AZOLINE COMPOUNDS SUBSTITUTED BY A CONDENSED RING SYSTEM

Abstract

Compounds of formula I are provided herein, as well as the use of these compounds for controlling invertebrate pests. Plant propagation material and agricultural and veterinary compositions including these compounds are also provided. Compounds for use as intermediate compounds in the preparation of the compounds of formula I are also described.

Claims

1. Azoline compounds of the formula I ##STR00046## wherein X.sup.1 is O or CH.sub.2; A is a group A.sup.1 or A.sup.2; wherein A.sup.1 is a group of following formula: ##STR00047## wherein # denotes the bond to an aromatic ring of formula (I); and W is selected from the group consisting of O and S; and A.sup.2 is a group —C(R.sup.7a)(R.sup.7b)—N(R.sup.52)—C(═O)—R.sup.62 B.sup.1, B.sup.2, B.sup.3, B.sup.4 and B.sup.5 are independently selected from the group consisting of N and CR.sup.2, wherein at most one of B.sup.1, B.sup.2, B.sup.3, B.sup.4 and B.sup.5 is N; R.sup.g1 and R.sup.g2 form together a bridging group selected from the group consisting of —CH.sub.2CH.sub.2O—, —OCH.sub.2CH.sub.2—, —CH.sub.2OCH.sub.2—, —OCH.sub.2O—, —CH.sub.2CH.sub.2S(O).sub.P—, —S(O).sub.pCH.sub.2CH.sub.2—, —CH.sub.2S(O)CH.sub.2—, —S(O).sub.pCH.sub.2S(O).sub.P—, —OCH.sub.2S(O)—, —S(O).sub.pCH.sub.2O—, —OCH.sub.2CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2O—, —CH.sub.2OCH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2OCH.sub.2—, —OCH.sub.2CH.sub.2O—, —OCH.sub.2H.sub.2—, —OCH.sub.2CH.sub.2—, —OCH.sub.2OCH.sub.2—, —CH.sub.2OCH.sub.2O—, —S(O).sub.pCH.sub.2CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2S(O).sub.p—, —CH.sub.2S(O)CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2S(O).sub.pCH.sub.2—, —S(O).sub.pCH.sub.2CH.sub.2S(O).sub.P—, —S(O).sub.pCH.sub.2S(O)CH.sub.2—, —CH.sub.2S(O).sub.pCH.sub.2S(O).sub.p—, —S(O).sub.pCH.sub.2CH.sub.2O—, —OCH.sub.2CH.sub.2S(O).sub.p—, —S(O).sub.pCH.sub.2OCH.sub.2—, —OCH.sub.2S(O)CH.sub.2—, —CH.sub.2OCH.sub.2S(O)— and —CH.sub.2S(O)CH.sub.2O—; wherein p is one of 0, 1, and 2, wherein each of H of the bridging group is a substituent independently selected from the group consisting of: hydrogen, halogen, methyl, halogenated methyl, hydroxyl, methoxy and halogenated methoxy; and wherein no more than two CH.sub.2 groups of the bridging group are replaced by a C═O group; R.sup.1 is C.sub.1-haloalkyl; each R.sup.2 is independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.2-haloalkoxy, and C.sub.1-C.sub.2-haloalkyl; R.sup.3a and R.sup.3b, independently of each other, are selected from the group consisting of hydrogen and halogen; R.sup.7a and R.sup.7b, independently of each other, are selected from the group consisting of hydrogen, cyano, methyl, and C.sub.1-haloalkyl; R.sup.51 and R.sup.52, independently of each other, are selected from the group consisting of hydrogen, C.sub.1-C.sub.3-alkyl, C.sub.2-C.sub.3-alkenyl, C.sub.2-C.sub.3-alkynyl, C.sub.1-C.sub.6-alkoxymethyl, and CH.sub.2—CN; R.sup.61 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkyl carrying no more than two radicals R.sup.81, C.sub.1-C.sub.6-haloalkyl carrying one radical R.sup.81, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl which may be substituted by 1 or 2 CN substituents, C.sub.3-C.sub.6-halocycloalkyl, —N(R.sup.101a)R.sup.101b, —CH═NOR.sup.91, phenyl, phenyl substituted with no more than five 1, 2, 3, 1, or 5 substituents R.sup.16, and a heterocyclic ring selected from rings E-1 to E-63 ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## wherein in rings E-1 to E-63 the zigzag line denotes an attachment point to the remainder of the molecule; k is 0, 1, 2 or 3; n is 0, 1 or 2; and R.sup.16 is as defined below; R.sup.62 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkyl substituted by no more than two radicals R.sup.82, C.sub.1-C.sub.6-haloalkyl carrying one radical R.sup.82, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl carrying a CN substituent, C.sub.3-C.sub.6-halocycloalkyl, —N(R.sup.102a)R.sup.102b, —C(═O)N(R.sup.112a)R.sup.112b, —CH═NOR.sup.92, phenyl, phenyl substituted with no more than five substituents R.sup.16, and a heterocyclic ring selected from rings of formulae E-1 to E-63 as defined above; each R.sup.81 is independently selected from the group consisting of OH, CN, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkyl carrying a CN substituent, C.sub.3-C.sub.8-cycloalkyl carrying a C.sub.1-haloalkyl substituent, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-haloalkylthio, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-haloalkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-haloalkylsulfonyl, —C(═O)N(R.sup.101c)R.sup.101d, phenyl, phenyl substituted with no more than five substituents R.sup.16, and a heterocyclic ring selected from rings E-1 to E-63 as defined above; each R.sup.82 is independently selected from the group consisting of OH, CN, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl carrying a CN substituent, C.sub.3-C.sub.6-cycloalkyl carrying a C.sub.1-haloalkyl substituent, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-haloalkylthio, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-haloalkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-haloalkylsulfonyl, —C(═O)N(R.sup.102c)R.sup.102d, phenyl, phenyl substituted with no more than five substituents R.sup.16, and a heterocyclic ring selected from rings E-1 to E-63 as defined above; R.sup.91 and R.sup.92, independently of each other, are selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, and C.sub.1-C.sub.6-haloalkyl; R.sup.101a, R.sup.102a, R.sup.102c and R.sup.112a, independently of each other, are selected the group consisting of from hydrogen and C.sub.1-C.sub.6-alkyl; R.sup.101b is selected from the group consisting of hydrogen, —C(═O)N(R.sup.14a)R.sup.14b, phenyl, phenyl substituted with no more than five substituents R.sup.16, and a heterocyclic ring selected from rings of formulae E-1 to E-42 as defined above; R.sup.102b is selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, CH.sub.2—CN, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, C.sub.3-C.sub.6-halocycloalkylmethyl, phenyl, phenyl substituted with no more than five substituents R.sup.16, and a heterocyclic ring selected from rings of formulae E-1 to E-42 as defined above; R.sup.101c is selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.3-alkynyl, and CH.sub.2—CN; R.sup.101d is selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, CH.sub.2—CN, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, C.sub.3-C.sub.6-halocycloalkylmethyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, phenyl, phenyl having no more than five substituents independently selected from the group consisting of hydrogen, halogen, cyano, nitro, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.2-C.sub.4-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, C.sub.1-C.sub.4-alkylthio, and C.sub.1-C.sub.4-haloalkylthio, and a heterocyclic ring selected from rings of formulae E-1 to E-63 as defined above; R.sup.102d and R.sup.112b, independently of each other, are selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl C.sub.3-C.sub.6-cycloalkyl carrying a CN substituent, C.sub.3-C.sub.6-halocycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, and C.sub.3-C.sub.6-halocycloalkylmethyl; R.sup.14a is selected from the group consisting of hydrogen and C.sub.1-C.sub.6-alkyl; R.sup.14b is selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, CH.sub.2—CN, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkoxy; and each R.sup.16 is one of: (i) independently selected from the group consisting of halogen, cyano, nitro, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.2-C.sub.4-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-halocycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-haloalkylthio, C.sub.1-C.sub.4-alkylsulfinyl, C.sub.1-C.sub.4-haloalkylsulfinyl, C.sub.1-C.sub.4-alkylsulfonyl, C.sub.1-C.sub.4-haloalkylsulfonyl, C.sub.1-C.sub.4-alkylcarbonyl, C.sub.1-C.sub.4-haloalkylcarbonyl, aminocarbonyl, C.sub.1-C.sub.4-alkylaminocarbonyl and di-(C.sub.1-C.sub.4-alkyl)aminocarbonyl; (ii) two R.sup.1 present on the same carbon atom of a saturated ring may form together ═O or ═S; or (iii) two R.sup.16 present on the same S or SO ring member of a heterocyclic ring may together form a group ═N(C.sub.1-C.sub.6-alkyl), ═NO(C.sub.1-C.sub.6-alkyl), ═NN(H)(C.sub.1-C.sub.6-alkyl) or ═NN(C.sub.1-C.sub.6-alkyl).sub.2; and N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof.

