CYCLIC COMPOUNDS SUBSTITUTED BY A CONDENSED RING SYSTEM

Abstract

Compounds of formula I

##STR00001##

defined herein are provided. Uses of these compounds for controlling invertebrate pests, protecting plant propagation material and providing an agricultural and a veterinary composition including the compounds are also described. Compounds for use as intermediate compounds in the preparation of compounds I are also described.

Claims

1. Compounds of the formula I ##STR00042## wherein X.sup.1 is selected from S, O and CH.sub.2; A is a group selected from A.sup.1 and A.sup.2; wherein A.sup.1 is a group of following formula: ##STR00043## wherein # denotes the bond to the aromatic ring of formula (I); and W is selected from 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, with the proviso that 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 —CH.sub.2CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2O—, —OCH.sub.2CH.sub.2—, —CH.sub.2OCH.sub.2—, —OCH.sub.2O—, —CH.sub.2CH.sub.2S(O)—, —S(O).sub.pCH.sub.2CH.sub.2—, —CH.sub.2S(O).sub.pCH.sub.2—, —S(O).sub.pCH.sub.2S(O)—, —OCH.sub.2S(O).sub.p—, —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—, —H.sub.2H.sub.2H.sub.2CH.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)—, —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)—, —S(O).sub.pCH.sub.2S(O).sub.pCH.sub.2—, —CH.sub.2S(O)CH.sub.2S(O)—, —S(O).sub.pCH.sub.2CH.sub.2O—, —OCH.sub.2CH.sub.2S(O)—, —S(O).sub.pCH.sub.2OCH.sub.2—, —OCH.sub.2S(O)CH.sub.2—, —CH.sub.2OCH.sub.2S(O).sub.p— and —CH.sub.2S(O)CH.sub.2O—; where p is one of 0, 1 and 2 where each 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 a 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 hydrogen and halogen; R.sup.7a and R.sup.7b, independently of each other, are selected from 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 a 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 which carries one or two radicals R.sup.81, C.sub.1-C.sub.6-haloalkyl which carries 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 which is substituted with up to 5 substituents R.sup.16, and a heterocyclic ring selected from rings E-1 to E-63 ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## where in rings E-1 to E-63 a zigzag line denotes an attachment point to a remainder of the molecule; k is one of 0, 1, 2 and 3; n is one of 0, 1 and 2; and R.sup.16 is as defined below; R.sup.62 is selected from a 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 one or two radicals R.sup.82, C.sub.1-C.sub.6-haloalkyl which carries 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.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl which carries 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 which is substituted with up to 5 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 OH, CN, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkyl which carries one of a CN substituent and 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 up to 5 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 OH, CN, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl which carries one of a CN substituent and 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 up to 5 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 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 from hydrogen and C.sub.1-C.sub.6-alkyl; R.sup.101b is selected from hydrogen, —C(═O)N(R.sup.14a)R.sup.14b, phenyl, phenyl substituted with up to 5 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 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 up to 5 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 a 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 a 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 which is substituted with up to 5 substituents 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.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; R.sup.102d and R.sup.112b, independently of each other, are selected from 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 which carries 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 a group consisting of hydrogen and C.sub.1-C.sub.6-alkyl; R.sup.14b is selected from a 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; each R.sup.16 is one of: (i) independently selected from a 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.16 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 at least one of the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.

2. The compounds as claimed in claim 1, where X.sup.1 is S.

3. The compounds as claimed in claim 1, where X.sup.1 is O.

4. The compounds as claimed in claim 1, where X.sup.1 is CH.sub.2.

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

6. The compounds as claimed in claim 1, where A is a group A.sup.1 and where R.sup.51 is hydrogen.

7. The compounds as claimed in claim 1, where R.sup.61 is selected from C.sub.1-C.sub.4-alkyl which carries one radical R.sup.81; and rings E-1 to E-63 as defined in claim 1; wherein R.sup.81 is selected from —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 hydrogen; and R.sup.101d is as defined in claim 1.

