ISOXAZOLINE DERIVATIVES AS INSECTICIDES

• US 20120316124A1
• Filed: 02/17/2011
• Published: 12/13/2012
• Est. Priority Date: 02/17/2010
• Status: Active Grant

• Current Assignee: Syngenta Crop Protection LLC (China National Chemical Corporation)
• Original Assignee: Syngenta Crop Protection LLC (China National Chemical Corporation)
• Inventors: Pitterna, Thomas, El Qacemi, Myriem, Cassayre, Jerome Yves, Renold, Peter, Bobosik, Vladimir
• Granted Patent: US 8,754,053 B2
• Time in Patent Office: Days
• US Class Current: 514/30
• CPC Class Codes: A01N 43/80 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
• CPC Class Codes: C07D 261/04 having one double bond between ring members or between a ring member and a non-ring member
• CPC Class Codes: C07D 413/10 linked by a carbon chain containing aromatic rings
• CPC Class Codes: C07D 413/12 linked by a chain containing hetero atoms as chain links
• CPC Class Codes: C07D 417/12 linked by a chain containing hetero atoms as chain links

Abstract

The present invention relates to compounds formula (I), wherein P is P1, P2, heterocyclyl or heterocyclyl substituted by one to five Z; and wherein A¹, A², A³, A⁴, G¹, R¹, R², R³, R⁴, R⁵, R⁶, R¹⁷, R¹⁸, R¹⁹ and R²⁰ are as defined in claim 1; or a salt or N-oxide thereof. Furthermore, the present invention relates to processes and intermediates for preparing compounds of formula (I), to insecticidal, acaricidal, nematicidal and molluscicidal compositions comprising the compounds of formula (I) and to methods of using the compounds of formula (I) to control insect, acarine, nematode and mollusc pests.

Claims

1. A compound of formula (I)

2. A compound according to claim 1, wherein

P is P1;

A¹, A², A³ and A⁴ are independently of each other C—

H, C—

R⁷, or nitrogen;

G¹ is oxygen or sulfur;

R¹ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy-, C₁-C₈alkylcarbonyl-, or C₁-C₈alkoxycarbonyl-;

R² is C₁-C₈alkyl or C₁-C₈alkyl substituted by one to five R⁸, C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkyl substituted by one to five R⁹, aryl-C₁-C₄alkylene- or aryl-C₁-C₄alkylene- wherein the aryl moiety is substituted by one to five R¹⁰, heterocyclyl-C₁-C₄alkylene- or heterocyclyl-C₁-C₄alkylene- wherein the heterocyclyl moiety is substituted by one to five R¹⁰, aryl or aryl substituted by one to five R¹⁰, heterocyclyl or heterocyclyl substituted by one to five R¹⁰, C₁-C₈alkylaminocarbonyl-C₁-C₄ alkylene, C₁-C₈haloalkylaminocarbonyl-C₁-C₄ alkylene, or C₃-C₈cycloalkyl-aminocarbonyl-C₁-C₄ alkylene;

R³ is C₁-C₈haloalkyl;

R⁴ is aryl or aryl substituted by one to five R¹¹, or heteroaryl or heteroaryl substituted by one to five R¹¹;

R⁵ is hydrogen;

R⁶ is hydrogen, C₁-C₈alkyl or C₁-C₈alkyl substituted by one to five R¹², C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkyl substituted by one to five R¹³, aryl-C₁-C₄alkylene- or aryl-C₁-C₄alkylene- wherein the aryl moiety is substituted by one to five R¹⁴, heterocyclyl-C₁-C₄alkylene- or heterocyclyl-C₁-C₄alkylene- wherein the heterocyclyl moiety is substituted by one to five R¹⁴, aryl or aryl substituted by one to five R¹⁴, or heterocyclyl or heterocyclyl substituted by one to five R¹⁴, C₁-C₄ alkoxycarbonyl-, C₁-C₄ alkenyloxycarbonyl-, C₁-C₄ alkynyloxycarbonyl-, benzyloxycarbonyl- or benzyloxycarbonyl- in which the benzyl group is optionally substituted by one to five R¹⁶;

