178)

(901) ##STR00535##

(902) A 5 mL microwave reaction vial was charged with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (0.150 g, 0.369 mmol), tert-butyl (Z)-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)phenylcarbonothioyl)glycinate (C178) (0.300 g, 0.493 mmol) and dioxane (2.0 mL). The mixture, under a nitrogen atmosphere, was placed in a microwave reactor and heated to 60 C. for 10 hours and 90 C. for 6 hours. After cooling the mixture was then treated with additional 4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (0.125 g, 0.309 mmol), placed in a microwave reactor and heated to 95 C. for 4 hours. After cooling, the crude mixture was diluted with ethyl acetate and diethyl ether, then washed with saturated sodium bicarbonate and brine. The organic phase was dried with sodium sulfate, concentrated, and purified by column chromatography (SiO.sub.2, eluting with a 0-100% gradient of ethyl acetate in hexanes) to afford the title compound as a yellow glass (0.230 g, 67%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.95 (d, J=4.5 Hz, 1H), 7.81 (d, J=1.7 Hz, 1H), 7.73 (dd, J=8.2, 1.7 Hz, 1H), 7.62 (d, J=8.2 Hz, 1H), 7.44 (s, 2H), 5.80 (dd, J=32.6, 9.6 Hz, 1H), 4.61 (p, J=8.9 Hz, 1H), 4.40 (d, J=4.4 Hz, 2H), 1.51 (s, 9H); .sup.19F NMR (376 MHz, CDCl.sub.3) 58.37, 69.37, 111.87; ESIMS m/z 623 ([MH].sup.).

Example 37: Preparation of 4-vinyl-1-naphthoic acid (C179)

(903) ##STR00536##

(904) To a stirred solution of 4-bromo-1-naphthoic acid (2.50 g, 9.98 mmol) in dimethyl sulfoxide (32.3 mL) was added potassium vinyltrifluoroborate (1.33 g, 9.96 mmol), potassium carbonate (3.85 g, 27.9 mmol) and [1,1-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (0.364 g, 0.498 mmol). The reaction mixture was heated in an 80 C. bath for 18 hours. The reaction mixture was cooled to ambient temperature and diluted with 1 N aqueous hydrochloric acid solution (150 mL) and water (150 mL). The mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to afford crude compound. The crude compound was purified by column chromatography (SiO.sub.2, eluting with 0-100% ethyl acetate gradient in hexanes) to afford the title compound as a bright yellow solid (1.36 g, 62%): mp 147-155 C.; .sup.1H NMR (300 MHz, acetone-d.sub.6) 11.42 (s, 1H), 9.16-9.03 (m, 1H), 8.31-8.25 (m, 2H), 7.77 (dd, J=7.7, 0.7 Hz, 1H), 7.70-7.57 (m, 3H), 5.95 (dd, J=17.2, 1.5 Hz, 1H), 5.62 (dd, J=11.1, 1.5 Hz, 1H); ESIMS m/z 197.1 ([MH].sup.).

Example 38: Preparation of 1-(4-Bromo-3-fluorophenyl)-2,2,2-trifluoroethan-1-ol (C180)

(905) ##STR00537##

(906) To a stirred solution of lithium acetate (0.016 g, 0.25 mmol) in dimethylformamide (2 mL) cooled in an ice bath were added 4-bromo-3-fluorobenzaldehyde (1.00 g, 4.93 mmol) and trimethyl(trifluoromethyl)silane (0.841 g, 5.91 mmol). The mixture was allowed to warm to room temperature. After 18 hours the mixture was portioned between diethyl ether and saturated aqueous ammonium chloride. The organic layer was washed brine (2), dried over sodium sulfate and concentrated to afford a light brown oil. The crude intermediate was taken up in tetrahydrofuran (20 mL) and treated with 1N aqueous hydrochloric acid solution (5 mL). After stirring for 18 hours at room temperature the reaction mixture was concentrated and the residue partitioned between diethyl ether and aqueous saturated sodium bicarbonate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to afford crude compound. Purification by column chromatography (SiO.sub.2, eluting with 10% ethyl acetate in hexanes) afforded the title compound as a pale oil (0.800 g, 60%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.60 (dd, J=8.3, 6.9 Hz, 1H), 7.30 (dd, J=9.1, 2.0 Hz, 1H), 7.15 (dq, J=8.3, 0.8 Hz, 1H), 5.02 (dd, J=6.5, 4.5 Hz, 1H), 2.65 (d, J=4.4 Hz, 1H).

Example 39: Preparation 1-Bromo-3-chloro-5-(2,2,2-trifluoroethyl)benzene (C181)

(907) ##STR00538##

(908) (3-Bromo-5-chlorophenyl)boronic acid (4 g, 17.00 mmol) was added to a flask with 2,2,2-trifluoroethan-1-amine hydrochloride (9.22 g, 68.0 mmol), sodium nitrite (5.87 g, 85 mmol), and ammonium chloride (3.64 g, 68.0 mmol). The reaction was heated to 100 C. overnight. At this point, the solvent was removed, and the residue was dissolved in dimethyl sulfoxide (20 mL). Potassium fluoride (1.976 g, 34.0 mmol) was added, and the mixture was heated to 100 C. for 2 hours. After cooling, the mixture was diluted with water and extracted with dichloromethane. After extraction and solvent removal, the residue was purified by silica gel chromatography eluting with hexanes. The title compound was recovered as a clear, colorless oil that crystallized upon standing (3.00 g, 64.5%):

(909) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.52 (t, J=1.8 Hz, 1H), 7.35 (s, 1H), 7.24 (s, 1H), 3.32 (q, J=10.5 Hz, 2H); .sup.19F NMR (376 MHz, CDCl.sub.3) 5-65.64; ESIMS m/z 274.0 ([M+H].sup.+).

Example 40: Preparation of 3-chloro-5-(2,2,2-trifluoroethyl)benzaldehyde (C182)

(910) ##STR00539##

(911) 1-Bromo-3-chloro-5-(2,2,2-trifluoroethyl)benzene (C181) (2 g, 7.31 mmol) was dissolved in tetrahydrofuran at 0 C., and isopropylmagnesium chloride-lithium chloride complex (1.3 M solution in tetrahydrofuran; 6.75 mL, 8.78 mmol) was added dropwise. The reaction mixture was stirred for 4 hours with warming to room temperature, and N,N-dimethylformamide (0.680 mL, 8.78 mmol) was added dropwise. The reaction mixture was stirred for 30 minutes, then 1 N aqueous hydrochloric acid was added, and the mixture was extracted with diethyl ether. The combined organic layers were washed with brine, dried over sodium sulfate and concentrated to a yellow oil. Purification by silica gel chromatography eluting 0-20% acetone in hexanes gave the title compound as a pale yellow oil (1.33 g, 82%): .sup.1H NMR (400 MHz, CDCl.sub.3) 9.98 (s, 1H), 7.90-7.78 (m, 1H), 7.71 (s, 1H), 7.56 (s, 1H), 3.45 (q, J=10.5 Hz, 2H); .sup.19F NMR (376 MHz, CDCl.sub.3) 65.67; IR (thin film) 1704 cm.sup.1; EIMS m/z 221 ([M].sup.+).

Example 41: Preparation of 3,5-dichloro-4-(difluoromethyl)benzaldehyde (C183)

(912) ##STR00540##

(913) To a stirred solution of methyl 3,5-dichloro-4-(difluoromethyl)benzoate (C189) (5.00 g, 19.6 mmol) in methylene chloride (20 mL) cooled in a 78 C. bath was added dropwise diisobutylaluminum hydride (1 M solution in tetrahydrofuran; 39.2 mL, 39.2 mmol). After 2 hours, the reaction mixture was treated with cold water and extracted with methylene chloride. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to afford crude compound. Purification by column chromatography (SiO.sub.2, 100-200 mesh, eluting with 5% ethyl acetate in petroleum ether) afforded the title compound as a pale brown solid (3.0 g, 66%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) 10.00 (s, 1H), 8.05 (s, 2H), 7.52 (t, J=52.0 Hz, 1H); IR (thin film) 1709, 1362, 1057 cm.sup.1; ESIMS m/z 224.0 ([M].sup.+).

Example 42: Preparation of 3-chloro-4,5-difluorobenzaldehyde (C184)

(914) ##STR00541##

(915) To a stirred solution of methyl(3-chloro-4,5-difluorophenyl)methanol (4.00 g, 22.4 mmol) in methylene chloride (150 mL) was added manganese dioxide (15.0 g, 179 mmol). After stirring for 12 hours at room temperature, the reaction mixture was filtered through Celite. The filtrate was concentrated under reduced pressure to afford the title compound as a colorless oil (3.5 g, 86%): .sup.1H NMR (300 MHz, CDCl.sub.3) 9.89 (s, 1H), 7.77-7.74 (m, 1H), 7.66-7.61 (m, 1H); IR (thin film) 3302, 1709, 750 cm.sup.1; ESIMS m/z 176.10 ([M].sup.+).

Example 43: Preparation of 4-((Z)-3-(3,4-dichloro-5-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F186)

(916) ##STR00542##

(917) Tetrakis(triphenylphosphine)palladium(0) (26.7 mg, 0.023 mmol) was added to a solution of 4-((Z)-3-(3-bromo-4,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F185) (0.08 g, 0.12 mmol) in toluene (1.1 mL) at room temperature. The reaction mixture was degassed by purging with nitrogen (310 minutes). Tributyl vinyl stannane (0.11 g, 0.35 mmol) was added to the reaction mixture. The reaction mixture was again degassed by purging with nitrogen (310 minutes) and stirred at 110 C. for 12 hours. The reaction mixture was quenched with water and then extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using 30% ethyl acetate in hexanes provided the title compound as a pale yellow gum (0.0231 g, 30%).

(918) The following compounds were prepared in like manner to the procedure outlined in Example 43:

4-((Z)-3-(4-Allyl-3,5-dichlorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F146)

(919) ##STR00543##

(920) Isolated as a pale yellow gum (0.115 g, 35%).

4-((Z)-3-(3,5-Dichloro-4-((E)-prop-1-en-1-yl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F147)

(921) ##STR00544##

(922) Isolated as a pale yellow solid (0.135 g, 42%).

4-((Z)-3-(3,5-Dichloro-4-(prop-1-en-2-yl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F148)

(923) ##STR00545##

(924) Isolated as a pale yellow gum (0.181 g, 57%).

4-((Z)-3-(4-Chloro-3,5-divinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F184)

(925) ##STR00546##

(926) Isolated as a yellow oil 0.0444 g, 90%).

4-((Z)-3-(3,4-Dichloro-5-(prop-1-en-2-yl)phenyl)-1,4,4,4-tetrafluoro-but-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F187)

(927) ##STR00547##

(928) Isolated as a yellow oil (0.052 g, 51%).

4-((Z)-3-(3,4-Dichloro-5-((E)-prop-1-en-1-yl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F188)

(929) ##STR00548##

(930) Isolated as a yellow gum (0.092 g, 65%).

4-((Z)-3-(3,4-Dichloro-5-ethynylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F189)

(931) ##STR00549##

(932) Isolated as a white gum (0.016 g, 28%).

4-((Z)-3-(3,4-Dichloro-5-(prop-1-yn-1-yl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F190)

(933) ##STR00550##

(934) Isolated as a yellow gum (0.017 g, 29%).

4-((Z)-3-(3,4-Dichloro-5-(3,3-dimethylbut-1-yn-1-yl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F191)

(935) ##STR00551##

(936) Isolated as a yellow gum (0.010 g, 19%).

4-((Z)-3-(3,4-Dichloro-5-cyanophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F192)

(937) ##STR00552##

(938) Isolated as a colorless oil (0.035 g, 52%).

4-((Z)-3-(3-Chloro-5-(3,3-dimethyl but-1-yn-1-yl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F212)

(939) ##STR00553##

(940) Isolated as a yellow gum (0.083 g, 87%).

4-((Z)-3-(3-(3,3-Dimethylbut-1-yn-1-yl)-4,5-difluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F216)

(941) ##STR00554##

(942) Isolated as an orange oil (0.038 g, 59%).

Example 44: Preparation of (Z)-4-(3-(3,4-difluorophenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F215)

(943) ##STR00555##

(944) Dichlorobis(triphenylphosphine)palladium(II) (18.93 mg, 0.027 mmol) was added to a solution of 4-((Z)-3-(3-bromo-4,5-dicflurorphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F185) (0.087 g, 0.135 mmol) in toluene (0.674 mL) at room temperature. The reaction mixture was degassed by purging with nitrogen (310 minutes). 2-(Tributylstannyl)pyridine (99 mg, 0.270 mmol) was added into the reaction mixture. The reaction mixture was again degassed by purging with nitrogen (310 minutes) and stirred at 110 C. for 4 hours. The reaction mixture was loaded directly onto a column with dichloromethane and methanol. Purification by flash column chromatography provided the title compound as an orange oil (0.011 g, 15%).

Example 45 Preparation of 4-((Z)-3-(3,4-dichloro-5-formylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (C185)

(945) ##STR00556##

(946) Osmium tetraoxide (2.5% in tert-butanol; 48 mg, 0.005 mmol) was added to a solution of 4-((Z)-3-(3,4-dichloro-5-vinylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F186) (0.06 g, 0.094 mmol) in tetrahydrofuran-water (2:1, 1.1 mL) at room temperature. The reaction mixture was stirred for 5 minutes. Sodium periodate (0.061 g, 0.282 mmol) was added to the reaction mixture. The reaction mixture was stirred at 20 C. for 12 hours. The reaction mixture was quenched with sodium bisulfate (100 mg) and then extracted with ethyl acetate (10 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using 40% ethyl acetate in hexanes provided the title compound as a pale yellow gum (0.050 g, 75%): .sup.1H NMR (400 MHz, CDCl.sub.3) 10.47 (s, 1H), 7.87 (dd, J=12.8, 1.9 Hz, 2H), 7.81-7.70 (m, 2H), 7.60-7.49 (m, 1H), 7.34 (d, J=6.5 Hz, 1H), 6.83 (d, J=7.6 Hz, 1H), 5.99-5.79 (m, 1H), 4.92-4.78 (m, 1H), 4.71 (p, J=9.0 Hz, 1H), 3.85 (dddd, J=15.2, 12.9, 7.6, 3.5 Hz, 2H), 1.51 (d, J=7.0 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 58.18, 68.49, 72.97, 110.05; ESIMS m/z 639 ([MH].sup.).

(947) The following compounds were prepared in like manner to the procedure outlined in Example 45:

4-((Z)-3-(3,4-Dichloro-5-formylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-3-oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-2-(trifluoromethyl)benzamide (C186)

(948) ##STR00557##

(949) Isolated as a white gum (0.074 g, 88%): .sup.1H NMR (400 MHz, CDCl.sub.3) 10.47 (s, 1H), 7.88 (dd, J=5.8, 1.9 Hz, 2H), 7.81-7.72 (m, 2H), 7.63 (d, J=8.1 Hz, 1H), 6.70-6.57 (m, 1H), 6.01-5.80 (m, 1H), 5.08-4.86 (m, 2H), 4.79-4.61 (m, J=9.3 Hz, 1H), 4.30-3.98 (m, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.08 (d, J=2.0 Hz), 68.49, 70.35 (d, J=3.9 Hz), 112.33; ESIMS m/z 655 ([MH].sup.).

4-((Z)-3-(3-Chloro-5-formylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (C187)

(950) ##STR00558##

(951) Isolated as an orange solid (0.800 g, 54%): .sup.1H NMR (400 MHz, CDCl.sub.3) 10.00 (d, J=0.6 Hz, 1H), 7.91-7.86 (m, 3H), 7.81 (d, J=5.6 Hz, 1H), 7.66 (s, 1H), 7.57 (d, J=8.1 Hz, 1H), 7.02 (t, J=6.4 Hz, 1H), 6.59 (d, J=7.6 Hz, 1H), 5.92 (dd, J=32.6, 9.6 Hz, 1H), 4.89-4.66 (m, 2H), 3.88 (ddd, J=19.5, 9.2, 6.5 Hz, 2H), 1.51 (d, J=7.0 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 59.28, 68.39, 70.36, 110.05; ESIMS m/z 606 ([MH].sup.).

Example 46: Preparation of 4-((Z)-3-(3,4-dichloro-5-(hydroxymethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (C188)

(952) ##STR00559##

(953) Sodium borohydride (18 mg, 0.468 mmol) was added to a solution of 4-((Z)-3-(3,4-dichloro-5-formylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (C185) (0.2 g, 0.312 mmol) in tetrahydrofuran (1.5 mL) at room temperature. The reaction mixture was stirred at 20 C. for 12 hours. The reaction mixture was quenched with water (5 mL) and then extracted with ethyl acetate (50 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using 35% ethyl acetate in hexanes provided the title compound as a pale yellow gum (0.110 g, 52%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.80 (t, J=2.0 Hz, 1H), 7.72 (d, J=6.7 Hz, 1H), 7.67 (dt, J=8.1, 1.7 Hz, 1H), 7.52 (d, J=2.0 Hz, 1H), 7.47-7.41 (m, 2H), 7.31 (d, J=7.2 Hz, 1H), 6.03-5.70 (m, 1H), 4.87 (p, J=7.1 Hz, 1H), 4.74 (s, 2H), 4.64 (p, J=9.0 Hz, 1H), 3.90-3.66 (m, 2H), 3.38 (s, 1H), 1.48 (dd, J=7.0, 2.6 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) 58.48, 67.37, 72.66, 110.57; ESIMS m/z 641 ([MH].sup.).

Example 47: Preparation of 4-((Z)-3-(3,4-dichloro-5-(difluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F195)

(954) ##STR00560##

(955) Bis(2-methoxyethyl)aminosulfur trifluoride (35 mg, 0.16 mmol) was added to a solution of 4-((Z)-3-(3,4-dichloro-5-formylphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (C185) (0.05 g, 0.078 mmol) in dichloromethane (0.5 mL) at room temperature. One drop of methanol was added and the reaction mixture was stirred at 20 C. for 12 hours. The reaction mixture was quenched with water (5 mL) and then extracted with ethyl acetate (15 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated. Purification by flash column chromatography using 35% ethyl acetate in hexanes provided the title compound as a white wax (0.028 g, 51%).

(956) The following compounds were prepared in like manner to the procedure outlined in Example 47:

4-((Z)-3-(3,4-Dichloro-5-(fluoromethyl)phenyl)-1,4,4,4-tetrafluoro-but-1-en-1-yl]-N((R)-1-oxo-1-(2,2,2-trifluoroethyl)amino)propan-2-yl]-2-(trifluoromethyl)benzamide (F194)

(957) ##STR00561##

(958) Isolated as a colorless gum (0.0931 g, 67%).

4-((Z)-3-(3,4-Dichloro-5-(difluoromethyl)phenyl)-1,4,4,4-tetrafluoro-but-1-enyl)-N((R)-3-oxo-2-(2,2,2-trifluoroethyl)isoxazolidin-4-yl)-2-(trifluoromethyl)benzamide (F199)

(959) ##STR00562##

(960) Isolated as a yellow gum (0.040 g, 53%).

4-((Z)-3-(3-Chloro-5-(difluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F213)

(961) ##STR00563##

(962) Isolated as an orange solid (0.062 g, 76%).

Methyl 3,5-dichloro-4-(difluoromethyl)benzoate (C189)

(963) ##STR00564##

(964) Isolated as a pale yellow solid (0.70 g, 63%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.02 (s, 2H), 7.50 (t, J=52.2 Hz, 1H), 3.99 (s, 3H); ESIMS m/z 254.2 ([M].sup.+).

Example 48: Preparation of 4-((Z)-3-(3-chloro-5-(2,2,2-trifluoroethoxy)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F207)

(965) ##STR00565##

(966) 4-((Z)-3-(3-Chloro-5-hydroxyphenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (C163) (0.070 g, 0.118 mmol) was dissolved in acetone (1.177 mL) and potassium carbonate (0.049 g, 0.353 mmol) and 2,2,2-trifluoroethyl trifluoromethanesulfonate (0.025 mL, 0.177 mmol) were added sequentially. The reaction mixture was stirred overnight. The solvent was removed. Purification of the residue on silica gel eluting with 0-30% acetone in hexanes provided the title compound as a clear colorless oil (0.016 g, 20.1%).

(967) The following compounds were prepared in like manner to the procedure outlined in Example 48:

4-((Z)-3-(3-Bromo-4-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N((R)-1-oxo-1-((2,2,2-trifluoroethyl)amino)propan-2-yl)-2-(trifluoromethyl)benzamide (F208)

(968) ##STR00566##

(969) Isolated as an orange oil (0.107 g, 55.6%).

(Z)-4-(3-(3-Bromo-4-(trifluoromethyl)phenyl)-1,4,4,4-tetrafluorobut-1-en-1-yl)-N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (F209)

(970) ##STR00567##

(971) Isolated as an off-white foam (0.116 g, 55.4%).

Example 49: Preparation of (Z)N-(2-(ethyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F167)

(972) ##STR00568##

(973) To a stirred solution of (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C2) (0.167 g, 0.34 mmol) in N,N-dimethylformamide (4 mL) were added (1-cyano-2-ethoxy-2-oxoethylidenaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (0.170 g, 0.40 mmol) and N-methyl morpholine (0.10 mL, 0.92 mmol). After 15 minutes the reaction mixture was treated with 2-amino-N-ethyl-N-(2,2,2-trifluoroethyl)acetamide hydrochloride (C171) (0.104 g, 0.47 mmol) and was stirred for 20 hours at room temperature. The mixture was partitioned between diethyl ether and 5% aqueous sodium bisulfate. The organic layer was washed with 5% aqueous sodium bisulfate (2), saturated aqueous sodium carbonate and brine, then dried over magnesium sulfate and concentrated under reduced pressure to afford crude compound. The crude compound was purified by column chromatography (SiO.sub.2) to afford the title compound as a yellow/orange gum (0.127 g, 56%).

(974) The following compound was prepared in like manner to the procedure outlined in Example 49:

tert-Butyl (Z)-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoyl)glycinate (C190)

(975) ##STR00569##

(976) Isolated as a brown foam (0.300 g, 42%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.85 (s, 1H), 7.80-7.73 (m, 1H), 7.64 (d, J=4.3 Hz, 1H), 7.44 (s, 2H), 6.37 (t, J=5.0 Hz, 1H), 5.83 (dd, J=32.5, 9.5 Hz, 1H), 4.68-4.54 (m, 1H), 4.11 (d, J=4.9 Hz, 2H), 1.50 (s, 9H); ESIMS m/z 610 ([M+H].sup.+).

Example 50: Preparation of N((R)-1-((3,3-difluorocyclobutyl)amino)-1-oxopropan-2-yl)-4-((Z)-1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F168)

(977) ##STR00570##

(978) To a stirred solution of (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzoic acid (C2) (0.250 g, 0.50 mmol) and (R)-2-amino-N-(3,3-difluorocyclobutyl)propanamide hydrochloride (C172) (0.162 g, 0.75 mmol) in methylene chloride (5 mL) were added 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (0.114 g, 0.59 mmol), 4-dimethylaminopyridine (0.75 g, 0.67 mmol) and triethylamine (0.20 mL, 1.43 mmol). After 20 hours the reaction mixture was diluted with methylene chloride (20 mL) and washed with 5% aqueous sodium bisulfate (3), saturated aqueous sodium carbonate (2) and brine. The combined organic extracts were dried over magnesium sulfate and concentrated under reduced pressure to afford crude compound. The crude compound was purified by column chromatography (SiO.sub.2, eluting with 0-45% ethyl acetate gradient in hexanes) to afford the title compound as a yellow oil (0.045 g, 14%).

Example 51: Preparation of (Z)-2-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)phenylthioamido)-N-(2,2,2-trifluoroethyl)acetamide (PF82)

(979) ##STR00571##

(980) To (Z)-(4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)phenylcarbonothioyl)glycine (C177) (0.044 g, 0.077 mmol) and 2-(1H-benzo[d][1,2,3]triazol-1-yl)-1,1,3,3-tetramethylisouronium hexafluorophosphate(V) (0.041 g, 0.108 mmol) in N,N-dimethylformamide (0.3 mL) was added 2,2,2-trifluoroethanamine (0.015 mL, 0.186 mmol). The mixture was stirred for 2 hours at room temperature and then partitioned between ethyl acetate and water. The organic layer was washed with water, 0.1 N aqueous hydrochloric acid solution, and brine, and concentrated under reduced pressure to afford crude compound. The crude compound was purified by column chromatography (SiO.sub.2, eluting with 0-100% ethyl acetate gradient in hexanes) to afford the title compound as a yellow foam (0.025 g, 45%).

Example 52: Preparation of (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(2-thioxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzothioamide (PF88) and (Z)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-N-(2-thioxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-2-(trifluoromethyl)benzamide (PF94)

(981) ##STR00572##

(982) A 5 mL microwave reactor vial was charged with (Z)N-(2-oxo-2-((2,2,2-trifluoroethyl)amino)ethyl)-4-(1,4,4,4-tetrafluoro-3-(3,4,5-trichlorophenyl)but-1-en-1-yl)-2-(trifluoromethyl)benzamide (F1) (0.11 g, 0.174 mmol) and 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (0.070 g, 0.174 mmol) in dichloroethane (3 mL). The mixture was placed in a microwave reactor and heated to 130 C. for 30 min. After cooling to room temperature, the reaction mixture was diluted with dichloromethane and washed with aqueous saturated sodium bicarbonate solution (2). The organic phase was dried with sodium sulfate, filtered, and concentrated. Purification by column chromatography (SiO.sub.2, eluting with 0-100% ethyl acetate gradient in hexanes) afforded the title compounds, (PF88) as a pale yellow glass (0.045 g, 31%) and (PF94) as a yellow glass (0.025 g, 20%).

Example 53: Preparation of tert-butyl (2-((2-hydroxy-2-methylpropyl)amino)-2-oxoethyl)carbamate (C191)

(983) ##STR00573##

(984) To a stirred solution of (tert-butoxycarbonyl)glycine (0.500 g, 2.85 mmol) in tetrahydrofuran (30 mL) cooled in a 78 C. bath was added N-methyl morpholine (0.433 g, 4.28 mmol). After 15 minutes isobutyl chloroformate (0.585 g, 4.28 mmol) was added. After an additional 15 minutes of stirring in a 78 C. bath the reaction mixture was treated with 1-amino-2-methyl-propan-2-ol (0.279 g, 3.14 mmol). The mixture was stirred an additional 1 hour at which time the reaction mixture was diluted with water. The mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to afford crude compound. Purification by column chromatography (SiO.sub.2, eluting with 40% ethyl acetate in petroleum ether) afforded the title compound as a colorless liquid (0.7 g, 70%): .sup.1H NMR (400 MHz, CDCl.sub.3) 6.55 (br s, 1H), 5.18 (br s, 1H), 3.86-3.80 (m, 2H), 3.29-3.28 (m, 2H), 1.45 (s, 6H), 1.22 (s, 9H); IR (thin film) 3335, 1698, 1275 cm.sup.1; ESIMS m/z 247.30 ([M+H].sup.+).

(985) The following compound was prepared in like manner to the procedure outlined in Example 53:

tert-Butyl (2-oxo-2-((2-oxopropyl)amino)ethyl)carbamate (C192)

(986) ##STR00574##

(987) Isolated as a colorless oil (0.60 g, 78%): .sup.1H NMR (300 MHz, CDCl.sub.3) 6.75 (br s, 1H), 5.13 (br s, 1H), 4.18-4.16 (m, 2H), 3.85-3.83 (m, 2H), 2.21 (s, 3H), 1.46 (s, 9H); IR (thin film) 3345, 1704, 1169 cm.sup.1; ESIMS m/z 131.20 ([MCO.sub.2C.sub.4H].sup.).

Example 54: Preparation of tert-butyl 1-methyl-2-(2,2,2-trifluoroethyl)hydrazine-1-carboxylate (C193)

(988) ##STR00575##

(989) To a stirred solution of tert-butyl 2-(2,2,2-trifluoroethyl)hydrazine-1-carboxylate (2.00 g, 9.34 mmol) in N,N-dimethylformamide (20 mL) cooled in an ice bath was added sodium hydride (0.450 g, 18.7 mmol). After 20 minutes the mixture was treated with methyl iodide (1.99 g, 14.0 mmol) and stirred for an additional 2 hours with cooling. The reaction mixture was then poured into ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to afford crude compound. Purification by column chromatography (SiO.sub.2) afforded the title compound as a yellow oil (1.8 g, 85%): .sup.1H NMR (400 MHz, CDCl.sub.3) 4.29 (br s, 1H), 3.49-3.46 (m, 2H), 3.03 (s, 3H), 1.47 (s, 9H).

Example 55: Preparation of tert-butyl 1,2-dimethyl-2-(2,2,2-trifluoroethyl)hydrazine-1-carboxylate (C194)

(990) ##STR00576##

(991) To a stirred solution of tert-butyl 2-(2,2,2-trifluoroethyl)hydrazine-1-carboxylate (1.00 g, 4.67 mmol) in N,N-dimethylformamide (10 mL) cooled in an ice bath were added sequentially sodium hydride (0.34 g, 14 mmol) and methyl iodide (1.99 g, 14 mmol). The mixture was allowed to warm to room temperature and stir for 12 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to afford crude compound. Purification by column chromatography (SiO.sub.2) afforded the title compound as a yellow oil (1.0 g, 88%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 3.63-3.45 (m, 2H), 2.88 (s, 3H), 2.67 (m, 3H), 1.35 (s, 9H); IR (thin film) 3422, 1694, 769 cm.sup.1.

Example 56: Preparation N-(2-(ethyl(2,2,2-trifluoroethyl)amino)-2-oxoethyl)-3,3-dimethylbutanamide (C195)

(992) ##STR00577##

(993) To a stirred solution of (tert-butoxycarbonyl)glycine (0.528 g, 3.01 mmol) in N,N-dimethylformamide (5 mL) cooled in an ice bath was added (1-cyano-2-ethoxy-2-oxoethylidenaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (1.88 g, 4.39 mmol) and diisopropylethylamine (0.60 mL, 3.45 mmol). After 15 minutes the reaction mixture was treated with N-ethyl-2,2,2-trifluoroethanamine hydrochloride (0.510 g, 3.11 mmol) and diisopropylethylamine (0.60 mL, 3.11 mmol) in N,N-dimethylformamide (2 mL). The mixture was allowed to warm to room temperature and was stirred for 20 hours. The mixture was partitioned between diethyl ether and 5% aqueous sodium bisulfate. The organic layer was washed with 5% aqueous sodium bisulfate (2), saturated aqueous sodium carbonate and brine, dried over magnesium sulfate, and concentrated under reduced pressure to afford the title compound as a red solid (0.710 g, 83%): mp 70-72 C.; .sup.1H NMR (400 MHz, CDCl.sub.3) 5.44 (s, 1H), 4.20-3.91 (m, 4H), minor rotamer 3.83 (q, J=8.4 Hz, 2H), minor rotamer 3.53 (q, J=7.1 Hz, 2H), major rotamer 3.44 (q, J=7.2 Hz, 2H), 1.45 (s, 9H), major rotamer 1.24 (t, J=7.2 Hz, 3H), minor rotamer 1.16 (t, J=7.1 Hz, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) major rotamer 69.57, minor rotamer 70.06; ESIMS m/z 228 ([M-C.sub.4H.sub.9].sup.+).

Example 57: Preparation of tert-butyl (R)-(1-oxo-1-(2-(2,2,2-trifluoroethyl)hydrazinyl)propan-2-yl)carbamate (C196)

(994) ##STR00578##

(995) Diisopropylethylamine (2.26 mL, 13.2 mmol), 2-chloro-1,3-dimethylimidazolidinium hexafluorophosphate (1.47 g, 5.29 mmol), and 1-hydroxy-7-azabenzotriazole (0.72 g, 5.29 mmol) were added to a solution of (tert-butoxycarbonyl)-D-alanine (1.00 g, 5.29 mmol) and 2-(2,2,2-trifluoroethyl)hydrazine hydrochloride (0.80 g, 0.5.29 mmol) in N,N-dimethylformamide (10 mL) at room temperature. The mixture was stirred for 12 hours then was diluted with dichloromethane. The organic layer was washed sequentially with a 2 N hydrochloric acid solution, 2 N aqueous sodium bicarbonate, water, and then brine. The organic layer was then dried over sodium sulfate, filtered, and concentrated. Purification by column chromatography (SiO.sub.2) provided the title compound as a white solid (0.60 g, 37%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.45 (s, 1H), 6.82 (d, J=7.2 Hz, 1H), 5.57 (d, J=4.50 Hz, 1H), 3.92-3.85 (m, 1H), 3.42-3.31 (m, 2H), 1.36 (s, 9H), 1.14 (d, J=6.9 Hz, 3H); IR (thin film) 3342, 1683 cm.sup.1; ESIMS m/z 284.40 ([MH].sup.).