8. The compounds as claimed in claim 7, where R.sup.61 is selected from methyl which carries one radical R.sup.81; ring E-44-1 and ring E-53-1 ##STR00051## wherein R.sup.81 is selected from —C(═O)N(R.sup.101c)R.sup.101d, wherein R.sup.101c and R.sup.101d are as defined in claim 7; ring E-1, ring E-7 and ring E-44-1, where in rings E-1 and E-7 k is 0; n in ring E-44-1 is one of 0, 1 and 2; and R.sup.16a in ring E-53-1 is selected from a 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).

9. The compounds as claimed in claim 1, wherein A is a group A2, wherein R.sup.7a is hydrogen; R.sup.7b is selected from hydrogen, CH.sub.3, CF.sub.3 and CN; R.sup.52 is selected from hydrogen and C.sub.1-C.sub.3-alkyl; and R.sup.62 is selected from 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 which carries a CN substituent; C.sub.3-C.sub.6-halocycloalkyl, phenyl, phenyl which is substituted with up to 5 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 CN, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl which carries one of a CN substituent and 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 up to 3 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 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.

10. The compounds as claimed in claim 9, wherein R.sup.7a and R.sup.7b are hydrogen; R.sup.52 is hydrogen; and R.sup.62 is selected from 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 which carries a CN substituent; and C.sub.3-C.sub.6-halocycloalkyl; where R.sup.82 is selected from CN, C.sub.3-C.sub.6-cycloalkyl which optionally carries a CN or 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.

11. The compounds as claimed in claim 1, where B.sup.1, B.sup.2, B.sup.3, B.sup.4 and B.sup.5 are CR.sup.2, where R.sup.2 is selected from halogen, C.sub.1-C.sub.2-haloalkoxy and C.sub.1-C.sub.2-haloalkyl.

12. The compounds as claimed in claim 1, where R.sup.2 is selected from hydrogen, F, Cl, Br, OCF.sub.3 and CF.sub.3.

13. The compounds as claimed in claim 1, where R.sup.g1 and R.sup.g2 form together a bridging group selected from —CH.sub.2CH.sub.2CH.sub.2— and —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—.

14. The compounds as claimed in claim 1, where R.sup.g1 and R.sup.g2 form together a bridging group selected from —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—.

15. The compounds as claimed in claim 1, where 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 hydrogen and fluorine.

17. A compound of formula II ##STR00052## 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 hydrogen and OR.sup.17, where R.sup.17 is selected from hydrogen, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-haloalkyl.

18. An agricultural or veterinary composition comprising at least one compound of the formula I as defined in claim 1, and at least one of a stereoisomer thereof and at least one agriculturally or veterinarily acceptable salt thereof; and at least one of an inert liquid agriculturally or veterinarily acceptable carrier and an inert solid agriculturally or veterinarily acceptable carrier.

19. (canceled)

20. (canceled)

21. A method for protecting at least one of a plant propagation material and-plants which grow therefrom from attack or infestation by invertebrate pests, wherein the method comprises treating the plant propagation material with a pesticidally effective amount of at least one compound of the formula I as defined in claim 1, a stereoisomer thereof or at least one agriculturally acceptable salt thereof.

Description

EXAMPLES

[0778] The present invention is now illustrated in further details by the following examples, without imposing any limitation thereto.

I. Preparation Examples

[0779] 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. Analytical HPLC column:

[0780] Method A: Analytical UPLC column: Phenomenex Kinetex 1.7 μm XB-C18 100A; 50×2.1 mm from Phenomenex, Germany. Elution: acetonitrile/water+0.1% trifluoroacetic acid (TFA) in a ratio from 5:95 to 100:0 in 1.5 min; 100% B 0.24 min; Flow: 0.8 mL/min to 1 mL/min in 1.5 min at 60° C. MS-method: quadrupole electrospray ionization, 80 V (positive mode).

[0781] .sup.1H-NMR: The signals are characterized by chemical shift (ppm, δ [delta]) vs. tetramethylsilane, respectively CDCl.sub.3 for .sup.13C-NMR, 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=quartet, t=triplet, d=doublet and s=singlet.

