Mesoionic insecticides
阅读说明：本技术 介离子杀虫剂 (Mesoionic insecticides ) 是由 C·W·小霍利奥克 于 2018-05-04 设计创作，主要内容包括：<Image he="421" wi="606" file="DDA0002359249410000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本申请公开了式1的化合物,包括其所有几何异构体和立体异构体,N-氧化物和盐,其中A、X、Y、Z、R<Sup>1</Sup>、R<Sup>2a</Sup>、R<Sup>2b</Sup>和Q如本公开所定义的。本申请还公开了包含式1的化合物的组合物,以及用于防治无脊椎害虫的方法,其包括使所述无脊椎害虫或其环境与生物学有效量的本发明的化合物或组合物接触。(The present application discloses compounds of formula 1, including all geometric and stereoisomers, N-oxides and salts thereof, wherein A, X, Y, Z, R 1 、R 2a 、R 2b And Q is as defined in this disclosure. Also disclosed are compositions comprising 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 a salt thereof,
wherein
X is O or S;
y is O or S;
a is a 5-, 6-or 7-membered ring containing a ring member selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2O, up to 2S and up to 3N, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and said sulfur atom ring members are independently selected from S (═ O)nEach ring being unsubstituted or substituted by up to 3 independently selected from R3Substituted with the substituent(s);
z is a direct bond; or is a1 to 4 atom chain containing chain members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O, up to 2S and up to 2N, wherein up to 2 carbon atom chain members are independently selected from C (═ O) and C (═ S), and said sulfur atom chain members are independently selected from S (═ O)nEach chain of 1 to 4 atoms being unsubstituted or substituted by up to 4 atoms independently selected from R5Or when R is substituted5When halogen, is substituted with up to 9 halogens;
R1is H or halogen; a 3 to 10 membered ring or a 7 to 11 membered ring system, each ring or ring system containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2O, up to 2S and up to 4N, wherein up to 3 carbon atoms are in the ringMembers are independently selected from C (═ O) and C (═ S), and said sulfur atom ring members are independently selected from S (═ O)u(＝NR19)zEach ring or ring system being unsubstituted or substituted by up to 8 groups independently selected from R4Substituted with the substituent(s); provided that when Z is a direct bond, R1Is not H or halogen;
R2aand R2bIndependently of one another H, halogen, cyano, C1-C3Alkyl radical, C2-C3Alkenyl or C2-C3An alkynyl group; or R2aAnd R2bTogether forming a 3 to 6 membered ring containing a ring member selected from carbon atoms and up to one heteroatom selected from O, N and S (O)n；
O is a 5 or 6 membered heteroaromatic ring which is unsubstituted or substituted with up to 3 independently selected from R6Substituted with the substituent(s);
each R is3Independently halogen, cyano, hydroxy, amino, nitro, C (═ O) OH, C (═ O) NH2、SO2NH2、C1-C4Alkyl radical, C1-C4Haloalkyl, C2-C4Alkenyl radical, C2-C4Haloalkenyl, C2-C4Alkynyl, C3-C7Cycloalkyl radical, C3-C7Halogenocycloalkyl, C4-C8Alkyl cycloalkyl radical, C4-C8Haloalkyl cycloalkyl, C4-C8Cycloalkylalkyl radical, C4-C8Halocycloalkylalkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C2-C6Alkoxycarbonyl group, C2-C6Halogenoalkoxycarbonyl, C2-C6Alkylcarbonyl or C2-C6A haloalkylcarbonyl group;