(996) The following compounds were prepared in like manner to the procedure outlined in Example 57:

tert-Butyl (R)-(1-(1-methyl-2-(2,2,2-trifluoroethyl)hydrazinyl)-1-oxopropan-2-yl)carba mate (C197)

(997) ##STR00579##

(998) Isolated as a yellow gum (0.90 g, 47%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 6.56 (d, J=8.1 Hz, 1H), 5.74 (br s, 1H), 4.83-4.78 (m, 1H), 3.65-3.58 (m, 2H), 2.96 (s, 3H), 1.35 (s, 9H), 1.13 (d, J=7.2 Hz, 3H); IR (thin film) 3419, 1698, 1167 cm.sup.1; ESIMS m/z 300.30 ([MH].sup.).

tert-Butyl (R)-(1-(1,2-dimethyl-2-(2,2,2-trifluoroethyl)hydrazinyl)-1-oxopropan-2-yl)carbamate (C198)

(999) ##STR00580##

(1000) Isolated as a yellow oil (0.50 g, 50%): .sup.1H NMR (300 MHz, DMSO-d.sub.6) 6.95 (br s, 1H), 4.95-4.78 (m, 1H), 3.77-3.31 (m, 2H), 2.84 (s, 3H), 2.64 (m, 3H), 1.35 (s, 9H), 1.13 (d, J=6.9 Hz, 3H); IR (thin film) 2979, 1709, 1168 cm.sup.1; ESIMS m/z 213.96 ([MCO.sub.2C.sub.4H.sub.9].sup.).

Example 58: Preparation of 1-(3,4-dichloro-5-methylphenyl)-2,2,2-trifluoroethan-1-one (C201)

(1001) ##STR00581##

(1002) To 5-bromo-1,2-dichloro-3-methylbenzene (6.9 g, 29 mmol) in tetrahydrofuran (65 mL) cooled in an ice bath under nitrogen was added isopropylmagnesium chloride lithium chloride complex in tetrahydrofuran (26.8 mL, 34.8 mmol). After 1 hour methyl 2,2,2-trifluoroacetate (3.79 mL, 37.7 mmol) was added. After 30 minutes, the ice bath was removed, and the solution was stirred for 1 hour. The reaction mixture was quenched with aqueous hydrochloric acid (2 N). The mixture was concentrated and extracted with dichloromethane. The organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated. Purification by column chromatography (SiO.sub.2, petroleum ether) provided the title compound as a white solid (5.9 g, 80%): .sup.1H NMR (400 MHz, CDCl.sub.3) 8.00 (s, 1H), 7.83 (s, 1H), 2.51 (s, 3H); EIMS m/z 256 ([M].sup.+).

(1003) Biological Assays

(1004) The following bioassays against Beet Armyworm (Spodoptera exigua), Cabbage Looper (Trichoplusia ni), Corn Earworm (Helicoverpa zea), Green Peach Aphid (Myzus persicae), and Yellow Fever Mosquito (Aedes aegypti), are included herein due to the damage they inflict. Furthermore, the Beet Armyworm, Corn Earworm, and Cabbage Looper are three good indicator species for a broad range of chewing pests. Additionally, the Green Peach Aphid is a good indicator species for a broad range of sap-feeding pests. The results with these four indicator species along with the Yellow Fever Mosquito show the broad usefulness of the molecules of Formula One in controlling pests in Phyla Arthropoda, Mollusca, and Nematoda (For further information see Methods for the Design and Optimization of New Active Ingredients, Modern Methods in Crop Protection Research, Edited by Jeschke, P., Kramer, W., Schirmer, U., and Matthias W., p. 1-20, 2012).

Example A: Bioassays on Beet Armyworm (Spodoptera Exigua, LAPHEG) (BAW), Corn Earworm (Helicoverpa Zea, HELIZE) (CEW), and Cabbage Looper (Trichoplusia Ni, TRIPNI) (CL)

(1005) Beet armyworm is a serious pest of economic concern for alfalfa, asparagus, beets, citrus, corn, cotton, onions, peas, peppers, potatoes, soybeans, sugar beets, sunflowers, tobacco, tomatoes, among other crops. It is native to Southeast Asia but is now found in Africa, Australia, Japan, North America, and Southern Europe. The larvae may feed in large swarms causing devastating crop losses. It is known to be resistant to several pesticides.

(1006) Cabbage looper is a serious pest found throughout the world. It attacks alfalfa, beans, beets, broccoli, Brussel sprouts, cabbage, cantaloupe, cauliflower, celery, collards, cotton, cucumbers, eggplant, kale, lettuce, melons, mustard, parsley, peas, peppers, potatoes, soybeans, spinach, squash, tomatoes, turnips, and watermelons, among other crops. This species is very destructive to plants due to its voracious appetite. The larvae consume three times their weight in food daily. The feeding sites are marked by large accumulations of sticky, wet, fecal material. It is known to be resistant to several pesticides.

(1007) Corn earworm is considered by some to be the most costly crop pest in North America. It often attacks valuable crops, and the harvested portion of the crop. This pest damages alfalfa, artichoke, asparagus, cabbage, cantaloupe, collard, corn, cotton, cowpea, cucumber, eggplant, lettuce, lima bean, melon, okra, pea, pepper, potato, pumpkin, snap bean, soybean, spinach, squash, sugarcane, sweet potato, tomato, and watermelon, among other crops. Furthermore, this pest is also known to be resistant to certain insecticides.

(1008) Consequently, because of the above factors control of these pests is important. Furthermore, molecules that control these pests (BAW, CEW, and CL), which are known as chewing pests, are useful in controlling other pests that chew on plants.

(1009) Certain molecules disclosed in this document were tested against BAW, CEW, and CL using procedures described in the following examples. In the reporting of the results, the BAW, CEW, & CL Rating Table was used (See Table Section).

(1010) Bioassays on BAW

(1011) Bioassays on BAW were conducted using a 128-well diet tray assay. One to five second instar BAW larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 g/cm.sup.2 of the test molecule (dissolved in 50 L of 90:10 acetone-water mixture) had been applied (to each of eight wells) and then allowed to dry. Trays were covered with a clear self-adhesive cover and held at 25 C., 14:10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the table entitled Table ABC: Biological Results (See Table Section).

(1012) Bioassays on CL

(1013) Bioassays on CL were conducted using a 128-well diet tray assay. One to five second instar CL larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 g/cm.sup.2 of the test molecule (dissolved in 50 L of 90:10 acetone-water mixture) had been applied (to each of eight wells) and then allowed to dry. Trays were covered with a clear self-adhesive cover and held at 25 C., 14:10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged. The results are indicated in the table entitled Table ABC: Biological Results (See Table Section).

Example B: Bioassays on Green Peach Aphid (Myzus Persicae, MYZUPE) (GPA)

(1014) GPA is the most significant aphid pest of peach trees, causing decreased growth, shriveling of the leaves, and the death of various tissues. It is also hazardous because it acts as a vector for the transport of plant viruses, such as potato virus Y and potato leafroll virus to members of the nightshade/potato family Solanaceae, and various mosaic viruses to many other food crops. GPA attacks such plants as broccoli, burdock, cabbage, carrot, cauliflower, daikon, eggplant, green beans, lettuce, macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, and zucchini, among other crops. GPA also attacks many ornamental crops such as carnation, chrysanthemum, flowering white cabbage, poinsettia, and roses. GPA has developed resistance to many pesticides. Consequently, because of the above factors control of this pest is important. Furthermore, molecules that control this pest (GPA), which is known as a sap-feeding pest, are useful in controlling other pests that feed on the sap from plants.

(1015) Certain molecules disclosed in this document were tested against GPA using procedures described in the following example. In the reporting of the results, the GPA & YFM Rating Table was used (See Table Section).

(1016) Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) true leaves, were used as test substrate. The seedlings were infested with 20-50 GPA (wingless adult and nymph stages) one day prior to chemical application. Four pots with individual seedlings were used for each treatment. Test molecules (2 mg) were dissolved in 2 mL of acetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm test molecule. The stock solutions were diluted 5 with 0.025% Tween 20 in water to obtain the solution at 200 ppm test molecule. A hand-held aspirator-type sprayer was used for spraying a solution to both sides of cabbage leaves until runoff. Reference plants (solvent check) were sprayed with the diluent only containing 20% by volume of acetone/methanol (1:1) solvent. Treated plants were held in a holding room for three days at approximately 25 C. and ambient relative humidity (RH) prior to grading. Evaluation was conducted by counting the number of live aphids per plant under a microscope. Percent Control was measured by using Abbott's correction formula (W. S. Abbott, A Method of Computing the Effectiveness of an Insecticide J. Econ. Entomol. 18 (1925), pp. 265-267) as follows.
Corrected % Control=100*(XY)/X where X=No. of live aphids on solvent check plants and Y=No. of live aphids on treated plants

(1017) The results are indicated in the table entitled Table ABC: Biological Results (See Table Section).

Example C: Bioassays on Yellow Fever Mosquito (Aedes Aegypti, AEDSAE) (YFM)

(1018) YFM prefers to feed on humans during the daytime and is most frequently found in or near human habitations. YFM is a vector for transmitting several diseases. It is a mosquito that can spread the dengue fever and yellow fever viruses. Yellow fever is the second most dangerous mosquito-borne disease after malaria. Yellow fever is an acute viral hemorrhagic disease and up to 50% of severely affected persons without treatment will die from yellow fever. There are an estimated 200,000 cases of yellow fever, causing 30,000 deaths, worldwide each year. Dengue fever is a nasty, viral disease; it is sometimes called breakbone fever or break-heart fever because of the intense pain it can produce. Dengue fever kills about 20,000 people annually. Consequently, because of the above factors control of this pest is important. Furthermore, molecules that control this pest (YFM), which is known as a sucking pest, are useful in controlling other pests that cause human and animal suffering.

(1019) Certain molecules disclosed in this document were tested against YFM using procedures described in the following paragraph. In the reporting of the results, the GPA & YFM Rating Table was used (See Table Section).

(1020) Master plates containing 400 g of a molecule dissolved in 100 L of dimethyl sulfoxide (DMSO) (equivalent to a 4000 ppm solution) are used. A master plate of assembled molecules contains 15 L per well. To this plate, 135 L of a 90:10 water:acetone mixture is added to each well. A robot (Biomek NXP Laboratory Automation Workstation) is programmed to dispense 15 L aspirations from the master plate into an empty 96-well shallow plate (daughter plate). There are 6 reps (daughter plates) created per master. The created daughter plates are then immediately infested with YFM larvae.

(1021) The day before plates are to be treated, mosquito eggs are placed in Millipore water containing liver powder to begin hatching (4 g. into 400 mL). After the daughter plates are created using the robot, they are infested with 220 L of the liver powder/larval mosquito mixture (about 1 day-old larvae). After plates are infested with mosquito larvae, a non-evaporative lid is used to cover the plate to reduce drying. Plates are held at room temperature for 3 days prior to grading. After 3 days, each well is observed and scored based on mortality. The results are indicated in the table entitled Table ABC: Biological Results (See Table Section).

(1022) Agriculturally Acceptable Acid Addition Salts, Salt Derivatives, Solvates, Ester Derivatives, Polymorphs, Isotopes, and Radionuclides

(1023) Molecules of Formula One may be formulated into agriculturally acceptable acid addition salts. By way of a non-limiting example, an amine function can form salts with hydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic, salicylic, malic, fumaric, oxalic, succinic, tartaric, lactic, gluconic, ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic, ethanesulfonic, hydroxyl-methanesulfonic, and hydroxyethanesulfonic acids. Additionally, by way of a non-limiting example, an acid function can form salts including those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Examples of preferred cations include sodium, potassium, and magnesium.

(1024) Molecules of Formula One may be formulated into salt derivatives. By way of a non-limiting example, a salt derivative may be prepared by contacting a free base with a sufficient amount of the desired acid to produce a salt. A free base may be regenerated by treating the salt with a suitable dilute aqueous base solution such as dilute aqueous sodium hydroxide, potassium carbonate, ammonia, and sodium bicarbonate. As an example, in many cases, a pesticide, such as 2,4-D, is made more water-soluble by converting it to its dimethylamine salt.

(1025) Molecules of Formula One may be formulated into stable complexes with a solvent, such that the complex remains intact after the non-complexed solvent is removed. These complexes are often referred to as solvates. However, it is particularly desirable to form stable hydrates with water as the solvent.

(1026) Molecules of Formula One may be made into ester derivatives. These ester derivatives can then be applied in the same manner as the molecules disclosed in this document is applied.

(1027) Molecules of Formula One may be made as various crystal polymorphs. Polymorphism is important in the development of agrochemicals since different crystal polymorphs or structures of the same molecule can have vastly different physical properties and biological performances.

(1028) Molecules of Formula One may be made with different isotopes. Of particular importance are molecules having .sup.2H (also known as deuterium) or .sup.3H (also known as tritium) in place of 1H. Molecules of Formula One may be made with different radionuclides. Of particular importance are molecules having .sup.14C. Molecules of Formula One having deuterium, tritium, or .sup.14C may be used in biological studies allowing tracing in chemical and physiological processes and half-life studies, as well as, MoA studies.

(1029) Stereoisomers

(1030) Molecules of Formula One may exist as one or more stereoisomers. Thus, certain molecules may be produced as racemic mixtures. It will be appreciated by those skilled in the art that one stereoisomer may be more active than the other stereoisomers. Individual stereoisomers may be obtained by known selective synthetic procedures, by conventional synthetic procedures using resolved starting materials, or by conventional resolution procedures. Certain molecules disclosed in this document can exist as two or more isomers. The various isomers include geometric isomers, diastereomers, and enantiomers. Thus, the molecules disclosed in this document include geometric isomers, racemic mixtures, individual stereoisomers, and optically active mixtures. It will be appreciated by those skilled in the art that one isomer may be more active than the others. The structures disclosed in the present disclosure are drawn in only one geometric form for clarity, but are intended to represent all geometric forms of the molecule.

(1031) Combinations

(1032) In another embodiment of this invention, molecules of Formula One may be used in combination (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more active ingredients.

(1033) In another embodiment of this invention, molecules of Formula One may be used in combination (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more active ingredients each having a MoA that is the same as, similar to, but more likelydifferent from, the MoA of the molecules of Formula One.

(1034) In another embodiment, molecules of Formula One may be used in combination (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more molecules having acaricidal, algicidal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal, and/or virucidal properties.

(1035) In another embodiment, the molecules of Formula One may be used in combination (such as, in a compositional mixture, or a simultaneous or sequential application) with one or more molecules that are antifeedants, bird repellents, chemosterilants, herbicide safeners, insect attractants, insect repellents, mammal repellents, mating disrupters, plant activators, plant growth regulators, and/or synergists.

(1036) In another embodiment, molecules of Formula One may also be used in combination (such as in a compositional mixture, or a simultaneous or sequential application) with one or more biopesticides.

(1037) In another embodiment, in a pesticidal composition combinations of a molecule of Formula One and an active ingredient may be used in a wide variety of weight ratios. For example, in a two component mixture, the weight ratio of a molecule of Formula One to an active ingredient, may be from about 100:1 to about 1:100; in another example the weight ratio may be about 50:1 to about 1:50; in another example the weight ratio may be about 20:1 to about 1:20; in another example the weight ratio may be about 10:1 to about 1:10; in another example the weight ratio may be about 5:1 to 1:5; in another example the weight ratio may be about 3:1 to about 1:3; in another example the weight ratio may be about 2:1 to about 1:2; and in a final example the weight ratio may be about 1:1 (See Table B). However, in general, weight ratios less than about 10:1 to about 1:10 are preferred. It is also preferred sometimes to use a three or four component mixture comprising a molecule of Formula One and one or more active ingredients.

(1038) TABLE-US-00003 TABLE B Weight Ratios Molecule of the Formula One:active ingredient 100:1 to 1:100 50:1 to 1:50 20:1 to 1:20 10:1 to 1:10 5:1 to 1:5 3:1 to 1:3 2:1 to 1:2 1:1

(1039) Weight ratios of a molecule of Formula One to an active ingredient may also be depicted as X:Y; wherein X is the parts by weight of a molecule of Formula One and Y is the parts by weight of active ingredient. The numerical range of the parts by weight for X is 0<X100 and the parts by weight for Y is 0<Y100 and is shown graphically in TABLE C. By way of non-limiting example, the weight ratio of a molecule of Formula One to an active ingredient may be 20:1.

(1040) TABLE-US-00004 TABLE C active ingredient 100 X, Y X, Y X, Y (Y) Parts by weight 50 X, Y X, Y X, Y X, Y X, Y 20 X, Y X, Y X, Y X, Y X, Y 15 X, Y X, Y X, Y X, Y X, Y 10 X, Y X, Y 5 X, Y X, Y X, Y X, Y 3 X, Y X, Y X, Y X, Y X, Y X, Y X, Y 2 X, Y X, Y X, Y X, Y X, Y 1 X, Y X, Y X, Y X, Y X, Y X, Y X, Y X, Y X, Y 1 2 3 5 10 15 20 50 100 molecule of Formula One (X) Parts by weight

(1041) Ranges of weight ratios of a molecule of Formula One to an active ingredient may be depicted as X.sub.1:Y.sub.1 to X.sub.2:Y.sub.2, wherein X and Y are defined as above.

(1042) In one embodiment, the range of weight ratios may be X.sub.1:Y.sub.1 to X.sub.2:Y.sub.2, wherein X.sub.1>Y.sub.1 and X.sub.2<Y.sub.2. By way of non-limiting example, the range of a weight ratio of a molecule of Formula One to an active ingredient may be between 3:1 and 1:3, inclusive of the endpoints.

(1043) In another embodiment, the range of weight ratios may be X.sub.1:Y.sub.1 to X.sub.2:Y.sub.2, wherein X.sub.1>Y.sub.1 and X.sub.2>Y.sub.2. By way of non-limiting example, the range of weight ratio of a molecule of Formula One to an active ingredient may be between 15:1 and 3:1, inclusive of the endpoints.

(1044) In another embodiment, the range of weight ratios may be X.sub.1:Y.sub.1 to X.sub.2:Y.sub.2, wherein X.sub.1<Y.sub.1 and X.sub.2<Y.sub.2. By way of non-limiting example, the range of weight ratios of a molecule of Formula One to an active ingredient may be between about 1:3 and about 1:20, inclusive of the endpoints.

(1045) Formulations

(1046) A pesticide is rarely suitable for application in its pure form. It is usually necessary to add other substances so that the pesticide may be used at the required concentration and in an appropriate form, permitting ease of application, handling, transportation, storage, and maximum pesticide activity. Thus, pesticides are formulated into, for example, baits, concentrated emulsions, dusts, emulsifiable concentrates, fumigants, gels, granules, microencapsulations, seed treatments, suspension concentrates, suspoemulsions, tablets, water soluble liquids, water dispersible granules or dry flowables, wettable powders, and ultra-low volume solutions.

(1047) Pesticides are applied most often as aqueous suspensions or emulsions prepared from concentrated formulations of such pesticides. Such water-soluble, water-suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or water dispersible granules, or liquids usually known as emulsifiable concentrates, or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the pesticide, a carrier, and surfactants. The concentration of the pesticide is usually from about 10% to about 90% by weight. The carrier is usually selected from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, are found among sulfonated lignins, condensed naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants such as ethylene oxide adducts of alkyl phenols.

(1048) Emulsifiable concentrates of pesticides comprise a convenient concentration of a pesticide, such as from about 50 to about 500 grams per liter of liquid dissolved in a carrier that is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially xylenes and petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are selected from conventional anionic and non-ionic surfactants.

(1049) Aqueous suspensions comprise suspensions of water-insoluble pesticides dispersed in an aqueous carrier at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the pesticide and vigorously mixing it into a carrier comprised of water and surfactants. Ingredients, such as inorganic salts and synthetic or natural gums may also be added, to increase the density and viscosity of the aqueous carrier. It is often most effective to grind and mix the pesticide at the same time by preparing the aqueous mixture and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.

(1050) Pesticides may also be applied as granular compositions that are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% by weight of the pesticide, dispersed in a carrier that comprises clay or a similar substance. Such compositions are usually prepared by dissolving the pesticide in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. Such compositions may also be formulated by making a dough or paste of the carrier and molecule and crushing and drying to obtain the desired granular particle size.

(1051) Dusts containing a pesticide are prepared by intimately mixing the pesticide in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the pesticide. Dusts may be applied as a seed dressing or as a foliage application with a dust blower machine.

(1052) It is equally practical to apply a pesticide in the form of a solution in an appropriate organic solvent, usually petroleum oil, such as the spray oils, which are widely used in agricultural chemistry.

(1053) Pesticides can also be applied in the form of an aerosol composition. In such compositions the pesticide is dissolved or dispersed in a carrier, which is a pressure-generating propellant mixture. The aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve.

(1054) Pesticide baits are formed when the pesticide is mixed with food or an attractant or both. When the pests eat the bait they also consume the pesticide. Baits may take the form of granules, gels, flowable powders, liquids, or solids. Baits may be used in pest harborages.

(1055) Fumigants are pesticides that have a relatively high vapor pressure and hence can exist as a gas in sufficient concentrations to kill pests in soil or enclosed spaces. The toxicity of the fumigant is proportional to its concentration and the exposure time. They are characterized by a good capacity for diffusion and act by penetrating the pest's respiratory system or being absorbed through the pest's cuticle. Fumigants are applied to control stored product pests under gas proof sheets, in gas sealed rooms or buildings or in special chambers.

(1056) Pesticides may be microencapsulated by suspending the pesticide particles or droplets in plastic polymers of various types. By altering the chemistry of the polymer or by changing factors in the processing, microcapsules may be formed of various sizes, solubility, wall thicknesses, and degrees of penetrability. These factors govern the speed with which the active ingredient within is released, which in turn, affects the residual performance, speed of action, and odor of the product.

(1057) Oil solution concentrates are made by dissolving pesticide in a solvent that will hold the pesticide in solution. Oil solutions of a pesticide usually provide faster knockdown and kill of pests than other formulations due to the solvents themselves having pesticidal action and the dissolution of the waxy covering of the integument increasing the speed of uptake of the pesticide. Other advantages of oil solutions include better storage stability, better penetration of crevices, and better adhesion to greasy surfaces.

(1058) Another embodiment is an oil-in-water emulsion, wherein the emulsion comprises oily globules which are each provided with a lamellar liquid crystal coating and are dispersed in an aqueous phase, wherein each oily globule comprises at least one molecule which is agriculturally active, and is individually coated with a monolamellar or oligolamellar layer comprising: (1) at least one non-ionic lipophilic surface-active agent, (2) at least one non-ionic hydrophilic surface-active agent and (3) at least one ionic surface-active agent, wherein the globules having a mean particle diameter of less than 800 nanometers.

(1059) Other Formulation Components

(1060) Generally, when the molecules disclosed in Formula One are used in a formulation, such formulation can also contain other components. These components include, but are not limited to, (this is a non-exhaustive and non-mutually exclusive list) wetters, spreaders, stickers, penetrants, buffers, sequestering agents, drift reduction agents, compatibility agents, anti-foam agents, cleaning agents, and emulsifiers. A few components are described forthwith.

(1061) A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations are: sodium lauryl sulfate; sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates.

(1062) A dispersing agent is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from reaggregating. Dispersing agents are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles redisperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersing agents have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to reaggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersing agents are sodium lignosulfonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulfonate formaldehyde condensates. Tristyrylphenol ethoxylate phosphate esters are also used. Non-ionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersing agents for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersing agents. These have very long hydrophobic backbones and a large number of ethylene oxide chains forming the teeth of a comb surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersing agents used in agrochemical formulations are: sodium lignosulfonates; sodium naphthalene sulfonate formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graft copolymers.

(1063) An emulsifying agent is a substance which stabilizes a suspension of droplets of one liquid phase in another liquid phase. Without the emulsifying agent the two liquids would separate into two immiscible liquid phases. The most commonly used emulsifier blends contain alkylphenol or aliphatic alcohol with twelve or more ethylene oxide units and the oil-soluble calcium salt of dodecylbenzenesulfonic acid. A range of hydrophile-lipophile balance (HLB) values from 8 to 18 will normally provide good stable emulsions. Emulsion stability can sometimes be improved by the addition of a small amount of an EO-PO block copolymer surfactant.

(1064) A solubilizing agent is a surfactant which will form micelles in water at concentrations above the critical micelle concentration. The micelles are then able to dissolve or solubilize water-insoluble materials inside the hydrophobic part of the micelle. The types of surfactants usually used for solubilization are non-ionics, sorbitan monooleates, sorbitan monooleate ethoxylates, and methyl oleate esters.

(1065) Surfactants are sometimes used, either alone or with other additives such as mineral or vegetable oils as adjuvants to spray-tank mixes to improve the biological performance of the pesticide on the target. The types of surfactants used for bioenhancement depend generally on the nature and mode of action of the pesticide. However, they are often non-ionics such as: alkyl ethoxylates; linear aliphatic alcohol ethoxylates; aliphatic amine ethoxylates.

(1066) A carrier or diluent in an agricultural formulation is a material added to the pesticide to give a product of the required strength. Carriers are usually materials with high absorptive capacities, while diluents are usually materials with low absorptive capacities. Carriers and diluents are used in the formulation of dusts, wettable powders, granules and water-dispersible granules.

(1067) Organic solvents are used mainly in the formulation of emulsifiable concentrates, oil-in-water emulsions, suspoemulsions, and ultra-low volume formulations, and to a lesser extent, granular formulations. Sometimes mixtures of solvents are used. The first main groups of solvents are aliphatic paraffinic oils such as kerosene or refined paraffins. The second main group (and the most common) comprises the aromatic solvents such as xylene and higher molecular weight fractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful as cosolvents to prevent crystallization of pesticides when the formulation is emulsified into water. Alcohols are sometimes used as cosolvents to increase solvent power. Other solvents may include vegetable oils, seed oils, and esters of vegetable and seed oils.

(1068) Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are not limited to, montmorillonite, bentonite, magnesium aluminum silicate, and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds or are synthetic derivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide. Another good anti-settling agent is xanthan gum.

(1069) Microorganisms can cause spoilage of formulated products. Therefore preservation agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxybenzoic acid sodium salt; methyl p-hydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT).

(1070) The presence of surfactants often causes water-based formulations to foam during mixing operations in production and in application through a spray tank. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane, while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

(1071) Green agents (e.g., adjuvants, surfactants, solvents) can reduce the overall environmental footprint of crop protection formulations. Green agents are biodegradable and generally derived from natural and/or sustainable sources, e.g. plant and animal sources. Specific examples are: vegetable oils, seed oils, and esters thereof, also alkoxylated alkyl polyglucosides.

(1072) Applications

(1073) Molecules of Formula One may be applied to any locus. Particular crop loci to apply such molecules include loci where alfalfa, almonds, apples, barley, beans, canola, corn, cotton, crucifers, lettuce, oats, oranges, pears, peppers, potatoes, rice, sorghum, soybeans, strawberries, sugarcane, sugar beets, sunflowers, tobacco, tomatoes, wheat, and other valuable crops are growing or the seeds thereof are going to be planted.

(1074) Molecules of Formula One may also be applied where plants, such as crops, are growing and where there are low levels (even no actual presence) of pests that can commercially damage such plants. Applying such molecules in such locus is to benefit the plants being grown in such locus. Such benefits, may include, but are not limited to: helping the plant grow a better root system; helping the plant better withstand stressful growing conditions; improving the health of a plant; improving the yield of a plant (e.g. increased biomass and/or increased content of valuable ingredients); improving the vigor of a plant (e.g. improved plant growth and/or greener leaves); improving the quality of a plant (e.g. improved content or composition of certain ingredients); and improving the tolerance to abiotic and/or biotic stress of the plant.

(1075) Molecules of Formula One may be applied with ammonium sulfate when growing various plants as this may provide additional benefits.

(1076) Molecules of Formula One may be applied on, in, or around plants genetically modified to express specialized traits, such as Bacillus thuringiensis or other insecticidal toxins, or those expressing herbicide resistance, or those with stacked foreign genes expressing insecticidal toxins, herbicide resistance, nutrition-enhancement, or any other beneficial traits.

(1077) Molecule of Formula One may be applied to the foliar and/or fruiting portions of plants to control pests. Such molecules will either come in direct contact with the pest, or the pest will consume such molecules when eating the plant or while extracting sap from the plant.

(1078) Molecule of Formula One may also be applied to the soil, and when applied in this manner, root and stem feeding pests may be controlled. The roots may absorb such molecules thereby taking it up into the foliar portions of the plant to control above ground chewing and sap feeding pests.

(1079) Systemic movement of pesticides in plants may be utilized to control pests on one portion of the plant by applying (for example by spraying a locus) a molecule of Formula One to a different portion of the plant. For example, control of foliar-feeding insects may be achieved by drip irrigation or furrow application, by treating the soil with for example pre- or post-planting soil drench, or by treating the seeds of a plant before planting.

(1080) Molecules of Formula One may be used with baits. Generally, with baits, the baits are placed in the ground where, for example, termites can come into contact with, and/or be attracted to, the bait. Baits can also be applied to a surface of a building, (horizontal, vertical, or slant surface) where, for example, ants, termites, cockroaches, and flies, can come into contact with, and/or be attracted to, the bait.

(1081) Molecules of Formula One may be encapsulated inside, or placed on the surface of a capsule. The size of the capsules can range from nanometer size (about 100-900 nanometers in diameter) to micrometer size (about 10-900 microns in diameter).

(1082) Molecules of Formula One may be applied to eggs of pests. Because of the unique ability of the eggs of some pests to resist certain pesticides, repeated applications of such molecules may be desirable to control newly emerged larvae.

(1083) Molecules of Formula One may be applied as seed treatments. Seed treatment may be applied to all types of seeds, including those from which plants genetically modified to express specialized traits will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis or other insecticidal toxins, those expressing herbicide resistance, such as Roundup Ready seed, or those with stacked foreign genes expressing insecticidal toxins, herbicide resistance, nutrition-enhancement, drought resistance, or any other beneficial traits. Furthermore, such seed treatments with molecules of Formula One may further enhance the ability of a plant to better withstand stressful growing conditions. This results in a healthier, more vigorous plant, which can lead to higher yields at harvest time. Generally, about 1 gram of such molecules to about 500 grams per 100,000 seeds is expected to provide good benefits, amounts from about 10 grams to about 100 grams per 100,000 seeds is expected to provide better benefits, and amounts from about 25 grams to about 75 grams per 100,000 seeds is expected to provide even better benefits.

(1084) Molecules of Formula One may be applied with one or more active ingredients in a soil amendment.

(1085) Molecules of Formula One may be used for controlling endoparasites and ectoparasites in the veterinary medicine sector or in the field of non-human-animal keeping. Such molecules may be applied by oral administration in the form of, for example, tablets, capsules, drinks, granules, by dermal application in the form of, for example, dipping, spraying, pouring on, spotting on, and dusting, and by parenteral administration in the form of, for example, an injection.

(1086) Molecules of Formula One may also be employed advantageously in livestock keeping, for example, cattle, sheep, pigs, chickens, salmon, and geese. They may also be employed advantageously in pets such as, horses, dogs, and cats. Particular pests to control would be fleas and ticks that are bothersome to such animals. Suitable formulations are administered orally to the animals with the drinking water or feed. The dosages and formulations that are suitable depend on the species.

(1087) Molecules of Formula One may also be used for controlling parasitic worms, especially of the intestine, in the animals listed above.

(1088) Molecules of Formula One may also be employed in therapeutic methods for human health care. Such methods include, but are limited to, oral administration in the form of, for example, tablets, capsules, drinks, granules, and by dermal application.

(1089) Molecules of Formula One may also be applied to invasive pests. Pests around the world have been migrating to new environments (for such pest) and thereafter becoming a new invasive species in such new environment. Such molecules may also be used on such new invasive species to control them in such new environments.

(1090) Consequently, in light of the above and the Tables in the Table Section, the following items are provided.