[0782] Abbreviations used are: d for day(s), h for hour(s), min for minute(s), r.t./room temperature for 20-25° C., THF for tetrahydrofuran, DCE for 1,2-dichloroethane, MTBE for methyl-tert-butylether, t.sub.R for retention time, Et.sub.3N for triethylamine, TLC for thin layer chromatography.

C.1 Compound Examples 1-1 to 1-9

[0783] Compound examples 1-1 to 1-9 correspond to compounds of formula C.1

##STR00041##

[0784] wherein R.sup.2a, R.sup.2b, R.sup.2c, X.sup.1 and R.sup.61 of each synthesized compound is defined in one row of table C.1 below.

[0785] The compounds with X.sup.1═S were synthesized in analogy to Synthesis Example S.1, and with X.sup.1═O in analogy to Synthesis Example S.2.

TABLE-US-00002 TABLE C.1 HPLC-MS: Ex. R.sup.2a, R.sup.2b, R.sup.2c X.sup.1 —R.sup.61 Method t.sub.R (min) [M + H].sup.+ 1-1 Cl, H, Cl S —CH.sub.2-(2-pyrimidinyl) A 1.440 550.0 1-2 Cl, H, Cl S —CH.sub.2-(2-pyridyl) A 1.267 549.0 1-3 Cl, H, Cl S —CH.sub.2—C(═O)—NHCH.sub.2CF.sub.3 A 1.432 596.9 1-4 Cl, H, Cl S -(1,1-dioxothiethan-3-yl) A 1.416 561.9 1-5 Cl, F, Cl S -(1,1-dioxothiethan-3-yl) A 1.428 579.6 1-6 Cl, F, Cl S -[(4R)-2-ethyl-3-oxo- A 1.464 590.4 isoxazolidin-4-yl] 1-7 Cl, F, Cl S —CH.sub.2-(2-pyrimidinyl) A 1.429 568.0 1-8 Cl, F, Cl S —CH.sub.2—C(═O)—NHCH.sub.2CF.sub.3 A 1.451 614.6 1-9 Cl, H, Cl O —CH.sub.2-(2-pyridyl) A

Synthesis Example S.1

7-[2-(3,5-Dichlorophenyl)-2-(trifluoromethyl)-3H-thiophen-4-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]indane-4-carboxamide

(Compound Example 1-3; Compound of Formula C.1, Wherein R.SUP.2a .and R.SUP.2c .are C1, R.SUP.2b .is H, X.SUP.1 .is S, and —R.SUP.61 .is —CH.SUB.2.—C(═O)—NHCH.SUB.2.CF.SUB.3.)

[0786] (7-Acetylindan-4-yl) trifluoromethanesulfonate (CAS 1312609-69-0) was synthesized as described in US 2011/0152246 (p. 118, compound I-IIIf).

Step 1: Methyl 7-acetylindane-4-carboxylate

[0787] To a solution of (7-acetylindan-4-yl) trifluoromethanesulfonate (40 g) in methanol (357 mL) were added Na.sub.2CO.sub.3 (27.5 g) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Pd(dppf)Cl.sub.2, 9.5 g). The solution was pressurized with carbon monoxide (50 Psi) and heated at 50° C. for 5 h. Then, the mixture was filtered and the filtrate was concentrated. The residue was dissolved in CH.sub.2Cl.sub.2 and washed with brine, dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (18.3 g, 64%).

[0788] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.9 (d, 1H), 7.7 (d, 1H), 4.0 (s, 3H), 3.3-3.2 (m, 4H), 2.6 (s, 3H), 2.1 (m, 2H).

Step 2: Methyl 7-[3-(3,5-dichlorophenyl)-4,4,4-trifluoro-but-2-enoyl]indane-4-carboxylate

[0789] To a solution of the product of step 1 (35 g) and 1-(3,5-dichlorophenyl)-2,2,2-trifluoroethanone (78 g, CAS 130336-16-2) in DCE (350 mL) was added K.sub.2CO.sub.3 (26.6 g) and Et.sub.3N (19.5 g). The reaction was stirred at reflux for 16 h. Then, the mixture was cooled to r.t., filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (57.1 g, 81%).