each R⁷ is independently halogen, cyano, nitro, C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈alkenyl, C₁-C₈haloalkenyl, C₁-C₈alkynyl, C₁-C₈haloalkynyl, C₃-C₁₀cycloalkyl, C₁-C₈alkoxy-, C₁-C₈haloalkoxy-, C₁-C₈alkylthio-, C₁-C₈haloalkylthio-, C₁-C₈alkylsulfinyl-, C₁-C₈haloalkyl-sulfinyl-, C₁-C₈alkylsulfonyl-, or C₁-C₈haloalkylsulfonyl-;

each R⁸ and R¹² is independently halogen, cyano, nitro, hydroxy, C₁-C₈alkoxy-, C₁-C₈haloalkoxy-, C₁-C₈alkylcarbonyl-, C₁-C₈alkoxycarbonyl-, mercapto, C₁-C₈alkylthio-, C₁-C₈haloalkylthio-, C₁-C₈alkylsulfinyl-, C₁-C₈haloalkylsulfinyl-, C₁-C₈alkylsulfonyl-, or C₁-C₈haloalkylsulfonyl-;

each R⁹ and R¹³ is independently halogen or C₁-C₈alkyl;

each R¹⁰, R¹¹ and R¹⁴ is independently halogen, cyano, nitro, C₁-C₈alkyl, C₁-C₈haloalkyl, C₂-C₈alkenyl, C₂-C₈haloalkenyl, C₂-C₈alkynyl, C₂-C₈haloalkynyl, hydroxy, C₁-C₈alkoxy-, C₁-C₈haloalkoxy-, mercapto, C₁-C₈alkylthio-, C₁-C₈haloalkylthio-, C₁-C₈alkylsulfinyl-, C₁-C₈haloalkylsulfinyl-, C₁-C₈alkylsulfonyl-, C₁-C₈haloalkylsulfonyl-, C₁-C₈alkylcarbonyl-, C₁-C₈alkoxycarbonyl-, aryl or aryl substituted by one to five R¹⁵, or heterocyclyl or heterocyclyl substituted by one to five R¹⁵;

each R¹⁵ is independently halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy-, or C₁-C₄haloalkoxy-;

each R¹⁶ is independently halogen, cyano, formyl, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₃-C₆ cycloalkyl.

3. A compound according to claim 1, wherein A¹ is C—

R⁷, A² is C—

H, A³ is C—

H or nitrogen and A⁴ is C—

H or nitrogen

4. A compound according to claim 1, wherein G¹ is oxygen.

5. A compound according to claim 1, wherein P is P1, P2, or a heterocycle selected from H1 to H9

6. A compound according to claim 1, wherein R¹ is hydrogen, methyl, ethyl, methylcarbonyl-, or methoxycarbonyl-.

7. A compound according to claim 1, wherein R² is C₁-C₈alkyl or C₁-C₈alkyl substituted by one to five R⁸, C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkyl substituted by one to five R⁹, aryl-C₁-C₄alkylene- or aryl-C₁-C₄alkylene- wherein the aryl moiety is substituted by one to five R¹⁰, heterocyclyl-C₁-C₄alkylene- or heterocyclyl-C₁-C₄alkylene- wherein the heterocyclyl moiety is substituted by one to five R¹⁰, aryl or aryl substituted by one to five R¹⁰, heterocyclyl or heterocyclyl substituted by one to five R¹⁰, C₁-C₈alkylaminocarbonyl-C₁-C₄ alkylene, C₁-C₈haloalkylaminocarbonyl-C₁-C₄ alkylene, or C₃-C₈cycloalkyl-aminocarbonyl-C₁-C₄ alkylene, wherein each aryl group is a phenyl group and each heterocycle group is selected from 1,2,3triazolyl, 1,2,4triazolyl, tetrazolyl, pyrimidinyl, pyrazinyl, pyridazinyl, tetrahydrothiophenyl, isoxazolinyl, pyridyl, tetrahydrofuranyl, imidazolyl, pyrazolyl, pyrrolyl, thiazolyl, oxetanyl, thietanyl, oxo-thietanyl and dioxo-thietanyl.