(1091) 1. A molecule having the following formula

(1092) ##STR00582##
wherein: (A) R.sup.1, R.sup.5, R.sup.6, R.sup.11, and R.sup.12 are each independently selected from the group consisting of H, F, Cl, Br, I, CN, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.4)haloalkoxy preferably, R.sup.1, R.sup.5, R.sup.6, R.sup.11, and R.sup.12 are H; (B) R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of H, F, Cl, Br, I, CN, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy preferably, R.sup.2, R.sup.3, and R.sup.4 are H, F, Cl, Br, CH.sub.3, or CHCH.sub.2; (C) R.sup.7 is (C.sub.1-C.sub.6)haloalkyl preferably R.sup.7 is CF.sub.3, CF.sub.2CH.sub.3, or CF.sub.2CH.sub.2CH.sub.3; (D) R.sup.9 is selected from the group consisting of (F), H, F, Cl, Br, I, CN, (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.1-C.sub.4)alkoxy, and (C.sub.1-C.sub.4)haloalkoxy preferably R.sup.9 is H; (E) R.sup.10 is selected from the group consisting of (F), F, Cl, Br, I, CN, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy preferably R.sup.10 is Cl, Br, I, CH.sub.3, or CF.sub.3; (F) R.sup.9 and R.sup.10 together can optionally form a 3- to 5-membered saturated or unsaturated, hydrocarbyl link, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, OH, and oxo; (G) Q.sup.1 and Q.sup.2 are each independently O or S preferably Q.sup.1 and Q.sup.2 are O; (H) R.sup.13 is selected from the group consisting of H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy preferably R.sup.13 is CH.sub.3 or CH.sub.2CH.sub.3; (I) R.sup.14 is selected from the group consisting of (K), (O), H, (C.sub.1-C.sub.4)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy preferably R.sup.14 is CH.sub.3 or CH.sub.2CH.sub.3; (J) R.sup.15 is selected from the group consisting of (K), H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, and (C.sub.1-C.sub.6)haloalkoxy preferably R.sup.15 is CH.sub.3 or CH.sub.2CH.sub.3; (K) R.sup.14 and R.sup.15 together can optionally form a 2- to 5-membered saturated, hydrocarbyl link, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, and CN preferably R.sup.14 and R.sup.15 together form a 2-membered saturated, hydrocarbyl link; (L) L is selected from the group consisting of (1) a bond, and (2) a (C.sub.1-C.sub.6)alkyl wherein said alkyl is optionally substituted with one or more substituents independently selected from the group consisting of F, Cl, CN, OH, and oxo; preferably L is a bond; (M) X is selected from the group consisting of (1) R.sup.17, and (2) a NR.sup.16R.sup.17, (3) OR.sup.17, and (4) SR.sup.17; preferably X is a bond or NR.sup.16R.sup.17; (N) R.sup.16 is selected from the group consisting of (O), (Q), H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.2-C.sub.6)alkenyloxy, (C.sub.1-C.sub.6)haloalkoxy, amino, and NHC(O)O(C.sub.1-C.sub.6)alkyl preferably R.sup.16 is CH.sub.3, CH.sub.2CH.sub.3, OCH.sub.3, OCH.sub.2CHCH.sub.2, NH.sub.2, or NHC(O)OC(CH.sub.3).sub.3; (O) R.sup.14 and R.sup.16 together can optionally form a 2- to 4-membered saturated link that is either (1) a hydrocarbyl link or (2) a heterohydrocarbyl link that contains one or more heteroatoms selected from the group consisting of nitrogen, sulfur, and oxygen, wherein said link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, OH, and oxo preferably R.sup.14 and R.sup.16 together form a 2- to 4-membered saturated link that is either (1) a hydrocarbyl link or (2) a heterohydrocarbyl link that contains one or more oxygen atoms; (P) R.sup.17 is selected from the group consisting of (Q), H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.3-C.sub.6)halocycloalkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.2-C.sub.6)alkenyloxy, (C.sub.1-C.sub.6)haloalkoxy, and (C.sub.1-C.sub.6)alkyl(C.sub.3-C.sub.6)cycloalkyl preferably R.sup.17 is CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH(CH.sub.3).sub.2, CH.sub.2CHCH.sub.2, CH.sub.2CCH, CH.sub.2CHF.sub.2, CH.sub.2CF.sub.3, CH.sub.2CH.sub.2CF.sub.3, CH.sub.2CF.sub.2CH.sub.3, CH(CH.sub.3)CF.sub.3, CH.sub.2CH.sub.2CH.sub.2CF.sub.3, CHCHCH.sub.2CF.sub.3, 3,3-difluorocyclobutyl, CH.sub.2CH.sub.2cyclopropyl, or CH.sub.2cyclobutyl; (Q) R.sup.16 and R.sup.17 together can optionally form a 2- to 6-membered saturated link that is either (1) a hydrocarbyl link or (2) a heterohydrocarbyl link that contains one or more heteroatoms selected from the group consisting of nitrogen, sulfur, and oxygen, wherein said link may optionally be substituted with one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, OH, and oxo; and agriculturally acceptable acid addition salts, salt derivatives, solvates, ester derivatives, crystal polymorphs, isotopes, resolved stereoisomers, and tautomers, of the molecules of Formula One.
2. A molecule according to 1 wherein (A) R.sup.1, R.sup.5, R.sup.6, R.sup.11, and R.sup.12 are H; (B) R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of H, F, Cl, Br, (C.sub.1-C.sub.6)alkyl, and (C.sub.2-C.sub.6)alkenyl; (C) R.sup.7 is (C.sub.1-C.sub.6)haloalkyl; (D) R.sup.9 is H; (E) R.sup.10 is selected from the group consisting of Cl, Br, I, (C.sub.1-C.sub.6)alkyl, and (C.sub.1-C.sub.6)haloalkyl; (G) Q.sup.1 and Q.sup.2 are O; (H) R.sup.13 is selected from the group consisting of H and (C.sub.1-C.sub.6)alkyl; (I) R.sup.14 is selected from the group consisting of (K), (O), H, and (C.sub.1-C.sub.4)alkyl; (J) R.sup.15 is selected from the group consisting of (K), H, and (C.sub.1-C.sub.6)alkyl; (K) R.sup.14 and R.sup.15 together can optionally form a 2- to 5-membered saturated, hydrocarbyl link; (L) L is a bond; (M) X is selected from the group consisting of (1) R.sup.17, and (2) a NR.sup.16R.sup.17; (N) R.sup.16 is selected from the group consisting of (O), H, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.2-C.sub.6)alkenyloxy, amino, and NHC(O)O(C.sub.1-C.sub.6)alkyl; (O) R.sup.14 and R.sup.16 together can optionally form a 2- to 4-membered saturated link that is either (1) a hydrocarbyl link or (2) a heterohydrocarbyl link that contains one or more oxygen atoms; (P) R.sup.17 is selected from the group consisting of H, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.3-C.sub.6)halocycloalkyl, and (C.sub.1-C.sub.6)alkyl(C.sub.3-C.sub.6)cycloalkyl.
3. A molecule according to 1 wherein said molecule is selected from one of the molecules in Table 2.
4. A molecule according to 1 wherein said molecule is selected from one of the molecules in Table 1.
5. A pesticidal composition comprising a molecule according to any one of 1, 2, 3, or 4, further comprising one or more active ingredients.
6. A pesticidal composition according to 5 wherein said active ingredient is from AIGA.
7. A pesticidal composition according to 5 wherein said active ingredient is selected from the group consisting of AI-1, 1,3-dichloropropene, chlorpyrifos, chlorpyrifos-methyl, hexaflumuron, methoxyfenozide, noviflumuron, spinetoram, spinosad, sulfoxaflor, and sulfuryl fluoride.
8. A pesticidal composition comprising a molecule according to any one of 1, 2, 3, or 4, further comprising a MoA Material.
9. A pesticidal composition according to 7 wherein said MoA Material is from MoAMGA.
10. A pesticidal composition according to any one of 5, 6, 7, 8, or 9, wherein the weight ratio of the molecule according to Formula One to said active ingredient is (a) 100:1 to 1:100; (b) 50:1 to 1:50; (c) 20:1 to 1:20; (d) 10:1 to 1:10; (e) 5:1 to 1:5; (f) 3:1 to 1:3; (g) 2:1 to 1:2; or (h) 1:1.
11. A process to control a pest said process comprising applying to a locus, a pesticidally effective amount of a molecule according to any one of the 1, 2, 3, or 4.
12. A process to control a pest said process comprising applying to a locus, a pesticidally effective amount of a pesticidal composition according to any one of the 5, 6, 7, 8, 9, or 10.
13. A molecule according to any one of 1, 2, 3, or 4, or a pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said molecule is in the form of agriculturally acceptable acid addition salt.
14. A molecule according to any one of 1, 2, 3, or 4, or a pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said molecule is in the form of a salt derivative.
15. A molecule according to any one of 1, 2, 3, or 4, or a pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said molecule is in the form of solvate.
16. A molecule according to any one of 1, 2, 3, or 4, or a pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said molecule is in the form of an ester derivative.
17. A molecule according to any one of 1, 2, 3, or 4, or a pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said molecule is in the form of a crystal polymorph.
18. A molecule according to any one of 1, 2, 3, or 4, or a pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said molecule has deuterium, tritium, and or .sup.14C.
19. A molecule according to any one of 1, 2, 3, or 4, or a pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said molecule is in the form of one or more stereoisomers.
20. A molecule according to any one of 1, 2, 3, or 4, or a pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said molecule is in the form of a resolved stereoisomer.
21. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said pesticidal composition further comprises another active ingredient.
22. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said pesticidal composition further comprises two more active ingredients.
23. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said active ingredient has a MOA different from the MoA of said molecule of Formula One.
24. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said pesticidal composition comprises an active ingredient having acaricidal, algicidal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal, and/or virucidal properties.
25. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said pesticidal composition comprises an active ingredient that is an antifeedant, bird repellent, chemosterilant, herbicide safener, insect attractant, insect repellent, mammal repellent, mating disrupter, plant activator, plant growth regulator, and/or synergist.
26. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said pesticidal composition comprises an active ingredient that is a biopesticide.
27. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said weight ratio of a molecule of Formula One to an active ingredient is 100:1 to 1:100.
28. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said weight ratio of a molecule of Formula One to an active ingredient is 50:1 to 1:50.
29. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said weight ratio of a molecule of Formula One to an active ingredient is 20:1 to 1:20.
30. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said weight ratio of a molecule of Formula One to an active ingredient is 10:1 to 1:10.
31. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said weight ratio of a molecule of Formula One to an active ingredient is 5:1 to 1:5.
32. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said weight ratio of a molecule of Formula One to an active ingredient is 3:1 to 1:3.
33. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said weight ratio of a molecule of Formula One to an active ingredient is 2:1 to 1:2.
34. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said weight ratio of a molecule of Formula One to an active ingredient is 1:1
35. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said weight ratio of a molecule of Formula One to an active ingredient is depicted as X:Y; wherein X is the parts by weight of a molecule of Formula One and Y is the parts by weight of active ingredient; further wherein the numerical range of the parts by weight for X is 0<X100 and the parts by weight for Y is 0<Y100; and further wherein X and Y are selected from Table C

(1093) TABLE-US-00005 TABLE C active ingredient 100 X, Y X, Y X, Y (Y) Parts by weight 50 X, Y X, Y X, Y X, Y X, Y 20 X, Y X, Y X, Y X, Y X, Y 15 X, Y X, Y X, Y X, Y X, Y 10 X, Y X, Y 5 X, Y X, Y X, Y X, Y 3 X, Y X, Y X, Y X, Y X, Y X, Y X, Y 2 X, Y X, Y X, Y X, Y X, Y 1 X, Y X, Y X, Y X, Y X, Y X, Y X, Y X, Y X, Y 1 2 3 5 10 15 20 50 100 molecule of Formula One (X) Parts by weight
36. A pesticidal composition according to 35 wherein a range of weight ratios of a molecule of Formula One to an active ingredient is depicted as X.sub.1:Y.sub.1 to X.sub.2:Y.sub.2; further wherein X.sub.1>Y.sub.1 and X.sub.2<Y.sub.2.
37. A pesticidal composition according to 35 wherein a range of weight ratios of a molecule of Formula One to an active ingredient is depicted as X.sub.1:Y.sub.1 to X.sub.2:Y.sub.2; further wherein X.sub.1>Y.sub.1 and X.sub.2>Y.sub.2.
38. A pesticidal composition according to 35 wherein a range of weight ratios of a molecule of Formula One to an active ingredient is depicted as X.sub.1:Y.sub.1 to X.sub.2:Y.sub.2; further wherein X.sub.1<Y.sub.1 and X.sub.2<Y.sub.2.
39. A pesticidal composition according to 35 wherein said composition is synergistic.
40. A process according to 12 wherein said pest is from Phylum Arthropoda.
41. A process according to 12 wherein said pest is from Phylum Mollusca.
42. A process according to 12 wherein said pest is from Phylum Nematoda.
43. A process according to 12 wherein said pests are are ants, aphids, beetles, bristletails, cockroaches, crickets, earwigs, fleas, flies, grasshoppers, leafhoppers, lice (including sea lice), locusts, mites, moths, nematodes, scales, symphylans, termites, thrips, ticks, wasps, and/or whiteflies.
44. A process according to 12 wherein said locus is where alfalfa, almonds, apples, barley, beans, canola, corn, cotton, crucifers, lettuce, oats, oranges, pears, peppers, potatoes, rice, sorghum, soybeans, strawberries, sugarcane, sugar beets, sunflowers, tobacco, tomatoes, wheat, and other valuable crops are growing or the seeds thereof are planted.
45. A pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, wherein said pesticidal composition further comprises ammonium sulfate.
46. A process according to 12 wherein said locus is where plants genetically modified to express specialized traits are planted.
47. A process according to 12 wherein said applying is done to the foliar and/or fruiting portions of plants.
48. A process according to 12 wherein said applying is done to the soil.
49. A process according to 12 wherein said applying is done by drip irrigation, furrow application, or pre- or post-planting soil drench.
50. A process according to 12 wherein said applying is done to the foliar and/or fruiting portions of plants, or by treating the seeds of a plant before planting.
51. A pesticidal composition comprising a molecule according to any one of 1, 2, 3, or 4, and a seed.
52. A process comprising applying a molecule according to any one of 1, 2, 3, or 4, or a pesticidal composition according to any of 5, 6, 7, 8, 9, or 10, to a seed.
53. A process comprising applying a molecule according to 1, 2, 3, or 4, to a locus that includes a non-human animal to control endoparasites and/or ectoparasites.
54. A process to produce a pesticidal composition, said process comprising mixing a molecule according to any one of claims 1, 2, 3, or 4, with one or more active ingredients.

(1094) The headings in this document are for convenience only and must not be used to interpret any portion hereof.

(1095) Table Section

(1096) TABLE-US-00006 TABLE 2 Structure and Preparation Method for F Series Molecules No. Structure Prep.* F1 13 F2 13 F3 13, 15 F4 14 F5 14 F6 13 F7 13 F8 0 15 F9 14 F10 14 F11 13 F12 13 F13 13 F14 13 F15 13 F16 13 F17 17 F18 00 13 F19 01 13 F20 02 13 F21 03 15 F22 04 13 F23 05 13 F24 06 15 F25 07 13 F26 08 13 F27 09 15 F28 0 15 F29 13 F30 13 F31 13 F32 13 F33 13 F34 16 F35 13 F36 13 F37 16 F38 0 13 F39 13 F40 13 F41 13 F42 13 F43 13 F44 16 F45 16 F46 16 F47 13 F48 0 13 F49 13 F50 13 F51 13 F52 16 F53 13 F54 15 F55 15 F56 13 F57 18 F58 0 13 F59 16 F60 16 F61 16 F62 13 F63 13 F64 13 F65 13 F66 13 F67 13 F68 0 15 F69 16 F70 16 F71 16 F72 16 F73 16 F74 16 F75 16 F76 16 F77 16 F78 0 16 F79 13 F80 16 F81 13 F82 13 F83 13 F84 13 F85 16 F86 16 F87 13 F88 0 13 F89 14 F90 14 F91 14 F92 14 F93 14 F94 14 F95 14 F96 13 F97 13 F98 0 13 F99 15 F100 13 F101 14 F102 16 F103 16 F104 15 F105 16 F106 13 F107 13 F108 0 16 F109 16 F110 16 F111 16 F112 13 F113 16 F114 16 F115 16 F116 16 F117 16 F118 00 16 F119 01 16 F120 02 16 F121 03 16 F122 04 16 F123 05 13 F124 06 13 F125 07 13 F126 08 15 F127 09 15 F128 0 13 F129 13 F130 16 F131 16 F132 13 F133 16 F134 16 F135 16 F136 16 F137 16 F138 0 16 F139 16 F140 F141 16 F142 16 F143 16 F144 13 F145 16 F146 43 F147 43 F148 0 43 F150 16 F153 16 F154 16 F155 16 F157 16 F158 13 F159 16 F160 16 F161 13 F162 0 16 F163 16 F164 13 F165 13 F166 15 F167 49 F168 50 F169 15 F170 15 F171 15 F172 0 15 F173 15 F174 13 F175 13 F176 13 F177 13 F178 13 F180 13 F181 13 F182 13 F183 0 13 F184 43 F185 13 F186 43 F187 43 F188 43 F189 43 F190 43 F191 43 F192 43 F193 0 13 F194 47 F195 47 F196 13 F197 13 F198 13 F199 47 F200 13 F201 13 F202 13 F203 0 13 F204 13 F205 13 F206 13 F207 48 F208 48 F209 48 F210 13 F211 13 F212 43 F213 0 47 F214 13 F215 44 F216 43 F217 13 *prepared according to example number

(1097) TABLE-US-00007 TABLE 3 Structure and Preparation Method for C Series Molecules No. Structure Prep.* C1 1 C2 1 C3 1 C4 1 C5 1 C6 00 1 C7 01 1 C8 02 1 C9 03 1 C10 04 1 C11 05 1 C12 06 1 C13 07 1 C14 08 1 C15 09 1 C16 0 1 C17 1 C18 1 C19 1 C20 1 C21 2 C22 3 C23 4 C24 5 C25 5, 7 C26 0 5 C27 5, 7 C28 6 C29 6 C30 6 C31 6 C32 7 C33 7 C34 8 C35 8 C36 0 8 C37 8 C38 8 C39 8 C40 8 C41 8 C42 9 C43 10 C44 10 C45 10 C46 0 11 C47 11 C48 11 C49 11 C50 11 C51 11 C52 12 C53 12 C54 12 C55 19 C56 0 19 C57 20 C58 20 C59 21 C60 21 C61 21 C62 21 C63 21 C64 21 C65 21 C66 0 21 C67 21 C68 22 C69 22 C70 22 C71 22 C72 22 C73 23 C74 24 C75 25 C76 0 26 C77 27 C78 28 C79 29 C80 30 C81 30 C82 31 C83 32 C84 33 C85 34 C86 0 1 C87 1 C88 1 C89 1 C90 1 C91 1 C92 1 C94 1 C95 1 C96 1 C97 0 1 C98 1 C99 1 C100 1 C101 1 C102 1 C103 1 C104 1 C105 1 C106 1 C107 00 1 C108 01 1 C109 02 1 C110 03 1 C111 04 1 C112 05 1 C113 06 1 C114 07 1 C115 08 3 C116 09 3 C117 0 3 C118 7 C119 8 C120 8 C121 8 C122 8 C123 8 C124 8 C125 8 C126 8 C127 0 8 C128 8 C129 8 C130 8 C131 8 C132 8 C133 8 C134 8 C135 8 C136 8 C137 0 8 C138 8 C139 8 C140 8 C141 10 C142 10 C143 10 C144 10 C145 10 C146 10 C147 0 11 C148 11 C149 11 C150 11 C151 11 C152 11 C153 11 C154 11 C155 11 C156 11 C157 0 11 C158 11 C159 11 C160 11 C161 11 C162 12 C163 13 C164 21 C165 21 C166 21 C167 0 21 C168 21 C169 21 C170 21 C171 21 C172 21 C173 22 C174 30 C175 31 C176 34 C177 0 35 C178 36 C179 37 C180 38 C181 39 C182 40 C183 41 C184 42 C185 45 C186 45 C187 0 45 C188 46 C189 47 C190 49 C191 53 C192 53 C193 54 C194 55 C195 56 C196 57 C197 0 57 C198 57 C199 8 C200 10 C201 58 *prepared according to example number