[0790] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.90 (s, 1H), 7.81 (d, 1H), 7.44 (d, 1H), 7.25 (s, 1H), 7.08 (s, 2H), 3.90 (s, 3H), 3.21 (t, 2H), 3.07 (t, 2H), 2.05 (m, 2H).

Step 3: 5-(3,5-Dichlorophenyl)-3-hydroxy-3-(7-methoxycarbonylindan-4-yl)-5-(trifluoromethyl)tetrahydrothiophene-2-carboxylic acid

[0791] To a solution of the product of step 2 (3.5 g) in THF (35 mL) was added 2-sulfanylacetic acid (CAS 68-11-1, 2.2 g) and Et.sub.3N (2.4 g). The mixture was stirred at r.t. for 16 h, and concentrated. Then, saturated aqueous NaHCO.sub.3 solution (50 mL) was added, and the aqueous layer was washed with MTBE (50 mL). Then, the aqueous layer was adjusted to pH 2 using aqueous 1 M HCl solution, and extracted with ethyl acetate (3×50 mL). The combined organic layers were evaporated to afford the product (3.4 g, 76%).

[0792] .sup.1H NMR (400 MHz, MeOH-d.sub.4): δ 7.79-7.69 (m, 3H), 7.52-7.41 (m, 2H), 3.90-3.80 (m, 4H), 3.22-2.88 (m, 7H), 2.12-2.03 (m, 2H)

Step 4: Methyl 7-[2-(3,5-dichlorophenyl)-2-(trifluoromethyl)-3H-thiophen-4-yl]indane-4-carboxylate

[0793] To a solution of the product of step 3 (6.2 g) in pyridine (60 mL) was added methanesulfonyl chloride (“MsCl”, 3 g) dropwise. The mixture was stirred at r.t. for 16 h, then poured into water (100 mL), and the aqueous layer was extracted with ethyl acetate (3×100 mL). The combined organic layers were washed with brine, dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was dissolved in DMF (20 mL) and stirred at 120° C. for 1 h. Then, the solvents were evaporated, water (100 mL) was added, and the aqueous layer was extracted with MTBE (3×100 mL). The combined organic layers were dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue which was purified by flash chromatography on silica gel to afford the product (1.2 g, 22%).

[0794] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.84 (d, 1H), 7.46-7.37 (m, 3H), 7.11 (d, 1H), 6.45 (s, 1H), 3.94-3.87 (m, 4H), 3.77-3.70 (m, 1H), 3.36-3.29 (m, 2H), 3.02-2.96 (m, 2H), 2.16-2.08 (m, 2H)

Step 5: 7-[2-(3,5-dichlorophenyl)-2-(trifluoromethyl)-3H-thiophen-4-yl]indane-4-carboxylic acid

[0795] To a solution of the product of step 4 (1.1 g) in THF (15 mL) was added LiOH (0.3 g) in water (1 mL). The mixture was stirred at r.t. for 16 h, and concentrated. Water (15 mL) was added and the pH adjusted to 2 using aqueous 1 M HCl solution. The aqueous layer was extracted with ethyl acetate (3×20 mL). The combined organic layers were washed with brine, dried (Na.sub.2SO.sub.4), filtered and concentrated to afford the product (1.0 g, 90%).

[0796] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.94 (d, 1H), 7.45-7.38 (m, 3H), 7.15 (d, 1H), 6.49 (s, 1H), 3.97-3.87 (m, 1H), 3.80-3.68 (m, 1H), 3.42-3.32 (m, 2H), 3.01 (m, 2H), 2.19-2.06 (m, 2H)

Step 6: 7-[2-(3,5-Dichlorophenyl)-2-(trifluoromethyl)-3H-thiophen-4-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]indane-4-carboxamide

[0797] To a solution of the product of step 5 (0.25 g), 2-amino-N-(2,2,2-trifluoroethyl)acetamide hydrochloride (0.1 g, CAS 1171331-39-7) and bromotripyrrolidinophosphonium hexafluorophosphate (“PyBroP”, 0.24 g) in CH.sub.2Cl.sub.2 (40 mL) at r.t. was added N,N-diisopropylethylamine (0.18 g). The reaction was stirred at r.t. overnight. Then, the reaction was quenched with water. The layers were separated, and the organic layer was dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel to afford the product (0.17 g, 65%).

