Heterocycle-substituted bicyclic azole pesticides

Abstract

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, N oxides, and salts thereof, wherein A, X1, X2, X3 and R2 are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention.

1 . A compound selected from Formula 1, an N-oxide or salt thereof, 
       
         
           
           
               
               
           
         
       
       wherein
 A is CH; 
 X 1  is CH and X 2  is CR 1 ; 
 X 3  is CH or CF; 
 R 1  is phenyl, pyridinyl, thiazolyl, oxazolyl, thiadiazolyl or oxadiazolyl, each being substituted with one R 3 , and optionally further substituted with 1 to 3 R x . 
 R 2  is H, halogen, cyano, nitro, C 1 -C 4  alkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy or C 1 -C 4  haloalkoxy; 
 R 3  is selected from the group consisting of 
 
       
         
           
           
               
               
           
         
         each R 4  is independently H or C 1 -C 4  alkyl; 
         each R 5  is independently H or C 1 -C 4  alkyl; or 
         R 4  and R 5  are taken together with the carbon atom to which they are attached to form a 3- to 6-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S) and the sulfur atom ring member is selected from S, S(O) or S(O) 2 , said ring being unsubstituted or substituted with up to 4 R x ; provided that R 4  and R 5  are attached to the same carbon atom; 
         p is 1, 2, 3 or 4; 
         R 6  is NR 13 R 14 , OR 15  or C(═NR 8 )R 9 ; or C 1 -C 6  alkyl substituted with at least one R y ; or C 3 -C 6  cycloalkyl, C 2 -C 6  alkenyl or C 2 -C 6  alkynyl, each unsubstituted or substituted with at least one R x ; 
         R 7  is H; 
         each R x  is independently halogen, cyano, nitro, hydroxy, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 3 -C 6  cycloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 3 -C 6  cycloalkoxy, C(═NR 8 )R 9 , C(O)OR 16 , C(O)NR 13 R 14 , OC(O)R 17 , NR 20 R 21 , NR 19 C(O)R 17 , C(O)R 17 , S(O) n R 18 , Si(R 23 ) 3 , OSi(R 23 ) 3  or Q; 
         each R y  is independently cyano, nitro, hydroxy, C 3 -C 6  cycloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 3 -C 6  cycloalkoxy, C(═NR 8 )R 9 , C(O)OR 16 , C(O)NR 13 R 14 , OC(O)R 17 , NR 20 R 21 , NR 19 C(O)R 17 , C(O)R 17 , S(O) n R 18 , Si(R 23 ) 3 , OSi(R 23 ) 3  or Q; 
         each R 8  is independently OR 10 , S(O) n R 11  or NHR 12 ; 
         each R 9  is independently H; or C 1 -C 6  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 6  alkenyl or C 2 -C 6  alkynyl, each unsubstituted or substituted with at least one R x ; or C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, C 3 -C 6  cycloalkoxy, C(O)OR 16 , C(O)NR 13 R 14 , NR 20 R 21 , NR 19 C(O)R 17 , C(O)R 17  or Q; 
         each R 10  is independently C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C(O)R 17 , S(O) n R 11  or Q; 
         each R 11  is independently C 1 -C 4  alkyl or C 1 -C 4  haloalkyl; 
         R 12  is C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C(O)R 17  or C(O)OR 16 ; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 13  is independently H, C 1 -C 6  alkyl, C 1 -C 4  haloalkyl, C 1 -C 4  hydroxyalkyl, C(O)R 22  or S(O) 2 R 22 ; or phenyl or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 14  is independently H, C 1 -C 6  alkyl or C 1 -C 4  haloalkyl; or 
         R 13  and R 14  are taken together with the nitrogen atom to which they are attached to form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S) and the sulfur atom ring member is selected from S, S(O) or S(O) 2 , said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         R 15  is C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 3 -C 6  cycloalkoxy or C 1 -C 4  haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 16  is independently H, C 1 -C 4  alkyl, C 1 -C 4  haloalkyl, C 3 -C 6  cycloalkyl or C 3 -C 6  halocycloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 17  is independently C 1 -C 4  alkyl, C 1 -C 4  haloalkyl, C 3 -C 6  cycloalkyl or C 3 -C 6  halocycloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 18  is independently C 1 -C 4  alkyl, C 1 -C 4  haloalkyl, C 3 -C 6  cycloalkyl, C 3 -C 6  halocycloalkyl, C 3 -C 6  cycloalkylalkyl or C 3 -C 6  halocycloalkylalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 19  is independently H or C 1 -C 4  alkyl; 
         each R 20  is independently H, C 1 -C 4  alkyl or C 1 -C 4  haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 21  is independently H, C 1 -C 4  alkyl or C 1 -C 4  haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; or 
         R 20  and R 21  are independently taken together with the nitrogen atom to which they are attached to form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S) and the sulfur atom ring member is selected from S, S(O) or S(O) 2 , said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 22  is independently C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy or NR 24 R 25 ; or phenyl or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 23  is independently C 1 -C 6  alkyl, C 3 -C 6  cycloalkyl or phenyl; 
         each R 24  is independently H or Q; or C 1 -C 6  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 6  alkenyl or C 2 -C 6  alkynyl, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each R 25  is independently H or Q; or C 1 -C 6  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 6  alkenyl or C 2 -C 6  alkynyl, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; or 
         R 24  and R 25  are taken together with the nitrogen atom to which they are attached to form a 3- to 10-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S) and the sulfur atom ring member is selected from S, S(O) or S(O) 2 , said ring being unsubstituted or substituted with up to 4 substituents independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; 
         each Q is independently phenyl, a 5- or 6-membered heterocyclic aromatic ring or a 3- to 6-membered heterocyclic non-aromatic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S) and the sulfur atom ring member is selected from S, S(O) or S(O) 2 , each ring unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C 1 -C 4  alkyl, C 3 -C 6  cycloalkyl, C 1 -C 4  haloalkyl, C 1 -C 4  alkoxy and C 1 -C 4  haloalkoxy; and 
         each n is independently 0, 1 or 2; 
         provided that when X 3  is CH; R 2  is H; R 3  is R 3b ; R 6  is a cyclopropyl substituted at the 1 position with R x ; R x  is C(O)NR 13 R 14 ; R 13  is CH 3  and R 14  is H, then R 1  is other than pyridine-4-yl substituted with one R 3  at the 2 position. 
       