(1098) TABLE-US-00008 TABLE 4 Analytical Data for Molecules in Table 2 Mp No. ( C.) Mass (m/z) .sup.1H NMR .sup.13C NMR; .sup.19F NMR; IR F1 635 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (d, .sup.19F NMR ([M + H].sup.+) J = 1.6 Hz, 1H), 7.79 (dd, J = 8.1, 1.7 (376 MHz, CDCl.sub.3) Hz, 1H), 7.61 (d, J = 8.1 Hz, 1H), 7.44 59.40, 69.32 (d, J = (s, 2H), 7.26 (d, J = 7.8 Hz, 1H), 6.98 2.2 Hz), 72.57, (t, J = 5.2 Hz, 1H), 5.85 (dd, J = 32.5, 109.75-115.20 (m) 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 4.25 (d, J = 5.1 Hz, 2H), 3.91 (qd, J = 9.0, 6.4 Hz, 2H) F2 649 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.84 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.7 Hz, 1H), 7.74 (dd, J = 8.0, 1.7 CDCl.sub.3) 59.29, 69.34 Hz, 1H), 7.53 (d, J = 8.1 Hz, 1H), 7.47 (d, J = 2.1 Hz), 72.64, (t, J = 6.4 Hz, 1H), 7.44 (s, 2H), 6.93 (d, 112.09 J = 7.8 Hz, 1H), 5.83 (dd, J = 32.5, 9.5 Hz, 1H), 4.92 (p, J = 7.1 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.83 (qdd, J = 8.8, 6.2, 2.5 Hz, 2H), 1.51 (d, J = 6.9 Hz, 3H) F3 659 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.89 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.81 (dd, J = 8.1, 1.7 CDCl.sub.3) 58.76 Hz, 1H), 7.55 (d, J = 8.1 Hz, 1H), 7.43 (d, J = 1.4 Hz), 69.29 (s, 2H), 6.91 (t, J = 6.4 Hz, 1H), 6.42 (s, (d, J = 2.3 Hz), 72.65 1H), 5.85 (dd, J = 32.5, 9.6 Hz, 1H), (t, J = 1.3 Hz), 112.04 4.61 (p, J = 8.8 Hz, 1H), 3.96 (qd, J = (d, J = 12.9 Hz) 9.1, 6.4 Hz, 2H), 1.78-1.64 (m, 2H), 1.23-1.13 (m, 2H) F4 646 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.79 (dd, J = 8.2, 1.7 CDCl.sub.3) 58.66, Hz, 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.44 69.31 (d, J = 2.3 Hz), (s, 2H), 6.75 (s, 1H), 6.62 (t, J = 5.7 Hz, 112.04 1H), 5.86 (dd, J = 32.6, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.31 (td, J = 7.1, 5.7 Hz, 2H), 1.62-1.53 (m, 2H), 1.39 (q, J = 7.0 Hz, 2H), 1.15-1.01 (m, 2H), 0.77-0.57 (m, 1H), 0.50-0.36 (m, 2H), 0.10-0.01 (m, 2H) F5 619 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.6 Hz, 1H), 7.79 (dd, J = 8.1, 1.7 CDCl.sub.3) 58.65, Hz, 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.44 69.31 (d, J = 2.3 Hz) (s, 2H), 6.68 (s, 1H), 6.57 (t, J = 5.9 Hz, 112.03 1H), 5.95-5.71 (m, 2H), 5.22 (dq, J = 17.1, 1.6 Hz, 1H), 5.14 (dq, J = 10.3, 1.4 Hz, 1H), 4.61 (p, J = 8.8 Hz, 1H), 3.92-3.81 (m, 2H), 1.76-1.50 (m, 2H), 1.18-0.99 (m, 2H) F6 579 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.67 (t, .sup.19F NMR (376 MHz, ([M H].sup.) J = 6.4 Hz, 1H), 7.48-7.34 (m, 5H), 7.11 CDCl.sub.3) 69.45 (t, J = 5.2 Hz, 1H), 5.73 (dd, J = 32.8, (d, J = 2.2 Hz), 72.45, 9.6 Hz, 1H), 4.59 (p, J = 8.9 Hz, 1H), 111.78 4.24 (d, J = 5.2 Hz, 2H), 3.90 (qd, J = 9.1, 6.4 Hz, 2H), 2.44 (s, 3H) F7 496 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.47 (t, ) .sup.19F NMR (376 MHz, ([M NHCH.sub.2CF.sub.3].sup.+) J = 6.5 Hz, 1H), 7.43 (s, 2H), 7.40 (d, CDCl.sub.3) 67.97- J = 1.3 Hz, 1H), 7.38 (d, J = 1.1 Hz, 2H), 70.44 (m), 72.52, 6.69 (d, J = 7.7 Hz, 1H), 5.72 (dd, J = 110.05-114.53 (m) 32.8, 9.6 Hz, 1H), 4.99-4.70 (m, 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.89 (qd, J = 9.0, 6.4 Hz, 2H), 2.43 (s, 3H), 1.52 (d, J = 7.0 Hz, 3H F8 605 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.43 (s, .sup.19F NMR (376 MHz, ([M H].sup.) 1H), 7.40 (d, J = 1.7 Hz, 1H), 7.34 (d, CDCl.sub.3) 69.43 J = 8.0 Hz, 1H), 7.18 (t, J = 6.4 Hz, 1H), (d, J = 2.3 Hz), 72.54 6.57 (s, 1H), 5.74 (dd, J = 32.8, 9.6 Hz, 111.77 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.93 (qd, J = 9.1, 6.4 Hz, 2H), 2.47 (s, 3H), 1.72- 1.54 (m, 2H), 1.23-1.05 (m, 2H) F9 566 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.43 (s, .sup.19F NMR (376 MHz, ([M + H].sup.+) 2H), 7.42 (s, 1H), 7.41-7.36 (m, 1H), CDCl.sub.3) 69.42 7.36-7.32 (m, 1H), 7.19 (d, J = 8.1 Hz, (d, J = 2.3 Hz), 111.73 1H), 6.78-6.61 (m, 1H), 5.92-5.65 (m, 2H), 5.22 (ddd, J = 17.2, 2.5, 1.4 Hz, 1H), 5.13 (dt, J = 10.3, 1.6 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.87 (tdt, J = 5.3, 3.4, 1.6 Hz, 2H), 2.46 (s, 3H), 1.67- 1.56 (m, 2H), 1.09 (td, J = 7.7, 4.9 Hz, 2H) F10 592 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.43 (s, .sup.19F NMR (376 MHz, ([M H].sup.) 3H), 7.41-7.36 (m, 2H), 6.73 (t, J = 5.7 CDCl.sub.3) 69.42 Hz, 1H), 6.57 (s, 1H), 5.73 (dd, J = 32.8, (d, J = 2.3 Hz), 110.57- 9.6 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 113.11 (m) 3.35 (td, J = 6.9, 5.7 Hz, 2H), 2.48 (s, 3H), 1.67-1.56 (m, 2H), 1.41 (q, J = 6.9 Hz, 2H), 1.17-1.04 (m, 2H), 0.67 (dddd, J = 14.9, 9.9, 5.2, 2.2 Hz, 1H), 0.51-0.37 (m, 2H), 0.17-0.00 (m, 2H) F11 607 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.82 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.6 Hz, 1H), 7.72 (dd, J = 8.0, 1.7 CDCl.sub.3) 59.16, Hz, 1H), 7.53 (d, J = 8.1 Hz, 1H), 7.44 69.32 (d, J = 2.3 Hz), (s, 2H), 7.09 (dd, J = 7.7, 2.0 Hz, 1H), 110.35-113.41 (m) 6.86 (t, J = 5.8 Hz, 1H), 5.92-5.61 (m, 2H), 5.24-5.03 (m, 2H), 4.80 (p, J = 7.0 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.80 (tq, J = 5.7, 1.8 Hz, 2H), 1.50 (d, J = 6.9 Hz, 3H) F12 633 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.90-7.79 .sup.19F NMR (376 MHz, ([M H].sup.) (m, 1H), 7.74 (dd, J = 8.1, 1.7 Hz, 1H), CDCl.sub.3) 59.16, 7.56 (d, J = 8.1 Hz, 1H), 7.44 (s, 2H), 69.33, 108.63- 6.86 (dd, J = 7.8, 1.7 Hz, 1H), 6.52 (t, 115.35 (m) J = 5.8 Hz, 1H), 5.97-5.68 (m, 1H), 4.71 (p, J = 7.0 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.33 (dtdd, J = 20.2, 13.2, 7.0, 5.7 Hz, 2H), 1.49 (d, J = 6.9 Hz, 3H), 1.39 (q, J = 7.0 Hz, 2H), 0.65 (dddt, J = 11.9, 8.4, 7.1, 4.9 Hz, 1H), 0.47-0.34 (m, 2H), 0.11-0.01 (m, 2H) F13 661 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.8 Hz, 1H), 7.76 (dd, J = 8.1, 1.8 CDCl.sub.3) 59.12, Hz, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.44 69.32 (d, J = 2.3 Hz), (s, 2H), 6.90 (d, J = 7.5 Hz, 1H), 5.82 69.79, 111.45- (dd, J = 32.6, 9.6 Hz, 1H), 5.24-5.06 (m, 112.65 (m) 1H), 4.61 (p, J = 8.9 Hz, 1H), 4.27 (dq, J = 14.9, 9.0 Hz, 1H), 3.85 (dq, J = 14.9, 8.7 Hz, 1H), 3.26 (s, 3H), 1.48 (d, J = 6.8 Hz, 3H) F14 553 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.43 (s, .sup.19F NMR (471 MHz, ([M + H].sup.+) 2H), 7.42-7.33 (m, 3H), 6.79 (d, J = 7.6 CDCl.sub.3) 69.42 Hz, 1H), 6.72 (t, J = 5.9 Hz, 1H), 5.87- (d, J = 8.9 Hz), 111.72 5.76 (m, 1H), 5.71 (dd, J = 32.9, 9.6 Hz, 1H), 5.19 (dq, J = 17.1, 1.6 Hz, 1H), 5.12 (dq, J = 10.2, 1.4 Hz, 1H), 4.76 (p, J = 7.0 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.88 (tt, J = 5.7, 1.7 Hz, 2H), 2.44 (s, 3H), 1.51 (d, J = 7.0 Hz, 3H) F15 581 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.43 (s, .sup.19F NMR (471 MHz, ([M + H].sup.+) 2H), 7.42-7.34 (m, 3H), 6.80 (d, J = 7.6 CDCl.sub.3) 69.43 Hz, 1H), 6.61 (t, J = 5.8 Hz, 1H), 5.71 (d, J = 8.7 Hz), 111.61 (dd, J = 32.9, 9.6 Hz, 1H), 4.71 (p, J = 7.0 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.44-3.20 (m, 2H), 2.45 (s, 3H), 1.50 (d, J = 6.9 Hz, 3H), 1.40 (q, J = 7.0 Hz, 2H), 0.66 (dddd, J = 15.0, 10.1, 5.1, 2.3 Hz, 1H), 0.48-0.40 (m, 2H), 0.08-0.02 (m, 2H) F16 623 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.84 (d, .sup.19F NMR (471 MHz, ([M + H].sup.+) J = 1.6 Hz, 1H), 7.74 (dd, J = 8.1, 1.6 CDCl.sub.3) 59.19, Hz, 1H), 7.55 (d, J = 8.1 Hz, 1H), 7.44 69.33 (d, J = 8.8 Hz), (s, 2H), 6.93 (dd, J = 7.8, 2.5 Hz, 1H), 111.97 (d, J = 19.7 Hz) 6.54 (t, J = 5.8 Hz, 1H), 5.93-5.71 (m, 1H), 4.73 (p, J = 7.0 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.37-3.10 (m, 2H), 1.56-1.40 (m, 5H), 1.40-1.24 (m, 2H), 0.88 (t, J = 7.3 Hz, 3H) F17 649 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.84 (d, .sup.19F NMR (471 MHz, ([M + H].sup.+) J = 1.7 Hz, 1H), 7.74 (dd, J = 8.0, 1.7 CDCl.sub.3) 59.36, Hz, 1H), 7.53 (d, J = 8.1 Hz, 1H), 7.47 69.81 (d, J = 5.9 Hz), (t, J = 6.4 Hz, 1H), 7.44 (s, 2H), 6.93 (d, 72.59 (d, J = 3.5 Hz), J = 7.8 Hz, 1H), 5.92 (dd, J = 17.9, 11.1 90.26 Hz, 1H), 4.92 (p, J = 7.1 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.83 (qdd, J = 8.8, 6.2, 2.5 Hz, 2H), 1.51 (d, J = 6.9 Hz, 3H) F18 657 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.76 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.5 Hz, 1H), 7.59-7.46 (m, 2H), 7.43 CDCl.sub.3) 69.36 (s, 3H), 7.00 (d, J = 7.6 Hz, 1H), 5.77 (d, J = 2.4 Hz), 72.41, (dd, J = 32.6, 9.6 Hz, 1H), 4.87 (p, J = 112.05 (d, J = 3.9 Hz) 7.1 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.90 (qd, J = 9.0, 6.3 Hz, 2H), 1.55 (d, J = 6.9 Hz, 3H) F19 645 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.78 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.2 Hz, 1H), 7.55 (d, J = 1.8 Hz, 2H), CDCl.sub.3) 69.37, 7.43 (s, 2H), 7.37 (t, J = 6.4 Hz, 1H), 72.35, 112.02 7.20 (t, J = 5.2 Hz, 1H), 5.78 (dd, J = 32.6, 9.6 Hz, 1H), 4.59 (p, J = 8.9 Hz, 1H), 4.27 (d, J = 5.2 Hz, 2H), 3.94 (qd, J = 9.0, 6.4 Hz, 2H) F20 675 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.8 Hz, 1H), 7.76 (dd, J = 8.1, 1.7 CDCl.sub.3) 59.16, 69.59, Hz, 1H), 7.59 (d, J = 8.2 Hz, 1H), 7.44 111.89 (t, J = 9.4 Hz) (s, 2H), 6.82 (d, J = 7.7 Hz, 1H), 5.82 (dd, J = 32.6, 9.6 Hz, 1H), 5.22-5.07 (m, 1H), 4.61 (p, J = 8.9 Hz, 1H), 4.37 (dq, J = 15.0, 9.1 Hz, 1H), 3.91-3.38 (m, 3H), 1.49 (d, J = 6.8 Hz, 3H), 1.32 (t, J = 7.1 Hz, 3H) F21 668 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.76 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.56 (dd, J = 8.1, 1.7 CDCl.sub.3) 69.34 Hz, 1H), 7.49 (d, J = 8.1 Hz, 1H), 7.43 (d, J = 2.3 Hz), 72.34, (s, 2H), 7.07 (t, J = 6.5 Hz, 1H), 6.81 112.02 (d, J = 13.4 Hz) (s, 1H), 5.79 (dd, J = 32.6, 9.6 Hz, 1H), 4.59 (p, J = 8.9 Hz, 1H), 3.94 (qd, J = 9.1, 6.4 Hz, 2H), 1.74-1.62 (m, 2H), 1.23-1.17 (m, 2H) F22 599 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.66 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 8.1 Hz, 1H), 7.59 (d, J = 1.7 Hz, CDCl.sub.3) 69.37 1H), 7.58-7.52 (m, 1H), 7.52-7.46 (m, (d, J = 2.4 Hz), 72.40, 2H), 7.43 (s, 2H), 5.80 (dd, J = 32.6, 112.09 9.7 Hz, 1H), 4.59 (p, J = 8.9 Hz, 1H), 4.29 (d, J = 5.1 Hz, 2H), 3.92 (qd, J = 9.0, 6.4 Hz, 2H) F23 613 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.63 (t, .sup.19F NMR (376 MHz, ([M H].sup.) J = 6.4 Hz, 1H), 7.59 (d, J = 8.1 Hz, CDCl.sub.3) 68.04- 1H), 7.56 (d, J = 1.6 Hz, 1H), 7.47 (dd, 70.81 (m), 72.46, J = 8.2, 1.7 Hz, 1H), 7.43 (s, 2H), 7.31 112.10 (d, J = 7.6 Hz, 1H), 5.78 (dd, J = 32.6, 9.6 Hz, 1H), 4.92 (p, J = 7.1 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.88 (pt, J = 12.1, 6.1 Hz, 2H), 1.55 (d, J = 7.0 Hz, 3H) F24 677 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.77 (dd, J = 8.2, 1.7 CDCl.sub.3) 59.12, Hz, 1H), 7.62 (d, J = 8.1 Hz, 1H), 7.44 69.27, 69.31 (s, 2H), 6.55 (d, J = 8.1 Hz, 1H), 5.82 (d, J = 2.3 Hz), 111.89 (dd, J = 32.5, 9.6 Hz, 1H), 5.18 (p, J = (d, J = 3.4 Hz) 7.2 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 4.45 (dq, J = 17.1, 8.7 Hz, 1H), 4.07 (dd, J = 16.0, 8.0 Hz, 1H), 3.91 (s, 3H), 1.50 (d, J = 6.9 Hz, 3H) F25 685 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.77 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.60-7.48 (m, 2H), 7.43 CDCl.sub.3) 69.37 (s, 2H), 7.10 (d, J = 7.7 Hz, 1H), 5.77 (d, J = 2.3 Hz), 69.56, (dd, J = 32.6, 9.6 Hz, 1H), 5.27-5.08 (m, 108.63-118.42 (m) 1H), 4.59 (p, J = 8.9 Hz, 1H), 4.37 (dq, J = 15.1, 9.1 Hz, 1H), 3.93-3.32 (m, 3H), 1.52 (d, J = 6.8 Hz, 3H), 1.32 (t, J = 7.2 Hz, 3H) F26 591 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.47- .sup.19F NMR (376 MHz, ([M + H].sup.+) 7.36 (m, 5H), 6.95 (t, J = 6.5 Hz, 1H), CDCl.sub.3) 72.51, 6.30 (d, J = 7.5 Hz, 1H), 5.78 (dd, J = 95.16, 95.18, 34.0, 9.8 Hz, 1H), 4.72 (p, J = 7.0 Hz, 114.28 1H), 4.26 (td, J = 14.3, 9.8 Hz, 1H), 4.10-3.83 (m, 2H), 2.46 (s, 3H), 1.65 (t, J = 18.4 Hz, 3H), 1.51 (d, J = 7.0 Hz, 3H) F27 705 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.7 Hz, 1H), 7.77 (dd, J = 8.2, 1.8 CDCl.sub.3) 59.12, Hz, 1H), 7.62 (d, J = 8.1 Hz, 1H), 7.44 69.31, 111.88 (s, 2H), 6.54 (d, J = 8.1 Hz, 1H), 6.03 (ddt, J = 16.8, 10.3, 6.4 Hz, 1H), 5.82 (dd, J = 32.5, 9.6 Hz, 1H), 5.47 (m, 2H), 5.21 (q, J = 7.2 Hz, 1H), 4.57 (m, 4H), 4.04 (dd, J = 15.8, 8.1 Hz, 1H), 1.49 (d, J = 6.9 Hz, 3H) F28 625 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.67 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 8.1 Hz, 1H), 7.62 (d, J = 1.7 Hz, 1H), CDCl.sub.3) 69.34 7.55 (dd, J = 8.2, 1.7 Hz, 1H), 7.42 (s, (d, J = 2.3 Hz), 72.48, 2H), 7.00 (t, J = 6.4 Hz, 1H), 6.80 (s, 112.01 (d, J = 14.3 Hz) 1H), 5.80 (dd, J = 32.5, 9.6 Hz, 1H), 4.59 (p, J = 8.9 Hz, 1H), 3.93 (dqd, J = 22.4, 9.1, 6.6 Hz, 2H), 1.79-1.64 (m, 2H), 1.24-1.16 (m, 2H) F29 643 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.89- .sup.19F NMR (376 MHz, ([M H].sup.) 7.82 (m, 1H), 7.75 (dd, J = 8.2, 1.8 Hz, CDCl.sub.3) 59.16, 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.42 (s, 72.59, 93.24- 2H), 7.15 (t, J = 6.5 Hz, 1H), 6.62 (d, 97.00 (m), 114.71 J = 7.7 Hz, 1H), 5.90 (dd, J = 33.8, 9.8 Hz, 1H), 4.84 (p, J = 7.1 Hz, 1H), 4.28 (td, J = 14.3, 9.7 Hz, 1H), 3.98-3.82 (m, 2H), 1.65 (t, J = 18.4 Hz, 3H), 1.51 (d, J = 6.9 Hz, 3H) F30 629 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.83 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.73 (dd, J = 8.1, 1.7 CDCl.sub.3) 59.27, Hz, 1H), 7.53 (d, J = 8.1 Hz, 1H), 7.45 69.37 (d, J = 2.2 Hz), (d, J = 7.2 Hz, 3H), 7.16 (d, J = 7.8 Hz, 109.45-115.35 (m), 1H), 6.02-5.51 (m, 2H), 4.88 (p, J = 7.0 122.98 (d, J = 8.9 Hz) Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.71- 3.37 (m, 2H), 1.49 (d, J = 6.9 Hz, 3H) F31 639 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.76 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.1 Hz, 1H), 7.52 (d, J = 1.1 Hz, CDCl.sub.3) 69.36 2H), 7.43 (s, 2H), 7.15 (t, J = 6.2 Hz, (d, J = 2.2 Hz), 111.99, 1H), 6.96 (d, J = 7.6 Hz, 1H), 6.05-5.60 122.83 (m, 2H), 4.82 (p, J = 7.1 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.78-3.48 (m, 2H), 1.54 (d, J = 7.0 Hz, 3H) F32 595 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.63 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 8.1 Hz, 1H), 7.57 (d, J = 1.7 Hz, CDCl.sub.3) 69.37 1H), 7.48 (dd, J = 8.2, 1.8 Hz, 1H), 7.43 (d, J = 2.8 Hz), 110.57- (s, 2H), 7.31 (t, J = 6.2 Hz, 1H), 7.24 (d, 115.35 (m), 122.85 J = 7.5 Hz, 1H), 6.05-5.64 (m, 2H), 4.86 (p, J = 7.0 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.72-3.47 (m, 2H), 1.54 (d, J = 6.9 Hz, 3H) F33 110-113 701 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.84 ([M + H].sup.+) (d, J = 7.2 Hz, 1H), 8.64 (t, J = 6.4 Hz, 1H), 8.11 (s, 1H), 8.06 (d, J = 7.6 Hz, 1H), 7.96 (s, 2H), 7.90-7.89 (m, 1H), 7.67 (d, J = 7.6 Hz, 1H), 6.85 (dd, J = 36.0, 10.0 Hz, 1H), 5.21-5.20 (m, 1H), 4.53-4.59 (m, 1H), 4.03-3.85 (m, 2H), 1.30 (d, J = 6.8 Hz, 3H) F34 89-92 713 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.09 ([M + H].sup.+) (br s, 1H), 8.16-8.12 (m, 2H), 8.09 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 8.4 Hz, 1H), 7.96 (s, 2H), 7.91-7.90 (m, 1H) 6.85 (dd, J = 35.6, 10.0, Hz, 1H), 5.22-5.17 (m, 1H), 3.97-3.89 (m, 2H), 1.40-1.37 (m, 2H), 1.03-1.01 (m, 2H) F35 124-127 686 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.80 ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.62 (t, J = 6.4 Hz, 1H), 8.11 (s, 1H), 8.08 (d, J = 8.0 Hz, 1H), 7.96 (s, 2H), 7.90 (s, 1H), 7.70 (d, J = 7.6 Hz, 1H), 6.85 (dd, J = 36.0, 10.0 Hz, 1H), 5.21-5.20 (m, 1H), 3.96-3.87 (m, 4H) F36 85-87 631 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.84 ([M + H].sup.+) (d, J = 7.2 Hz, 1H), 8.63 (t, J = 6.4 Hz, 1H), 8.10 (s, 1H), 8.05-8.03 (m, 2H), 8.00 (d, J = 6.4 Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H), 6.84 (dd, J = 36.0, 10.0 Hz, 1H), 5.21-5.20 (m, 1H), 4.53-4.59 (m, 1H), 4.05-3.85 (m, 2H), 1.30 (d, J = 7.2 Hz, 3H) F37 56-58 643 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.10 ([M + H].sup.+) (br s, 1H), 8.16 (t, J = 6.4 Hz, 1H), 8.11 (s, 1H), 8.08 (d, J = 8.4 Hz, 1H), 8.02 (s, 1H), 8.00 (d, J = 6.4 Hz, 2H), 6.84 (dd, J = 36.0, 10.4 Hz, 1H), 5.24-5.21 (m, 1H), 3.95-3.87 (m, 2H), 1.02 (t, J = 4.4 Hz, 2H), 0.66 (t, J = 4.8 Hz, 2H) F38 82-85 615 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.88 ([M H].sup.) (t, J = 6.0 Hz, 1H), 8.61 (t, J = 6.4 Hz, 1H), 8.10 (s, 1H), 8.07 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 6.4 Hz, 2H), 7.71 (d, J = 8.4 Hz, 1H), 6.83 (dd, J = 35.6, 10.4 Hz, 1H), 5.24-5.23 (m, 1H), 4.05-3.88 (m, 4H) F39 66-68 625 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.10 ([M + H].sup.+) (s, 1H), 8.18-7.99 (m, 4H), 7.80 (s, 2H), 7.67 (s, 1H), 6.88 (dd, J = 36.0, 10.2 Hz, 1H), 5.24-5.18 (m, 1H), 3.99-3.87 (m, 2H), 1.09-0.98 (m, 2H), 0.97-0.87 (m, 2H F40 101-103 590 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.80 ([M + H].sup.+) (t, J = 5.7 Hz, 1H), 8.64 (t, J = 6.0 Hz, 1H), 8.12 (s, 1H), 8.08 (d, J = 8.1 Hz, 1H), 7.81 (s, 2H), 7.71-7.69 (m, 2H), 6.87 (dd, J = 36.0, 10.2 Hz, 1H), 5.24- 5.18 (m, 1H), 4.02-3.90 (m, 4H) F41 599 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.10 IR (thin film) ([M + H].sup.+) (s, 1H), 8.17-8.07 (m, 3H), 8.02 (d, J = 3463, 3289, 1682, 8.4 Hz, 2H), 7.75 (d, J = 8.8 Hz, 1H), 1168, 666 cm.sup.1 7.67 (d, J = 8.8 Hz, 1H), 6.84 (dd, J = 36.0, 10.2 Hz, 1H), 5.21-5.16 (m, 1H), 3.97-3.89 (m, 2H), 1.40-1.37 (m, 2H), 1.02-0.98 (m, 2H) F42 613 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.84 IR (thin film) ([M + H].sup.+) (d, J = 8.0 Hz, 1H), 8.64 (t, J = 6.4 Hz, 3412, 2924, 1652, 1H), 8.10 (s, 1H), 8.05 (t, J = 6.4 Hz, 1275 cm.sup.1 2H), 7.74 (d, J = 8.8 Hz, 1H), 7.69-7.64 (m, 2H), 6.83 (dd, J = 35.6, 9.6 Hz, 1H), 5.20-5.16 (m, 1H), 4.52-4.49 (m, 1H), 4.01-3.87 (m, 2H), 1.32-1.09 (m, 3H) F43 599 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.88 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.63 (t, J = 6.4 Hz, 3348, 2924, 1657, 1H), 8.11 (s, 1H), 8.07 (d, J = 8.0 Hz, 607 cm.sup.1 1H), 8.00 (d, J = 1.2 Hz, 1H), 7.74- 7.65 (m, 3H), 6.83 (dd, J = 36.0, 10.0 Hz, 1H), 5.21-5.16 (m, 1H), 4.00-3.92 (m, 4H) F44 73-76 735 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.85 ([M + H].sup.+) (d, J = 7.5 Hz, 1H), 8.63 (s, 1H), 8.18- 7.97 (m, 4H), 7.67 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 36.3, 10.2 Hz, 1H), 5.25- 5.19 (m, 1H), 4.53-4.49 (m, 1H), 4.00- 3.86 (m, 2H), 1.30 (d, J = 7.2 Hz, 3H) F45 81-84 747 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.10 ([M + H].sup.+) (s, 1H), 8.17-7.96 (m, 6H), 6.87 (dd, J = 35.7, 10.2 Hz, 1H), 5.26-5.19 (m, 1H), 3.99-3.87 (m, 2H), 1.41-1.38 (m, 2H), 1.03-0.99 (m, 2H) F46 99-102 721 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.87 ([M + H].sup.+) (d, J = 5.7 Hz, 1H), 8.62 (d, J = 6.3 Hz, 1H), 8.18-8.05 (m, 4H), 7.71 (d, J = 6.3 Hz, 1H), 6.87 (dd, J = 36.0, 10.2 Hz, 1H), 5.26-5.19 (m, 1H), 4.02-3.90 (m, 4H) F47 613 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.77 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 8.1 Hz, 1H), 7.61 (d, J = 1.6 Hz, CDCl.sub.3) 69.37 1H), 7.51 (dd, J = 8.2, 1.7 Hz, 1H), 7.43 (d, J = 2.2 Hz), 69.89, (s, 2H), 7.41 (s, 1H), 5.79 (dd, J = 32.6, 111.97 (d, J = 3.3 Hz) 9.6 Hz, 1H), 4.59 (p, J = 8.9 Hz, 1H), 4.37 (d, J = 4.1 Hz, 2H), 4.09 (q, J = 8.9 Hz, 2H), 3.19 (s, 3H) F48 657 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.80 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.63 (d, J = 8.1 Hz, CDCl.sub.3) 69.36, 1H), 7.55 (dd, J = 8.2, 1.6 Hz, 1H), 7.17 69.88, 111.89 (q, J = 4.1 Hz, 1H), 5.77 (dd, J = 32.6, 9.6 Hz, 1H), 4.59 (p, J = 8.9 Hz, 1H), 4.36 (d, J = 4.1 Hz, 2H), 4.19-4.02 (m, 3H), 3.19 (s, 3H) F49 627 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.72 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 8.1 Hz, 1H), 7.60 (d, J = 1.7 Hz, CDCl.sub.3) 69.36 1H), 7.50 (dd, J = 8.2, 1.7 Hz, 1H), 7.43 (d, J = 8.7 Hz), 69.77 (s, 2H), 7.30 (d, J = 7.3 Hz, 1H), 5.77 (t, J = 8.9 Hz), 111.54- (dd, J = 32.6, 9.5 Hz, 1H), 5.16 (p, J = 112.50 (m) 6.9 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 4.39-4.23 (m, 1H), 3.84 (dq, J = 15.0, 8.9 Hz, 1H), 3.27 (s, 3H), 1.51 (d, J = 6.8 Hz, 3H) F50 671 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.78 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.58 (d, J = 8.1 Hz, CDCl.sub.3) 69.36, 1H), 7.53 (dd, J = 8.1, 1.7 Hz, 1H), 69.75, 111.15- 7.43 (s, 2H), 7.06 (d, J = 7.4 Hz, 1H), 112.61 (m) 5.75 (dd, J = 32.6, 9.6 Hz, 1H), 5.22- 5.09 (m, 1H), 4.58 (p, J = 8.8 Hz, 1H), 4.31 (dq, J = 15.0, 9.1 Hz, 1H), 3.85 (dq, J = 15.0, 8.8 Hz, 1H), 3.27 (d, J = 0.8 Hz, 3H), 1.51 (d, J = 6.8 Hz, 3H) F51 631 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.81-7.72 (m, 1H), CDCl.sub.3) 59.33, 7.64 (d, J = 8.0 Hz, 1H), 7.44 (s, 2H), 69.31, 69.90, 6.88 (s, 1H), 5.83 (dd, J = 32.5, 9.6 111.89 (d, J = 32.2 Hz) Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 4.34 (d, J = 4.1 Hz, 2H), 4.16-4.00 (m, 2H), 3.22-3.15 (m, 3H) F52 66-68 638 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.86 ([M H].sup.) (s, 1H), 7.80 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.42 (s, 1H), 7.38- 7.37 (m, 1H), 6.74-6.69 (m, 1H), 6.40 (d, J = 7.2 Hz, 1H), 5.89-5.74 (m, 2H), 4.78-4.71 (m, 1H), 4.64-4.55 (m, 1H), 3.97-3.89 (m, 2H), 1.52 (d, J = 7.2 Hz, 3H) F53 607 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.23 IR (thin film) ([M + H].sup.+) (d, J = 8.1 Hz, 1H), 8.13 (s, 1H), 8.04 (s, 3440, 2927, 1716, 3H), 7.66 (d, J = 8.1 Hz, 1H), 6.88 (dd, 1175 cm.sup.1 J = 35.6, 10.2 Hz, 1H), 5.28-5.21 (m, 1H), 5.02-4.93 (m, 1H), 4.64-4.59 (m, 1H), 4.09-4.00 (m, 1H), 3.57-3.31 (m, 2H), 1.23-1.19 (br s, 3H) F54 661 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.79 (dd, J = 8.1, 1.8 CDCl.sub.3) 58.82, Hz, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.44 69.31, 73.25, (s, 2H), 7.12 (t, J = 6.4 Hz, 1H), 5.83 111.88 (dd, J = 32.6, 9.6 Hz, 1H), 5.26 (s, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.92 (dqd, J = 37.0, 9.1, 6.4 Hz, 2H), 1.70 (s, 6H) F55 762 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.77 (dd, J = 8.0, 1.7 CDCl.sub.3) 59.19 Hz, 1H), 7.59 (d, J = 7.8 Hz, 1H), 7.44 (d, J = 6.3 Hz), 69.31 (s, 2H), 7.18 (s, 1H), 6.60 (d, J = 73.8 (d, J = 2.3 Hz), 69.69 Hz, 2H), 5.82 (dd, J = 32.5, 9.6 Hz, 1H), (d, J = 12.5 Hz), 111.89; 4.88 (s, 1H), 4.59 (m, 1H), 3.68 (d, J = rotamers 45.3 Hz, 1H), 1.52 (s, 12H); rotamers F56 658 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.80 (dd, J = 8.1, 1.7 CDCl.sub.3) 58.79, Hz, 1H), 7.60 (d, J = 8.1 Hz, 1H), 7.44 66.61, 69.31, (s, 2H), 6.57 (s, 1H), 5.85 (dd, J = 32.5, 111.93 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 2.95 (dd, J = 8.6, 6.8 Hz, 2H), 2.57-2.31 (m, 2H), 1.76-1.65 (m, 2H), 1.33-1.28 (m, 2H) F57 664 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.7 Hz, 1H), 7.76 (m, 1H), 7.60 (d, CDCl.sub.3) 59.12, J = 8.1 Hz, 1H), 7.44 (s, 2H), 6.67 (d, 69.31 (d, J = 2.3 Hz), J = 7.9 Hz, 1H), 5.81 (dd, J = 32.6, 9.6 69.40, 111.85 Hz, 1H), 5.65 (m, 1H), 4.59 (m, 1H), 4.45 (dq, J = 15.2, 8.9 Hz, 1H), 4.11 (s, 2H), 4.00 (dq, J = 15.2, 8.6 Hz, 1H), 1.50 (d, J = 6.9 Hz, 3H) F58 657 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (s, .sup.13C NMR (101 MHz, ([M + H].sup.+) 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.57-7.50 CDCl.sub.3) 169.85, 166.53, (m, 1H), 7.42 (s, 2H), 6.91 (s, 1H), 6.33 157.06 (d, J.sub.CF = 252.8 Hz), (s, 1H), 5.92 (dd, J = 33.7, 9.8 Hz, 1H), 136.98 (d, J.sub.CF = 5.7 Hz), 4.27 (td, J = 14.7, 14.3, 9.7 Hz, 1H), 135.96, 132.74, 131.21, 3.94 (ddd, J = 18.9, 9.3, 6.5 Hz, 2H), 129.10, 128.60, 127.91, 1.64 (t, J = 18.4 Hz, 3H), 1.28-1.16 (m, 127.33, 127.29, 125.17, 3H), 0.93-0.84 (m, 1H) 124.32, 122.57-121.90 (m), 121.60, 99.98, 53.13, 48.63- 47.10 (m), 28.27, 23.04- 22.23 (m), 19.91 F59 689 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.85 IR (thin film) ([M H].sup.) (d, J = 8.0 Hz, 1H), 8.63 (t, J = 6.4 Hz, 3293, 2924, 1651, 1H), 8.10-8.00 (m, 4H), 7.67 (d, J = 8.0 1170 cm.sup.1 Hz, 1H), 6.84 (dd, J = 35.6, 10.4 Hz, 1H), 5.25-5.20 (m, 1H), 4.53-4.49 (m, 1H), 4.02-3.87 (m, 2H), 1.30 (d, J = 7.6 Hz, 3H) F60 703 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.10 IR (thin film) ([M + H].sup.+) (s, 1H), 8.17-7.99 (m, 6H), 6.85 (dd, J = 3437, 1663, 1119, 35.6, 10.0 Hz, 1H), 5.23-5.21 (m, 1H), 749 cm.sup.1 4.00-3.83 (m, 2H), 1.40-1.33 (m, 2H), 1.03-1.00 (m, 2H) F61 105-107 626 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (s, ([M + H].sup.+) 1H) 7.79 (d, J = 8.4 Hz, 1H), 7.66 (d, J = 7.6 Hz, 1H), 7.42 (s, 1H), 7.37 (s, 1H), 6.69-6.64 (m, 2H), 5.90-5.74 (m, 2H), 4.62-4.57 (m, 1H), 4.22 (d, J = 5.6 Hz, 2H), 3.99-3.91 (m, 2H) F62 631 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.84 .sup.13C NMR (101 MHz, ([M + H].sup.+) (s, 1H), 7.74 (dd, J = 8.1, 1.7 Hz, 1H), CDCl.sub.3) 168.92, 167.79, 7.56 (d, J = 8.1 Hz, 1H), 7.52 (t, J = 6.5 157.06 (d, J.sub.CF = 253.1 Hz), Hz, 1H), 7.42 (s, 2H), 7.17 (t, J = 5.1 136.92 (d, J.sub.CF = 3.4 Hz), Hz, 1H), 5.91 (dd, J = 33.8, 9.7 Hz, 135.13, 134.54, 133.45, 1H), 4.38-4.20 (m, 3H), 3.87 (qd, J = 133.16, 131.25, 129.12, 9.0, 6.4 Hz, 2H), 1.65 (t, J = 18.4 Hz, 127.70 (d, J.sub.CF = 5.8 Hz), 3H) 125.22, 124.40, 122.83- 122.35 (m), 121.67, 103.78, 48.56-47.56 (m), 43.74, 40.64 (dd, J = 70.8, 35.6 Hz), 23.38-21.79 (m) F63 593 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.90-7.79 .sup.19F NMR (471 MHz, ([M H].sup.) (m, 1H), 7.74 (dd, J = 8.1, 1.7 Hz, 1H), CDCl.sub.3) 59.09, 69.32, 7.56 (d, J = 8.1 Hz, 1H), 7.44 (s, 2H), 111.85 6.88 (dd, J = 7.8, 2.0 Hz, 1H), 6.50 (t, J = 5.6 Hz, 1H), 5.82 (ddd, J = 32.6, 9.6, 0.8 Hz, 1H), 4.71 (p, J = 7.0 Hz, 1H), 4.59 (q, J = 8.9 Hz, 1H), 3.27 (qd, J = 7.3, 5.6 Hz, 2H), 1.49 (d, J = 6.9 Hz, 3H), 1.12 (t, J = 7.3 Hz, 3H) F64 559 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.65 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 8.1 Hz, 1H), 7.58 (d, J = 1.6 Hz, CDCl.sub.3) 69.37, 111.86 1H), 7.49 (dd, J = 8.2, 1.7 Hz, 1H), 7.43 (s, 2H), 7.10 (d, J = 7.5 Hz, 1H), 6.37 (t, J = 5.7 Hz, 1H), 5.77 (dd, J = 32.5, 9.6 Hz, 1H), 4.70 (p, J = 7.0 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 3.40-3.15 (m, 2H), 1.52 (d, J = 6.9 Hz, 3H), 1.16 (t, J = 7.3 Hz, 3H) F65 647 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.85 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.76 (dd, J = 8.1, 1.7 CDCl.sub.3) 59.09 (d, J = Hz, 1H), 7.57 (d, J = 8.1 Hz, 1H), 7.49 16.2 Hz), 69.34, 74.46- (s, 2H), 7.41-7.17 (m, 2H), 5.85 (dd, J = 80.70 (m), 111.92 (dd, 32.6, 9.6 Hz, 1H), 4.78-4.43 (m, 2H), J = 49.8, 32.3 Hz) 4.21 (d, J = 5.1 Hz, 2H), 1.32-1.27 (m, 3H) F66 613 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.75- .sup.19F NMR (471 MHz, ([M H].sup.) 7.65 (m, 1H), 7.61 (d, J = 1.7 Hz, 1H), CDCl.sub.3) 69.34, 77.5, 7.52 (dd, J = 8.2, 1.8 Hz, 1H), 7.43 (s, 111.95 2H), 7.34 (t, J = 5.0 Hz, 1H), 7.12 (d, J = 9.4 Hz, 1H), 5.80 (dd, J = 32.6, 9.6 Hz, 1H), 4.83-4.41 (m, 2H), 4.27 (dd, J = 5.1, 1.4 Hz, 2H), 1.34 (d, J = 7.0 Hz, 3H) F67 703 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.98 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.65-7.59 (m, 1H), CDCl.sub.3) 69.34 7.52 (dd, J = 8.1, 1.7 Hz, 1H), 7.43 (d, (d, J = 8.9 Hz), 72.42, J = 4.6 Hz, 2H), 7.35 (d, J = 8.1 Hz, 108.78-113.05 (m) 1H), 7.02 (d, J = 7.7 Hz, 1H), 5.74 (dd, J = 32.6, 9.6 Hz, 1H), 4.90 (h, J = 7.0 Hz, 1H), 4.70-4.45 (m, 1H), 3.88 (tddd, J = 14.9, 12.5, 8.9, 6.1 Hz, 2H), 1.56 (d, J = 7.0 Hz, 3H) F68 649 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.91 (d, .sup.19F NMR (471 MHz, ([M + H].sup.+) J = 1.6 Hz, 1H), 7.90-7.81 (m, 1H), CDCl.sub.3) 60.56, 7.49-7.42 (m, 1H), 7.45 (s, 2H), 7.15 (t, 69.37 (d, J = 8.9 Hz), J = 6.5 Hz, 1H), 5.94-5.78 (m, 1H), 4.63 72.61 (t, J = 9.0 Hz), (p, J = 8.7 Hz, 1H), 4.24 (s, 2H), 3.90 112.15 (d, J = 32.7 Hz) (m, 2H), 2.91 (s, 3H) F69 607 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.45 IR (thin film) ([M + H].sup.+) (d, J = 7.2 Hz, 1H), 8.65 (t, J = 6.0 Hz, 3285, 2929, 1653, 1H), 8.07-8.02 (m, 2H), 7.66 (d, J = 8.1 1167 cm.sup.1 Hz, 1H), 7.45 (s, 2H), 6.78 (dd, J = 36.0, 10.2 Hz, 1H), 4.95-4.89 (m, 1H), 4.53- 4.48 (m, 1H), 4.02-3.86 (m, 2H), 2.35 (s, 6H), 1.32 (d, J = 7.2 Hz, 3H) F70 619 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.10 IR (thin film) ([M + H].sup.+) (s, 1H), 8.17 (t, J = 6.6 Hz, 1H), 8.08 (s, 3339, 2925, 1661, 2H), 8.01 (d, J = 8.4 Hz, 1H), 7.44 (s, 1165 cm.sup.1 2H), 6.79 (dd, J = 30.0, 9.9 Hz, 1H), 4.96-4.89 (m, 1H), 3.96-3.90 (m, 2H), 2.35 (s, 6H), 1.40-1.29 (m, 2H), 1.08- 1.01 (m, 2H) F71 593 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.88 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz 1H), 8.63 (t, J = 6.0 Hz, 3321, 2918, 1654, 1H), 8.07 (s, 1H), 8.04 (s, 1H), 7.70 (d, 1166 cm.sup.1 J = 7.8 Hz, 1H), 7.45 (s, 2H), 6.78 (dd, J = 35.7, 9.9 Hz, 1H), 4.96-4.89 (m, 1H), 4.02-3.90 (m, 4H), 2.35 (s, 6H) F72 627 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.97 IR (thin film) ([M + H].sup.