8. A compound according to claim 1, wherein R² is C₁-C₈alkyl or C₁-C₈alkyl substituted by one to five R⁸, C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkyl substituted by one to five R⁹, phenyl-C₁-C₄alkylene- or phenyl-C₁-C₄alkylene- wherein the phenyl moiety is substituted by one to five R¹⁰, pyridyl-C₁-C₄alkylene- or pyridyl-C₁-C₄alkylene- wherein the pyridyl moiety is substituted by one to four R¹⁰, oxetanyl or oxetanyl substituted by one to five R¹⁰, thietanyl or thietanyl substituted by one to five R¹⁰, oxo-thietanyl or oxo-thietanyl substituted by one to five R¹⁰, or dioxo-thietanyl or dioxo-thietanyl substituted by one to five R¹⁰.

9. A compound according to claim 1, wherein R³ is chlorodifluoromethyl or trifluoromethyl.

10. A compound according to claim 1, wherein R⁴ is aryl or aryl substituted by one to five R¹¹.

11. A compound according to claim 1, wherein

R¹⁷ and R¹⁸ are independently selected from hydrogen, halogen, cyano, C₁-C₄alkyl, C₁-C₄haloalkyl;

R¹⁹ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy, C₁-C₈alkylcarbonyl, or C₁-C₈alkoxycarbonyl;

R²⁰ is C₁-C₄alkylcarbonyl, C₁-C₄haloalkylcarbonyl, C₃-C₆cycloalkylcarbonyl, C₃-C₆halocycloalkylcarbonyl or C(═

O)R²¹;

R²¹ is aryl or aryl substituted by one to five R²², heterocyclyl or heterocyclyl substituted by one to five R²², wherein each aryl group is a phenyl group and each heterocyclyl group is selected from pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrahydrothiophenyl, tetrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl, benzothiazolyl, oxetanyl, thietanyl, oxo-thietanyl, dioxo-thietanyl, pyrrolidinyl, tetrahydrofuranyl, [1,3]dioxolanyl, piperidinyl, piperazinyl, [1,4]dioxanyl, morpholinyl, 2,3-dihydro-benzofuranyl, benzo[1,3]dioxolanyl, 2,3-dihydro-benzo[1,4]dioxinyl, thiazolidinyl, and 3,4-dihydro-2H-benzo[b][1,4]dioxepinyl;

each R²² is independently bromo, chloro, fluoro, cyano, nitro, oxo, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, methyl-N═

, methylthio, phenyl or phenyl substituted by one to three halogen.

12. A compound according to claim 1, wherein R⁶ is C₁-C₈alkyl or C₁-C₈alkyl substituted by one to five R¹², phenyl-methylene- or phenyl-methylene wherein the phenyl moiety is substituted by one to five R¹⁴.

13. A compound according to claim 1, wherein

A¹ is C—

R⁷, A² is C—

H, A³ is C—

H and A⁴ is C—

H;

G¹ is oxygen;

R¹ is hydrogen, methyl or ethyl;