2. The compounds as claimed in claim 1, wherein X.sup.1 is O.

3. The compounds as claimed in claim 1, wherein X.sup.1 is CH.sub.2.

4. The compounds as claimed in claim 1, where W is O.

5. The compounds as claimed in claim 1, wherein A is a group A.sup.1, wherein R.sup.51 is hydrogen, and R.sup.61 is as defined in claim 1.

6. The compounds as claimed in claim 1, wherein R.sup.61 is selected from the group consisting of C.sub.1-C.sub.2-alkyl carrying one radical R.sup.81, C.sub.1-C.sub.2-haloalkyl carrying one radical R.sup.81, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl substituted by no more than CN substituents C.sub.3-C.sub.6-halocycloalkyl; and a heterocyclic ring selected from rings E-44 and E-53; wherein R.sup.81 is selected from the group consisting of C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl carrying a CN substituent, C.sub.3-C.sub.6-cycloalkyl carrying a C.sub.1-haloalkyl substituent, C.sub.3-C.sub.6-halocycloalkyl, —C(═O)N(R.sup.101c)R.sup.101d, and a heterocyclic ring selected from rings E-1 to E-63 as defined in claim 1; wherein R.sup.101c is selected from the group consisting of hydrogen and C.sub.1-C.sub.4-alkyl; and R.sup.101d is selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, and C.sub.1-C.sub.6-haloalkyl.

7. The compounds as claimed in claim 1, wherein R.sup.61 is selected from rings E-44-1 and E-53-1 ##STR00055## and R.sup.81 is selected from rings E-44-1 and E-57-1 ##STR00056## wherein n is one of 0, 1 and 2; and R.sup.16a is selected from the group consisting of hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.2-C.sub.4-haloalkynyl and CH.sub.2—(C.sub.3-C.sub.6-cycloalkyl).

8. The compounds as claimed in claim 1, wherein A is a group A.sup.2, wherein R.sup.7a is hydrogen; R.sup.7b is selected from the group consisting of hydrogen, CH.sub.3, CF.sub.3, and CN; R.sup.52 is selected from the group consisting of hydrogen and C.sub.1-C.sub.3-alkyl; and R.sup.62 is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.4-alkyl substituted by one radical R.sup.82, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl carrying a CN substituent, C.sub.3-C.sub.6-halocycloalkyl, phenyl, phenyl substituted with no more than five substituents R.sup.16, and a heterocyclic ring selected from rings of formulae E-1 to E-63 as defined in claim 1; where R.sup.82 is selected from the group consisting of CN, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl C.sub.3-C.sub.6-cycloalkyl carrying a CF.sub.3 substituent; C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-haloalkylthio, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-haloalkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-haloalkylsulfonyl, phenyl, phenyl substituted with no more than three substituents R.sup.16, and a heterocyclic ring selected from rings E-1 to E-63 as defined in claim 1; and R.sup.16 in phenyl and in rings E-1 to E-63 is selected from the group consisting of halogen, cyano, 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.

9. The compounds as claimed in claim 8, wherein R.sup.7a and R.sup.7b are hydrogen; R.sup.52 is hydrogen; and R.sup.62 is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.4-alkyl substituted by one radical R.sup.82, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl carrying a CN substituent, and C.sub.3-C.sub.6-halocycloalkyl; wherein R.sup.82 is selected from the group consisting of CN, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl carrying a CN substituent, C.sub.3-C.sub.6-cycloalkyl carrying a CF.sub.3 substituent, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-haloalkylthio, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-haloalkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl, and C.sub.1-C.sub.6-haloalkylsulfonyl.

10. The compounds as claimed in claim 1, where B.sup.1, B.sup.3, B.sup.4 and B.sup.5 are CR.sup.2 wherein R.sup.2 is as defined in claim 1, and B.sup.2 is CR.sup.2, wherein R.sup.2 is selected from the group consisting of halogen, C.sub.1-C.sub.2-haloalkoxy, and C.sub.1-C.sub.2-haloalkyl.

11. The compounds as claimed in claim 1, wherein R.sup.2 is selected from the group consisting of hydrogen, F, Cl, Br, OCF.sub.3 and CF.sub.3.

12. The compounds as claimed in claim 1, wherein R.sup.g1 and R.sup.g2 form together a bridging group selected from the group consisting of —CH.sub.2CH.sub.2O—, —OCH.sub.2CH.sub.2—, —CH.sub.2OCH.sub.2—, —OCH.sub.2O—, —CH.sub.2CH.sub.2S—, —SCH.sub.2CH.sub.2—, —CH.sub.2SCH.sub.2—, —SCH.sub.2S—, —OCH.sub.2S—, —SCH.sub.2O—, —CH.sub.2CH.sub.2S(O)—, —S(O)CH.sub.2CH.sub.2—, —CH.sub.2S(O)CH.sub.2—, —CH.sub.2CH.sub.2S(O).sub.2—, —S(O).sub.2CH.sub.2CH.sub.2—, —CH.sub.2S(O).sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2O—, and —OCH.sub.2CH.sub.2CH.sub.2-.

13. The compounds as claimed in claim 12, wherein R.sup.g1 and R.sup.g2 form together the bridging group selected from the group consisting of —CH.sub.2CH.sub.2O—, —OCH.sub.2CH.sub.2—, —CH.sub.2OCH.sub.2—, —OCH.sub.2O—, —CH.sub.2CH.sub.2S—, and —SCH.sub.2CH.sub.2—.

14. The compounds as claimed in claim 12, wherein R.sup.g1 and R.sup.g2 form together the bridging group selected from the group consisting of —CH.sub.2CH.sub.2O—, —CH.sub.2OCH.sub.2—, —OCH.sub.2O—, —CH.sub.2CH.sub.2S—, —CH.sub.2SCH.sub.2—, —CH.sub.2CH.sub.2S(O)—, —CH.sub.2S(O)CH.sub.2—, —CH.sub.2CH.sub.2S(O).sub.2—, —CH.sub.2S(O).sub.2CH.sub.2—, and —CH.sub.2CH.sub.2CH.sub.2O—.

15. The compounds as claimed in claim 1, wherein R.sup.1 is CF.sub.3.

16. The compounds as claimed in claim 1, where R.sup.3a and R.sup.3b are, independently of each other, selected from one of hydrogen and fluorine.

17. The compounds as claimed in claim 1, of formula IA ##STR00057## wherein R.sup.g1 and R.sup.g2 are as defined in claim 1; R.sup.2a is Cl, R.sup.2b is F, R.sup.2c is Cl; and R.sup.61 is CH.sub.2—C(O)—N(H)—R.sup.101d, wherein R.sup.101d is selected from the group consisting of C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkyl substituted with up to two fluorine atoms, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, CH.sub.2—CN, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, and C.sub.3-C.sub.6-cycloalkylmethyl; and N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof.

18. The compounds as claimed in claim 1, of formula IA ##STR00058## wherein R.sup.g1 and R.sup.g2 are as defined in claim 1; R.sup.2a is Cl, R.sup.2b is F, R.sup.2c is Cl; and R.sup.61 is —CH.sub.2—R.sup.81, wherein R.sup.81 is selected from rings E-5, E-6, E-7, E-19, E-25, E-27, E-44-1 and E-57-1 as defined in claim 1 ring E-5 carrying up to two substituents R.sup.16, ring E-6 carrying up to two substituents R.sup.16, ring E-7 carrying up to two substituents R.sup.16, ring E-19 carrying up to two substituents R.sup.16, and ring E-27 carrying up to two substituents R.sup.16, wherein each R.sup.16 is independently selected from the group consisting of halogen, cyano, nitro, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-haloalkyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-haloalkoxy, C.sub.1-C.sub.2-alkylthio, C.sub.1-C.sub.2-haloalkylthio, C.sub.1-C.sub.2-alkylsulfinyl, C.sub.1-C.sub.2-haloalkylsulfinyl, C.sub.1-C.sub.2-alkylsulfonyl, C.sub.1-C.sub.2-haloalkylsulfonyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.3-C.sub.4-halocycloalkyl, C.sub.2-C.sub.3-alkenyl, and C.sub.2-C.sub.3-alkynyl; and where ring E-25 carries one R.sup.1 substituent on the nitrogen atom in the 1-position and one of zero, one, and two further substituents R.sup.16, wherein the one R.sup.16 substituent bound in the 1-position is selected from the group consisting of C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.2-haloalkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.3-C.sub.4-halocycloalkyl, C.sub.2-C.sub.3-alkenyl, and C.sub.2-C.sub.3-alkynyl; and N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof.