     
     
         2 . (canceled) 
     
     
         3 . (canceled) 
     
     
         4 . (canceled) 
     
     
         5 . The compound of  claim 4  wherein
 R 1  is phenyl, pyridinyl, thiazolyl, oxazolyl or oxadiazolyl, each being substituted with one R 3 , and optionally further substituted with 1 to 3 R x . 
 
     
     
         6 . (canceled) 
     
     
         7 . A composition comprising a compound of  claim 1  and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent. 
     
     
         8 . The composition of  claim 7  wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cycloxaprid, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin, flufensulfone, fluorpyram, flupiprole, flupyradifurone, fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, heptafluthrin, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, monofluthrin, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin, pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumuron, all strains of  Bacillus thuringiensis , entomopathogenic bacteria, all strains of  Nucleo polyhedrosis  viruses, entomopathogenic viruses and entomopathogenic fungi. 
     
     
         9 . The composition of  claim 8  wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, 3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide, buprofezin, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin, flufensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthirn, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluthrin, nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, tetramethylfluthrin, triazamate, triflumuron, all strains of  Bacillus thuringiensis  and all strains of  Nucleo polyhedrosis  viruses. 
     
     
         10 . A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of  claim 1 . 
     
     
         11 . A treated seed comprising a compound of  claim 1  in an amount of from about 0.0001 to 1% by weight of the seed before treatment.