+) (d, J = 7.8 Hz, 1H), 8.11 (s, 1H), 8.05 3418, 2927, 1652, (d, J = 8.1 Hz, 1H), 7.81 (s, 2H), 7.68 749 cm.sup.1 (s, 1H), 7.60 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 36.0, 10.2 Hz, 1H), 5.24-5.17 (m, 1H), 4.99-4.97 (m, 1H), 4.29-4.14 (m, 2 H), 3.23 (s, 3H), 1.29 (d, J = 6.8 Hz, 3H) F73 625 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.97 IR (thin film) ([M H].sup.) (d, J = 7.6 Hz, 1H), 8.11 (s, 1H), 8.04 3435, 2924, 1651, (d, J = 8.0 Hz, 1H), 8.00 (s, 2H), 7.74 750 cm.sup.1 (d, J = 8.4 Hz, 1H), 7.67 (d, J = 6.8 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), 6.83 (dd, J = 35.6, 9.8 Hz, 1H), 5.20-5.16 (m, 1H), 4.98-4.94 (m, 1H), 4.24-4.11 (m, 2H), 3.22 (s, 3H), 1.28 (d, J = 6.8 Hz, 3H) F74 613 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.80 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.12 (s, 1H), 8.07 (d, 3406, 2926, 1661, J = 8.8 Hz, 1H), 8.00 (s, 1H), 7.74-7.65 749 cm.sup.1 (m, 3H), 6.83 (dd, J = 35.6, 10.0 Hz, 1H), 5.21-5.16 (m, 1H), 4.22-4.15 (m, 4H), 3.14 (s, 3H) F75 693 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.97 IR (thin film) ([M + H].sup.+) (d, J = 7.2 Hz, 1H), 8.10 (s, 1H), 8.05- 3412, 1652 cm.sup.1 8.00 (m, 3H), 7.95 (s, 1H), 7.60 (d, J = 8.1 Hz, 1H), 6.86 (dd, J = 35.7, 9.9 Hz, 1H), 5.26-5.19 (m, 1H), 4.99-4.94 (m, 1H), 4.34-4.08 (m, 2H), 3.22 (s, 3H) F76 705 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.81 IR (thin film) ([M + H].sup.+) (t, J = 5.4 Hz, 1H), 8.11 (s, 1H), 8.08 (d, 3411, 1661 cm.sup.1 J = 8.4 Hz, 1H), 8.00 (s, 2H), 7.70 (d, J = 8.1 Hz, 1H), 6.86 (dd, J = 35.4, 9.9 Hz, 1H), 5.26-5.20 (m, 1H), 4.23-4.18 (m, 3H), 3.14 (s, 3H), 1.26 (d, J = 7.2 Hz, 3H) F77 735 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.79 IR (thin film) ([M + H].sup.+) (d, J = 5.4 Hz, 1H), 8.18-8.05 (m, 4H), 3411, 1661 cm.sup.1 7.70 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 36.3, 10.2 Hz, 1H) 5.23-5.19 (m, 1H), 4.23-4.19 (m, 4H), 3.14 (s, 3H) F78 749 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.97 IR (thin film) ([M + H].sup.+) (d, J = 6.6 Hz, 1H), 8.17-8.02 (m, 4H), 3411, 1652 cm.sup.1 7.60 (d, J = 8.1 Hz, 1H), 6.86 (dd, J = 36.0, 9.6 Hz, 1H), 5.25-5.19 (m, 1H), 4.98-4.95 (m, 1H), 4.35-4.10 (m, 2H), 3.22 (s, 3H), 1.28 (d, J = 6.0 Hz, 3H) F79 699 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.81 IR (thin film) ([M H].sup.) (d, J = 8.0 Hz, 1H), 8.61 (t, J = 6.0 Hz, 3429, 2927, 1649, 1H), 8.09 (s, 2H), 8.05 (d, J = 8.0 Hz, 1116 cm.sup.1 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.61 (d, J = 6.8 Hz, 1H), 6.81 (dd, J = 36.0, 9.6 Hz, 1H), 5.17-5.16 (m, 1H), 4.53-4.49 (m, 1H), 4.01-3.86 (m, 2H), 1.30 (d, J = 6.8 Hz, 3H) F80 712 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.08 IR (thin film) ([M H].sup.) (br s, 1H), 8.13-8.08 (m, 2H), 8.06 (s, 3436, 2926, 1667, 2H), 8.00 (d, J = 8.0 Hz, 1H), 7.85 (d, 1275, 750 cm.sup.1 J = 8.4 Hz, 1H), 7.61 (d, J = 8.4 Hz, 1H), 6.85 (dd, J = 35.6, 10.0 Hz, 1H), 5.17-5.16 (m, 1H), 4.03-3.89 (m, 2H), 1.42-1.33 (m, 2H), 1.03-1.01 (m, 2H) F81 643 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.94 IR (thin film) ([M H].sup.) (d, J = 7.6 Hz, 1H), 8.10 (s, 1H), 8.04 3432, 2927, 1647, (d, J = 8.4 Hz, 1H), 8.00 (d, J = 6.4 Hz, 1262, 749 cm.sup.1 2H), 7.60 (d, J = 8.0 Hz, 1H), 6.82 (dd, J = 35.6, 10.4 Hz, 1H), 5.23-5.21 (m, 1H), 4.99-4.93 (m, 1H), 4.32-4.26 (m, 1H), 4.15-4.02 (m, 1H), 3.22 (s, 3H), 1.29 (d, J = 6.8 Hz, 3H) F82 629 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.76 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.10 (s, 1H), 8.07 (d, 3418, 2927, 1651, J = 8.4 Hz, 1H), 8.00 (d, J = 6.0 Hz, 749 cm.sup.1 2H), 7.70 (d, J = 8.4 Hz, 1H), 6.82 (dd, J = 35.6, 9.6 Hz, 1H), 5.23-5.22 (m, 1H), 4.39-4.36 (m, 1H), 4.23-4.19 (m, 3H), 3.14 (s, 3H) F83 715 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.97 IR (thin film) ([M + H].sup.+) (d, J = 8.1 Hz, 1H), 8.11 (s, 1H), 8.05 3405, 2929, 1651, (d, J = 8.7 Hz, 1H), 7.96 (s, 2H), 7.90- 748 cm.sup.1 7.89 (m, 1H), 7.60 (d, J = 8.4 Hz, 1H), 6.87 (dd, J = 36.0, 10.2 Hz, 1H), 5.22- 5.21 (m, 1H), 4.99-4.94 (m, 1H), 4.34- 4.08 (m, 2H), 3.22 (s, 3H), 1.29 (d, J = 6.9 Hz, 3H) F84 701 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.80 IR (thin film) ([M + H].sup.+) (t, J = 5.4 Hz, 1H), 8.12 (s, 1H), 8.08- 3402, 2926, 1660, 8.06 (m, 1H), 7.96 (s, 2H), 7.90 (s, 1H), 748 cm.sup.1 7.70 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 36.0, 10.2 Hz, 1H), 5.22-5.20 (m, 1H), 4.23-4.16 (m, 4H), 3.14 (s, 3H) F85 639 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.88 (s, IR (thin film) ([M + H].sup.+) 1H), 7.79 (d, J = 7.8 Hz, 1H), 7.64 (d, 3437, 2924, 1661, J = 7.8 Hz, 1H), 7.44 (s, 1H), 7.37 (s, 1266, 1170, 764 cm.sup.1 1H), 6.76-6.72 (m, 1H), 5.84-5.65 (m, 2H), 5.47-5.31 (m, 1H), 4.64-4.60 (m, 1H), 4.34-4.31 (m, 2H), 4.12-4.03 (q, J = 8.7 Hz, 2H), 3.17 (s, 3H) F86 85-88 653 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.86 (s, ([M + H].sup.+) 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), 7.43 (s, 1H), 7.37 (s, 1H), 7.01-6.90 (m, 1H), 5.94-5.65 (m, 3H), 5.46-5.34 (m, 1H), 5.16-5.11 (m, 1H), 4.33-4.25 (m, 1H), 3.88-3.80 (m, 1H), 3.26 (s, 3H), 1.54 (d, J = 6.9 Hz, 3H) F87 646 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.83 (d, .sup.19F NMR (471 MHz, ([M + H].sup.+) J = 1.8 Hz, 1H), 7.73 (dt, J = 9.0, 2.7 Hz, CDCl.sub.3) 59.32, 72.56, 1H), 7.59-7.52 (m, 2H), 7.42 (d, J = 5.2 102.60-107.05 (m), Hz, 2H), 7.22-7.13 (m, 1H), 5.91 (ddd, 115.08 J = 33.9, 9.7, 1.6 Hz, 1H), 4.39-4.19 (m, 2H), 3.85 (qd, J = 8.9, 6.3 Hz, 2H), 1.98- 1.78 (m, 3H), 1.07 (t, J = 7.4 Hz, 3H) F88 672 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.82 (d, .sup.19F NMR (471 MHz, ([M + H].sup.+) J = 1.8 Hz, 1H), 7.73 (ddd, J = 8.3, 4.2, CDCl.sub.3) 58.73, 72.6, 1.6 Hz, 1H), 7.46 (dd, J = 8.1, 4.5 Hz, 101.74-107.92 (m), 1H), 7.42 (s, 2H), 6.92 (q, J = 6.1 Hz, 115.12 2H), 5.92 (dd, J = 33.9 9.7 Hz, 1H), 4.31 (td, J = 14.6, 9.8 Hz, 1H), 3.89 (qd, J = 9.0, 6.4 Hz, 2H), 2.02 1.72 (m, 2H), 1.64 1.56 (m, 2H), 1.18 1.12 (m, 2H), 1.07 (t, J = 7.4 Hz, 3H) F89 687 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.98-7.84 .sup.19F NMR (471 MHz, ([M H].sup.) (m, 1H), 7.80 (dd, J = 8.1, 1.7 Hz, 1H), CDCl.sub.3) 58.56, 66.16, 7.53 (d, J = 8.1 Hz, 1H), 7.44 (s, 2H), 69.29, 111.68 6.61 (d, J = 3.8 Hz, 2H), 5.86 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.34 (q, J = 6.6 Hz, 2H), 2.27-2.07 (m, 2H), 1.88-1.72 (m, 2H), 1.72-1.54 (m, 2H), 1.17-1.04 (m, 2H) F90 673 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.80 (dd, J = 8.0, 1.7 CDCl.sub.3) 58.66, 65.10 Hz, 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.44 (d, J = 10.7 Hz), 69.30, (s, 2H), 6.79 (t, J = 6.1 Hz, 1H), 6.59 (s, 111.97 1H), 5.86 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.8 Hz, 1H), 3.53 (q, J = 6.3 Hz, 2H), 2.34 (qt, J = 10.8, 6.5 Hz, 2H), 1.70-1.57 (m, 2H), 1.22-1.07 (m, 2H) F91 647 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.94-7.83 .sup.19F NMR (471 MHz, ([M H].sup.) (m, 1H), 7.79 (dd, J = 8.1, 1.7 Hz, 1H), CDCl.sub.3) 58.57, 69.30, 7.53 (d, J = 8.1 Hz, 1H), 7.44 (s, 2H), 111.96 (d, J = 32.3 Hz) 6.65 (s, 1H), 6.47 (t, J = 5.5 Hz, 1H), 5.85 (dd, J = 32.6, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.26 (ddd, J = 8.6, 7.4, 5.7 Hz, 2H), 1.66 (d, J = 3.0 Hz, 1H), 1.63-1.57 (m, 2H), 1.39 (q, J = 7.1 Hz, 2H), 1.18-1.00 (m, 2H), 0.91 (d, J = 6.6 Hz, 6H) F92 655 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.80 (dd, J = 8.2, 1.8 CDCl.sub.3) 58.70, 69.31, Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.44 96.76, 111.99 (s, 2H), 6.76 (t, J = 6.2 Hz, 1H), 6.54 (d, J = 32.5 Hz) (s, 1H), 5.85 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.68 (td, J = 13.6, 6.3 Hz, 2H), 1.71-1.65 (m, 2H), 1.60 (t, J = 18.6 Hz, 3H), 1.23-1.10 (m, 2H) F93 645 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.95-7.83 .sup.19F NMR (471 MHz, ([M H].sup.) (m, 1H), 7.79 (dd, J = 8.1, 1.7 Hz, 1H), CDCl.sub.3) 58.58, 69.30, 7.52 (d, J = 8.1 Hz, 1H), 7.44 (s, 2H), 112.02 6.71 (s, 1H), 6.49 (t, J = 5.7 Hz, 1H), 5.85 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.26 (dd, J = 7.3, 5.6 Hz, 2H), 2.45 (dt, J = 15.2, 7.5 Hz, 1H), 1.96-1.81 (m, 2H), 1.79-1.61 (m, 2H), 1.63-1.52 (m, 2H), 1.16-1.05 (m, 2H), 1.02 (d, J = 6.6 Hz, 2H) F94 615 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.80 (dd, J = 8.1, 1.7 CDCl.sub.3) 58.58, 69.30, Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.44 112.02 (s, 2H), 6.69 (t, J = 5.3 Hz, 1H), 6.65 (s, 1H), 5.86 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 4.04 (dd, J = 5.2, 2.6 Hz, 2H), 2.24 (t, J = 2.6 Hz, 1H), 1.73-1.59 (m, 2H), 1.21-1.06 (m, 2H) F95 641 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97-7.82 .sup.19F NMR (471 MHz, ([M H].sup.) (m, 1H), 7.79 (dd, J = 8.1, 1.7 Hz, 1H), CDCl.sub.3) 58.70, 69.30, 7.55 (d, J = 8.1 Hz, 1H), 7.44 (s, 2H), 111.99 (d, J = 32.8 Hz), 6.78 (t, J = 6.3 Hz, 1H), 6.60 (s, 1H), 123.08 (dd, J = 56.0, 6.06-5.55 (m, 2H), 4.61 (p, J = 8.9 Hz, 15.5 Hz) 1H), 3.66 (tdd, J = 15.0, 6.2, 4.0 Hz, 2H), 1.74-1.55 (m, 2H), 1.20-1.08 (m, 2H) F96 673 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.79 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.71 (dd, J = 8.1, 1.7 CDCl.sub.3) 58.98, 69.32 Hz, 1H), 7.47 (t, J = 4.1 Hz, 2H), 7.43 (d, J = 8.7 Hz), 72.64, (s, 2H), 5.81 (dd, J = 32.6, 9.6 Hz, 1H), 111.94 4.60 (p, J = 8.9 Hz, 1H), 4.11 (m, 2H), 3.27 (d, J = 31.4 Hz, 3H), 1.36-1.33 (m, 2H), 1.32-1.28 (m, 2H) F97 639 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.69 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 8.1 Hz, 1H), 7.58 (d, J = 1.7 Hz, CDCl.sub.3) 69.36, 72.58, 1H), 7.51 (dd, J = 8.3, 1.7 Hz, 1H), 7.42 111.68 (s, 2H), 6.87 (s, 1H), 5.78 (dd, J = 32.5, 9.6 Hz, 1H), 4.58 (p, J = 8.8 Hz, 1H), 4.29-4.09 (m, 2H), 3.32 (s, 3H), 1.58- 1.46 (m, 2H), 1.40-1.30 (m, 2H) F98 661 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86- .sup.19F NMR (471 MHz, ([M H].sup.) 7.77 (m, 2H), 7.71 (d, J = 8.1 Hz, 1H), CDCl.sub.3) 59.23, 69.32, 7.50 (d, J = 8.0 Hz, 1H), 7.44 (s, 2H), 72.55 (d, J = 8.6 Hz), 7.43-7.30 (m, 1H), 5.83 (ddd, J = 32.6, 109.09-114.80 (m) 9.6, 1.6 Hz, 1H), 4.84 (q, J = 7.2 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 3.85 (tdd, J = 15.0, 9.3, 6.6 Hz, 1H), 3.67 (dtd, J = 17.5, 8.9, 4.2 Hz, 1H), 1.87 (dt, J = 14.2, 7.1 Hz, 1H), 1.75 (dt, J = 14.1, 7.2 Hz, 1H), 0.94 (t, J = 7.4 Hz, 3H) F99 661 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (s, .sup.19F NMR (471 MHz, ([M + H].sup.+) 1H), 7.80 (dd, J = 8.1, 1.7 Hz, 1H), 7.58 CDCl.sub.3) 60.53, 69.32 (d, J = 8.1 Hz, 1H), 7.45 (s, 2H), 5.85 (d, J = 8.5 Hz), rotamers (dd, J = 32.6, 9.5 Hz, 1H), 4.94 (d, J = 69.96 (t, J = 8.8 Hz) & 16.1 Hz, 1H), 4.63 (p, J = 8.9 Hz, 1H), 70.49 (t, J = 8.4 Hz), 4.28 (d, J = 11.5 Hz, 1H), 4.18-3.78 (m, 111.88 (d, J = 33.2 Hz) 2H), 3.21 (s, 3H), 2.88 (s, 3H) F100 627 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.65 (dd, .sup.19F NMR (471 MHz, ([M H].sup.) J = 8.2, 4.5 Hz, 1H), 7.60 (dd, J = 3.9, CDCl.sub.3) 68.53-70.20 1.4 Hz, 1H), 7.50 (dt, J = 8.2, 2.1 Hz, (m), 72.49 (d, J = 9.9 1H), 7.43 (d, J = 4.4 Hz, 2H), 7.27 (d, Hz), 110.53-114.49 (m) J = 2.7 Hz, 1H), 7.09 (dd, J = 8.0, 4.4 Hz, 1H), 5.78 (dd, J = 32.5, 9.6 Hz, 1H), 4.87-4.66 (m, 1H), 4.69-4.41 (m, 1H), 4.10-3.92 (m, 1H), 3.85 (dtdd, J = 17.8, 8.9, 5.6, 3.2 Hz, 1H), 2.05-1.94 (m, 1H), 1.89-1.75 (m, 1H), 1.26 (qd, J = 5.2, 4.3, 2.3 Hz, 3H) F101 629 .sup.1H NMR (300 MHz, Methanol-d.sub.4) IR (thin film) ([M H].sup.) 8.07 (d, J = 1.6 Hz, 1H), 8.06-7.97 (m, 3289, 3082, 2362, 1H), 7.80 (d, J = 8.2 Hz, 1H), 7.78 (s, 1681, 1643, 1598, 2H), 6.48 (dd, J = 34.1, 9.8 Hz, 1H), 1552, 1246, 1165, 4.96 (q, J = 9.2 Hz, 1H), 4.28-4.07 (m, 1118, 811, 733, 1H), 3.05-2.80 (m, 2H), 2.78-2.46 (m, 672 cm.sup.1 2H), 1.63-1.42 (m, 2H), 1.21-1.03 (m, 2H) F102 619 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.93 IR (thin film) ([M H].sup.) (d, J = 7.6 Hz, 1H), 8.06 (s, 1H), 8.03 3404, 2929, 1664 cm.sup.1 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 7.6 Hz, 1H), 7.44 (s, 2H), 6.74 (dd, J = 36.0, 10.0 Hz, 1H), 4.98-4.89 (m, 1H), 4.32- 4.25 (m, 1H), 4.15-4.09 (m, 2H), 3.28 (s, 3H), 2.35 (s, 6H), 1.28 (d, J = 6.8 Hz, 3H) F103 605 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.77 IR (thin film) ([M H].sup.) (t, J = 6.0 Hz, 1H), 8.07 (s, 1H), 8.04 (s, 3399, 1661, 1167 cm.sup.1 1H), 7.68 (d, J = 8.0 Hz, 1H), 7.44 (s, 2H), 6.75 (dd, J = 36.0, 10.4 Hz, 1H), 4.94-4.89 (m, 1H), 4.22-4.16 (m, 4H), 3.14 (s, 3H), 2.32 (s, 6H) F104 675 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.86 (s, .sup.19F NMR (376 MHz, ([M + H].sup.+) 1H), 7.77 (m, 1H), 7.65 (d, J = 8.1 Hz, CDCl.sub.3) 59.08, 69.30 1H), 7.44 (s, 2H), 6.80 (d, J = 5.4 Hz, (d, J = 2.3 Hz), 69.76, 1H), 5.82 (dd, J = 32.6, 9.6 Hz, 1H), 111.87 (dd, J = 4.8, 4.56 (m, 2H), 4.17 (dq, J = 14.9, 8.9 Hz, 2.3 Hz) 1H), 3.92 (dq, J = 15.1, 9.0 Hz, 1H), 3.61 (dt, J = 11.8, 5.7 Hz, 1H), 3.49 (m, 1H), 2.81 (m, 1H), 2.04 (m, 2H), 1.68 (m, 1H) F105 590 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.79 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.12 (s, 1H), 8.08 (d, 3400, 2929, 1661, J = 8.1 Hz, 1H), 7.81 (s, 2H), 7.70-7.67 1171 cm.sup.1 (m, 2H), 6.87 (dd, J = 36.6, 10.5 Hz, 1H), 5.24-5.18 (m, 1H), 4.23-4.06 (m, 4H), 2.35 (s, 3H) F106 661 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.31 IR (thin film) ([M + H].sup.+) (d, J = 7.1 Hz, 1H), 8.14 (s, 1H), 8.08- 3421, 2925, 1731, 8.04 (m, 3H), 7.67 (d, J = 7.6 Hz, 1H), 769 cm.sup.1 6.87 (dd, J = 36.0, 10.4 Hz, 1H), 5.27- 5.22 (m, 1H), 5.10-5.03 (m, 1H), 4.71- 4.67 (m, 1H), 4.45-4.37 (m, 2H), 4.15- 4.11 (m, 1H) F107 88-93 685 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.89 ([M H].sup.) (t, J = 6.0 Hz, 1H), 8.64 (t, J = 6.4 Hz, 1H), 8.11 (s, 1H), 8.08 (d, J = 8.7 Hz, 2H), 7.86 (d, J = 8.4 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.62 (d, J = 8.4 Hz, 1H), 6.85 (dd, J = 35.7, 9.9 Hz, 1H), 5.19-5.18 (m, 1H), 4.02-3.90 (m, 4H) F108 725 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.26 IR (thin film) ([M H].sup.) (br s, 1H), 8.14 (s, 1H), 8.06 (d, J = 7.2 3429, 2925, 1667, Hz, 1H), 7.96 (s, 2H), 7.91 (s, 1H), 7.58 749 cm.sup.1 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 35.4, 9.9 Hz, 1H), 5.22-5.21 (m, 1H), 4.22- 4.21 (m, 2H), 3.17 (s, 3H), 1.08-1.02 (m, 2H), 0.85-0.81 (m, 2H) F109 655 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.85 IR (thin film) ([M H].sup.) (d, J = 7.2 Hz, 1H), 8.63 (t, J = 6.6 Hz, 3284, 2923, 1641, 1H), 8.11 (s, 1H), 8.06 (d, J = 8.1 Hz, 845 cm.sup.1 1H), 7.93 (s, 1H), 7.85 (s, 1H), 7.80 (s, 1H), 7.67 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 36.0, 10.2 Hz, 1H), 5.23-5.17 (m, 1H), 4.53-4.48 (m, 1H), 4.01-3.86 (m, 2H), 1.28 (d, J = 6.0 Hz, 3H) F110 677 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.89 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.63 (t, J = 6.4 Hz, 3330, 2927, 1660, 1H), 8.11-8.00 (m, 4H), 7.71 (d, J = 8.4 1163, 670 cm.sup.1 Hz, 1H), 6.84 (dd, J = 36.0, 10.4 Hz, 1H), 5.25-5.21 (m, 1H), 3.98-3.91 (m, 4H) F111 78-80 665 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.84 (s, ([M H].sup.) 1H) 7.79 (d, J = 8.0 Hz, 1H), 7.54 (d, J = 7.6 Hz, 1H), 7.41 (s, 1H), 7.36 (s, 1H), 6.72-6.64 (dd, J = 17.6, 12.0 Hz, 1H), 6.38 (br s, 1H), 5.88-5.74 (m, 2H), 4.61-4.56 (m, 1H), 4.22-4.15 (m, 2H), 3.33 (s, 3H), 1.25-1.17 (m, 3H), 0.89- 0.86 (m, 1H) F112 607 ([M H].sup.) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.83 (d, .sup.19F NMR (376 MHz, J = 1.7 Hz, 1H), 7.73 (dd, J = 8.1, 1.8 CDCl.sub.3) 59.16, 72.60, Hz, 1H), 7.52 (d, J = 8.0 Hz, 1H), 7.49 92.33-97.71 (m), (d, J = 2.1 Hz, 1H), 7.45 (d, J = 8.3 Hz, 115.49; 1H), 7.24 (dd, J = 8.4, 2.1 Hz, 1H), 7.18 IR (thin film) (t, J = 6.5 Hz, 1H), 6.63 (d, J = 7.7 Hz, 3286, 1647, 1543 cm.sup.1 1H), 5.94 (dd, J = 33.9, 9.8 Hz, 1H), 4.84 (p, J = 7.1 Hz, 1H), 4.31 (ddd, J = 15.8, 13.1, 9.7 Hz, 1H), 3.89 (qdd, J = 8.8, 6.4, 2.0 Hz, 2H), 1.68-1.55 (m, 3H), 1.51 (d, J = 7.0 Hz, 3H) F113 652 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.89 (s, IR (thin film) ([M + H].sup.+) 1H), 7.83 (d, J = 8.4 Hz, 1H), 7.58 (d, 3382, 2925, 1673, J = 8.4 Hz, 1H), 7.41 (s, 1H), 7.37 (s, 1160, 764 cm.sup.1 1H), 6.71-6.63 (m, 1H), 6.38 (br s, 1H), 5.93-5.74 (m, 2H), 4.63-4.57 (m, 1H), 4.02-3.86 (m, 2H), 1.19-1.17 (m, 2H), 0.90-0.86 (m, 2H) F114 657 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.30 IR (thin film) ([M + H].sup.+) (br s, 1H), 8.13 (s, 1H), 8.05 (d, J = 8.0 3437, 2924, 1667, Hz, 1H), 8.00 (d, J = 6.0 Hz, 2H), 7.59 750 cm.sup.1 (d, J = 8.7 Hz, 1H), 6.84 (dd, J = 35.6, 10.0 Hz, 1H), 5.24-5.23 (m, 1H), 4.21- 4.10 (m, 2H), 3.18 (s, 3H), 1.04-1.01 (m, 2H), 0.86-0.83 (m, 2H) F115 639 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.26 IR (thin film) ([M + H].sup.+) (s, 1H), 8.14 (s, 1H), 8.06 (d, J = 8.4 Hz, 3430, 2925, 1668, 1H), 7.80 (s, 2H), 7.69 (s, 1H), 7.59 (d, 749 cm.sup.1 J = 8.1 Hz, 1H), 6.87 (dd, J = 35.4, 9.9 Hz, 1H), 5.24-5.17 (m, 1H), 4.22 (br s, 2H), 3.17 (s, 3H), 1.08-1.00 (m, 2H), 0.85-0.83 (m, 2H) F116 667 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.10 IR (thin film) ([M H].sup.) (br s, 1H), 8.17-8.07 (m, 3H), 8.02 (d, 3421, 2925, 1667, J = 8.1 Hz, 1H), 7.93 (s, 1H), 7.84 (s, 1166, 750 cm.sup.1 1H), 7.80-7.79 (m, 1H), 6.87 (dd, J = 36.0, 9.9 Hz, 1H), 5.23-5.17 (m, 1H), 3.96-3.87 (m, 2H), 1.40-1.25 (m, 2H), 1.03-0.99 (m, 2H) F117 717 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.26 IR (thin film) ([M + H].sup.+) (s, 1H), 8.13 (s, 1H), 8.06-7.99 (m, 3H), 3429, 2920, 1260, 7.59 (d, J = 8.0 Hz, 1H), 6.85 (dd, J = 750 cm.sup.1 36.0, 10.4 Hz, 1H), 5.25-5.20 (m, 1H), 4.20-4.18 (m, 2H), 3.18 (s, 3H), 1.28- 1.23 (m, 2H), 1.03-0.99 (m, 2H) F118 761 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.26 IR (thin film) ([M + H].sup.+) (br s, 1H), 8.17-8.14 (m, 2H), 8.06 (d, 3442, 2931, 1667, J = 8.1 Hz, 1H), 7.95 (s, 1H), 7.59 (d, 748 cm.sup.1 J = 8.1 Hz, 1H), 6.87 (dd, J = 35.4, 9.3 Hz, 1H), 5.25-5.19 (m, 1H), 4.20-4.18 (m, 2H), 3.19 (s, 3H), 1.28-1.26 (m, 2H), 1.04-1.00 (m, 2H) F119 633 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.27 IR (thin film) ([M + H].sup.+) (s, 1H), 8.11 (s, 1H), 8.05 (d, J = 8.1 3436, 2925, 1637, Hz, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.44 750 cm.sup.1 (s, 2H), 6.87 (dd, J = 36.0, 10.2 Hz, 1H), 4.96-4.92 (m, 1H), 4.22-4.20 (m, 2H), 3.17 (s, 3H), 2.35 (s, 6H), 1.20- 0.98 (m, 2H), 0.82-0.79 (m, 2H) F120 640 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.24 IR (thin film) ([M + H].sup.+) (s, 1H), 8.14 (s, 1H), 8.06 (d, J = 8.4 3444, 2926, 1667, Hz, 1H), 7.99 (s, 1H), 7.75 (d, J = 8.4 1261 cm.sup.1 Hz, 1H), 7.67 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 8.1 Hz, 1H), 6.86 (dd, J = 36.0, 9.9 Hz, 1H), 5.21-5.15 (m, 1H), 4.23 (br s, 2H), 3.18 (s, 3H), 1.04-1.00 (m, 2H), 0.93-0.79 (m, 2H) F121 655 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.85 IR (thin film) ([M H].sup.) (d, J = 7.2 Hz, 1H), 8.63 (t, J = 6.6 Hz, 3284, 2923, 1641, 1H), 8.11 (s, 1H), 8.06 (d, J = 8.1 Hz, 845 cm.sup.1 1H), 7.93 (s, 1H), 7.85 (s, 1H), 7.80 (s, 1H), 7.67 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 36.0, 10.2 Hz, 1H), 5.23-5.17 (m, 1H), 4.53-4.48 (m, 1H), 4.01-3.86 (m, 2H), 1.28 (d, J = 6.0 Hz, 3H) F122 643 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.73 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.63 (t, J = 6.0 Hz, 3360, 2925, 1657, 1H), 8.12 (s, 1H), 8.08 (d, J = 8.1 Hz, 1163 cm.sup.1 1H), 7.93 (s, 1H), 7.85 (s, 1H), 7.80- 7.79 (m, 1H), 7.71 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 35.7, 10.2 Hz, 1H), 5.20- 5.17 (m, 1H), 4.04-3.90 (m, 4H) F123 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.74 (d, .sup.19F NMR (376 MHz, J = 1.5 Hz, 1H), 7.57-7.39 (m, 4H), CDCl.sub.3) 69.48 7.27-7.18 (m, 2H), 7.03 (d, J = 7.6 Hz, (d, J = 2.4 Hz), 72.40, 1H), 5.79 (dd, J = 32.8, 9.7 Hz, 1H), 112.78 4.88 (p, J = 7.1 Hz, 1H), 4.59 (dddt, J = 18.9, 14.3, 9.9, 4.9 Hz, 1H), 3.89 (qdd, J = 8.9, 6.3, 1.9 Hz, 2H), 1.54 (d, J = 7.0 Hz, 3H) F124 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.77 (d, .sup.19F NMR (376 MHz, J = 1.2 Hz, 1H), 7.59-7.35 (m, 6H), CDCl.sub.3) 69.47 7.31-7.18 (m, 1H), 5.80 (dd, J = 32.8, (d, J = 2.3 Hz), 72.33, 9.7 Hz, 1H), 4.61 (p, J = 9.1 Hz, 1H), 112.79 4.26 (d, J = 5.2 Hz, 2H), 4.01-3.85 (m, 2H) F125 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.75 (d, .sup.19F NMR (376 MHz, J = 1.7 Hz, 1H), 7.60-7.37 (m, 4H), CDCl.sub.3) 69.49 7.32-7.18 (m, 2H), 7.10 (t, J = 6.5 Hz, (d, J = 2.3 Hz), 72.61, 1H), 5.81 (dd, J = 32.8, 9.6 Hz, 1H), 112.79 4.61 (p, J = 8.9 Hz, 1H), 4.02-3.76 (m, 2H), 1.45 (q, J = 4.2 Hz, 2H), 0.88 (q, J = 4.2 Hz, 2H) F126 579 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.82 (d, .sup.19F NMR (471 MHz, ([M H].sup.) J = 1.8 Hz, 1H), 7.76-7.67 (m, 1H), 7.53 CDCl.sub.3) 59.29, 69.36 (d, J = 8.1 Hz, 1H), 7.44 (s, 2H), 7.13- (t, J = 7.3 Hz), 112.12 7.03 (m, 1H), 6.84 (s, 1H), 6.06 (s, 1H), (dd, J = 32.7, 8.2 Hz) 5.83 (dd, J = 32.6, 9.6 Hz, 1H), 4.72 (dt, J = 7.8, 6.6 Hz, 1H), 4.60 (p, J = 8.9 Hz, 1H), 1.93 (ddd, J = 13.8, 7.6, 6.2 Hz, 1H), 1.77 (dp, J = 14.4, 7.3 Hz, 1H), 0.98 (t, J = 7.4 Hz, 3H) F127 551 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.89-7.85 .sup.19F NMR (471 MHz, ([M H].sup.) (m, 1H), 7.78 (dd, J = 8.1, 1.8 Hz, 1H), CDCl.sub.3) 59.28, 69.31 7.62 (d, J = 8.1 Hz, 1H), 7.44 (s, 2H), (d, J = 8.4 Hz), 111.99 6.78 (t, J = 4.7 Hz, 1H), 6.22 (s, 1H), (d, J = 32.4 Hz) 5.83 (dd, J = 32.5, 9.6 Hz, 1H), 5.68- 5.58 (m, 1H), 4.61 (p, J = 8.9 Hz, 1H), 4.20 (s, 1H), 4.19 (s, 1H) F128 622 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (s, .sup.19F NMR (376 MHz, ([M + H].sup.+) 1H), 7.78 (d, J = 7.4 Hz, 1H), 7.53 (d, CDCl.sub.3) 58.69, 72.64, J = 7.9 Hz, 1H), 7.50-7.42 (m, 2H), 92.07-98.57 (m), 7.23 (d, J = 9.1 Hz, 1H), 6.92 (s, 1H), 115.55 6.32 (s, 1H), 5.96 (dd, J = 3.39 9.7 Hz, 1H), 4.37-4.25 (m, 1H), 3.94 (ddd, J = 18.3, 9.1, 6.5 Hz, 2H), 1.61 (t, J = 18.5 Hz, 3H), 1.25-1.18 (m, 2H), 1.03-0.94 (m, 1H), 0.92-0.84 (m, 1H) F129 596 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.6 Hz, 1H), 7.77 (dd, J = 8.1, 1.6 CDCl.sub.3) 59.21, 72.54, Hz, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.49 92.43-97.26 (m), (d, J = 2.1 Hz, 1H), 7.45 (d, J = 8.3 Hz, 115.50 1H), 7.24 (dd, J = 8.4, 2.1 Hz, 1H), 6.70 (d, J = 5.8 Hz, 1H), 6.61 (t, J = 5.3 Hz, 1H), 5.95 (dd, J = 34.0, 9.8 Hz, 1H), 4.31 (ddd, J = 15.8, 13.1, 9.8 Hz, 1H), 4.22 (dd, J = 5.4, 2.4 Hz, 2H), 4.01-3.88 (m, 2H), 1.62 (t, J = 18.4 Hz, 3H) F130 727 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.26 IR (thin film) ([M + H].sup.+) (br s, 1H), 8.14 (s, 1H), 8.09 (s, 1H), 3435, 2926, 1667, 8.05 (d, J = 8.0 Hz, 1H), 7.85 (s, 1H), 749 cm.sup.1 7.61-7.56 (m, 2H), 6.84 (dd, J = 36.0, 10.0 Hz, 1H), 5.18-5.13 (m, 1H), 4.22- 4.21 (m, 2H), 3.17 (s, 3H), 1.04-1.02 (m, 2H), 0.85-0.83 (m, 2H) F131 609 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.10 IR (thin film) ([M + H].sup.+) (s, 1H), 8.63 (t, J = 8.4 Hz, 1H), 8.15- 3458, 2926, 1671, 8.11 (m, 2H), 8.09 (d, J = 9.2 Hz, 1H), 1167 cm.sup.1 7.99-7.94 (m, 1H), 7.51 (d, J = 9.2 Hz, 1H), 7.69 (s, 1H), 6.84 (dd, J = 36.0, 10.0 Hz, 1H), 5.18-5.14 (m, 1H), 3.95- 3.91 (m, 2H), 1.03-1.01 (m, 2H), 0.85- 0.81 (m, 2H) F132 595 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.84 IR (thin film) ([M H].sup.) (d, J = 7.2 Hz, 1H), 8.64 (t, J = 6.4 Hz, 3428, 2925, 1650, 1H), 8.10 (s, 1H), 8.05 (d, J = 8.0 Hz, 1167 cm.sup.1 1H), 7.97 (d, J = 6.4 Hz, 1H), 7.68-7.64 (m, 2H), 7.53-7.48 (m, 1H), 6.83 (dd, J = 36.0, 10.4 Hz, 1H), 5.18-5.13 (m, 1H), 4.52-4.49 (m, 1H), 3.99-3.87 (m, 2H), 1.30 (d, J = 7.2 Hz, 3H) F133 639 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.26 IR (thin film) ([M + H].sup.+) (s, 1H), 8.14 (s, 1H), 8.06 (d, J = 8.4 Hz, 3430, 2925, 1668, 1H), 7.80 (s, 2H), 7.69 (s, 1H), 7.59 (d, 749 cm.sup.1 J = 8.1 Hz, 1H), 6.87 (dd, J = 35.4, 9.9 Hz, 1H), 5.24-5.17 (m, 1H), 4.22 (br s, 2H), 3.17 (s, 3H), 1.08-1.00 (m, 2H), 0.85-0.83 (m, 2H) F134 633 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.27 IR (thin film) ([M + H].sup.+) (s, 1H), 8.11 (s, 1H), 8.05 (d, J = 8.1 3436, 2925, 1637, Hz, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.44 750 cm.sup.1 (s, 2H), 6.87 (dd, J = 36.0, 10.2 Hz, 1H), 4.96-4.92 (m, 1H), 4.22-4.20 (m, 2H), 3.17 (s, 3H), 2.35 (s, 6H), 1.20- 0.98 (m, 2H), 0.82-0.79 (m, 2H) F135 640 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.24 IR (thin film) ([M + H].sup.+) (s, 1H), 8.14 (s, 1H), 8.06 (d, J = 8.4 3444, 2926, 1667, Hz, 1H), 7.99 (s, 1H), 7.75 (d, J = 8.4 1261 cm.sup.1 Hz, 1H), 7.67 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 8.1 Hz, 1H), 6.86 (dd, J = 36.0, 9.9 Hz, 1H), 5.21-5.15 (m, 1H), 4.23 (br s, 2H), 3.18 (s, 3H), 1.04-1.00 (m, 2H), 0.93-0.79 (m, 2H) F136 609 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.10 IR (thin film) ([M + H].sup.+) (s, 1H), 8.17 (t, J = 7.4 Hz, 1H), 8.11 (s, 3431, 2925, 1650 cm.sup.1 1H), 8.08 (d, J = 7.6 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 10.4 Hz, 1H), 7.71 (d, J = 8.4 Hz, 1H), 7.55 (d, J = 8.4 Hz, 1H), 6.81 (dd, J = 35.6, 9.6 Hz, 1H), 5.20-5.15 (m, 1H), 3.95-3.91 (m, 2H), 1.23-1.08 (m, 2H), 0.86-0.81 (m, 2H) F137 657 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.79 IR (thin film) ([M + H].sup.+) (t, J = 5.6 Hz, 1H), 8.12 (br s, 1H), 8.08 3412, 2924, 1660, (d, J = 7.6 Hz, 1H), 7.93 (s, 1H), 7.85 1260, 750 cm.sup.1 (s, 1H), 7.79 (s, 1H), 7.69 (d, J = 8.0 Hz, 1H), 6.85 (dd, J = 35.6, 9.6 Hz, 1H), 5.23-5.18 (m, 1H), 4.22-4.16 (m, 4H), 3.14 (s, 3H) F138 657 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.83 IR (thin film) ([M + H].sup.+) (d, J = 7.8 Hz, 1H), 8.62 (t, J = 6.0 Hz, 3310, 1653, 1169 cm.sup.1 1H), 8.12-8.03 (m, 3H), 7.71-7.64 (m, 3H), 6.85 (dd, J = 36.0, 9.9 Hz, 1H), 5.20-5.14 (m, 1H), 4.53-4.48 (m, 1H), 4.01-3.89 (m, 2H), 1.30 (d, J = 7.2 Hz, 3H) F139 669 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.10 IR (thin film) ([M + H].sup.+) (s, 1H), 8.16-8.00 (m, 5H), 7.71 (s, 2H), 3459, 1667, 1165 cm.sup.1 6.84 (dd, J = 36.0, 10.0 Hz, 1H), 5.20- 5.16 (m, 1H), 3.95-3.91 (m, 2H), 1.38- 1.33 (m, 2H), 1.08-1.02 (m, 2H) F140 659 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.86 IR (thin film) ([M + H].sup.+) (s, 1H), 7.79 (d, J = 9.0 Hz, 1H), 7.61- 3431, 2922, 1663, 7.60 (m, 1H), 7.45 (s, 2H), 6.94-6.87 1260, 749 cm.sup.1 (m, 1H), 6.48 (d, J = 15.6 Hz, 1H), 5.89 (dd, J = 9.6 Hz, 32.4 Hz, 1H), 5.05-5.00 (m, 1H), 4.63-4.60 (m, 1H), 3.11-3.05 (m, 2H), 1.49 (d, J = 7.2 Hz, 3H) F141 631 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.84 IR (thin film) ([M + H].sup.+) (d, J = 7.8 Hz, 1H), 8.65 (t, J = 6.3 Hz, 3281, 3098, 1644 cm.sup.1 1H), 8.10 (s, 2H), 8.06 (d, J = 8.1 Hz, 2H), 7.67-7.60 (m, 2H), 6.91 (dd, J = 9.9, 36.0 Hz, 1H), 5.35-5.28 (m, 1H), 4.53-4.48 (m, 1H), 4.02-3.86 (m, 2H), 1.30 (d, J = 6.9 Hz, 3H) F142 661 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.85 IR (thin film) ([M + H].sup.) (d, J = 9.0 Hz 1H), 8.63 (t, J = 6.0 Hz, 1731, 1267, 1049 cm.sup.1 1H), 8.13 (s, 1H), 8.09-8.00 (m, 4H), 7.65 (t, J = 8.1 Hz, 1H), 6.88-6.72 (m, 1H), 5.37-5.24 (m, 1H), 4.51 (t, J = 9.0 Hz, 1H), 4.05-3.84 (m, 2H), 1.29 (d, J = 6.0 Hz, 3H) F143 677 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.30 IR(thin film) ([M + H].sup.+) (d, J = 9.3 Hz, 1H), 8.14 (s, 1H), 8.07 1732, 1266, 1173, (d, J = 6.0 Hz, 1H), 8.02 (br s, 2H), 7.67 1049 cm.sup.1 (d, J = 8.1 Hz, 1H), 7.44 (t, J = 52.2 Hz, 1H), 6.89-6.74 (m, 1H), 5.30 (t, J = 9.0 Hz, 1H), 5.11-5.02 (m, 1H), 4.77 (t, J = 9.0 Hz, 1H), 4.43-4.33 (m, 2H), 4.13 (t, J = 6.3 Hz, 1H) F144 613 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.86 (s, IR (thin film) ([M + H].sup.+) 1H), 7.79 (d, J = 8.0 Hz, 1H), 7.58 (d, 3462, 1682, 1116 cm.sup.1 J = 8.0 Hz, 1H), 7.49 (s, 1H), 7.47 (s, 1H), 7.26-7.21 (m, 1H), 6.64-6.60 (m, 1H), 6.33 (d, J = 7.6 Hz, 1H), 5.91 (dd, J = 9.6, 32.0 Hz, 1H), 4.73-4.61 (m, 1H), 4.20-4.15 (m, 1H), 3.98-3.90 (m, 2H), 1.33-1.28 (m, 3H) F145 717 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.26 IR (thin film) ([M + H].sup.+) (s, 1H), 8.13 (s, 1H), 8.06-7.99 (m, 3H), 3429, 2920, 1260, 7.59 (d, J = 8.0 Hz, 1H), 6.85 (dd, J = 750 cm.sup.1 10.4, 36.0 Hz, 1H), 5.25-5.20 (m, 1H), 4.20-4.18 (m, 2H), 3.18 (s, 3H), 1.28- 1.23 (m, 2H), 1.03-0.99 (m, 2H) F146 653 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.84 IR (thin film) ([M + H].sup.+) (d, J = 8.0 Hz, 1H), 8.63 (t, J = 6.4 Hz, 3429, 2998, 1660, 1H), 8.11 (s, 1H), 8.06 (d, J = 8.4 Hz, 1030 cm.sup.1 1H), 7.84-7.81 (m, 2H), 7.68 (d, J = 5.6 Hz, 1H), 6.84 (dd, J = 10.0, 36.0 Hz, 1H), 5.92-5.83 (m, 1H), 5.19-5.15 (m, 1H), 5.09 (d, J = 8.4 Hz, 1H), 4.98 (d, J = 17.2 Hz, 1H), 4.54-4.47 (m, 1H), 4.03-3.85 (m, 2H), 3.64 (d, J = 6.0 Hz, 2H), 1.30 (d, J = 7.6 Hz, 3H) F147 653 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.84 IR (thin film) ([M + H].sup.