19. The compounds as claimed in claim 17, of formula IA ##STR00059## wherein R.sup.g1 and R.sup.g2 are as defined in claim 1; R.sup.2a is Cl, R.sup.2b is F, R.sup.2c is Cl; and R.sup.61 is selected from the group consisting of rings E-2, E-4, E-6, E-8, E-9, E-44-1, E-46, E-51 and E-53-1 as defined in claim 1, ring E-2 carrying up to two substituents R.sup.16, ring E-4 carrying up to two substituents R.sup.16, ring E-6 carrying up to two substituents R.sup.16, ring E-8 carrying up to two substituents R.sup.16, ring E-9 carrying up to two substituents R.sup.16, and ring E-46 carrying up to two substituents R.sup.16, wherein each R.sup.16 is independently selected from the group consisting of halogen, cyano, nitro, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-haloalkyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-haloalkoxy, C.sub.1-C.sub.2-alkylthio, C.sub.1-C.sub.2-haloalkylthio, C.sub.1-C.sub.2-alkylsulfinyl, C.sub.1-C.sub.2-haloalkylsulfinyl, C.sub.1-C.sub.2-alkylsulfonyl, C.sub.1-C.sub.2-haloalkylsulfonyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.3-C.sub.4-halocycloalkyl, C.sub.2-C.sub.3-alkenyl, and C.sub.2-C.sub.3-alkynyl; and where ring E-51 is a ring of formula E-51-1 ##STR00060## wherein R.sup.16b is selected from the group consisting of hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-haloalkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.3-C.sub.4-halocycloalkyl, C.sub.2-C.sub.3-alkenyl, and C.sub.2-C.sub.3-alkynyl; and N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof.

20. The compounds as claimed in claim 1, of formula IA ##STR00061## wherein R.sup.g1 and R.sup.g2 are as defined in claim 1; R.sup.2a is Cl, R.sup.2b is F, R.sup.2c is Cl; and R.sup.61 is selected from the group consisting of C.sub.2-C.sub.4-alkyl, C.sub.2-C.sub.4-alkyl substituted with up to two fluorine atoms, cyclopropyl, C.sub.3-C.sub.5-halocycloalkyl, CH.sub.2—(C.sub.3-C.sub.5-halocycloalkyl), CH.sub.2-(1-cyano-(C.sub.3-C.sub.5-cycloalkyl)), C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, CH.sub.2—CN, and —CH═NOR.sup.91, wherein R.sup.91 is selected from one of C.sub.1-C.sub.3-alkyl and C.sub.1-C.sub.3-haloalkyl; and N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof.

21. The compounds as claimed in claim 1, of formula IA ##STR00062## wherein R.sup.g1 and R.sup.g2 are as defined in claim 1; R.sup.2a is Cl R.sup.2b is F, R.sup.2c is Cl; and R.sup.61 is N(H)R.sup.101b, wherein R.sup.101b is selected from the group consisting of —C(O)—N(H)R.sup.14b and rings E-1 and E-7 as defined in claim 1, wherein R.sup.14b is selected from the group consisting of C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-haloalkyl, and cyclopropyl; and wherein rings E-1 and E-7 k is one of 0, 1 and 2; and each R.sup.16 is independently selected from halogen, cyano, nitro, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-haloalkyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-haloalkoxy, C.sub.1-C.sub.2-alkylthio, C.sub.1-C.sub.2-haloalkylthio, C.sub.1-C.sub.2-alkylsulfinyl, C.sub.1-C.sub.2-haloalkylsulfinyl, C.sub.1-C.sub.2-alkylsulfonyl, C.sub.1-C.sub.2-haloalkylsulfonyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.3-C.sub.4-halocycloalkyl, C.sub.2-C.sub.3-alkenyl, and C.sub.2-C.sub.3-alkynyl; and N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof.

22. A compound of formula II ##STR00063## wherein B.sup.1, B.sup.2, B.sup.3, B.sup.4, B.sup.5, X.sup.1, R.sup.1, R.sup.3a, R.sup.3b, R.sup.g1 and R.sup.g2 are as defined in claim 1; and Y is selected from the group consisting of hydrogen and OR.sup.17, wherein R.sup.17 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4-alkyl, and C.sub.1-C.sub.4-haloalkyl.

23. At least one of an agricultural and a veterinary composition comprising: at least one of: (i) at least one compound of the formula I, as defined in claim 1, (ii) a stereoisomer thereof, and (ii) at least one agriculturally or veterinarily acceptable salt thereof; and at least one of at least one inert liquid agricultural or veterinarily acceptable carrier and at least one solid agriculturally or veterinarily acceptable carrier.

24. (canceled)

25. (canceled)

26. A method for protecting at least one plant propagation material and plants that grow therefrom from at least of attack and infestation by invertebrate pests, the method comprising treating the plant propagation material with a pesticidally effective amount of at least one of: (i) at least one compound of the formula I as defined in claim 1, (ii) a stereoisomer thereof, and (iii) at least one agriculturally acceptable salt thereof.

Description

EXAMPLES

[1010] The present invention is now illustrated in further details by the following examples, without imposing any limitation thereto.

ABBREVIATIONS

[1011] TLC thin layer chromatography [1012] r.t. room temperature (20-25° C.) [1013] PE petrol ether [1014] TFA trifluoroacetic acid [1015] EtOAc ethyl acetate [1016] THF tetrahydrofuran [1017] t-BuOH tert-butanol [1018] DMAP 4-(dimethylamino)-pyridine [1019] LDA lithiumdiisopropylamide [1020] TsCl tosylchloride [1021] MTBE methyl-tert-butyl ether [1022] DMF N,N-dimethylformamide [1023] DCM dichloromethane [1024] PyBrOP bromo-tris-pyrrolidino phosphoniumhexafluorophosphate [1025] NBS N-bromosuccinimide [1026] MeOH methanol [1027] TEA trimethylamine [1028] dppf 1,1′-bis(diphenylphosphino)ferrocen [1029] MeCN acetonitrile [1030] EtOH ethanol [1031] m-CPBA meta-chloroperbenzoic acid [1032] PPh.sub.3 triphenylphosphine

I. Preparation Examples

[1033] Compounds can be characterized e.g. by coupled High Performance Liquid Chromatography/mass spectrometry (HPLC/MS), by .sup.1H-NMR and/or by their melting points.

[1034] Analytical HPLC column:

[1035] HPLC method 1: Phenomenex Kinetex 1.7 μm XB-C18 100A; 50×2.1 mm; mobile phase: A: water+0.1% trifluoroacetic acid (TFA); B: acetonitrile+0.1% TFA; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0.8-1.0 ml/min in 1.51 minutes at 60° C.

[1036] HPLC method 2: Phenomenex Kinetex 1.7 μm XB-C18 100A; 50×2.1 mm; mobile phase: A: water+0.1% trifluoroacetic acid (TFA); B: acetonitrile+0.1% TFA; gradient: 5-100% B in 1.25 minutes; 100% B 0.70 min; flow: 0.8-1.0 ml/min in 1.51 minutes at 60° C. MS method: ESI positive, Mass range (m/z): 100-700.

[1037] .sup.1H-NMR: The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m=multiplett, q=quartett, t=triplett, d=doublet and s=singlett.

Preparation Examples

Example 1: Synthesis of 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-(1,1-dioxothietan-3-yl)-2,3-dihydrobenzothiophene-7-carboxamide (Compound I-7)

Step 1: Preparation of tert-butyl 4-bromo-2-fluoro-benzoate

[1038] To a solution of 4-bromo-2-fluoro-benzoic acid (100.0 g, 0.46 mol) in THF/t-BuOH (800 mL/400 mL) was added Boc.sub.2O (150.0 g, 0.69 mol) and DMAP (5.6 g, 46.0 mmol), the mixture was stirred at 80° C. for 13h. TLC (PE:EtOAc=10:1) showed the reaction was completed. After removal of the solvent, the residue was dissolved in water and extracted with EtOAc (500 mL×3), the organic layer was dried over Na.sub.2SO.sub.4 and concentrated to give the crude product, which was purified by column chromatography (PE:EtOAc=100:1) to give the title compound (120.0 g, 95.5%) as a colorless oil.