R² is C₁-C₈alkyl or C₁-C₈alkyl substituted by one to five R⁸, C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkyl substituted by one to five R⁹, phenyl-C₁-C₄alkylene- or phenyl-C₁-C₄alkylene- wherein the phenyl moiety is substituted by one to five R¹⁰, pyridyl-C₁-C₄alkylene- or pyridyl-C₁-C₄alkylene- wherein the pyridyl moiety is substituted by one to four R¹⁰, oxetanyl or oxetanyl substituted by one to five R¹⁰, thietanyl or thietanyl substituted by one to five R¹⁰, oxo-thietanyl or oxo-thietanyl substituted by one to five R¹⁰, or dioxo-thietanyl or dioxo-thietanyl substituted by one to five R¹⁰, C₁-C₈alkylaminocarbonyl-C₁-C₄ alkylene, C₁-C₈haloalkylaminocarbonyl-C₁-C₄ alkylene, or C₃-C₈cycloalkyl-aminocarbonyl-C₁-C₄ alkylene;

R³ is chlorodifluoromethyl or trifluoromethyl;

R⁴ is 3,5-dibromo-phenyl-, 3,5-dichloro-phenyl-, 3,5-bis-(trifluoromethyl)-phenyl-, 3,4-dichloro-phenyl-, 3,4,5-trichloro-phenyl- or 3-trifluoromethyl-phenyl-

R⁵ is hydrogen;

R⁶ is C₁-C₈alkyl or C₁-C₈alkyl substituted by one to five R¹², phenyl-C₁-C₄alkylene- or phenyl-C₁-C₄alkylene- wherein the phenyl moiety is substituted by one to five R¹⁴;

R⁷ is independently bromo, chloro, fluoro, cyano, nitro, methyl, ethyl, trifluoromethyl, vinyl, methoxy, difluoromethoxy, or trifluoromethoxy;

each R⁸ is independently bromo, chloro, fluoro, methoxy, or methylthio;

each R⁹ is methyl;

each R¹⁰ is independently bromo, chloro, fluoro, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, or trifluoromethoxy;

each R¹² is independently bromo, chloro, fluoro, methoxy, or methylthio;

each R¹⁴ is independently bromo, chloro, fluoro, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, or trifluoromethoxy.

14. A compound according to claim 1, wherein

A¹ is C—

R⁷, A² is C—

H, A³ is C—

H and A⁴ is C—

H;

G¹ is oxygen;

R¹ is hydrogen;

R² is C₁-C₈alkyl or C₁-C₈alkyl substituted by one to three halogen atoms, C₃-C₁₀cycloalkyl or C₃-C₁₀cycloalkyl substituted by one or two methyl groups, phenyl-C₁-C₄alkylene- or phenyl-C₁-C₄alkylene- wherein the phenyl moiety is substituted by one to five R¹⁰, pyridyl-C₁-C₄alkylene- or pyridyl-C₁-C₄alkylene- wherein the pyridyl moiety is substituted by one to four R¹⁰, thietanyl, oxo-thietanyl or dioxo-thietanyl;

R³ is trifluoromethyl;

R⁴ is 3,5-dichloro-phenyl;

R⁵ is hydrogen;

R⁶ is C₁-C₈alkyl;

R⁷ is methyl;

each R¹⁰ is independently bromo, chloro, fluoro, cyano or methyl.

15. A compound of formula Int-I

16. A method of controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1.

17. An insecticidal, acaricidal, nematicidal or molluscicidal composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1, optionally comprising one or more additional compounds having biological activity.

18. A combination product comprising a pesticidally effective amount of a component A and a pesticidally effective amount of component B, wherein component A is a compound of formula (I) as defined in claim 1, and component B is imidacloprid, enrofloxacin, praziquantel, pyrantel embonate, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, fipronil, ivermectin, omeprazole, tiamulin, benazepril, milbemycin, cyromazine, thiamethoxam, pyriprole, deltamethrin, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, selamectin, carprofen, metaflumizone, moxidectin, methoprene (including S-methoprene), clorsulon, pyrantel, amitraz, triclabendazole, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, nemadectin, albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, tetramisole, levamisole, pyrantel pamoate, oxantel, morantel, triclabendazole, epsiprantel, fipronil, lufenuron, ecdysone or tebufenozide.