Mixtures of mesoionic pesticides

1. A composition comprising (a) at least one compound selected from compounds of Formula 1, N-oxides, and salts thereof,

wherein

R 1 is phenyl optionally substituted with up to 5 substituents independently selected from R 3 , or pyridinyl optionally substituted with up to 4 substituents independently selected from R 3 ;

R 2 is C 1 -C 4 haloalkyl; or thiazolyl, pyridinyl or pyrimidinyl, each optionally substituted with up to 2 substituents independently selected from the group consisting of halogen and C 1 -C 4 alkyl;

each R 3 is independently halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C(R 4 )═NOR 4 or Q;

each R 4 is independently C 1 -C 4 alkyl;

Z is CH═CH or S; and

each Q is independently phenyl or pyridinyl, each optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy;

and

(b) at least one invertebrate pest control agent selected from the group consisting of abamectin, acetamiprid, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid, flubendiamide, flufenoxuron, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methomyl, methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl, phosmet, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, tebufenozide, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, triflumuron, Bacillus thuringiensis delta-endotoxins, Bacillus thuringiensis and nucleo polyhedrosis viruses;

provided that (a) when R 1 is unsubstituted phenyl and R 2 is CF 3 , then Z is S; (b) when R 1 is 2-fluorophenyl and R 2 is 2-chloro-5-thiazolyl, then Z is S; and (c) when R 1 is 2-fluorophenyl or 3-(trifluoromethoxy)phenyl and R 2 is 6-chloro-3-pyridinyl, then Z is CH═CH.

2. The composition of claim 1 wherein component (a) is a compound of Formula 1 wherein

R 1 is phenyl optionally substituted with up to 3 substituents independently selected from R 3 , or pyridinyl optionally substituted with up to 2 substituents independently selected from R 3 .

3. The composition of claim 2 wherein component (a) is a compound of Formula 1 wherein

R 1 is phenyl optionally substituted with up to 3 substituents independently selected from R 3 ; and

each R 3 is independently halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy or Q.

4. The composition of claim 2 wherein component (a) is a compound of Formula 1 wherein

R 1 is pyridinyl optionally substituted with up to 2 substituents independently selected from R 3 ; and

each R 3 is independently halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy or Q.

5. The composition of claim 3 wherein component (a) is a compound of Formula 1 wherein

R 2 is C 1 -C 4 haloalkyl.

6. The composition of claim 3 wherein component (a) is a compound of Formula 1 wherein

R 2 is thiazolyl, pyridinyl or pyrimidinyl, each optionally substituted with up to 2 substituents independently selected from the group consisting of halogen and C 1 -C 4 alkyl.

7. The composition of claim 3 wherein component (a) is a compound of Formula 1 wherein

Z is CH═CH.

8. The composition of claim 3 wherein component (a) is a compound of Formula 1 wherein

Z is S.

9. The composition of claim 1 wherein component (a) is a compound of Formula 1 selected from the group consisting of:

1-[(2-chloro-5-thiazolyl)methyl]-3-(2,6-difluorophenyl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-3-(2,6-dimethoxyphenyl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-2-hydroxy-3-(2-methoxyphenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(3,5-dimethoxyphenyl)-1-[(6-fluoro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-fluoro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-3-[3-(trifluoromethyl)phenyl]-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-chloro-3-pyridinyl)methyl]-3-(2-fluoro-3-methoxyphenyl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(4-fluorophenyl)-2-hydroxy-1-[(2-methyl-5-thiazolyl)methyl]-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

2-hydroxy-4-oxo-3-phenyl-1-(5-thiazolylmethyl)-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(2-fluorophenyl)-1-[(6-fluoro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-fluoro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-3-[3-(trifluoromethoxy)phenyl]-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(5-bromo-2-methoxyphenyl)-1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-chloro-3-pyridinyl)methyl]-3-[2-chloro-5-(trifluoromethyl)phenyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-fluoro-3-pyridinyl)methyl]-3-[2-fluoro-3-(trifluoromethyl)phenyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-3-[3-(6-fluoro-3-pyridinyl)-5-(trifluoromethoxy)phenyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-3-[3-chloro-5-(trifluoromethoxy)phenyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-3-[3-chloro-5-(trifluoromethyl)phenyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-3-(2,3,6-trifluorophenyl)-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(3-chloro-2,6-difluorophenyl)-1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(2,3-difluorophenyl)-1-[(6-fluoro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(5-chloro-2-methoxyphenyl)-1-[(6-fluoro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(5-chloro-2-methoxyphenyl)-1-[(2-chloro-5-thiazolyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-fluoro-3-pyridinyl)methyl]-2-hydroxy-3-[2-methoxy-5-(trifluoromethyl)phenyl]-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-2-hydroxy-3-[2-methoxy-5-(trifluoromethyl)phenyl]-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(2,4-difluorophenyl)-2-hydroxy-4-oxo-1-(5-thiazolylmethyl)-4H-pyrido[1,2-c]pyrimidinium inner salt;

3-(2-fluorophenyl)-2-hydroxy-4-oxo-1-[(2-methyl-5-thiazolyl)methyl]-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(2-chloro-6-fluorophenyl)-1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-3-(2-ethoxyphenyl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-fluoro-3-pyridinyl)methyl]-3-[2-fluoro-5-(trifluoromethoxy)phenyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-2-hydroxy-3-(3-methylphenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-3-(3-methoxyphenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-chloro-3-pyridinyl)methyl]-3-(2-fluorophenyl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-chloro-3-pyridinyl)methyl]-3-(2,5-difluorophenyl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(5-chloro-2-fluorophenyl)-1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-3-(2,4,6-trifluorophenyl)-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-chloro-3-pyridinyl)methyl]-3-(2,3-difluorophenyl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(5-bromo-2-fluorophenyl)-1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-chloro-3-pyridinyl)methyl]-3-(2,6-difluorophenyl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-3-[3-(trifluoromethoxy)phenyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(6-bromo-3-pyridinyl)methyl]-3-(2,4-difluorophenyl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-2-hydroxy-3-(3-methoxyphenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-[3-bromo-5-(trifluoromethoxy)phenyl]-1-[(2-chloro-5-thiazolyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-[3-bromo-5-(trifluoromethyl)phenyl]-1-[(2-chloro-5-thiazolyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(3-chloro-2-fluorophenyl)-1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