[1039] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.69-7.78 (m, 1H) 7.26-7.34 (m, 2H) 1.58 (s, 9H)

Step 2: tert-Butyl 4-bromo-2-fluoro-3-(2-hydroxyethyl)benzoate

[1040] To a solution of tert-butyl 4-bromo-2-fluoro-benzoate (60.0 g, 0.22 mol) in THF was added LDA (130 mL, 0.26 mol) drop wise at −78° C., the mixture was stirred at this temperature for 4h, then oxirane (77.0 g, 1.75 mol) was added. The mixture was stirred at this temperature for another 6h, then the reaction mixture was poured into aq. NH.sub.4Cl (300 mL) and extracted with EtOAc (400 mL×3). The organic layer was dried over Na.sub.2SO.sub.4 and concentrated to give the crude product, which was purified by silica gel chromatograph (PE:EtOAc=10:1-5:1) to give the title compound (14.0 g, 20.0%) as a yellow solid.

[1041] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.61 (t, J=8.03 Hz, 1H) 7.40 (d, J=8.28 Hz, 1H) 3.87 (t, J=6.90 Hz, 2H) 3.16 (t, J=6.90, 2.51 Hz, 2H) 1.60 (s, 9H)

Step 3: tert-Butyl 4-bromo-2-fluoro-3-[2-(p-tolylsulfonyloxy)ethyl]benzoate

[1042] To a solution of tert-butyl 4-bromo-2-fluoro-3-(2-hydroxyethyl)benzoate (10.0 g, 31.4 mmol) in pyridine was added TsCl (9.0 g, 47.2 mmol) in portions at 0° C. The mixture was stirred at 15° C. for 14h. TLC (PE:EtOAc=10:1) showed the reaction was complete. After removal of the solvent, the residue was dissolved in water, extracted with MTBE (200 mL×3), the organic layer was dried over Na.sub.2SO.sub.4 and concentrated to give the crude product (17 g), which was used directly in the next step without further purification.

[1043] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.61 (t, J=8.16 Hz, 1H) 7.40 (d, J=8.82 Hz, 1H) 3.87 (t, J=6.84 Hz, 2H) 3.15 (td, J=6.84, 2.65 Hz, 2H) 1.59 (s, 9H)

Step 4: tert-Butyl 4-bromo-2,3-dihydrobenzothiophene-7-carboxylate

[1044] To a solution of tert-butyl 4-bromo-2-fluoro-3-[2-(p-tolylsulfonyloxy)ethyl]benzoate (17.0 g crude, 54.1 mmol) in DMF (200 mL) was added Na.sub.2S (5.0 g, 65.0 mmol), the mixture was stirred at 60° C. for 14h. TLC (PE:EtOAc=10:1) showed the reaction was complete. After removal of the solvent, the residue was dissolved in EtOAc and washed with water (100 mL×2), the organic layer was dried over Na.sub.2SO.sub.4 and concentrated to give the crude product, which was purified by column chromatography (PE:EtOAc=10:1) to give the title compound (6.9 g, 70.0% for 2 steps) as a colorless oil.

[1045] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.62 (d, J=8.38 Hz, 1H) 7.19 (d, J=8.38 Hz, 1H) 3.38 (d, J=7.06 Hz, 2H) 3.31 (d, J=7.06 Hz, 2H) 1.60 (s, 9H)

Step 5: tert-butyl 4-acetyl-2,3-dihydrobenzothiophene-7-carboxylate

[1046] To a solution of tert-butyl 4-bromo-2,3-dihydrobenzothiophene-7-carboxylate (6.9 g, 22.0 mmol) in DMF/H.sub.2O (200 mL/60 mL) was added K.sub.2CO.sub.3 (6.2 g, 44.9 mmol) and Pd(PPh.sub.3).sub.2Cl.sub.2 (0.34 g, 0.44 mmol), then tributyl(1-ethoxyvinyl)stannane (9.5 g, 26.4 mmol) was added, the mixture was stirred at 110° C. under N.sub.2 for 3h. TLC (PE:EtOAc=5:1) showed the reaction was completed. To the resulting mixture was added KF (50 g) and stirred for an additional 1 h. After removal of the solvent, the residue was dissolved in water and extracted with EtOAc (100 mL×3), the organic layer was dried over Na.sub.2SO.sub.4 and concentrated, then the residue was dissolved in aq. HCl/THF (0.6 M) and stirred for 12h. After that, it was extracted with EtOAc (100 mL×3), the organic layer was dried over Na.sub.2SO.sub.4 and concentrated to give the crude product, which was purified by column chromatography (PE:EtOAc=20:1) to give the title compound (2.8 g, 45.8%) as a yellow solid.

[1047] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.86 (d, J=7.94 Hz, 1H) 7.48 (d, J=7.94 Hz, 1H) 3.62 (t, J=8.16 Hz, 2H), 3.21-3.31 (m, 2H) 2.60 (s, 3H) 1.62 (s, 9H)

Step 6: tert-Butyl 4-[(E/Z)-3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-but-2-enoyl]-2,3-dihydrobenzothiophene-7-carboxylate

[1048] ##STR00035##

[1049] To a solution of tert-butyl 4-acetyl-2,3-dihydrobenzothiophene-7-carboxylate (2.8 g, 10.1 mmol) and 1-(3,5-dichloro-4-fluoro-phenyl)-2,2,2-trifluoro-ethanone 3 (5.2 g, 20.1 mol) in 1,2-dichloroethane (80 mL) was added K.sub.2CO.sub.3 (2.1 g, 15.1 mmol), then triethylamine (1.5 g, 15.1 mmol) was added. The mixture was stirred for at 120° C. under N.sub.2 for 14h. TLC (PE:EtOAc=10:1) showed the reaction was complete. After removal of the solvent, the residue was purified by silica gel chromatography (PE:EtOAc=80:1) to give the title compound (6.0 g, crude as a mixture of E/Z isomers) as a yellow solid.

[1050] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.30-7.36 (m, 2H) 7.21 (d, J=6.02 Hz, 2H) 3.45-3.53 (m, 2H) 3.22-3.32 (m, 2H), 1.64 (s, 9H)

Step 7: tert-Butyl 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzothiophene-7-carboxylate

[1051] ##STR00036##

[1052] To a solution of tert-butyl 4-[(E/Z)-3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-but-2-enoyl]-2,3-dihydrobenzothiophene-7-carboxylate (6.0 g crude, 11.5 mol) in 1,2-dichloroethane (120 mL) was added NH.sub.2OH.HCl (1.6 g. 23.0 mmol) and tetrabutylammoniumbromide (0.6 g, 1.9 mmol), then a solution of NaOH (1.8 g, 45.0 mmol) in water (30 mL) was added drop wise. The mixture was stirred for 3h, TLC (PE:EtOAc=10:1) showed the reaction was complete. Then the reaction solution was separated and the organic layer was dried over Na.sub.2SO.sub.4, concentrated to give the crude product, which was purified by silica gel chromatograph (PE:EtOAc=80:1) to give the title compound (3.8 g, 70.3% for 2 steps) as a solid.

[1053] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.84 (d, J=7.94 Hz, 1H) 7.59 (d, J=6.17 Hz, 2H) 7.01 (d, J=8.38 Hz, 1H) 4.14 (d, J=17.20 Hz, 1H) 3.75 (d, J=17.20 Hz, 1H) 3.64 (q, J=8.09 Hz, 2H) 3.29-3.38 (m, 2H) 1.63 (s, 9H)

Step 8: 4-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzothiophene-7-carboxylic acid

[1054] ##STR00037##

[1055] To a solution of tert-butyl 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzothiophene-7-carboxylate (3.8 g, 7.1 mmol) in DCM (100 mL) was added TFA (30 mL), then the mixture was stirred at r.t. for 3h. TLC (PE:EtOAc=10:1) showed the reaction was complete. After removal of the solvent, the residue was washed with hexane to give the title compound (2.8 g, 82%) as a solid.