+) (d, J = 8.0 Hz, 1H), 8.63 (t, J = 6.4 Hz, 3307, 2925, 1660, 1H), 8.12 (s, 1H), 8.06 (d, J = 6.4 Hz, 1117, 672 cm.sup.1 1H), 7.87-7.81 (m, 2H), 7.67 (d, J = 8.4 Hz, 1H), 6.86 (dd, J = 10.0, 36.0 Hz, 1H), 6.34-6.19 (m, 1H), 6.07-6.01 (m, 1H), 5.22-5.15 (m, 1H), 4.55-4.47 (m, 1H), 4.03-3.85 (m, 2H), 1.51-1.49 (m, 3H), 1.30 (d, J = 6.8 Hz, 3H) F148 653 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.88 IR (thin film) ([M + H].sup.+) (d, J = 7.5 Hz, 1H), 8.65 (t, J = 6.3 Hz, 3435, 2999, 1660, 1H), 8.12 (s, 1H), 8.06 (d, J = 8.4 Hz, 1027 cm.sup.1 1H), 7.86 (s, 2H), 7.67 (d, J = 8.1 Hz, 1H), 6.88 (dd, J = 9.9, 35.7 Hz, 1H), 5.43 (s, 1H), 5.23-5.17 (m, 1H), 4.93 (s, 1H), 4.53-4.48 (m, 1H), 4.04-3.86 (m, 2H), 1.97 (s, 3H), 1.30 (d, J = 6.9 Hz, 3H) F150 645 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.31 IR (thin film) ([M + H].sup.+) (d, J = 7.8 Hz, 1H), 8.14 (s, 2H), 8.08 3854, 3418, 2926, (d, J = 7.8 Hz, 2H), 7.67-7.60 (m, 2H), 2350, 1641 cm.sup.1 6.93 (dd, J = 10.8, 35.6 Hz, 1H), 5.35- 5.29 (m, 1H), 5.11-5.09 (m, 1H), 4.70- 4.66 (m, 1H), 4.66-4.36 (m, 2H), 4.16- 4.10 (m, 1H) F153 601 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.87 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.62 (t, J = 6.3 Hz, 3306, 1661, 1166, 1H), 8.11 (s, 1H), 8.07 (d, J = 8.1 Hz, 750 cm.sup.1 1H), 7.91-7.85 (m, 2H), 7.72 (d, J = 8.1 Hz, 1H), 6.83 (dd, J = 9.9, 35.7 Hz, 1H), 5.24-5.18 (m, 1H), 4.04-3.87 (m, 4H) F154 615 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.83 IR (thin film) ([M + H].sup.+) (d, J = 7.8 Hz, 1H), 8.61 (t, J = 6.0 Hz, 3422, 2928, 1651, 1H), 8.08-8.00 (m, 2H), 7.89-7.83 (m, 750 cm.sup.1 2H), 7.66 (d, J = 7.8 Hz, 1H), 6.81 (dd, J = 10.5, 36.0 Hz, 1H), 5.22-5.15 (m, 1H), 4.52-4.47 (m, 1H), 4.01-3.84 (m, 2H), 1.28 (d, J = 7.5 Hz, 3H) F155 613 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.32 IR (thin film) ([M + H].sup.+) (d, J = 8.1 Hz, 1H), 8.14 (s, 1H), 8.07 1674, 1171 cm.sup.1 (d, J = 8.1 Hz, 1H), 7.77-7.72 (m, 2H), 7.68 (d, J = 8.1 Hz, 1H), 6.83 (dd, J = 9.9, 35.7 Hz, 1H), 5.22-5.16 (m, 1H), 5.11-5.02 (m, 1H), 4.72-4.66 (m, 1H), 4.44-4.33 (m, 2H), 4.16-4.10 (m, 1H) F157 583 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.87 IR (thin film) ([M + H].sup.+) (t, J = 5.7 Hz, 1H), 8.62 (t, J = 6.0 Hz, 3309, 1697, 750 cm.sup.1 1H), 8.12 (s, 1H), 8.08 (d, J = 7.8 Hz, 1H), 7.71-7.60 (m, 3H), 7.52 (d, J = 8.4 Hz, 1H), 6.85 (dd, J = 9.9, 36.0 Hz, 1H), 5.24-5.17 (m, 1H), 4.02-3.82 (m, 4H) F158 595 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.88 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.63 (t, J = 6.0 Hz, 3306, 2925, 1661, 1H), 8.11 (s, 1H), 8.07 (d, J = 7.5 Hz, 1166, 750 cm.sup.1 1H), 7.76 (s, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.59 (d, J = 9.0 Hz, 1H), 7.21 (d, J = 8.4 Hz, 1H), 6.84 (dd, J = 10.2, 36.3 Hz, 1H), 5.04-4.98 (m, 1H), 4.02-3.92 (m, 4H), 3.87 (s, 3H) F159 599 .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.84 IR (thin film) ([M + H].sup.+) (d, J = 8.0 Hz, 1H), 8.63 (t, J = 6.4 Hz, 3291, 1651, 1168, 1H), 8.10 (s, 1H), 8.04 (d, J = 8.4 Hz, 673 cm.sup.1 1H), 7.76-7.73 (m, 2H), 7.68 (d, J = 8.0 Hz, 1H), 6.78 (dd, J = 9.6, 35.6 Hz, 1H), 5.23-5.14 (m, 1H), 4.55-4.53 (m, 1H), 4.03-3.83 (m, 2H), 1.30 (d, J = 7.2 Hz, 3H) F160 585 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.87 IR (thin film) ([M + H].sup.+) (t, J = 5.7 Hz, 1H), 8.62 (t, J = 6.3 Hz, 3303, 1667, 1166, 1H), 8.11-8.04 (m, 2H), 7.77-7.66 (m, 749 cm.sup.1 3H), 6.81 (dd, J = 10.2, 36.0 Hz, 1H), 5.22-5.16 (m, 1H), 4.02-3.92 (m, 4H) F161 609 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.84 IR (thin film) ([M + H].sup.+) (d, J = 7.5 Hz, 1H), 8.64 (t, J = 6.0 Hz, 3421, 2924, 1650, 1H), 8.10 (s, 1H), 8.05 (d, J = 9.0 Hz, 1260 cm.sup.1 1H), 7.75 (s, 1H), 7.66 (d, J = 8.1 Hz, 1H), 7,59 (d, J = 7.8 Hz, 1H), 7.21 (d, J = 8.7 Hz, 1H), 6.83 (dd, J = 9.9, 35.7 Hz, 1H), 5.04-4.98 (m, 1H), 4.53-4.48 (m, 1H), 4.04-3.92 (m, 2H), 3.87 (s, 3H), 1.30 (d, J = 7.2 Hz, 3H) F162 677 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.84 IR (thin film) ([M + H].sup.+) (d, J = 7.2 Hz, 1H), 8.63 (t, J = 5.7 Hz, 3297, 2925, 1656, 1H), 8.10 (s, 1H), 8.05 (d, J = 7.8 Hz, 1167, 750 cm.sup.1 1H), 7.83 (s, 1H), 7.67-7.61 (m, 2H), 7.35 (d, J = 8.4 Hz, 1H), 6.84 (dd, J = 10.2, 36,0 Hz, 1H), 5.09-5.03 (m, 1H), 4.94-4.85 (m, 2H), 4.53-4.48 (m, 1H), 4.04-3.80 (m, 2H), 1.30 (d, J = 6.9 Hz, 3H) F163 607 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.75 IR (thin film) ([M + H].sup.+) (t, J = 6.0 Hz, 1H), 8.14 (t, J = 5.7 Hz, 3422, 1671, 842 cm.sup.1 1H), 7.94 (s, 1H), 7.90 (d, J = 7.5 Hz, 1H), 7.80 (s, 2H), 7.61 (d, J = 7.8 Hz, 1H), 7.06 (dd, J = 9.9, 36.0 Hz, 1H), 4.30-4.27 (m, 1H), 3.97-3.88 (m, 4H), 2.08 (s, 3H) F164 607 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.84 IR (thin film) ([M + H].sup.+) (d, J = 7.2 Hz, 1H), 8.64 (t, J = 6.3 Hz, 3425, 2925, 1651, 1H), 8.10 (s, 1H), 8.06 (d, J = 8.4 Hz, 1275, 750 cm.sup.1 1H), 7.73 (s, 1H), 7.66 (d, J = 8.1 Hz, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.42 (d, J = 8.1 Hz, 1H), 6.84 (dd, J = 9.9, 36.0 Hz, 1H), 5.08-5.02 (m, 1H), 4.53-4.48 (m, 1H), 3.99-3.85 (m, 2H), 2.74-2.66 (m, 2H), 1.30 (d, J = 7.2 Hz, 3H), 1.19 (t, J = 7.2 Hz, 3H) F165 593 .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.89 IR (thin film) ([M + H].sup.+) (t, J = 6.3 Hz, 1H), 8.64 (t, J = 6.6 Hz, 3386, 2926, 1657, 1H), 8.11 (s, 1H), 8.08 (d, J = 8.1 Hz, 750 cm.sup.1 1H), 7.73 (s, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.56 (d, J = 7.8 Hz, 1H), 7.42 (d, J = 7.8 Hz, 1H), 6.85 (dd, J = 9.9, 36.0 Hz, 1H), 5.09-5.02 (m, 1H), 4.02-3.90 (m, 4H), 2.74-2.67 (m, 2H), 1.17 (t, J = 7.5 Hz, 3H) F166 648 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.7 Hz, 1H), 7.80 (dd, J = 8.1, 1.7 CDCl.sub.3) 59.30, 69.32, Hz, 1H), 7.61 (d, J = 8.1 Hz, 1H), 7.44 75.38, 111.93; (s, 2H), 6.84 (d, J = 9.6 Hz, 1H), 5.84 IR (thin film) (dd, J = 32.5, 9.6 Hz, 1H), 5.26-5.10 1667, 1258, 1208, (m, 1H), 4.68-4.50 (m, 1H), 3.75 (s, 3 1173, 1118, 807, H), 2.92-2.69 (m, 2H) 666 cm.sup.1 F167 661 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.87 (d, IR (thin film) ([M + H].sup.+) J = 1.6 Hz, 1H), 7.78 (dd, J = 8.1, 1.7 1654, 1141, 1118 cm.sup.1 Hz, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.44 (s, 2H), 6.92 (t, J = 4.2 Hz, 1H), 5.83 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), major rotamer 4.36 (d, J = 4.1 Hz, 2H), minor rotamer 4.28 (d, J = 4.2 Hz, 1H), major rotamer 4.06 (q, J = 8.8 Hz, 2H), minor rotamer 3.89 (q, J = 8.3 Hz, 1H), minor rotamer 3.57 (q, J = 7.1 Hz, 1H), major rotamer 3.51 (q, J = 7.2 Hz, 2H), major rotamer 1.29 (t, J = 7.2 Hz, 2H), minor rotamer 1.19 (t, J = 7.1 Hz, 1H). F168 657 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (471 MHz, ([M + H].sup.+) J = 1.6 Hz, 1H), 7.76 (dd, J = 8.1, 1.7 Hz, 1H), 7.55 (d, J = 8.1 Hz, 1H), 7.44 CDCl.sub.3) 59.04, 69.30 (s, 2H), 7.41 (d, J = 7.0 Hz, 1H), 6.94 (d, J = 8.6 Hz), 84.57 (d, J = 7.7 Hz, 1H), 5.84 (dd, J = 32.5, (dtt, J = 199.2, 12.8, 9.6 Hz, 1H), 4.79 (p, J = 7.1 Hz, 1H), 6.4 Hz), 97.82-98.39 4.61 (p, J = 8.9 Hz, 1H), 4.20-4.09 (m, (m), 112.06 (d, J = 1H), 2.97-2.80 (m, 2H), 2.52-2.34 (m, 32.8 Hz); 2H), 1.49 (d, J = 6.9 Hz, 3H) IR (thin film) 1640. 1174, 1138, 1118, 732 cm.sup.1 F169 665 .sup.1H NMR (300 MHz, CDCl.sub.3) 9.36 (s, IR (thin film) ([M + H].sup.+) 1H), 7.85 (s, 1H), 7.76 (d, J = 8.3 Hz, 1641 cm.sup.1 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.44 (s, 2H), 6.70 (d, J = 7.4 Hz, 1H), 5.83 (dd, J = 32.5, 9.6 Hz, 1H), 5.34 (m, 1H), 4.60 (p, J = 8.8 Hz, 1H), 4.30 (dt, J = 17.0, 8.4 Hz, 1H), 4.15 (dq, J = 16.8, 8.6 Hz, 1H), 1.52 (d, J = 6.9 Hz, 3H) F170 643 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.85 (d, IR (thin film) ([M + H].sup.+) J = 1.7 Hz, 1H), 7.76 (m, 1H), 7.56 (d, 1648 cm.sup.1 J = 8.1 Hz, 1H), 7.39 (m, 5H), 6.99 (m, 2H), 6.91 (m, 2H), 6.47 (d, J = 7.5 Hz, 1H), 5.83 (dd, J = 32.8, 9.8 Hz, 1H), 5.06 (s, 2H), 4.78 (p, J = 7.0 Hz, 1H), 4.59 (p, J = 9.0 Hz, 1H), 3.90 (dq, J = 11.7, 9.0, 6.5 Hz, 2H), 1.52 (d, J = 7.0 Hz, 3H) F171 661 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.86 (s, IR (thin film) ([M + H].sup.+) 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.65 (d, 1661 cm.sup.1 J = 8.1 Hz, 1H), 7.44 (s, 2H), 6.41 (d, J = 5.3 Hz, 1H), 5.83 (dd, J = 32.5, 9.6 Hz, 1H), 4.59 (m, 2H), 4.08 (dq, J = 14.9, 9.0 Hz, 1H), 3.83 (m, 1H), 3.59 (m, 2H), 2.95 (m, 1H), 2.08 (m, 1H) F172 HRMS-ESI (m/z) .sup.1H NMR (500 MHz, DMSO-d.sub.6) 8.82 IR (thin film) [M + H].sup.+ calcd for (dd, J = 7.8, 1.5 Hz, 1H), 8.13-8.09 (m, 3261, 3061, 1637, C.sub.23H.sub.18Cl.sub.3F.sub.7N.sub.2O.sub.2, 1H), 8.05 (s, 2H), 8.03 (dd, J = 8.1, 1.7 1552 cm.sup.1 593.0395; Hz, 1H), 7.60 (d, J = 8.1 Hz, 1H), 6.79 found, 593.0402 (dd, J = 35.8, 10.1 Hz, 1H), 5.25 (p, J = 9.4 Hz, 1H), 4.91 (p, J = 7.0 Hz, 1H), 3.08 (s, 3H), 2.86 (s, 3H), 1.25 (d, J = 6.9 Hz, 3H) F173 HRMS-ESI (m/z) .sup.1H NMR (500 MHz, DMSO-d.sub.6) 8.73 IR (thin film) [M + H].sup.+ calcd for (dd, J = 7.6, 1.3 Hz, 1H), 8.10 (d, J = 1652, 1552 cm.sup.1 C.sub.22H.sub.16Cl.sub.3F.sub.7N.sub.2O.sub.2, 1.6 Hz, 1H), 8.04 (d, J = 10.4 Hz, 3H), 579.0238; 7.88 (q, J = 4.7 Hz, 1H), 7.70 (d, J = found, 579.0241 8.1 Hz, 1H), 6.79 (dd, J = 35.7, 10.1 Hz, 1H), 5.25 (p, J = 9.4 Hz, 1H), 4.42 (p, J = 7.2 Hz, 1H), 2.63 (d, J = 4.6 Hz, 3H), 1.27 (d, J = 7.1 Hz, 3H) F174 659 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.83 (d, .sup.19F NMR (471 MHz, ([M + H].sup.+) J = 1.8 Hz, 1H), 7.74 (dt, J = 8.4, 2.5 CDCl.sub.3) 59.09, 72.58, Hz, 1H), 7.53 (dd, J = 8.1, 4.4 Hz, 1H), 103.79-105.98 (m), 7.42 (d, J = 3.0 Hz, 2H), 7.20 (t, J = 6.5 115.07 Hz, 1H), 6.64 (dd, J = 7.7, 4.9 Hz, 1H), 5.90 (ddd, J = 33.9, 9.7, 2.6 Hz, 1H), 4.95-4.78 (m, 1H), 4.31 (td, J = 14.6, 9.8 Hz, 1H), 3.88 (tt, J = 9.1, 7.4 Hz, 2H), 1.95-1.78 (m, 2H), 1.51 (dd, J = 7.0, 1.4 Hz, 3H), 1.07 (t, J = 7.4 Hz, 3H) F175 643 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (s, .sup.19F NMR (376 MHz, ([M + H].sup.+) 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.56 (d, CDCl.sub.3) 59.18, 69.26 J = 8.1 Hz, 1H), 7.50 (s, 1H), 7.47 (s, (d, J = 2.1 Hz), 72.60, 1H), 7.42 (s, 1H), 7.06 (t, J = 6.4 Hz, 88.20 (d, J = 7.0 Hz), 1H), 6.59 (d, J = 7.6 Hz, 1H), 5.88 (dd, 112.61; J = 32.6, 9.7 Hz, 1H), 4.82 (p, J = 7.0 IR (thin film) Hz, 1H), 4.69 (p, J = 8.9 Hz, 1H), 3.98- 3288, 1729, 1647 cm.sup.1 3.83 (m, 2H), 1.93 (t, J = 18.2 Hz, 3H), 1.52 (d, J = 7.0 Hz, 3H) F176 661 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (s, .sup.19F NMR (376 MHz, ([M + H].sup.+) 1H), 7.79 (d, J = 8.0 Hz, 1H), 7.58 (d, CDCl.sub.3) 59.10, 65.69, J = 8.0 Hz, 1H), 7.39 (s, 1H), 7.32 (s, 69.28 (d, J = 2.2 Hz), 1H), 7.22 (s, 1H), 6.63 (s, 1H), 6.31 (d, 72.58, 112.78; J = 8.4 Hz, 1H), 5.87 (dd, J = 32.5, 9.8 IR (thin film) Hz, 1H), 4.77-4.59 (m, 2H), 4.04-3.87 3272, 1640, 1539 cm.sup.1 (m, 2H), 3.38 (q, J = 10.4 Hz, 2H), 1.51 (d, J = 7.0 Hz, 3H) F177 643 .sup.1H NMR (500 MHz, CDCl.sub.3) 7.87 (s, .sup.19F NMR (471 MHz, ([M + H].sup.+) 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.63 (d, CDCl.sub.3) 59.03, 70.32, J = 8.1 Hz, 1H), 7.40 (s, 2H), 6.51 (d, 113.08, 118.37-123.39 J = 4.5 Hz, 1H), 6.01 (td, J = 55.7, 2.9 (m) Hz, 1H), 5.84 (dd, J = 33.9, 9.5 Hz, 1H), 5.02 (t, J = 8.4 Hz, 1H), 4.97-4.91 (m, 1H), 4.36 (tdd, J = 15.8, 9.4, 2.8 Hz, 1H), 4.28-4.07 (m, 3H) F178 675 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.89 (s, IR (thin film) ([M + H].sup.+) 1H), 7.81 (d, J = 8.0 Hz, 1H), 7.64 (d, 3268, 1728, 1659, J = 8.3 Hz, 1H), 7.40 (s, 1H), 7.33 (s, 1538 cm.sup.1 1H), 7.22 (s, 1H), 6.39 (s, 1H), 5.88 (dd, J = 32.6, 9.7 Hz, 1H), 5.04 (t, J = 8.2 Hz, 1H), 5.00-4.87 (m, 1H), 4.74- 4.56 (m, 1H), 4.33-4.05 (m, 3H), 3.39 (q, J = 10.6 Hz, 2H) F180 661 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (s, .sup.19F NMR (376 MHz, ([M + H].sup.+) 1H), 7.81 (d, J = 8.2 Hz, 1H), 7.74 (d, CDCl.sub.3) 59.03, 62.80, J = 8.2 Hz, 1H), 7.65 (d, J = 8.0 Hz, 69.07 (d, J = 2.2 Hz), 1H), 7.57 (s, 1H), 7.43 (d, J = 7.7 Hz, 70.29, 112.11; 1H), 6.37 (s, 1H), 5.89 (dd, J = 32.6, IR (thin film) 9.6 Hz, 1H), 5.04 (t, J = 8.4 Hz, 1H), 3268, 1669, 1533 cm.sup.1 4.99-4.90 (m, 1H), 4.71 (p, J = 9.0 Hz, 1H), 4.31-4.07 (m, 3H) F181 663 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.6 Hz, 1H), 7.83-7.76 (m, 1H), CDCl.sub.3) 57.94, 59.15, 7.58 (d, J = 8.1 Hz, 1H), 7.35 (s, 1H), 69.27 (d, J = 2.5 Hz), 7.27 (s, 1H), 7.17 (s, 1H), 6.86 (t, J = 72.59, 112.15 (d, 6.3 Hz, 1H), 6.47 (d, J = 7.5 Hz, 1H), J = 2.6 Hz); 5.85 (dd, J = 32.5, 9.7 Hz, 1H), 4.78 (p, IR (thin film) J = 7.1 Hz, 1H), 4.66 (p, J = 8.9 Hz, 3284, 1652, 1540 cm.sup.1 1H), 3.93 (qd, J = 8.9, 6.4 Hz, 2H), 1.52 (d, J = 7.0 Hz, 3H) F182 663 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.5 Hz, 1H), 7.78 (dd, J = 8.3, 1.7 CDCl.sub.3) 57.82, 59.15, Hz, 1H), 7.57 (d, J = 8.1 Hz, 1H), 7.53 69.39 (d, J = 2.2 Hz), (d, J = 1.6 Hz, 1H), 7.39-7.31 (m, 2H), 72.59, 112.62 (d, J = 6.86 (s, 1H), 6.46 (d, J = 7.5 Hz, 1H), 2.3 Hz); 5.87 (dd, J = 32.6, 9.7 Hz, 1H), 4.78 (p, IR (thin film) J = 7.1 Hz, 1H), 4.67 (p, J = 8.9 Hz, 3285, 1648, 1545, 1H), 3.92 (qd, J = 9.0, 6.4 Hz, 2H), 1497 cm.sup.1 1.52 (d, J = 7.0 Hz, 3H) F183 663 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.4 Hz, 1H), 7.78 (d, J = 8.2 Hz, CDCl.sub.3) 57.85, 59.15, 1H), 7.58 (d, J = 8.1 Hz, 1H), 7.52 (d, 69.52 (d, J = 2.4 Hz), J = 8.4 Hz, 1H), 7.36 (s, 1H), 7.31 (dd, 72.59, 112.31; J = 8.3, 2.1 Hz, 1H), 6.78 (t, J = 6.4 Hz, IR (thin film) 1H), 6.42 (d, J = 7.5 Hz, 1H), 5.86 (dd, 3284, 1646, 1540, J = 32.6, 9.6 Hz, 1H), 4.76 (p, J = 7.2 1491 cm.sup.1 Hz, 1H), 4.66 (q, J = 8.9 Hz, 1H), 4.00- 3.87 (m, 2H), 1.51 (d, J = 7.0 Hz, 4H) F184 629 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.85 (s, .sup.19F NMR (376 MHz, ([M H].sup.) 1H), 7.75 (d, J = 8.3 Hz, 1H), 7.52 (d, CDCl.sub.3) 59.23 (d, J = J = 8.0 Hz, 1H), 7.48 (s, 2H), 7.38 (q, 4.8 Hz), 66.70-70.14 J = 6.7, 5.8 Hz, 1H), 7.14 (dd, J = 17.4, (m), 72.62, 108.70- 11.0 Hz, 2H), 6.80 (d, J = 7.8 Hz, 1H), 115.95 (m) 6.02-5.83 (m, 1H), 5.74 (d, J = 17.4 Hz, 2H), 5.45 (d, J = 11.0 Hz, 2H), 4.89 (p, J = 7.1 Hz, 1H), 4.67 (p, J = 9.0 Hz, 1H), 3.99-3.74 (m, 2H), 1.51 (d, J = 6.9 Hz, 3H) F185 692 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.89- .sup.19F NMR (376 MHz, ([M H].sup.) 7.82 (m, 2H), 7.76 (dd, J = 8.0, 1.7 Hz, CDCl.sub.3) 59.24, 69.31 1H), 7.60 (d, J = 2.1 Hz, 1H), 7.56 (d, (d, J = 2.2 Hz), 72.97 J = 8.1 Hz, 1H), 7.48 (d, J = 2.1 Hz, (d, J = 271.5 Hz), 112.04 1H), 6.77 (d, J = 7.6 Hz, 1H), 5.84 (dd, (d, J = 14.3 Hz) J = 32.5, 9.6 Hz, 1H), 4.86 (p, J = 7.0 Hz, 1H), 4.60 (p, J = 8.8 Hz, 1H), 3.88 (dddd, J = 15.6, 9.0, 7.6, 1.8 Hz, 2H), 1.52 (d, J = 7.0 Hz, 3H) F186 639 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.77 (dd, J = 8.0, 1.7 CDCl.sub.3) 56.83-60.72 Hz, 1H), 7.55 (dd, J = 8.1, 2.8 Hz, 1H), (m), 67.67-71.03 7.50-7.37 (m, 2H), 7.22-7.03 (m, 2H), (m), 72.94 (d, J = 6.65 (dd, J = 7.8, 4.7 Hz, 1H), 5.93- 254.5 Hz), 113.05 (d, 5.81 (m, 1H), 5.76 (ddd, J = 17.5, 13.4, J = 249.6 Hz) 0.9 Hz, 1H), 5.56-5.37 (m, 1H), 4.84 (p, J = 7.1 Hz, 1H), 4.66 (dt, J = 12.8, 9.1 Hz, 1H), 4.04-3.69 (m, 2H), 1.51 (d, J = 6.9 Hz, 3H) F187 653 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.84 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.74 (dd, J = 8.0, 1.7 CDCl.sub.3) 51.53-61.54 Hz, 1H), 7.61-7.48 (m, 2H), 7.43 (d, (m), 67.07-70.14 J = 2.2 Hz, 1H), 7.14 (d, J = 2.2 Hz, (m), 72.64, 113.01 1H), 7.07-6.95 (m, 1H), 5.86 (dd, J = 32.7, 9.7 Hz, 1H), 5.27 (p, J = 1.5 Hz, 1H), 5.04-4.97 (m, 1H), 4.92 (p, J = 7.1 Hz, 1H), 4.62 (p, J = 9.0 Hz, 1H), 3.93- 3.72 (m, 2H), 2.10 (t, J = 1.2 Hz, 3H), 1.51 (d, J = 6.9 Hz, 3H) F188 653 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.84 (s, .sup.19F NMR (376 MHz, ([M H].sup.) 1H), 7.75 (dd, J = 8.1, 1.8 Hz, 1H), 7.53 CDCl.sub.3) 57.06-61.17 (dd, J = 8.1, 3.6 Hz, 1H), 7.45-7.30 (m, (m), 67.37-70.81 3H), 6.92-5.75 (m, 4H), 4.88 (p, J = 7.1 (m), 72.61, 110.79- Hz, 1H), 4.62 (ddq, J = 13.1, 9.0, 4.3 115.95 (m) Hz, 1H), 3.86 (qdd, J = 8.9, 6.3, 2.5 Hz, 2H), 2.01-1.73 (m, 3H), 1.51 (d, J = 6.9 Hz, 3H) F189 638 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.6 Hz, 1H), 7.83-7.71 (m, 1H), 7.57 CDCl.sub.3) 59.14, 67.97- (d, J = 8.1 Hz, 1H), 7.54-7.40 (m, 2H), 70.44 (m), 72.59, 6.87 (t, J = 6.5 Hz, 1H), 6.46 (d, J = 7.5 106.38-115.05 (m) Hz, 1H), 5.85 (ddd, J = 32.6, 9.7, 5.1 Hz, 1H), 4.78 (p, J = 7.1 Hz, 1H), 4.61 (p, J = 9.1 Hz, 1H), 4.03-3.84 (m, 2H), 3.52-3.39 (m, 1H), 1.52 (d, J = 7.0 Hz, 3H) F190 649 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.91- .sup.19F NMR (376 MHz, ([M H].sup.) 7.82 (m, 1H), 7.77 (dd, J = 8.2, 1.7 Hz, CDCl.sub.3) 59.15, 66.85- 1H), 7.61-7.50 (m, 1H), 7.45-7.34 (m, 70.44 (m), 72.59, 2H), 6.95 (t, J = 6.4 Hz, 1H), 6.51 (d, 108.10-114.23 (m) J = 7.6 Hz, 1H), 5.83 (dd, J = 32.6, 9.8 Hz, 1H), 4.79 (p, J = 7.1 Hz, 1H), 4.58 (p, J = 8.9 Hz, 1H), 4.02-3.83 (m, 2H), 2.14 (s, 3H), 1.52 (d, J = 7.0 Hz, 3H) F191 691 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (s, .sup.19F NMR (376 MHz, ([M H].sup.) 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.63-7.54 CDCl.sub.3) 56.24-60.94 (m, 1H), 7.41-7.33 (m, 2H), 6.68 (s, (m), 67.15-69.91 (m), 1H), 6.35 (d, J = 7.5 Hz, 1H), 5.84 (dd, 73.26, 112.60 (d, J = J = 32.6, 9.7 Hz, 1H), 4.73 (p, J = 7.2 21.4 Hz) Hz, 1H), 4.58 (p, J = 8.7 Hz, 1H), 4.03- 3.80 (m, 2H), 1.51 (d, J = 7.0 Hz, 3H), 1.35 (s, 9H) F192 636 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.78 (dd, J = 8.1, 1.8 CDCl.sub.3) 59.23, 67.15- Hz, 1H), 7.75 (s, 1H), 7.65 (d, J = 2.1 70.73 (m), 72.59, Hz, 1H), 7.58 (d, J = 8.1 Hz, 1H), 7.15 107.51-115.88 (m) (t, J = 6.4 Hz, 1H), 6.70 (d, J = 7.7 Hz, 1H), 5.96-5.74 (m, 1H), 4.84 (p, J = 7.1 Hz, 1H), 4.68 (p, J = 8.7 Hz, 1H), 3.97- 3.81 (m, 2H), 1.52 (d, J = 7.0 Hz, 3H) F193 675 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.85 (dd, .sup.19F NMR (376 MHz, ([M H].sup.) J = 9.3, 1.8 Hz, 1H), 7.80-7.71 (m, 1H), CDCl.sub.3) 57.66-60.42 7.61 (d, J = 2.2 Hz, 1H), 7.56 (d, J = 8.1 (m), 69.34 (d, J = 2.3 Hz, 2H), 7.26 (s, 1H), 6.75 (d, J = 7.7 Hz), 72.58, 87.48, Hz, 1H), 5.86 (dd, J = 32.6, 9.6 Hz, 106.98-114.23 (m) 1H), 4.86 (p, J = 7.0 Hz, 1H), 4.67 (p, J = 8.9 Hz, 1H), 4.01-3.81 (m, 2H), 2.18-1.93 (m, 3H), 1.52 (dd, J = 7.0, 4.5 Hz, 3H) F194 643 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.90- .sup.19F NMR (376 MHz, ([M H].sup.) 7.82 (m, 1H), 7.75 (dd, J = 8.1, 1.7 Hz, CDCl.sub.3) 58.60-60.17 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.52 (s, (m), 68.68-69.62 (m), 1H), 7.44 (d, J = 2.1 Hz, 1H), 7.34 (t, 72.63 (d, J = 2.5 Hz), J = 6.5 Hz, 1H), 6.82 (d, J = 7.7 Hz, 73.34, 107.80-115.05 1H), 5.99-5.77 (m, 1H), 5.58 (s, 1H), (m) 5.46 (s, 1H), 4.86 (p, J = 7.1 Hz, 1H), 4.66 (h, J = 9.0 Hz, 1H), 3.94-3.77 (m, 2H), 1.51 (d, J = 7.0 Hz, 3H) F195 661 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (s, .sup.19F NMR (376 MHz, ([M H].sup.) 1H), 7.78 (dd, J = 8.1, 1.7 Hz, 1H), CDCl.sub.3) 59.2, 69.36, 7.63 (d, J = 12.0 Hz, 2H), 7.57 (d, J = 72.66, 110.57, 115.6 8.1 Hz, 1H), 7.09-7.02 (m, 1H), 6.88 (t, J = 54.6 Hz, 1H), 6.62 (d, J = 7.6 Hz, 1H), 5.87 (dd, J = 32.5, 9.6 Hz, 1H), 4.82 (p, J = 7.1 Hz, 1H), 4.70 (p, J = 8.9 Hz, 1H), 4.02-3.73 (m, 2H), 1.51 (d, J = 7.0 Hz, 3H) F196 651 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.78 (dd, J = 8.1, 1.7 CDCl.sub.3) 59.07 (d, J = Hz, 1H), 7.62 (d, J = 8.1 Hz, 1H), 7.47 3.0 Hz), 67.15-69.91 (d, J = 2.0 Hz, 1H), 7.44 (d, J = 2.1 Hz, (m), 70.35 (d, J = 4.9 Hz), 1H), 7.09 (dd, J = 17.5, 11.0 Hz, 1H), 109.22-116.70 (m) 6.64 (d, J = 4.6 Hz, 1H), 5.96-5.82 (m, 1H), 5.78 (d, J = 17.4 Hz, 1H), 5.56- 5.46 (m, 1H), 5.09-4.86 (m, 2H), 4.65 (p, J = 9.0 Hz, 1H), 4.33-4.02 (m, 3H) F197 705 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.77 (dd, J = 8.0, 1.7 CDCl.sub.3) 59.12 (d, J = Hz, 1H), 7.66-7.57 (m, 2H), 7.49 (d, J = 3.4 Hz), 69.32 (d, J = 2.0 Hz, 1H), 6.85 (d, J = 4.1 Hz, 1H), 2.1 Hz), 70.40 (d, J = 5.86 (dd, J = 32.5, 9.6 Hz, 1H), 5.02- 6.8 Hz), 109.22-114.23 4.88 (m, 2H), 4.61 (p, J = 8.9 Hz, 1H), (m) 4.28-4.01 (m, 3H) F198 672 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.79 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.62 (d, J = 8.1 Hz, CDCl.sub.3) 69.33 (d, J = 1H), 7.56 (dd, J = 8.2, 1.6 Hz, 1H), 2.3 Hz), 70.28, 110.63- 7.43 (s, 2H), 6.79 (dd, J = 11.5, 4.4 Hz, 114.49 (m) 1H), 5.78 (dd, J = 32.6, 9.6 Hz, 1H), 5.07-4.91 (m, 2H), 4.58 (p, J = 8.9 Hz, 1H), 4.31-4.05 (m, 3H) F199 674 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 2.0 Hz, 1H), 7.78 (ddd, J = 10.2, CDCl.sub.3) 59.07 (d, J = 7.0, 2.0 Hz, 2H), 7.69-7.57 (m, 2H), 1.4 Hz), 69.35 (d, J = 6.95 (t, J = 54.6 Hz, 1H), 6.59 (dd, J = 2.3 Hz), 70.34, 111.83 13.3, 4.4 Hz, 1H), 5.98-5.81 (m, 1H), (d, J = 46.3 Hz), 115.77 5.05-4.84 (m, 2H), 4.80-4.65 (m, 1H), 4.34-4.02 (m, 3H) F200 592 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.71 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.53 (d, J = 8.1 Hz, CDCl.sub.3) 69.37, 72.46, 1H), 7.48 (dd, J = 10.7, 2.1 Hz, 1H), 111.55 7.44 (s, 2H), 7.24 (d, J = 16.1 Hz, 1H), 7.12-6.97 (m, 1H), 6.88 (t, J = 5.3 Hz, 1H), 5.91-5.65 (m, 2H), 5.51-5.40 (m, 1H), 4.62 (dp, J = 13.5, 9.0 Hz, 1H), 4.23 (d, J = 5.3 Hz, 2H), 3.93 (qd, J = 9.0, 6.3 Hz, 2H) F201 604 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.68 (s, .sup.19F NMR (376 MHz, ([M H].sup.) 1H), 7.46 (d, J = 1.6 Hz, 3H), 7.44 (s, CDCl.sub.3) 69.37, 72.51, 2H), 6.97 (dd, J = 17.4, 11.0 Hz, 1H), 73.27, 111.56 6.76 (d, J = 7.6 Hz, 1H), 5.80 (d, J = 8.8 Hz, 1H), 5.76-5.65 (m, 1H), 5.51- 5.35 (m, 1H), 4.83 (p, J = 7.1 Hz, 1H), 4.60 (p, J = 8.9 Hz, 1H), 3.86 (dqd, J = 27.8, 9.1, 6.4 Hz, 2H), 1.57-1.44 (m, 3H) F202 662 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.82 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.7 Hz, 1H), 7.72 (ddd, J = 9.7, 6.2, CDCl.sub.3) 59.46, 62.62, 3.9 Hz, 2H), 7.54 (s, 1H), 7.51 (d, J = 69.52, 72.74, 109.56, 8.1 Hz, 1H), 7.44 (dd, J = 8.9, 2.0 Hz, 111.73 1H), 7.29-7.24 (m, 1H), 5.86 (dd, J = 32.5, 9.5 Hz, 1H), 4.94 (p, J = 7.1 Hz, 1H), 4.72 (p, J = 8.8 Hz, 1H), 3.87- 3.67 (m, 2H), 1.50 (d, J = 6.9 Hz, 3H) F203 650 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.90- .sup.19F NMR (376 MHz, ([M H].sup.) 7.81 (m, 1H), 7.77 (dd, J = 8.1, 1.7 CDCl.sub.3) 59.53, 62.59, Hz, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.54 69.48 (d, J = 2.3 Hz), (s, 1H), 7.50 (t, J = 6.5 Hz, 1H), 7.44 72.63, 109.50 (dd, J = 8.9, 2.0 Hz, 1H), 7.24 (t, J = 5.2 Hz, 1H), 5.88 (dd, J = 32.5, 9.5 Hz, 1H), 4.72 (p, J = 8.8 Hz, 1H), 4.25 (d, J = 5.1 Hz, 2H), 3.86 (qd, J = 9.0, 6.5 Hz, 2H) F204 618 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.70 (d, .sup.19F NMR (376 MHz, ([M H].sup.) J = 1.6 Hz, 1H), 7.56 (d, J = 8.2 Hz, CDCl.sub.3) 69.35, 70.30, 1H), 7.49 (dd, J = 8.3, 1.8 Hz, 1H), 75.43, 1114.59 7.44 (s, 2H), 7.11-6.99 (m, 1H), 6.57 (d, J = 3.9 Hz, 1H), 5.84-5.78 (m, 1H), 5.78-5.70 (m, 1H), 5.51-5.42 (m, 1H), 5.06-4.80 (m, 1H), 4.60 (p, J = 8.9 Hz, 1H), 4.30-4.01 (m, 4H) F205 647 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (s, .sup.19F NMR (376 MHz, ([M + H].sup.+) 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.74 (d, CDCl.sub.3) 59.12, 62.80, J = 8.2 Hz, 1H), 7.58 (d, J = 11.0 Hz, 69.10 (d, J = 2.3 Hz), 2H), 7.42 (d, J = 8.2 Hz, 1H), 6.67 (s, 72.58, 112.08; 1H), 6.36 (d, J = 7.4 Hz, 1H), 5.88 (dd, IR (thin film) J = 32.6, 9.6 Hz, 1H), 4.89-4.58 (m, 2H), 3288, 1652, 1540 cm.sup.1 3.93 (pd, J = 8.9, 6.5 Hz, 2H), 1.51 (d, J = 7.0 Hz, 3H) F206 633 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.89 (d, .sup.19F NMR (376 MHz, ([M + H].sup.+) J = 1.7 Hz, 1H), 7.84-7.77 (m, 1H), CDCl.sub.3) 59.27, 62.80, 7.74 (d, J = 8.2 Hz, 1H), 7.62 (d, J = 69.09 (d, J = 2.3 Hz), 8.1 Hz, 1H), 7.57 (s, 1H), 7.43 (d, J = 72.54, 112.13 (d, J = 8.1 Hz, 1H), 6.64 (dd, J = 10.0, 5.3 Hz, 2.9 Hz); 2H), 5.89 (dd, J = 32.6, 9.6 Hz, 1H), IR (thin film) 4.71 (p, J = 8.9 Hz, 1H), 4.22 (d, J = 5.3 3299, 1655, 1538 cm.sup.1 Hz, 2H), 3.95 (qd, J = 8.9, 6.5 Hz, 2H) F207 675 ([M H].sup.) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.95-7.83 .sup.19F NMR (376 MHz, (m, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.57 CDCl.sub.3) 59.13, 69.19 (d, J = 8.1 Hz, 1H), 7.10 (s, 1H), 6.94 (t, (d, J = 2.4 Hz), 72.58, J = 2.0 Hz, 1H), 6.91 (s, 1H), 6.84 (t, 73.82, 113.00 J = 6.4 Hz, 1H), 6.44 (d, J = 7.5 Hz, (d, J = 54.0 Hz); 1H), 5.85 (dd, J = 32.6, 9.7 Hz, 1H), IR (thin film) 4.77 (p, J = 7.0 Hz, 1H), 4.62 (p, J = 9.2 3290, 2963, 1652, Hz, 1H), 4.36 (q, J = 7.9 Hz, 2H), 4.05- 1538 cm.sup.1 3.81 (m, 2H), 1.51 (d, J = 7.0 Hz, 3H) F208 691 ([M H].sup.) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (s, .sup.19F NMR (376 MHz, 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.76 (s, CDCl.sub.3) 58.18-59.72 1H), 7.73 (d, J = 8.2 Hz, 1H), 7.58 (d, (m), 62.84, 68.86 (d, J = J = 8.1 Hz, 1H), 7.47 (d, J = 8.2 Hz, 2.3 Hz), 72.58, 112.07; 1H), 6.70 (s, 1H), 6.37 (s, 1H), 5.88 (dd, IR (thin film) J = 32.6, 9.6 Hz, 1H), 4.70 (dt, J = 18.1, 3289, 3087, 1651, 8.9 Hz, 2H), 3.94 (p, J = 8.1, 7.6 Hz, 1540 cm.sup.1 2H), 1.52 (d, J = 7.0 Hz, 3H) F209 679 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.91-7.87 .sup.19F NMR (376 MHz, (m, 1H), 7.80 (d, J = 1.8 Hz, 1H), 7.79- CDCl.sub.3) 59.36, 62.85, 7.75 (m, 1H), 7.73 (d, J = 8.2 Hz, 1H), 69.09 (d, J = 2.3 Hz), 7.61 (d, J = 8.1 Hz, 1H), 7.48 (d, J = 72.56, 112.16 (d, J = 8.4 Hz, 1H), 7.10 (s, 1H), 6.88 (s, 1H), 2.7 Hz); 5.89 (dd, J = 32.6, 9.6 Hz, 1H), 4.71 (p, IR (thin film) J = 8.9 Hz, 1H), 4.41-4.14 (m, 2H), 3.92 3302, 3084, 1655, (qd, J = 9.0, 6.6 Hz, 2H) 1537 cm.sup.1 F211 617 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, .sup.19F NMR (376 MHz, J = 1.7 Hz, 1H), 7.77 (dd, J = 8.1, 1.7 CDCl.sub.3) 59.39, 61.54 Hz, 1H), 7.66-7.57 (m, 3H), 7.45 (t, J = (d, J = 12.4 Hz), 69.69 6.5 Hz, 1H), 7.31-7.21 (m, 1H), 7.04 (t, (d, J = 2.4 Hz), 72.51, J = 5.1 Hz, 1H), 5.90 (dd, J = 32.6, 9.6 112.48, 113.88 (q, J = Hz, 1H), 4.72 (p, J = 8.9 Hz, 1H), 4.26 12.7 Hz); (d, J = 5.1 Hz, 2H), 3.92 (qd, J = 9.0, IR (thin film) 6.4 Hz, 2H) 3294, 1656, 1539 cm.sup.1 F212 EIMS 658 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.83 (d, .sup.19F NMR (376 MHz, J = 1.6 Hz, 1H), 7.73 (dd, J = 8.1, 1.7 CDCl.sub.3) 59.30, 69.24, Hz, 1H), 7.58 (t, J = 6.5 Hz, 1H), 7.51 72.64, 113.27 (d, J = (d, J = 8.1 Hz, 1H), 7.40-7.37 (m, 1H), 29.5 Hz) 7.30 (d, J = 1.5 Hz, 1H), 7.29 (d, J = 1.9 Hz, 1H), 7.02 (d, J = 7.8 Hz, 1H), 5.86 (dd, J = 32.7, 9.8 Hz, 1H), 4.91 (p, J = 7.1 Hz, 1H), 4.74-4.51 (m, 1H), 3.83 (dtd, J = 12.3, 8.8, 6.3 Hz, 2H), 1.50 (d, J = 6.9 Hz, 3H), 1.31 (s, 9H) F213 EIMS 628 .sup.1H NMR (300 MHz, CDCl.sub.3) 7.85 (t, IR (thin film) J = 1.9 Hz, 1H), 7.76 (dd, J = 8.2, 1.8 3266, 2922, 1653, Hz, 1H), 7.64-7.50 (m, 3H), 7.44 (s, 1114 cm.sup.1 1H), 7.35 (s, 1H), 6.97-6.41 (m, 2H), 5.88 (ddd, J = 32.7, 9.7, 7.4 Hz, 1H), 4.85 (p, J = 7.0 Hz, 1H), 4.70 (p, J = 8.9 Hz, 1H), 3.89-3.72 (m, 2H), 1.51 (d, J = 7.0 Hz, 3H) F214 661 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.83 (dd, .sup.19F NMR (376 MHz, J = 12.3, 1.8 Hz, 1H), 7.74 (dd, J = 8.1, CDCl.sub.3) 59.34 (d, J = 1.7 Hz, 1H), 7.63 (t, J = 6.5 Hz, 1H), 24.1 Hz), 68.79, 70.14, 7.54 (d, J = 8.1 Hz, 1H), 7.41-7.37 (m, 72.59, 129.23 (d, J = 1H), 7.22 (ddd, J = 10.2, 6.7, 2.2 Hz, 21.5 Hz), 132.24 (d, J = 1H), 7.07 (d, J = 7.7 Hz, 1H), 5.83 (dd, 21.5 Hz) J = 32.6, 9.6 Hz, 1H), 4.95-4.81 (m, 1H), 4.71-4.50 (m, 1H), 3.94-3.76 (m, 2H), 1.49 (dd, J = 7.0, 4.1 Hz, 3H) F215 565 ([M H].sup.) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.88 (d, .sup.19F NMR (376 MHz, J = 1.7 Hz, 1H), 7.79 (dd, J = 8.1, 1.8 CDCl.sub.3) 59.31, 68.79, Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 7.38 70.14, 72.54, 129.10 (dt, J = 4.7, 2.0 Hz, 1H), 7.26 (s, 2H), (d, J = 21.3 Hz), 132.13 6.89 (t, J = 6.6 Hz, 1H), 6.76 (t, J = 5.2 (d, J = 21.4 Hz) Hz, 1H), 5.83 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.9 Hz, 1H), 4.23 (d, J = 5.3 Hz, 2H), 3.94 (qd, J = 9.0, 6.5 Hz, 2H) F216 EIMS 660 .sup.1H NMR (400 MHz, CDCl.sub.3) 7.87 (d, .sup.19F NMR (376 MHz, J = 2.1 Hz, 1H), 7.78 (dt, J = 8.0, 2.4 CDCl.sub.3) 58.10-59.82 Hz, 1H), 7.57 (dd, J = 8.1, 2.7 Hz, 1H), (m), 69.67 (t, J = 3.0 Hz), 7.51 (t, J = 6.2 Hz, 1H), 7.45-7.36 (m, 73.05 (d, J = 303.2 Hz), 1H), 7.25-7.12 (m, 1H), 7.03 (d, J = 7.6 129.41 (d, J = 21.5 Hz,) Hz, 1H), 5.89 (ddd, J = 32.8, 9.7, 4.8 135.70 (dd, J = 285.5, Hz, 1H), 4.80 (q, J = 7.0 Hz, 1H), 4.61 21.1 Hz) (dt, J = 14.4, 9.0 Hz, 1H), 3.99-3.78 (m, 2H), 1.50 (dd, J = 6.9, 3.8 Hz, 3H), 1.33 (d, J = 3.4 Hz, 9H) F217 645 ([M H].sup.) .sup.1H NMR (400 MHz, CDCl.sub.3) 7.85 (dd, .sup.19F NMR (376 MHz, J = 11.4, 1.9 Hz, 1H), 7.79-7.69 (m, 1H), CDCl.sub.3) 59.44, 69.09, 7.58 (dd, J = 11.7, 7.2 Hz, 2H), 7.39 (dt, 70.51, 72.56 (d, J = J = 4.8, 1.8 Hz, 2H), 7.27-7.17 (m, 1H), 1.6 Hz), 129.27 (d, J = 5.86 (dd, J = 32.6, 9.6 Hz, 1H), 4.69- 21.5 Hz), 132.28 (d, J = 4.57 (m, 1H), 4.22 (dd, J = 6.8, 5.1 Hz, 21.4 Hz) 3H), 3.89 (qd, J = 9.1, 6.5 Hz, 1H)