[0798] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.5 (d, 1H), 7.45-7.40 (m, 3H), 7.40-7.35 (m, 1H), 7.1 (d, 1H), 6.9 (m, 1H), 6.4 (s, 1H), 4.25 (d, 2H), 4.0-3.9 (m, 2H), 3.85 (d, 1H), 3.7 (d, 1H), 3.2 (m, 2H), 3.0 (m, 2H), 2.2-2.05 (m, 2H)

Synthesis Example S.2

7-[2-(3,5-Dichlorophenyl)-2-(trifluoromethyl)-3 h-furan-4-yl]-N-(2-pyridylmethyl)indane-4-carboxamide

(Compound Example 1-9; Compound of Formula C.1, Wherein R.SUP.2a .and R.SUP.2c .are Cl, R.SUP.2b .is H, X.SUP.1 .is O and —R.SUP.61 .is —CH.SUB.2.-(2-Pyridyl)

[0799] 4-Iodo-7-methoxy-indane (CAS 1560647-89-3) was synthesized as described in WO 2014/019344 (p. 428, compound 67-5).

[0800] 4-Bromo-2-(3,5-dichlorophenyl)-2-(trifluoromethyl)-3h-furan was synthesized as described in WO2013/026724 (p. 298, Step E).

Step 1: Ethyl 7-methoxyindane-4-carboxylate

[0801] To a solution of 4-iodo-7-methoxy-indane (48 g) in ethanol (800 mL) were added Na.sub.2CO.sub.3 (55.5 g) and [1,1′-bis(diphenylphosphino)ferrocene]dichloro-palladium(II) (Pd(dppf)C.sub.2, 4 g). The solution was pressurized with carbon monoxide (50 Psi) and heated at 70° C. for 4 h. Then, the mixture was filtered and the filtrate was concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (30 g, 78%).

[0802] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.90 (d, 1H), 6.71 (d, 1H), 4.34 (q, 2H), 3.88 (s, 3H), 3.30 (t, 2H), 2.86 (t, 2H), 2.20-2.10 (m, 2H), 1.39 (t, 3H).

Step 2: Ethyl 7-hydroxyindane-4-carboxylate

[0803] To a solution of the product of step 1 (30 g) in CH.sub.2CH.sub.2 (500 mL) at −78° C. was added BBr.sub.3 (68.7 g) dropwise, and the reaction was stirred at 0° C. for 5 h. Then, ethanol (50 mL) was added dropwise at 0° C. and the mixture was stirred at 20° C. for 5 h. Water (200 mL) was added and the aqueous phase extracted with CH.sub.2CH.sub.2 (3×200 mL). The combined organic layers were dried (Na.sub.2SO.sub.4), filtered and concentrated to give the crude product (30 g), which was used in the next step without any further purification.

[0804] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.81 (d, 1H), 6.69 (d, 1H), 5.7 (br. s, OH), 4.34 (q, 2H), 3.31 (t, 2H), 2.86 (t, 2H), 2.20-2.10 (m, 2H), 1.39 (t, 3H).

Step 3: Ethyl 7-(trifluoromethylsulfonyloxy)indane-4-carboxylate

[0805] To the crude product of step 2 (30 g) and Et.sub.3N (29.7 g) in CH.sub.2Cl.sub.2 (500 mL) at 0° C. was added triflic anhydride (“Tf.sub.2O”, 61.6 g), and the reaction was stirred at 10° C. for 2h. Water (200 mL) was added and the aqueous layer extracted with CH.sub.2Cl.sub.2 (3×200 mL). The combined organic layers were dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (30 g, 61%).