[1056] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=13.29 (br. s., 1H) 7.75-7.91 (m, 4H) 7.35 (d, J=7.94 Hz, 1H) 4.30-4.43 (m, 2H), 3.45-3.52 (m, 2H) 3.21-3.28 (m, 2H)

Step 9: 4-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-(1,1-dioxothietan-3-yl)-2,3-dihydrobenzothiophene-7-carboxamide (compound I-7)

[1057] ##STR00038##

[1058] To a solution of 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzothiophene-7-carboxylic acid (200 mg, 0.42 mmol), 1,1-dioxothietan-3-amine hydrochloride (0.08 g, 0.5 mmol, 1.2 equiv.) and PyBrop (0.23 g, 0.5 mmol, 1.2 equiv.) in dichloromethane (20 mL) was added Hünig base (0.17 g, 1.33 mmol, 3.2 equiv.) at room temperature. The mixture was stirred over night and a saturated aqueous solution of NH.sub.4Cl was added. Extraction with dichloromethane (50 mL×2) afforded an organic layer that was washed with water, dried over Na.sub.2SO.sub.4 and concentrated in vacuum. Purification of the residue via silica gel chromatography afforded the title compound (190 mg, 76%).

[1059] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.59 (m, 3H), 7.28 (m, 1H), 7.01 (m, 1H), 4.86 (m, 1H), 4.61 (m, 2H), 4.15 (m, 3H), 3.76 (d, 1H), 3.50-3.68 (m, 2H), 3.31 (m, 2H).

Example 2

[1060] In analogy to steps 5 to 9 of example 1, compounds of the formulae I-1 to I-5, I-11 to I-12, I-14 to I-19 and I-28 were prepared. The starting material tert-butyl 4-bromo-2,3-dihydrobenzofuran-7-carboxylate was used instead.

Step 1: tert-Butyl 4-bromo-2,3-dihydrobenzofuran-7-carboxylate

[1061] To a solution of tert-butyl 4-bromo-2-fluoro-3-(2-hydroxyethyl)benzoate (10.0 g, 31.4 mmol) in DMF (2 L) was added Cs.sub.2CO.sub.3 (15.4 g, 47.2 mmol), the mixture was stirred at 90° C. for 14h. TLC (PE:EtOAc=5:1) showed the reaction was complete. After removal of the solvent, the residue was dissolved in water and extracted with EtOAc (300 mL×3), the organic layer was dried over Na.sub.2SO.sub.4 and concentrated to give the crude product, which was purified by column chromatography (PE:EtOAc=10:1) to give the title compound (6.5 g, 69.5%) as a solid.

[1062] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.52 (d, J=8.38 Hz, 1H) 6.98 (d, J=8.82 Hz, 1H) 4.75 (t, J=8.82 Hz, 2H) 3.21 (t, J=8.82 Hz, 2H) 1.57 (s, 9H).

Example 3

[1063] In analogy to steps 5 to 9 of example 1, compounds of the formulae I-22 to I-24, I-29, I-35 to I-41 were prepared. The starting material methyl 7-bromo-1,3-dihydroisobenzofuran-4-carboxylate was used instead.

Step 1: 1,2-Bis(bromomethyl)-3-nitro-benzene

[1064] To a solution of 1,2-dimethyl-3-nitro-benzene (102 g, 0.675 mol) and NBS (258.3 g, 1.45 mol) in CCl.sub.4 (450 mL) was added benzoyl peroxide (1.68 g, 6.8 mmol) in one portion. The reaction mixture was stirred and refluxed at 90° C. under N.sub.2 for 2h, additional benzoyl peroxide (6.5 g, 0.027 mol) was added and the reaction mixture was stirred and refluxed at 90° C. under N.sub.2 for 2h and then cooled to room temperature. The reaction mixture was filtered and washed with CCl.sub.4. The yellow filtrate was concentrated to give 1,2-bis(bromomethyl)-3-nitrobenzene as a crude oil. The crude product was purified by column chromatography (PE:EtOAc=60:1) to give the title compound (crude 180 g, 87.3%) as an oil.

[1065] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.85 (d, J=7.94 Hz, 1H) 7.73 (d, J=7.94 Hz, 1H) 7.47-7.55 (m, 1H) 4.87 (s, 2H) 4.78 (s, 2H).

Step 2: 4-Nitro-1,3-dihydroisobenzofuran

[1066] To a flask containing 1,2-bis(bromomethyl)-3-nitro-benzene (180 g, 0.59 mol,) was added neutralized alumina (816 g, 8 mol) and toluene (1 L) and the suspension was heated at an external temperature of 120° C. for 18 hours. The reaction mixture was filtered to remove the alumina and washed with ethyl acetate. The filtrate was concentrated to give a yellow solid which was purified by silica gel chromatography (PE:EtOAc=20:1) to give the title compound (17.5 g, 18%) as an oil.

[1067] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.14 (d, J=7.94 Hz, 1H), 7.55-7.59 (m, 1H), 7.47-7.52 (m, 1H), 5.54 (s, 2H), 5.21 (s, 2H).

Step 3: 1,3-Dihydroisobenzofuran-4-amine

[1068] A solution of 4-nitro-1,3-dihydroisobenzofuran (50 g, 0.303 mol) in MeOH (800 mL) was hydrogenated with Pd/C (5 g) under H.sub.2 at 50 psi. The reaction was filtered and then concentrated to give the desired title compound (35 g, 85.5%) as a solid.

[1069] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.05-7.15 (m, 1H), 6.68 (d, J=7.15 Hz, 1H), 6.58 (d, J=7.65 Hz, 1H), 5.12 (br. s., 2H), 5.04 (br. s., 2H), 3.56 (br. s., 2H).

Step 4: tert-Butyl N-(1,3-dihydroisobenzofuran-4-yl)carbamate

[1070] To a solution of 1,3-dihydroisobenzofuran-4-amine (36 g, 0.267 mol) in THF (500 mL) was added TEA (54.4 g, 0.533 mol) and Boc.sub.2O (87.2 g, 0.400 mol) in dropwise. The mixture was stirred and heated at an external temperature of 80° C. for 6 h. The reaction was filtered, diluted into water (300 mL), extracted with EtOAc (500 mL×3), the organic layer was washed brine (100 mL), dried over Na.sub.2SO.sub.4, filtered and concentrated under reduce pressure to give the crude product. The crude product was purified by column chromatography (PE:EtOAc=30:1) to give the title compound (35 g, 55.9%) as a solid.

[1071] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.59 (d, J=7.94 Hz, 1H), 7.23-7.32 (m, 1H), 6.98 (d, J=7.50 Hz, 1H), 6.30 (br. s., 1H), 5.15 (s, 2H), 5.11 (s, 2H), 1.55 (s, 9H).

Step 5: tert-Butyl N-(7-bromo-1,3-dihydroisobenzofuran-4-yl)carbamate

[1072] To a solution of tert-butyl N-(1,3-dihydroisobenzofuran-4-yl)carbamate (25 g, 0.085 mol) in DMF (300 mL), NBS (16.6 g, 0.094 mol) was added in portions at 0° C. The reaction mixture was stirred at 25° C. under N.sub.2 for 3h. The reaction was filtered, diluted into water (1000 mL), extracted with EtOAc (500 mL×3), the organic layer was washed brine (300 mL), dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure to give the crude product. The crude product was purified by column chromatography (PE:EtOAc=50:1) to give the title compound (25 g, 74.8%).

[1073] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.49 (d, J=8.28 Hz, 1H), 7.33 (d, J=8.53 Hz, 1H), 6.26 (br. s., 1H), 5.16 (s, 2H), 5.08 (s, 2H), 1.51 (s, 9H).

Step 6: Methyl 7-(tert-butoxycarbonylamino)-1,3-dihydroisobenzofuran-4-carboxylate

[1074] To a stirred solution of tert-butyl N-(7-bromo-1,3-dihydroisobenzofuran-4-yl)carbamate (30 g, 0.095 mol) in MeOH (800 mL) in a 1 L autoclave, Na.sub.2CO.sub.3 (30.4 g, 0.286 mol) and Pd(dppf)Cl.sub.2 (5 g) was added, the mixture was stirred and heated at 120° C. under CO at 1 MPa for 18 h. After cooling to room temperature, the mixture was filtered, concentrated, the residue was purified by chromatography on silica gel (PE:EtOAc=10:1) to give the title compound (24 g, 85.7%).

[1075] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.93 (q, J=8.53 Hz, 2H) 6.28 (br. s., 1H) 5.42 (s, 2H) 5.10 (s, 2H) 3.90 (s, 3H) 1.55 (s, 9H).