(1099) TABLE-US-00009 TABLE 5 Structure and Preparation Method for FC Series Compounds No. Structure Prep.* FC1 13 FC2 13 *prepared according to example number

(1100) TABLE-US-00010 TABLE 6 Structure and Preparation Method for CC Series Molecules No. Structure Prep* CC1 1 *prepared according to example number

(1101) TABLE-US-00011 TABLE 7 Analytical Data for Compounds in Table 5 Mp .sup.13C NMR; No. ( C.) Mass (m/z) .sup.1H NMH .sup.19F NMR; IR FC1 568 .sup.1H NMR (300 MHz, .sup.13C NMR (75 ([M + H].sup.+) CDCl.sub.3) 7.85 (d, J = MHz, CDCl.sub.3) 8.3 Hz, 2H), 7.78- 169.73, 167.13, 7.71 (m, 1H), 7.65- 159.34 (d, J.sub.CF = 7.57 (m, 3H), 7.43 256.1 Hz), (s, 2H), 5.79 (dd, J = 143.29, 134.76, 32.8, 9.6 Hz, 1H), 134.28, 133.99, 4.60 (p, J = 8.9 Hz, 133.62, 131.99, 1H), 4.27 (d, J = 5.1 128.92, 127.60, Hz, 2H), 3.94 (qd, J = 125.77, 125.27- 9.0, 6.4 Hz, 2H), 124.64 (m), 3.52-3.22 (m, 1H) 122.08, 99.74 (d, J.sub.CF = 15.0 Hz), 47.03, 43.78, 26.35 (d, J = 8.8 Hz) FC2 582 .sup.1H NMR (300 MHz, .sup.13C NMR (75 ([M + H].sup.+) CDCl.sub.3) 7.82 (d, J = MHz, CDCl.sub.3) 8.2 Hz, 2H), 7.65- 173.19, 166.50, 7.56 (m, 2H), 7.43 159.35 (d, J.sub.CF = (s, 2H), 7.32 (dd, J = 256.0 Hz), 7.5, 2.1 Hz, 1H), 134.76, 134.58, 5.78 (ddd, J = 32.8, 134.28, 133.91, 9.6, 0.9 Hz, 1H), 133.54, 131.99, 5.07-4.86 (m, 1H), 128.92, 128.14, 4.60 (p, J = 8.9 Hz, 127.57, 127.17 1H), 4.12-3.71 (m, 124.84 (d, J.sub.CF = 2H), 1.55 (t, J = 6.8 7.1 Hz), f99.58, Hz, 4H) 49.35, 34.66, 18.54.