[0806] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.93 (d, 1H), 7.14 (d, 1H), 4.38 (q, 2H), 3.37 (t, 2H), 3.05 (t, 2H), 2.20-2.10 (m, 2H), 1.40 (t, 3H).

Step 4: Ethyl 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indane-4-carboxylate

[0807] To a solution of the product of step 3 (21 g) in DMF (300 mL) was added 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (“bis(pinacolato)diboron”, CAS 73183-34-3, 23.6 g) and Pd(dppf)Cl.sub.2, (0.45 g). The mixture was heated at 80° C. for 16h, diluted with water and extracted with MTBE (3×200 mL). The combined organic layers were dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (15 g, 76%).

[0808] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.79 (d, 1H), 7.65 (d, 1H), 4.37 (q, 2H), 3.26 (t, 2H), 3.15 (t, 2H), 2.20-2.10 (m, 2H), 1.40 (t, 3H), 1.35 (s, 12H).

Step 5: Ethyl 7-[2-(3,5-dichlorophenyl)-2-(trifluoromethyl)-3 h-furan-4-yl]indane-4-carboxylate

[0809] To a solution of the product of step 4 (44 mg) and 4-bromo-2-(3,5-dichlorophenyl)-2-(trifluoromethyl)-3H-furan (50 mg) in toluene (2 mL) was added CsF (43 mg) and Pd(PPh.sub.3).sub.2)Cl.sub.2 (10 mg). The reaction was heated at 100° C. in a sealed tube for 16 h, then filtered and concentrated. The residue was purified by preparative TLC (petroleum ether/ethyl acetate 10:1) to afford the product.

[0810] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.84 (d, 1H), 7.55-7.48 (m, 2H), 7.44-7.40 (m, 1H), 7.01-6.92 (m, 2H), 4.40-4.33 (m, 2H), 3.83 (d, 1H), 3.42-3.31 (m, 3H), 2.97-2.86 (m, 2H), 2.21-2.08 (m, 2H), 1.42-1.38 (m, 3H).

Step 6: 7-[2-(3,5-Dichlorophenyl)-2-(trifluoromethyl)-3H-furan-4-yl]indane-4-carboxylic acid

[0811] Hydrolysis of the product of step 5 in analogy to Synthesis Example S.1 (step 5).

Step 7: 7-[2-(3,5-Dichlorophenyl)-2-(trifluoromethyl)-3H-furan-4-yl]-N-(2-pyridylmethyl)indane-4-carboxamide

[0812] Amidation of the product of step 6 in analogy to Synthesis Example S.1 (step 6).

II. Evaluation of Pesticidal Activity

[0813] 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)

[0814] 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.

[0815] 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%.

[0816] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 at 300 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.2 Green Peach Aphid (Myzus persicae)

[0817] 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.

[0818] 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.

[0819] 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.

[0820] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.3 Vetch Aphid (Megoura viciae)

[0821] 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.

[0822] 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.

[0823] 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.

[0824] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.4 Tobacco Budworm (Heliothis virescens)

[0825] 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.

[0826] 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.

[0827] 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.

[0828] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.5 Boll Weevil (Anthonomus grandis)

[0829] For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96-well-microtiter plates containing an insect diet and 5-10 A. grandis eggs.

[0830] 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.

[0831] 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.

[0832] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.6 Mediterranean Fruitfly (Ceratitis capitata)

[0833] 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.

[0834] 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.

[0835] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.7 Orchid Thrips (Dichromothrips Corbetti)

[0836] 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.

[0837] 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 resealable 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.

[0838] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 at 300 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.8 Rice Green Leafhopper (Nephotettix virescens)

[0839] 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 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.

[0840] In this test, the compounds 1-1, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.9 Red Spider Mite (Tetranychus kanzawai)

[0841] 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.

[0842] 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.

[0843] In this test, the compounds 1-2, 1-4, 1-5, 1-6, and 1-8 at 300 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.10 Southern Armyworm (Spodoptera eridania)

[0844] 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).

[0845] 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.

[0846] In this test, the compounds 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 and 1-8 at 10 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.11 Green Soldier Stink Bug (Nezara viridula)

[0847] 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.

[0848] 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.