Step 7: Methyl 7-amino-1,3-dihydroisobenzofuran-4-carboxylate

[1076] To a stirred solution of methyl 7-(tert-butoxycarbonylamino)-1,3-dihydroisobenzofuran-4-carboxylate (20 g, 0.095 mol) in DCM (800 mL), TFA (80 mL) was added dropwise at OoC, the mixture was stirred at 18° C. for 18 h. The mixture was concentrated, diluted into aq. Na.sub.2CO.sub.3 solution (500 mL), extracted with EtOAc (300 mL×3) dried over Na.sub.2SO.sub.4, concentrated to give the title compound (15 g, crude).

[1077] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=7.76 (d, J=8.28 Hz, 1H) 6.56 (d, J=8.28 Hz, 1H) 5.35 (s, 2H) 4.99 (s, 2H) 3.83 (s, 3H)

Step 8: Methyl 7-bromo-1,3-dihydroisobenzofuran-4-carboxylate

[1078] To a stirred solution of methyl 7-amino-1,3-dihydroisobenzofuran-4-carboxylate (15 g, 0.078 mol) in MeCN (500 mL), CuBr (16.8 g, 0.116 mol) and tert-butyl nitrite (12 g, 0.116 mol) was added, the mixture was stirred at 68° C. for 18 h. The mixture was filtered, concentrated, the residue was purified by chromatography on silica gel (PE:EtOAc=50:1) to give the title compound (15 g, crude).

[1079] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=8.05 (d, J=7.94 Hz, 1H) 7.86 (d, J=7.94 Hz, 1H) 5.38 (dd, J=−10.36, 1.54 Hz, 4H) 3.95 (s, 3H) 2.64 (s, 3H).

Example 4

[1080] In analogy to example 3, compounds of formulae I-51 and I-52 were prepared using 4-nitro-1,3-dihydro-2-benzothiophene as starting material

[1081] To a solution of 1,2-bis(bromomethyl)-3-nitro-benzene (185.0 g, 0.6 mol) in EtOH (3 L) was added the Na.sub.2S.9H2O (144.2 g, 0.6 mol), then the mixture was heated under reflux for 10 h. The mixture was concentrated to remove EtOH, then water (500 mL) was added and extracted with DCM (500 mL×4), the combined organic layer was washed with brine (300 mL×2), dried over Na.sub.2SO.sub.4 and concentrated, purified by silica gel column chromatography (PE:EtOAc=50:1 to 20:1) to give the title compound (80.1 g, yield 36.9%).

[1082] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=4.34 (s, 2H) 4.72 (s, 2H) 7.38-7.48 (m, 1H) 7.57 (d, J=7.5 Hz, 1H) 8.11 (d, J=8.4 Hz, 1H).

Example 5: 7-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,2-dioxo-1,3-dihydro-2-benzothiophene-4-carboxylic acid

[1083] ##STR00039##

[1084] To a solution of 7-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-1,3-dihydro-2-benzothiophene-4-carboxylic acid (2.5 g, 0.0052 mol) in DCM (100 mL) was added m-CPBA (2.4 g, 0.0115 mol) at 0° C. Then it was stirred at 20° C. under N.sub.2 for 12h. The reaction mixture was concentrated. The crude product was purified by preparative HPLC to give the title compound (1.5 g, 58%).

[1085] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=4.33-4.51 (m, 2H) 4.63 (d, J=5.29 Hz, 2H) 4.77 (s, 2H) 7.71-7.85 (m, 3H) 8.07 (d, J=8.38 Hz, 1H).

Example 6

[1086] In analogy to example 5, all other sulfur oxidation products, such as compounds I-42 to I-50 were prepared.

Example 7: Synthesis of N-[[4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzofuran-7-yl]methyl]butanamide (compound I-16)

Step 1: [4-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzofuran-7-yl]methanol

[1087] ##STR00040##

[1088] To a solution of 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzofuran-7-carboxylic acid (6 g, 13 mmol) in THF (100 mL) was added BH.sub.3.Me.sub.2S (3.9 mL, 39 mmol) at 0° C. The mixture was stirred at 25° C. for 15h. The reaction mixture was quenched with MeOH (39 mL) and concentrated to give the product, which was purified by column chromatography (PE:EtOAc=20:1-10:1) to give the title compound (4 g, 69%).

[1089] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=3.42-3.52 (m, 2H) 3.73 (d, J=17.07 Hz, 1H) 4.14 (br. s., 1H) 4.64-4.73 (m, 4H) 6.82 (d, J=7.78 Hz, 1H) 7.20 (d, J=7.78 Hz, 1H) 7.59 (d, J=6.02 Hz, 2H).

Step 2: [4-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzofuran-7-yl]methyl methanesulfonate

[1090] ##STR00041##

[1091] To a solution of [4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzofuran-7-yl]methanol (4 g, 9 mmol) in DCM (60 mL) was added TEA (2.7 g, 27 mmol) and MsCl (2 g, 18 mmol) at 0° C. The mixture was stirred at 25° C. for 10h. Then the reaction mixture was diluted with aq. NH.sub.4Cl (100 mL) and extracted with EtOAc (100 mL×3), the combined organic layers were dried over Na.sub.2SO.sub.4 and concentrated, then the residue was purified by silica gel chromatograph (PE:EtOAc=15:1˜10:1) to give the title compound (4.6 g, 98%).

[1092] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=3.16 (s, 3H) 3.46-3.57 (m, 2H) 3.70 (s, 1H) 4.16 (s, 1H) 4.61 (s, 2H) 4.72 (t, J=8.91 Hz, 2H) 6.84 (d, J=8.03 Hz, 1H) 7.23-7.29 (m, 1H) 7.60 (d, J=6.02 Hz, 2H)

Step 3: 3-[7-(Azidomethyl)-2,3-dihydrobenzofuran-4-yl]-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazole

[1093] ##STR00042##

[1094] To a solution of [4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzofuran-7-yl]methyl methanesulfonate (4.6 g, 9 mmol) in DMF (60 mL) was added NaN.sub.3 (1.2 g, 18 mmol) and the mixture was stirred at 25° C. under N.sub.2 for 13h. The reaction mixture was diluted with water (100 mL) and extracted with MTBE (100 mL×3), the combined organic layers are dried over with Na.sub.2SO.sub.4 and concentrated to give the title compound (4 g, 97.6%).

[1095] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=3.38-3.49 (m, 2H) 3.71 (d, J=17.64 Hz, 1H) 4.06-4.11 (m, 1H) 4.27 (br. s., 2H) 4.60 (t, J=8.82 Hz, 2H) 6.80 (d, J=7.94 Hz, 1H) 7.08 (d, J=7.94 Hz, 1H) 7.53 (d, J=5.73 Hz, 2H).

Step 4: [4-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzofuran-7-yl]methanamine

[1096] ##STR00043##

[1097] To a solution of 3-[7-(azidomethyl)-2,3-dihydrobenzofuran-4-yl]-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazole (4 g, 8 mmol) in THF (80 mL) and H.sub.2O (80 mL) was added PPh.sub.3 (2.7 g, 10 mmol), the mixture was stirred at 85° C. under N.sub.2 for 2h. The mixture was extracted with EtOAc (100 mL×3), the combined organic layers are dried over Na.sub.2SO.sub.4 and concentrated, then the residue was purified by silica gel chromatography (DCM:MeOH=15:1-10:1) to give the title compound (1.5 g, 40%).

[1098] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=3.39-3.54 (m, 2H) 3.72 (d, J=17.20 Hz, 1H) 3.83 (s, 2H) 4.12 (d, J=17.20 Hz, 1H), 4.66 (t, J=8.82 Hz, 2H) 6.80 (d, J=7.50 Hz, 1H) 7.13 (d, J=7.94 Hz, 1H) 7.59 (d, J=6.17 Hz, 2H).

Step 5: N-[[4-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzofuran-7-yl]methyl]butanamide compound I-16)

[1099] ##STR00044##

[1100] To a solution of 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2,3-dihydrobenzofuran-7-yl]methanamine (0.15 g, 0.33 mmol) in THF (10 mL) was added triethylamine (0.07 g, 0.67 mmol, 2.0 equiv.), followed by n-butyric chloride (0.04 g, 0.4 mmol, 1.2 equiv.) at room temperature and stirred over night. The reaction mixture was concentrated in vacuum and the residue was purified via silica gel chromatography to yield the title compound (0.11 g, 65%).

[1101] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ=0.93 (t, 3H), 1.63 (m, 2H), 2.18 (m, 2H), 3.37-3.55 (m, 2H), 3.72 (d, 1H), 4.11 (d, 1H), 4.40 (m, 1H), 4.65 (m, 2H), 6.10 (br. s, 1H), 6.79 (m, 1H), 7.17 (m, 1H), 7.69 (m, 2H).