(1102) TABLE-US-00012 TABLE 8 Structure and Preparation Method for PF Series Molecules No. Structure Prep.* PF1 13 PF2 16 PF3 000 16 PF4 001 13 PF6 002 13 PF7 003 13 PF8 004 13 PF10 005 16 PF12 006 16 PF13 007 16 PF14 008 16 PF15 009 16 PF16 010 16 PF18 011 16 PF19 012 16 PF20 013 16 PF22 014 16 PF24 015 16 PF25 016 16 PF26 017 16 PF27 018 16 PF28 019 16 PF31 020 16 PF32 021 16 PF33 022 16 PF35 023 16 PF37 024 16 PF39 025 16 PF41 026 16 PF42 027 16 PF43 028 16 PF44 029 16 PF45 030 16 PF47 031 16 PF48 032 16 PF49 033 16 PF50 034 16 PF51 035 16 PF60 036 16 PF62 037 16 PF82 038 51 PF88 039 52 PF94 040 52 PF96 041 13 PF98 042 13 *prepared according to example number

(1103) TABLE-US-00013 TABLE 9 Analytical Data for Molecules in Table 8 Mp .sup.13C NMR; No. ( C.) Mass (m/z) .sup.1H NMR .sup.19F NMR; IR PF1 78-80 629 ([M + H].sup.+) .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.87 (d, J = 6.9 Hz, 1H), 8.69 (t, J = 6.0 Hz, 1H), 8.30 (d, J = 7.5 Hz, 1H), 8.07 (s, 2H), 7.95 (s, 1H), 7.73-7.61 (m, 4H), 6.30 (dd, J = 9.9, 33.9 Hz, 1H), 5.35- 5.29 (m, 1H), 4.60- 4.56 (m, 1H), 4.11- 3.91 (m, 2H), 1.36 (d, J = 6.9 Hz, 3H) PF2 715 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.97 (d, J = 3429, 2998, 7.2 Hz, 1H), 8.10 (s, 1659, 1031 2H), 8.04 (d, J = 7.8 cm.sup.1 Hz, 1H), 7.86 (d, J = 8.1 Hz, 1H), 7.61- 7.56 (m, 2H), 6.85 (dd, J = 9.9, 36.0 Hz, 1H), 5.19-5.12 (m, 1H), 4.99-4.94 (m, 1H), 4.37-4.08 (m, 2H), 3.13 (s, 3H), 1.23 (d, J = 7.2 Hz, 3H) PF3 729 ([M + H].sup.+) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 9.26 (br s, 3435, 2926, 1H), 8.14 (s, 1H), 8.09 1667, 749 (s, 1H), 8.05 (d, J = cm.sup.1 8.0 Hz, 1H), 7.85 (s, 1H), 7.61-7.56 (m, 2H), 6.84 (dd, J = 10.0, 36.0 Hz, 1H), 5.18-5.13 (m, 1H), 4.22-4.21 (m, 2H), 3.17 (s, 3H), 1.04- 1.02 (m, 2H), 0.85- 0.83 (m, 2H) PF4 701 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.79 (t, J = 3439, 2997, 5.4 Hz, 1H), 8.12 (s, 1661, 1031 1H), 8.11-8.05 (m, cm.sup.1 2H), 7.86 (d, J = 8.4 Hz, 1H), 7.69 (d, J = 8.1 Hz, 1H), 7.62- 7.59 (m, 1H), 6.85 (dd, J = 9.9, 36.0 Hz, 1H), 5.19-5.13(m, 1H), 4.25-4.16 (m, 4H), 3.14 (s, 3H) PF6 597 ([M + H].sup.+) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 8.78 (t, J = 3435, 2997, 6.0 Hz, 1H), 8.12 (s, 1436, 1031 1H), 8.07 (d, J = 8.0 cm.sup.1 Hz, 1H), 7.97 (d, J = 6.4 Hz, 1H), 7.71- 7.67 (m, 2H), 7.53- 7.48 (m, 1H), 6.83 (dd, J = 10.4, 36.4 Hz, 1H), 5.19-5.14 (m, 1H), 4.23-4.16 (m, 2H), 3.14 (s, 2H), 1.26 (d, J = 9.6 Hz, 3H) PF7 595 ([M H].sup.) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 8.84 (d, J = 3428, 2925, 7.2 Hz, 1H), 8.64 (t, 1650, 1167 J = 6.4 Hz, 1H), 8.10 cm.sup.1 (s, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.97 (d, J = 6.4 Hz, 1H), 7.68- 7.64 (m, 2H), 7.53- 7.48 (m, 1H), 6.83 (dd, J = 10.4, 36.0 Hz, 1H), 5.18-5.13 (m, 1H), 4.52-4.49 (m, 1H), 3.99-3.87 (m, 2H), 1.30 (d, J = 7.2 Hz, 3H) PF8 611 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.97 (d, J = 3432, 2927, 7.8 Hz, 1H), 8.11 (s, 1647, 1262, 1H), 8.05 (d, J = 7.1 749 cm.sup.1 Hz, 1H), 7.97 (d, J = 6.3 Hz, 1H), 7.70- 7.69 (m, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.53- 7.49 (m, 1H), 6.85 (dd, J = 9.9, 35.7 Hz, 1H), 5.19-5.13 (m, 1H), 4.99-4.94 (m, 1H), 4.33-4.25 (m, 1H), 4.16-4.13 (m, 1H), 3.22 (s, 3H), 1.29 (d, J = 6.9 Hz, 3H) PF10 623 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 9.24 (br s, 3435, 2999, 1H), 8.12 (s, 1H), 8.04 1656, 1030 (d, J = 8.1 Hz, 1H), cm.sup.1 7.95 (d, J = 6.9 Hz, 1H), 7.69-7.67 (m, 1H), 7.56-7.45 (m, 2H), 6.84 (dd, J = 10.2, 36.0 Hz, 1H), 5.17-5.10 (m, 1H), 4.18-4.14 (m, 2H), 3.17 (s, 3H), 1.08- 1.06 (m, 2H), 0.84- 0.81 (m, 2H) PF12 625 ([M H].sup.) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 8.80 (t, J = 3433, 3914, 5.6 Hz, 1H), 8.10 (s, 1662 cm.sup.1 1H), 8.07 (d, J = 8.4 Hz, 1H), 7.83 (s, 1H), 7.69-7.67 (m, 1H), 7.64 (s, 1H), 6.81 (dd, J = 10.0, 35.6 Hz, 1H), 5.12-5.07 (m, 1H), 4.23-4.17 (m, 4H), 3.14 (s, 3H), 2.42 (s, 3H) PF13 627 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.84 (d, J = 3414, 2925, 7.8 Hz, 1H) 8.65 (t, 1651 cm.sup.1 J = 6.0 Hz, 1H), 8.09 (s, 1H), 8.05 (d, J = 7.8 Hz, 1H), 7.83 (s, 1H), 7.67 (d, J = 6.9 Hz, 2H), 6.82 (dd, J = 10.2, 36.0 Hz, 1H), 5.12-5.06 (m, 1H), 4.53-4.48 (m, 1H), 4.04-3.86 (m, 2H), 2.42 (s, 3H), 1.32 (d, J = 6.9 Hz, 3H) PF14 641 ([M + H].sup.+) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 8.96 (d, J = 3285, 2949, 7.2 Hz, 1H), 8.09 (s, 1656 cm.sup.1 1H), 8.04 (d, J = 8.8 Hz, 1H), 7.83 (s, 1H), 7.64 (s, 1H), 7.59 (d, J = 8.4 Hz, 1H), 6.80 (dd, J = 10.4, 35.6 Hz, 1H), 5.09-5.06 (m, 1H), 4.98-4.94 (m, 1H), 4.28-4.26 (m, 1H), 4.15-4.13 (m, 1H), 3.22 (s, 3H), 2.42 (s, 3H), 1.28 (d, J = 6.8 Hz, 3H) PF15 639 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 9.10 (s, 3462, 2930, 1H), 8.17 (t, J = 6.3 1679, 1116 Hz, 1H), 8.10 (s, 2H), cm.sup.1 8.02 (d, J = 7.5 Hz, 1H), 7.82 (s, 1H), 7.64 (s, 1H), 6.83 (dd, J = 9.9, 36.0 Hz, 1H), 5.12- 5.06 (m, 1H), 3.96- 3.87 (m, 2H), 2.42 (s, 3H), 1.40-136 (m, 2H), 1.03-0.98 (m, 2H) PF16 653 ([M + H].sup.+) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 9.26 (s, 3445, 1661, 1H), 8.12 (s, 1H), 8.05 1031 cm.sup.1 (d, J = 8.0 Hz, 1H), 7.82 (s, 1H), 7.64 (s, 1H), 7.58 (d, J = 8.4 Hz, 1H), 6.82 (dd, J = 10.4, 36.0 Hz, 1H), 5.11-5.06 (m, 1H), 4.19 (br s, 2H), 3.19 (s, 3H), 2.41 (s, 3H), 1.29-1.26 (m, 2H), 0.87-0.79 (m, 2H) PF18 597 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.81 (t, J = 3429, 1661, 5.4 Hz, 1H), 8.12 (s, 1030 cm.sup.1 1H), 8.07 (d, J = 7.8 Hz, 1H), 7.82 (d, J = 10.5 Hz, 1H), 7.71- 7.66 (m, 2H), 7.56 (d, J = 9.0 Hz, 1H), 6.83 (dd, J = 10.2, 35.7 Hz, 1H), 5.21-5.14 (m, 1H), 4.40-4.37 (m, 1H), 4.25-4.15 (m, 3H), 3.14 (s, 3H) PF19 597 ([M + H].sup.+) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 8.84 (d, J = 3431, 2925, 7.2 Hz, 1H), 8.64 (t, 1650 cm.sup.1 J = 6.0 Hz, 1H), 8.10 (s, 1H), 8.05 (d, J = 8.4 Hz, 1H), 7.81 (d, J = 10.4 Hz, 1H), 7.71- 7.67 (m, 2H), 7.56 (d, J = 8.4 Hz, 1H), 6.81 (dd, J = 10.0, 35.6 Hz, 1H), 5.20-5.15 (m, 1H), 4.53-4.95 (m, 1H), 3.99-3.86 (m, 2H), 1.30 (d, J = 7.2 Hz, 3H) PF20 609 ([M H].sup.) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 8.97 (d, J = 3431, 2925, 7.8 Hz, 1H), 8.11 (s, 1650 cm.sup.1 1H), 8.04 (d, J = 8.7 Hz, 1H), 7.81 (d, J = 10.5 Hz, 1H), 7.71 (t, J = 8.4 Hz, 1H), 7.59- 7.53 (m, 2H), 6.82 (dd, J = 10.2, 36.0 Hz, 1H), 5.20-5.14 (m, 1H), 4.99-4.94 (m, 1H), 4.28-4.01 (m, 2H), 3.29 (s, 3H), 1.28 (d, J = 6.2 Hz, 3H) PF22 623 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 9.26 (s, 3429, 1668, 1H), 8.14 (s, 1H), 8.06 1030 cm.sup.1 (d, J = 8.4 Hz, 1H), 7.81 (d, J = 9.6 Hz, 1H), 7.71 (t, J = 7.8 Hz, 1H), 7.58-7.52 (m, 2H), 6.83 (dd, J = 9.9, 36.0 Hz, 1H), 5.20- 5.14 (m, 1H), 4.21 (br s, 2H), 3.18 (s, 3H), 1.28-1.23 (m, 2H), 0.95-0.79 (m, 2H) PF24 657 ([M H].sup.) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.81- 3400, 3316, 8.77 (m, 1H), 8.12 (s, 2928, 1661, 1H), 8.08 (d, J = 8.4 1267 cm.sup.1 Hz, 1H), 7.99 (s, 1H), 7.87-7.85 (d, J = 8.1 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.60 (d, J = 8.4 Hz, 1H), 6.85 (dd, J = 9.9, 35.7 Hz, 1H), 5.20-5.14 (m, 1H), 4.25-4.16 (m, 4H), 3.14 (s, 3H) PF25 55-57 658 ([M + H].sup.+) .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.84 (d, J = 7.5 Hz, 1H), 8.65 (t, J = 6.6 Hz, 1H), 8.10 (s, 1H), 8.05 (d, J = 8.4 Hz, 1H), 7.98 (s, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.67 (dd, J = 7.8, 8.1 Hz, 2H), 6.85 (dd, J = 9.9, 35.7 Hz, 1H), 5.20-5.14 (m, 1H), 4.53-4.48 (m, 1H), 3.99-3.89 (m, 2H), 1.30 (d, J = 6.9 Hz, 3H) PF26 59-61 671 ([M + H].sup.+) .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.97 (d, J = 7.8 Hz, 1H), 8.11 (s, 1H), 8.04 (d, J = 8.1 Hz, 1H), 7.98 (s, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.59 (d, J = 8.1 Hz, 2H), 6.85 (dd, J = 9.6, 35.7 Hz, 1H), 5.20- 5.13 (m, 1H), 4.99- 4.94 (m, 1H), 4.34- 4.08 (m, 2H), 3.22 (s, 3H), 1.29 (d, J = 7.2 Hz, 3H) PF27 63-65 669 ([M + H].sup.+) .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.01 (s, 1H), 8.18-7.97 (m, 5H), 7.88 (d, J = 8.4 Hz, 1H), 7.59 (dd, J = 1.8, 8.4 Hz, 1H), 6.86 (dd, J = 10.2, 36.3 Hz, 1H), 5.20-5.14 (m, 1H), 3.98-3.87 (m, 2H), 1.03-0.99 (m, 2H), 0.87-0.84 (m, 2H) PF28 71-73 683 ([M + H].sup.+) .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.26 (s, 1H), 8.14 (s, 1H), 8.06 (d, J = 8.1 Hz, 1H), 7.98 (s, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.58 (d, J = 8.1 Hz, 1H), 7.90 (s, 1H), 6.86 (dd, J = 10.2, 36.0 Hz, 1H), 5.20-5.14 (m, 1H), 4.21 (br s, 2H), 3.18 (br s, 3H), 1.30-1.26 (m, 2H), 1.05-1.01 (m, 2H) PF31 671 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.97 (d, J = 3430, 1658, 7.2 Hz, 1H), 8.11 (br 1025, 705 s, 1H), 8.05 (d, J = 8.4 cm.sup.1 Hz, 1H), 7.93 (br s, 1H), 7.84-7.79 (m, 2H), 7.60 (d, J = 8.1 Hz, 1H), 6.86 (dd, J = 10.2, 35.7 Hz, 1H), 5.23-5.17 (m, 1H), 4.99-4.94 (m, 1H), 4.33-4.25 (m, 1H), 4.16-4.11 (m, 1H), 3.22 (s, 3H), 1.29 (d, J = 7.2 Hz, 3H) PF32 667 ([M H].sup.) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 9.10 (br s, 3421, 2925, 1H), 8.17-8.07 (m, 1667, 1166, 3H), 8.02 (d, J = 8.1 750 cm.sup.1 Hz, 1H), 7.93 (s, 1H), 7.84 (s, 1H), 7.80- 7.79 (m, 1H), 6.87 (dd, J = 9.9, 36.0 Hz, 1H), 5.23-5.17 (m, 1H), 3.96-3.87 (m, 2H), 1.40-1.25 (m, 2H), 1.03-0.99 (m, 2H) PF33 683 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 9.26 (br s, 3428, 1660, 1H), 8.14 (br s, 1H), 1030, 704 8.06 (d, J = 7.8 Hz, cm.sup.1 1H), 7.92 (br s, 1H), 7.84 (br s, 1H), 7.80 (d, J = 1.5 Hz, 1H), 7.58 (d, J = 8.1 Hz, 1H), 6.87 (dd, J = 9.9, 35.4 Hz, 1H), 5.23- 5.16 (m, 1H), 4.21- 4.19 (m, 2H), 3.29 (s, 3H), 1.30-1.26 (m, 2H), 1.04-1.02 (m, 2H) PF35 657 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.79 (t, J = 3399, 2925, 5.7 Hz, 1H), 8.12 (br 1661, 749 s, 2H), 8.08 (d, J = 8.1 cm.sup.1 Hz, 1H), 7.71-7.67 (m, 3H), 6.86 (dd, J = 9.9, 36.0 Hz, 1H), 5.21- 5.14 (m, 1H), 4.23- 4.16 (m, 4H), 3.14 (s, 3H) PF37 671 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.97 (d, J = 3436, 1660, 7.5 Hz, 1H), 8.11 (s, 1031, 702 2H), 8.04 (d, J = 7.8 cm.sup.1 Hz, 1H), 7.71 (s, 2H), 7.59 (d, J = 8.1 Hz, 1H), 6.85 (dd, J = 9.9, 36.0 Hz, 1H), 5.20- 5.14 (m, 1H), 4.99- 4.94 (m, 1H), 4.33- 4.08 (m, 2H), 3.21 (s, 3H), 1.28 (d, J = 6.9 Hz, 3H) PF39 683 ([M + H].sup.+) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 9.26 (br s, 3431, 1659, 1H), 8.14-8.11 (m, 1029, 703 2H), 8.05 (d, J = 8.0 cm.sup.1 Hz, 1H), 7.73-7.68 (m, 2H), 7.58 (d, J = 8.4 Hz, 1H), 6.84 (dd, J = 10.0, 36.0 Hz, 1H), 5.22-5.19 (m, 1H), 4.23-4.19 (m, 2H), 3.19 (s, 3H), 1.29- 1.28 (m, 2H), 1.08- 1.03 (m, 2H) PF41 645 ([M H].sup.) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 8.80 (t, J = 3411, 2927, 5.6 Hz, 1H), 8.17 (s, 1670, 1261, 1H), 8.12-8.07 (m, 750 cm.sup.1 3H), 7.94 (s, 1H), 7.72 (d, J = 8.4 Hz, 1H), 6.94 (dd, J = 10.0, 35.6 Hz, 1H), 5.39- 5.32 (m, 1H), 4.23- 4.27 (m, 4H), 3.14 (s, 3H) PF42 105-107 645 ([M H].sup.) .sup.1H NMR (300 MHz, CDCl.sub.3) 7.88 (s, 1H), 7.80 (d, J = 8.6 Hz, 1H), 7.64 (s, 1H), 7.63- 7.51 (m, 3H), 6.81 (t, J = 6.5 Hz, 1H), 6.44 (d, J = 7.5 Hz, 1H), 5.88 (dd, J = 32.5, 9.6 Hz, 1H), 4.84- 4.61 (m, 2H), 3.93 (qd, J = 9.0, 6.5 Hz, 2H), 1.51 (d, J = 7.0 Hz, 3H) PF43 661 ([M + H].sup.+) .sup.1H NMR (400 MHz, IR (thin film) DMSO-d.sub.6) 8.97 (d, J = 3409, 3299, 7.2 Hz, 1H), 8.17 (s, 2988, 1651, 1H), 8.12 (d, J = 8.4 750 cm.sup.1 Hz, 1H), 8.06 (d, J = 5.7 Hz, 1H), 7.94 (s, 2H), 7.60 (d, J = 5.7 Hz, 1H), 6.92 (dd, J = 10.0, 35.6 Hz, 1H), 5.39-5.34 (m, 1H), 4.99-4.93 (m, 1H), 4.35-4.24 (m, 1H), 4.15-4.09 (m, 1H), 3.22 (s, 3H), 1.29 (d, J = 6.8 Hz, 3H) PF44 52-54 659 ([M + H].sup.+) .sup.1H NMR (300 MHz, CDCl.sub.3) 9.12 (s, 2H), 8.17-7.95 (m, 6H), 6.95 (dd, J = 9.9, 36.0 Hz, 1H), 5.40-5.34 (m, 1H), 3.96-3.90 (m, 2H), 1.41-1.37 (m, 2H), 1.03-0.99 (m, 2H) PF45 62-65 673 ([M + H].sup.+) .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.26 (s, 1H), 8.16 (d, J = 5.7 Hz, 2H), 8.09 (s, 1H), 8.07 (d, J = 6.3 Hz, 1H), 7.95 (s, 1H), 7.65 (d, J = 5.7 Hz, 1H), 6.93 (dd, J = 7.8, 26.7 Hz, 1H), 5.38-5.34 (m, 1H), 4.40-4.20 (m, 2H), 3.18 (s, 3H), 1.28-1.27 (m, 2H), 1.04-1.02 (m, 2H) PF47 133-136 593 ([M + H].sup.+) .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.79 (t, J = 5.4 Hz, 1H), 8.12 (s, 1H), 8.07 (d, J = 7.8 Hz, 1H), 7.71-7.60 (m, 2H), 7.49 (s, 2H), 6.70 (dd, J = 35.7, 10.2 Hz, 1H), 5.04- 4.96 (m, 1H), 4.25- 4.17 (m, 4H), 3.15 (s, 3H), 2.38 (s, 3H) PF48 90-93 593 ([M + H].sup.+) .sup.1H NMR (400 MHz, CDCl.sub.3) 8.83 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 6.4 Hz, 1H), 8.08 (s, 1H), 8.05 (d, J = 7.6 Hz, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.62 (s, 1H), 7.47 (s, 2H), 6.78 (dd, J = 9.6, 35.6 Hz, 1H), 5.02-4.95 (m, 1H), 4.54-4.47 (m, 1H), 4.03-3.85 (m, 2H), 2.35 (s, 3H), 1.30 (d, J = 8.0 Hz, 3H) PF49 71-74 607 ([M + H].sup.+) .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.96 (d, J = 7.2 Hz, 1H), 8.09 (s, 1H), 8.04 (d, J = 8.1 Hz, 1H), 7.62 (s, 1H), 7.59 (d, J = 8.1 Hz, 1H), 7.47 (s, 2H), 6.94 (dd, J = 10.2, 35.1 Hz, 1H), 5.00-4.94 (m, 2H), 4.48-4.00 (m, 2H), 3.22 (s, 3H), 2.37 (s, 3H), 1.28 (d, J = 6.9 Hz, 3H) PF50 75-78 605 ([M + H].sup.+) .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.09 (s, 1H) 8.16 (t, J = 8.4 Hz, 1H), 8.09-8.06 (m, 2H), 8.01 (d, J = 7.6 Hz, 1H), 7.61 (s, 1H), 7.48 (s, 2H), 6.79 (dd, J = 10.0, 36.0 Hz, 1H), 5.03-4.98 (m, 1H), 3.97-3.88 (m, 2H), 2.35 (s, 3H), 1.40- 1.37 (m, 2H), 1.03- 1.00 (m, 2H) PF51 86-89 619 ([M + H].sup.+) .sup.1H NMR (300 MHz, DMSO-d.sub.6) 9.26 (br s, 1H), 8.12 (s, 1H), 8.06 (d, J = 8.1 Hz, 1H), 7.61 (s, 1H), 7.57 (d, J = 8.1 Hz, 1H), 7.47 (s, 2H), 6.82 (dd, J = 9.9, 36.0 Hz, 1H), 5.00- 4.97 (m, 1H), 4.21 (br s, 2H), 3.18 (br s, 3H), 2.35 (s, 3H) 1.30- 1.26 (m, 2H), 1.05- 1.02 (m, 2H) PF60 609 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 8.75 (d, J = 3431, 2925, 7.5 Hz, 1H), 8.59 (t, 1650 cm.sup.1 J = 6.0 Hz, 1H), 7.88 (s, 3H), 7.71 (d, J = 8.1 Hz, 1H), 7.54 (d, J = 7.8 Hz, 1H), 6.66 (dd, J = 10.2, 36.6 Hz, 1H), 4.73-4.60 (m, 1H), 4.52-4.45 (m, 1H), 4.05-3.85 (m, 2H), 1.62 (t, J = 18.9 Hz, 3H), 1.31 (d, J = 6.9 Hz, 3H) PF62 623 ([M + H].sup.+) .sup.1H NMR (300 MHz, IR (thin film) DMSO-d.sub.6) 9.02 (s, 3431, 2925, 1H), 8.16 (t, J = 6.3 1650 cm.sup.1 Hz, 1H), 7.88 (s, 2H), 7.78-7.70 (m, 3H), 6.67 (dd, J = 10.5, 36.6 Hz, 1H), 4.68- 4.65 (m, 1H), 3.96- 3.91 (m, 2H), 1.68 (t, J = 18.9 Hz, 3H), 1.41- 1.35 (m, 2H), 1.23- 1.20 (m, 2H) PF82 648 ([M H].sup.) .sup.1H NMR (400 MHz, .sup.19F NMR CDCl.sub.3) 8.16 (s, 1H), (376 MHz, 7.82 (s, 1H), 7.75 (d, J = CDCl.sub.3) 8.3 Hz, 1H), 7.60 (d, 58.34, 69.35, J = 8.2 Hz, 1H), 7.43 72.47, 111.91 (s, 2H), 6.29-6.21 (m, 1H), 5.81 (dd, J = 32.6, 9.6 Hz, 1H), 4.60 (p, J = 8.9 Hz, 1H), 4.52 (d, J = 4.7 Hz, 2H), 4.00 (qd, J = 8.9, 6.5 Hz, 2H) PF88 663 ([M H].sup.) .sup.1H NMR (500 MHz, .sup.19F NMR CDCl.sub.3) 8.55 (t, J = (471 MHz, 5.1 Hz, 1H), 8.19 (t, J = CDCl.sub.3) 6.1 Hz, 1H), 7.83 (d, 58.18, 69.35 J = 1.7 Hz, 1H), 7.75 (d, J = 8.8 Hz), 70.58 (dd, J = 8.2, 1.8 Hz, (t, J = 9.0 Hz), 111.95 1H), 7.66-7.56 (m, (d, J = 32.7 Hz) 1H), 7.43 (s, 2H), 5.82 (dd, J = 32.6, 9.6 Hz, 1H), 4.80 (d, J = 5.1 Hz, 2H), 4.61 (p, J = 8.8 Hz, 1H), 4.46 (qd, J = 8.9, 5.9 Hz, 2H) PF94 649 ([M H].sup.) .sup.1H NMR (400 MHz, .sup.19F NMR CDCl.sub.3) 9.03 (s, 1H), (376 MHz, 7.90 (d, J = 1.7 Hz, CDCl.sub.3) 1H), 7.83 (dd, J = 8.1, 59.21, 69.30, 1.7 Hz, 1H), 7.65 (d, J = 70.67, 112.02 8.1 Hz, 1H), 7.44 (s, 2H), 7.11 (s, 1H), 5.86 (dd, J = 32.5, 9.5 Hz, 1H), 4.68-4.57 (m, 1H), 4.56 (d, J = 5.4 Hz, 2H), 4.43 (qd, J = 9.0, 5.9 Hz, 2H) PF96 663 ([M H].sup.) .sup.1H NMR (400 MHz, .sup.19F NMR CDCl.sub.3) 9.68 (t, J = (376 MHz, 6.0 Hz, 1H), 7.93- CDCl.sub.3) 7.87 (m, 1H), 7.82 59.24 (d, J = (dd, J = 8.1, 1.7 Hz, 1.7 Hz), 69.32 (d, 1H), 7.64 (d, J = 8.1 J = 2.2 Hz), 70.63, Hz, 1H), 7.45 (s, 2H), 109.75-114.23 (m) 7.36 (d, J = 8.1 Hz, 1H), 6.08-5.76 (m, 1H), 5.57-5.34 (m, 1H), 4.62 (p, J = 8.9 Hz, 1H), 4.52-4.22 (m, 2H), 1.59 (d, J = 6.7 Hz, 3H) PF98 675 ([M H].sup.) .sup.1H NMR (400 MHz, .sup.19F NMR CDCl.sub.3) 9.01 (s, 1H), (376 MHz, 7.93-7.84 (m, 1H), CDCl.sub.3) 7.80 (dd, J = 8.1, 1.7 58.84 (t, J = 1.8 Hz, 1H), 7.53 (d, J = Hz), 69.30 (d, J = 2.3 8.3 Hz, 1H), 7.43 (s, Hz), 70.82 (d, J = 18 2H), 6.61 (s, 1H), 5.85 Hz) 112.05 (dd, J = 32.5, 9.6 Hz, 1H), 4.61 (p, J = 8.8 Hz, 1H), 4.47 (qd, J = 9.1, 5.9 Hz, 2H), 1.96- 1.86 (m, 2H), 1.38- 1.26 (m, 2H)

(1104) TABLE-US-00014 BAW, CEW, & CL Rating Table % Control (or Mortality) Rating 50-100 A More than 0-Less than 50 B Not Tested C No activity noticed in this bioassay D

(1105) TABLE-US-00015 GPA & YFM Rating Table % Control (or Mortality) Rating 80-100 A More than 0-Less than 80 B Not Tested C No activity noticed in this bioassay D

(1106) TABLE-US-00016 TABLE ABC Biological Results Pests No. BAW CL GPA YFM F1 A A C C F2 A A C C F3 A A A C F4 A A C C F5 A A C C F6 A A C C F7 A A C C F8 A A C C F9 A A C C F10 A A C C F11 A A C C F12 A A C C F13 A A C C F14 A A C C F15 A A C C F16 A A C C F17 A A C C F18 A A C C F19 A A C C F20 A A C C F21 A A C C F22 A A C C F23 A A C C F24 A A C C F25 A A C C F26 A A C C F27 A A C C F28 A A C C F29 A A C C F30 A A C C F31 A A C C F32 A A C C F33 A A C A F34 A A C A F35 A A C A F36 A A C A F37 A A C A F38 A A C A F39 A A C A F40 A A C A F41 A A C A F42 A A C A F43 A A C A F44 A A C A F45 A A C A F46 A A C A F47 A A C C F48 A A C C F49 A A C C F50 A A C C F51 A A C C F52 A A C A F53 A A C A F54 A A C C F55 A A C C F56 A A C C F57 A A C C F58 A A C C F59 A A C A F60 A A C A F61 A A C A F62 A A C C F63 A A C C F64 A A C C F65 A A C C F66 A A C C F67 A A C C F68 A A C A F69 A A C A F70 A A C A F71 A A C B F72 A A C A F73 A A C A F74 A A C A F75 A A C A F76 A A C A F77 A A C A F78 A A C A F79 A A C A F80 A A C A F81 A A C A F82 A A C A F83 A A C A F84 A A C A F85 A A C A F86 A A C A F87 A A C C F88 A A C C F89 A A C C F90 A A C C F91 A A C C F92 A A C C F93 A A C C F94 A A C C F95 A A C C F96 A A C C F97 A A C C F98 A A C C F99 A A C A F100 A A C C F101 A A C C F102 A A C A F103 A A C B F104 A A C C F105 A A C C F106 A A C C F107 A A C C F108 A A C C F109 A A C C F110 A A C C F111 A A C C F112 A A C C F113 A A C A F114 A A C A F115 A A C B F116 A A C A F117 A A C C F118 A A C B F119 A A C B F120 A A C B F121 A A C C F122 A A C B F123 A A C C F124 A A C C F125 A A C C F126 A A C C F127 A A C C F128 A A C C F129 A A C C F130 A A C A F131 A A C A F132 A A C B F133 A A C B F134 A A C B F135 A A C B F136 A A C B F137 A A C B F138 A A C A F139 A A C A F140 A A C C F141 A A C A F142 A A C A F143 A A C A F144 A A C A F145 A A C C F146 A A B B F147 A A C A F148 A A C D F150 A A C C F153 A A C A F154 A A C C F155 A A A A F157 A A C A F158 A A C D F159 A A C A F160 A A A A F161 A A C A F162 A A C D F163 A A C A F164 A A C B F165 A A C B F166 A A C C F167 A A A A F168 A A C C F169 A A C C F170 A A C C F171 A A C C F172 A A C B F173 A A C D F174 A A C C F175 A A C C F176 A A C C F177 A A A A F178 A A C C F180 A A A D F181 A A C C F182 A A C C F183 A A C C F184 A A C C F185 A A C C F186 A A C C F187 A A C C F188 A A C C F189 A A C C F190 A A C C F191 A A C C F192 A A C C F193 A A C C F194 A A C C F195 A A C C F196 A A C C F197 A A C C F198 A A C C F199 A A C C F200 A A C C F201 A A C C F202 A A C C F203 A A C C F204 A A C C F205 A A C B F206 A A C D F207 A A C C F208 A A C A F209 A A C A F210 A A C B F211 A A C D F212 A A C C F213 A A C C F214 A A C C F215 A A C C F216 A A C C F217 A A C C PF1 A A C A PF2 A A C A PF3 A A C A PF4 A A C A PF6 A A A A PF7 A A C B PF8 A A C B PF10 A A C A PF12 A A C B PF13 A A C B PF14 A A C A PF15 A A C B PF16 A A B A PF18 A A C B PF19 A A C B PF20 A A C B PF22 A A C B PF24 A A A A PF25 A A C B PF26 A A C C PF27 A A A B PF28 A A C C PF31 A A C B PF32 A A B A PF33 A A C B PF35 A A C B PF37 A A C B PF39 A A C B PF41 A A C C PF42 A A C C PF43 A A C C PF44 A A C C PF45 A A C C PF47 A A C D PF48 A A C C PF49 A A C C PF50 A A C C PF51 A A C C PF60 A A C C PF62 A A C D PF82 A A C A PF88 A A C C PF94 A A C A PF96 A A C C PF98 A A C C
Comparative Data

(1107) Bioassays on BAW and CL were conducted according to the procedures outlined in Example A: Bioassays on Beet Armyworm (BAW) and Cabbage Looper (CL) using the indicated concentrations. The results are indicated in Table CD1 and Table CD2.

(1108) TABLE-US-00017 TABLE CD1 043 5 g/cm.sup.2 0.5 g/cm.sup.2 0.05 g/cm.sup.2 No. R.sup.10 BAW CL BAW CL BAW CL FC1 H 100* 100 100 100 0 0 F22 Cl 100 100 100 100 100 100 F19 Br 100 100 100 100 100 100 F6 CH.sub.3 100 100 100 100 F1 CF.sub.3 100 100 100 100 100 100 *Percent control (or mortality)

(1109) TABLE-US-00018 TABLE CD2 044 5 g/cm.sup.2 0.5 g/cm.sup.2 0.05 g/cm.sup.2 No. R.sup.10 BAW CL BAW CL BAW CL FC2 H 100* 100 100 100 0 0 F23 Cl 100 100 100 100 81 100 F18 Br 100 100 100 100 100 100 F67 I 100 100 100 100 100 100 F7 CH.sub.3 100 100 100 100 F2 CF.sub.3 100 100 100 100 100 100 *Percent control (or mortality)