2-hydroxy-4-oxo-1-(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-2-hydroxy-4-oxo-3-(4′-(trifluoromethyl)[1,1′-biphenyl]-3-yl)-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-3-(4′-fluoro[1,1′-biphenyl]-3-yl)-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

3-(5-chloro-2-fluorophenyl)-1-[(6-fluoro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

8-[(6-chloro-3-pyridinyl)methyl]-6-(2,3-difluorophenyl)-7-hydroxy-5-oxo-5H-thiazolo[3,2-a]pyrimidinium inner salt;

3-(2,4-difluorophenyl)-1-[(6-fluoro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt;

1-[(2-chloro-5-thiazolyl)methyl]-2-hydroxy-4-oxo-3-[4-(trifluoromethyl)-2-pyridinyl]-4H-pyrido[1,2-a]pyrimidinium inner salt; and

3-(4-cyano-2-fluorophenyl)-1-[(6-chloro-3-pyridinyl)methyl]-2-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidinium inner salt.

10. The composition of claim 1 further comprising at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

11. The composition of claim 10 further comprising at least one additional biologically active compound or agent.

12. The composition of claim 11 wherein the at least one additional biologically active compound or agent is a fungicide.

13. A composition for protecting an animal from an invertebrate parasitic pest comprising a parasiticidally effective amount of a composition of claim 1 and at least one carrier.

14. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a composition of claim 1 .

15. The method of claim 14 wherein the environment is a plant.

16. The method of claim 14 wherein the environment is a seed coated with the composition comprising the compound of claim 1 and optionally a film former or adhesive agent.

17. A treated seed comprising a composition of claim 1 in an amount of from about 0.0001 to 1% by weight of the seed before treatment.

18. A composition comprising (a) at least one compound selected from compounds of Formula 1, N-oxides, and salts thereof,

wherein

R 1 is phenyl optionally substituted with up to 5 substituents independently selected from R 3 , or pyridinyl optionally substituted with up to 4 substituents independently selected from R 3 ;

R 2 is C 1 -C 4 haloalkyl; or thiazolyl, pyridinyl or pyrimidinyl, each optionally substituted with up to 2 substituents independently selected from the group consisting of halogen and C 1 -C 4 alkyl;

each R 3 is independently halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C(R 4 )═NOR 4 or Q;

each R 4 is independently C 1 -C 4 alkyl;

Z is CH═CH or S; and

each Q is independently phenyl or pyridinyl, each optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy;

and at least one additional biologically active compound or agent selected from the group consisting of

(b) at least one invertebrate pest control agent selected from the group consisting of abamectin, acetamiprid, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid, flubendiamide, flufenoxuron, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methomyl, methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl, phosmet, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, tebufenozide, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, triflumuron, Bacillus thuringiensis delta-endotoxins, Bacillus thuringiensis and nucleo polyhedrosis viruses; and

(c) at least one fungicide;

provided that when the at least one additional biologically active compound or agent is selected from group (b) and (i) when R 1 is unsubstituted phenyl and R 2 is CF 3 , then Z is S; (ii) when R 1 is 2-fluorophenyl and R 2 is 2-chloro-5-thiazolyl, then Z is S; and (iii) when R 1 is 2-fluorophenyl or 3-(trifluoromethoxy)phenyl and R 2 is 6-chloro-3-pyridinyl, then Z is CH═CH.

19. The composition of claim 18 wherein the at least one fungicide is selected from the group consisting of 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, acibenzolar, aldimorph, amisulbrom, azaconazole, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, binomial, biphenyl, bitertanol, blasticidin-S, Bordeaux mixture (Tribasic copper sulfate), boscalid/nicobifen, bromuconazole, bupirimate, buthiobate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, cyazofamid, cyflunamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, discostrobin, dithianon, dodemorph, dodine, econazole, etaconazole, edifenphos, epoxiconazole, ethaboxam, ethirimol, ethridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferfurazoate, ferimzone, fluazinam, fludioxonil, flumetover, fluopicolide, fluoxastrobin, fluquinconazole, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminum, fthalide, fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazole, guazatine, imazalil, imibenconazole, iminoctadine, iodicarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isoconazole, isoprothiolane, isotianil, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb, mapanipyrin, mefenoxam, mepronil, metalaxyl, metconazole, methasulfocarb, metiram, metominostrobin/fenominostrobin, mepanipyrim, metrafenone, miconazole, myclobutanil, neo-asozin (ferric methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, paclobutrazol, penconazole, pencycuron, penflufen, penthiopyrad, perfurazoate, phosphonic acid, picobenzamid, picoxystrobin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propamocarb-hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pryazophos, pyrifenox, pyrimethanil, pyrifenox, pyriofenone, pyroInitrine, pyroquilon, quinconazole, quinoxyfen, quintozene, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolyfluanid, triadimefon, triadimenol, triarimol, triazoxide, tridemorph, trimorphamide, tricyclazole, trifloxystrobin, triforine, triticonazole, uniconazole, validamycin, valifenalate, vinclozolin, zineb, ziram, and zoxamide.