[1102] In analogy to the above described examples, compounds I-1 to I-57 as shown in tables C.1 and C.2 were prepared.

##STR00045##

TABLE-US-00002 TABLE C.1 compounds of formula I-A with R.sup.2a = R.sup.2c = Cl, R.sup.2b = F m/z No. R.sup.g1 R.sup.g2 A method t.sub.R [min] [M + H].sup.+ I-1 #—CH.sub.2—CH.sub.2—O—* pyrimidin-2-ylmethylcarbamoyl 1 1.354 554.9 I-2 #—CH.sub.2—CH.sub.2—O—* (1,1-dioxothietan-3-yl)carbamoyl 1 1.341 567.0 I-3 #—CH.sub.2—CH.sub.2—O—* [2-oxo-2-(2,2,2- 1 1.366 602.1 trifluoroethylamino)ethyl]carbamoyl I-4 #—CH.sub.2—CH.sub.2—O—* 2-pyridylmethylcarbamoyl 1 1.169 554.1 I-5 #—CH.sub.2—CH.sub.2—O—* [2-(allylamino)-2-oxo- 1 1.336 560.1 ethyl]carbamoyl I-6 #—CH.sub.2—CH.sub.2—S—* pyrimidin-2-ylmethylcarbamoyl 1 1.356 570.9 I-7 #—CH.sub.2—CH.sub.2—S—* (1,1-dioxothietan-3-yl)carbamoyl see Example 1 I-8 #—CH.sub.2—CH.sub.2—S—* [2-oxo-2-(2,2,2- 1 1.353 618.0 trifluoroethylamino)ethyl]carbamoyl I-9 #—CH.sub.2—CH.sub.2—S—* 2-pyridylmethylcarbamoyl 1 1.192 570.0 I-10 #—CH.sub.2—CH.sub.2—S—* [2-(allylamino)-2-oxo- 1 1.347 576.0 ethyl]carbamoyl I-11 #—CH.sub.2—CH.sub.2—O—* (3,3,3- 1 1.407 559.0 trifluoropropanoylamino)methyl I-12 #—CH.sub.2—CH.sub.2—O—* [(4S)-2-ethyl-3-oxo-isoxazolidin-4- 1 1.387 576.0 yl]carbamoyl I-13 #—CH.sub.2—CH.sub.2—S—* [(4S)-2-ethyl-3-oxo-isoxazolidin-4- 1 1.385 592.0 yl]carbamoyl I-14 #—CH.sub.2—CH.sub.2—O—* [(2-ethylsulfonylacetyl)amino]methyl 1 1.334 583.0 I-15 #—CH.sub.2—CH.sub.2—O—* (cyclopropanecarbonylamino)methyl 1 1.385 517.0 I-16 #—CH.sub.2—CH.sub.2—O—* (butanoylamino)methyl 1 1.402 519.0 I-17 #—CH.sub.2—CH.sub.2—O—* acetamidomethyl 1 1.318 491.0 I-18 #—CH.sub.2—CH.sub.2—O—* (propanoylamino)methyl 1 1.360 505.0 I-19 #—CH.sub.2—CH.sub.2—O—* [(2- 1 1.306 569.1 methylsulfonylacetyl)amino]methyl I-20 #—CH.sub.2—CH.sub.2—S(═O)—* pyrimidin-2-ylmethylcarbamoyl 1 1.146 586.9 I-21 #—CH.sub.2—CH.sub.2—S(═O).sub.2—* pyrimidin-2-ylmethylcarbamoyl 1 1.215 602.9 I-22 #—CH.sub.2—O—CH.sub.2—* [2-oxo-2-(2,2,2- 1 1.331 601.9 trifluoroethylamino)ethyl]carbamoyl I-23 #—CH.sub.2—O—CH.sub.2—* (2-ethyl-3-oxo-isoxazolidin-4- 1 1.336 576.0 yl)carbamoyl I-24 #—CH.sub.2—O—CH.sub.2—* pyrimidin-2-ylmethylcarbamoyl 1 1.303 555.0 I-26 #—CH.sub.2—CH.sub.2—CH.sub.2—O—* methoxycarbonyl 1 1.443 492.0 I-27 #—CH.sub.2—CH.sub.2—CH.sub.2—O—* CO.sub.2H 1 1.341 477.9 I-28 #—CH.sub.2—CH.sub.2—O—* (2-ethyl-3-oxo-isoxazolidin-4- 1 1.404 576.0 yl)carbamoyl I-29 #—CH.sub.2—O—CH.sub.2—* 2-pyridylmethyl carbamoyl 1 1.154 554.0 I-30 #—CH.sub.2—CH.sub.2—CH.sub.2—O—* pyrimidin-2-ylmethylcarbamoyl 1 1.352 569.0 I-31 #—CH.sub.2—CH.sub.2—CH.sub.2—O—* 2-pyridylmethylcarbamoyl 2 1.162 568.0 I-32 #—CH.sub.2—CH.sub.2—CH.sub.2—O—* [2-oxo-2-(2,2,2- 1 1.357 616.0 trifluoroethylamino)ethyl]carbamoyl I-33 #—CH.sub.2—CH.sub.2—CH.sub.2—O—* (1,1-dioxothietan-3-yl)carbamoyl 1 1.328 580.9 I-34 #—CH.sub.2—CH.sub.2—CH.sub.2—O—* [(4R)-2-ethyl-3-oxo-isoxazolidin-4- 1 1.376 590.0 yl]carbamoyl I-35 #—CH.sub.2—O—CH.sub.2—* [2-(allylamino)-2-oxo- 1 1.300 229.6 ethyl]carbamoyl I-36 #—CH.sub.2—O—CH.sub.2—* cyclobutylcarbamoyl 1 1.423 516.7 I-37 #—CH.sub.2—O—CH.sub.2—* thietan-3-ylcarbamoyl 1 1.372 534.9 I-38 #—CH.sub.2—O—CH.sub.2—* cyclopropylmethylcarbamoyl 1 1.377 517.0 I-39 #—CH.sub.2—O—CH.sub.2—* cyclopropylcarbamoyl 1 1.325 502.9 I-40 #—CH.sub.2—O—CH.sub.2—* [(4S)-2-ethyl-3-oxo-isoxazolidin-4- 1 1.296 575.9 yl]carbamoyl I-41 #—CH.sub.2—O—CH.sub.2—* (1,1-dioxothietan-3-yl)carbamoyl 1 1.259 567.0 I-42 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* pyrimidin-2-ylmethylcarbamoyl 1 1.239 602.6 I-43 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* 2-pyridylmethylcarbamoyl 1 1.137 603.4 I-44 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* [2-oxo-2-(2,2,2- 1 1.235 649.9 trifluoroethylamino)ethyl]carbamoyl I-45 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* [2-(allylamino)-2-oxo- 1 1.206 608.0 ethyl]carbamoyl I-46 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* cyclobutylcarbamoyl 1 1.297 565.0 I-47 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* cyclopropylmethylcarbamoyl 1 1.332 564.6 I-48 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* cyclopropylcarbamoyl 1 1.248 550.9 I-49 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* [(4S)-2-ethyl-3-oxo-isoxazolidin-4- 1 1.266 623.6 yl]carbamoyl I-50 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* thietan-3-ylcarbamoyl 1 1.322 582.5 I-51 #—CH.sub.2—S—CH.sub.2—* (1,1-dioxothietan-3-yl)carbamoyl 1 1.380 580.8 I-52 #—CH.sub.2—S—CH.sub.2—* pyrimidin-2-ylmethylcarbamoyl 1 1.333 571.0 I-53 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* (1,1-dioxothietan-3-yl)carbamoyl 1 1.332 564.6 I-54 #—CH.sub.2—S(═O).sub.2—CH.sub.2—* [(4R)-2-ethyl-3-oxo-isoxazolidin-4- 1 1.249 624.0 yl]carbamoyl I-58 #—CH.sub.2—CH.sub.2—CH.sub.2—O—* (butanoylamino)methyl 1 1.344 519.1.sup.a .sup.a.sup.1H-NMR of I-58 (400 MHz, CDCl.sub.3): δ = 1.15 (m, 3H), 1.94-2.08 (m, 2H), 2.22 (m, 2H), 3.01 (m, 2H), 3.73 (d, 1H), 4.09 (d, 1H), 4.18-4.29 (m, 2H), 4.40 (d, 2H), 5.97 (m, 1H), 6.85 (d, 1H), 7.17 (d, 1H), 7.58 (m, 2H). #attachment point in position of R.sup.g1 *attachment point in position of R.sup.g2

TABLE-US-00003 TABLE C.2 compounds of formula I-A with R.sup.2a = R.sup.2c = Cl, R.sup.2b = H t.sub.R m/z No. R.sup.g1 R.sup.g2 A method [min] [M + H].sup.+ I-56 #—O—CH.sub.2—O—* pyrimidin-2-ylmethylcarbamoyl 1 1.272 539.0 I-57 #—CH.sub.2—CH.sub.2—CH.sub.2—O—* pyrimidin-2-ylmethylcarbamoyl 1 1.377 552.4

II. Evaluation of Pesticidal Activity:

[1103] The activity of the compounds of formula I of the present invention can be demonstrated and evaluated by the following biological test.

B.1 Diamond Back Moth (Plutella xylostella)

[1104] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water:aceteone. Surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol). The test solution was prepared at the day of use.

[1105] Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dishes lined with moist filter paper and inoculated with ten 3.sup.rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0-100%.

[1106] In this test, compounds I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-28, I-29, I-30, I-31, I-32, I-33, I-34, I-35, I-36, I-37, I-38, I-39, I-41, I-42, I-44, I-46, I-47, I-48, I-51, I-52, I-56, I-57 at 300 ppm showed at least 75% mortality in comparison with untreated controls.

B.2 Green Peach Aphid (Myzus persicae)

[1107] For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.

[1108] The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications.

After application, 5-8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23±1° C. and about 50±5% relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.

[1109] In this test, compounds I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-26, I-28, I-30, I-31, I-32, I-33, I-34, I-37, I-41, I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-49, I-50, I-54, I-56, I-57 at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.3 Vetch Aphid (Megoura viciae)

[1110] For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.

[1111] The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 μl, using a custom built micro atomizer, at two replications.

[1112] After application, the leaf disks were air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23±1° C. and about 50±5% relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed.

[1113] In this test, compounds I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-28, I-30, I-31, I-32, I-33, I-34, I-37, I-41, I-43, I-46, I-47, I-48, I-50, I-54 at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.4 Tobacco Budworm (Heliothis virescens)

[1114] For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.

[1115] The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 μl, using a custom built micro atomizer, at two replications.

[1116] After application, microtiter plates were incubated at about 28±1° C. and about 80±5% relative humidity for 5 days. Egg and larval mortality was then visually assessed.

[1117] In this test, compounds I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-26, I-28, I-30, I-31, I-32, I-33, I-34, I-37, I-40, I-41, I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-49, I-50, I-54, I-56, I-57 at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.5 Boll Weevil (Anthonomus grandis)

[1118] For evaluating control of boll weevil (Anthonomusgrandis) the test unit consisted of 96-well-microtiter plates containing an insect diet and 5-10 A. grandis eggs. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 μl, using a custom built micro atomizer, at two replications.

[1119] After application, microtiter plates were incubated at about 25±1° C. and about 75±5% relative humidity for 5 days. Egg and larval mortality was then visually assessed.

[1120] In this test, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-26, I-27, I-28, I-30, I-31, I-32, I-33, I-34, I-37, I-40, I-41, I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-49, I-50, I-54, I-56, I-57 at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.6 Mediterranean Fruitfly (Ceratitis capitata)

[1121] For evaluating control of Mediterranean fruitfly (Ceratitis capitata) the test unit consisted of microtiter plates containing an insect diet and 50-80 C. capitata eggs. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 μl, using a custom built micro atomizer, at two replications.

[1122] After application, microtiter plates were incubated at about 28±1° C. and about 80±5% relative humidity for 5 days. Egg and larval mortality was then visually assessed.

[1123] In this test, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-28, I-30, I-31, I-32, I-33, I-34, I-37, I-40, I-41, I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-49, I-50, I-54 at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.7 Orchid Thrips (Dichromothrips Corbetti)

[1124] Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1:1 mixture of acetone:water (vol:vol), plus Kinetic HV at a rate of 0.01% v/v.

[1125] Thrips potency of each compound was evaluated by using a floral-immersion technique. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry in Petri dishes. Treated petals were placed into individual re-sealable plastic along with about 20 adult thrips. All test arenas were held under continuous light and a temperature of about 28° C. for duration of the assay. After 3 days, the numbers of live thrips were counted on each petal. The percent mortality was recorded 72 hours after treatment.

[1126] In this test, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-28, I-29, I-30, I-31, I-32, I-33, I-34, I-35, I-36, I-37, I-38, I-39, I-40, I-41, I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-49, I-50, I-51, I-52, I-53, I-54, I-56, I-57 at 300 ppm showed at least 75% mortality in comparison with untreated controls.

B.8 Rice Green Leafhopper (Nephotettix virescens)

[1127] Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 1:1 acetone:water (vol:vol), and 0.01% vol/vol surfactant (Kinetic HV) was added. Potted rice seedlings were sprayed with 5-6 ml test solution, air dried, covered with Mylar cages cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29° C. and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.

[1128] In this test, I-1, I-2, I-4, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-28, I-30, I-31, I-33, I-34, I-36, I-37, I-38, I-39, I-52 at 300 ppm showed at least 75% mortality in comparison with untreated controls.

B.9 Red Spider Mite (Tetranychus kanzawai)

[1129] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: acetone. Add surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol). The test solution was prepared at the day of use.

[1130] Potted cowpea beans of 4-5 days of age were cleaned with tap water and sprayed with 1-2 ml of the test solution using air driven hand atomizer. The treated plants were allowed to air dry and afterwards inoculated with 30 or more mites by clipping a cassava leaf section from rearing population. Treated plants were placed inside a holding room at about 25-27° C. and about 50-60% relative humidity. Percent mortality was assessed 72 hours after treatment.

[1131] In this test, I-7, I-9, I-11, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-28, I-29, I-34, I-54 at 300 ppm showed at least 75% mortality in comparison with untreated controls.

B.10 Southern Armyworm (Spodoptera eridania)

[1132] The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v).

[1133] Lima bean plants (variety Sieva) were grown 2 plants to a pot and selected for treatment at the 1.sup.st true leaf stage. Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. About 10 to 11 armyworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at about 25° C. and about 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants.

[1134] In this test, I-6, I-7, I-9, I-10, I-11, I-15, I-17, I-18, I-20, I-21, I-33, I-34, I-37, I-38, I-39, I-42, I-43, I-47, I-48 at 10 ppm showed at least 75% mortality in comparison with untreated controls.

B.11 Green Soldier Stink Bug (Nezara viridula)

[1135] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: acetone. Surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol). The test solution was prepared at the day of use.

[1136] Soybean pods were placed in glass Petri dishes lined with moist filter paper and inoculated with ten late 3rd instar N. viridula. Using a hand atomizer, approximately 2 ml solution is sprayed into each Petri dish. Assay arenas were kept at about 25° C. Percent mortality was recorded after 5 days.

[1137] In this test, I-1, I-2, I-3, I-4, I-6, I-7, I-8, I-9, I-10, I-11, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-28, I-29, I-33, I-34 at 300 ppm showed at least 75% mortality in comparison with untreated controls.

B.12 Neotropical Brown Stink Bug (Euschistus heros)

[1138] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: acetone. Surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol). The test solution was prepared at the day of use.

[1139] Soybean pods were placed in microwavable plastic cups and inoculated with ten adult stage E. heros. Using a hand atomizer, approximately 1 ml solution is sprayed into each cup, insects and food present. A water source was provided (cotton wick with water). Each treatment was replicated 2-fold. Assay arenas were kept at about 25° C. Percent mortality was recorded after 5 days.

[1140] In this test, I-1, I-2, I-6, I-7, I-9, I-10, I-11, I-15, I-17, I-18, I-20, I-23 at 100 ppm showed at least 75% mortality in comparison with untreated controls.

B.13 Brown Marmorated Stink Bug (Halyomorpha halys)

[1141] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water:acetone. Surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol). The test solution was prepared at the day of use.

[1142] Row peanuts and soybean seeds were placed into microwavable plastic cups and inoculated with five adult stage H. halys. Using a hand atomizer, approximately 1 ml solution is sprayed into each cup, insects and food present. A water source was provided (cotton wick with water). Each treatment is replicated 4-fold. Assay arenas are kept at about 25° C. Percent mortality was recorded after 5 days.

[1143] In this test I-6, I-7, I-8, I-9, I-15, I-17, I-18, I-20, I-21, I-34, I-37 at 100 ppm showed at least 75% mortality in comparison with untreated controls.