each R is4Independently halogen, cyano, hydroxy, amino, nitro, SF5、OCN、SCN、CHO、C(＝O)OH、C(＝O)NH2、C(＝S)NH2、SO2NH2、C(＝O)R13、C(＝O)OR13、NHR13、NR13R14、C(＝O)NR16R14、C(＝S)NR16R14、SO2NR16R14、OC(＝O)R16、OC(＝O)OR13、OC(＝O)NR16R14、N(R16)C(＝O)R16、N(R16)C(＝O)OR14、N(R16)C(＝O)NR16R17、OSO2R13、OSO2NR16R17、NR16SO2R13、NR16SO2NR16R17、Si(R13R14R15)、C(＝NR16)R17、C(＝NOR16)R17、C(＝NNR16R17)R18、C(＝NN(C(＝O)R14)R16)R17、C(＝NN(C(＝O)OR14)R16)R17、C(＝NN(C(＝O)NR16R17)R16)R17、C(＝NOR16)NR16R17、ON＝CR16R17、ONR16R17、S(＝O)(＝NR16)R17、SO2NR16C(＝O)NR17R18、P(＝X2)R13R14、OP(＝X2)R13R14、OP(＝X2)(OR13)R14、OP(＝X2)(OR13)OR14、N＝CR16R17、NR16N＝CR17R18、NR16NR17R18、NR16C(＝X2)NR17R18、NR16C(＝NR16)NR17R18、NR16NR16C(＝X2)NR17R18Or NR16NR16SO2NR17R18(ii) a Or
Each R is4Independently is C1-C8Alkyl radical, C2-C8Alkenyl radical, C2-C8Alkynyl, C3-C10Cycloalkyl radical, C4-C10Alkyl cycloalkyl radical, C4-C10Cycloalkylalkyl radical, C6-C14Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C8Cycloalkenyl radical, C1-C8Alkoxy radical, C3-C8Cycloalkoxy, C4-C10Cycloalkylalkoxy radical, C3-C10Cycloalkoxyalkyl radical, C3-C10Cycloalkoxy alkoxy, C2-C8Alkenyloxy radical, C2-C8Alkynyloxy, C1-C8Alkylthio radical, C1-C8Alkylsulfinyl radical, C1-C8Alkylsulfonyl radical, C3-C8Cycloalkylthio radical, C3-C8Cycloalkyl sulfinyl radical, C3-C8Cycloalkylsulfonyl radical, C4-C10Cycloalkylalkylthio radical, C4-C10Cycloalkyl alkylsulfinyl radical, C4-C10Cycloalkylalkylsulfonyl radical, C2-C8Alkenylthio radical, C2-C8Alkenylsulfinyl, C2-C8Alkenylsulfonyl radical, C2-C8Alkynylthio, C2-C8Alkynylsulfinyl or C2-C8Alkynylsulfonyl, each of which is unsubstituted or at least one independently selected from R12Substituted with the substituent(s); or
Each R is4Independently is Z1Q1(ii) a Or
Two R4The substituents together form a 5-to 7-membered carbocyclic or heterocyclic ring, each ring containing a ring member selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2O, up to 2S and up to 3N, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and said sulfur atom ring members are independently selected from S (═ O)nEach ring is optionally substituted with up to 3 substituents independently selected from the group consisting of: halogen, cyano, hydroxy, amino, nitro, C (═ O) OH, C (═ O) NH2、SO2NH2、C1-C4Alkyl radical, C1-C4Haloalkyl, C2-C4Alkenyl radical, C2-C4Haloalkenyl, C2-C4Alkynyl, C3-C7Cycloalkyl radical, C3-C7Halogenocycloalkyl, C4-C8Alkyl cycloalkyl radical, C4-C8Haloalkyl cycloalkyl, C4-C8Cycloalkylalkyl radical, C4-C8Halocycloalkylalkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C2-C6Alkoxycarbonyl group, C2-C6Halogenoalkoxycarbonyl, C2-C6Alkylcarbonyl group, C2-C6Halogenoalkylcarbonyl group, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl and C1-C4An alkylsulfonyl group;
each R is5Independently halogen, cyano, nitro, C1-C3Alkyl radical, C1-C3Haloalkyl, C2-C3Alkenyl radical, C2-C3Haloalkenyl, C2-C3Alkynyl, C (═ O) OR8、C(＝O)NR9R10Or Z1Q2；
Each R is6Independently halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10Or Si (R)7)3(ii) a Or C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C6Cycloalkenyl radical, C2-C6Alkylcarbonyl or C2-C6Alkoxycarbonyl, each of which is unsubstituted orSubstituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10And Si (R)7)3；
Each R is7、R8、R9And R10Independently is C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkylalkyl or C3-C6Cycloalkenyl, each of which is unsubstituted or substituted with at least one substituent independently selected from: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Halogenoalkylthio, C1-C4Haloalkylsulfinyl radical, C1-C4Haloalkylsulfonyl group, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C2-C4Alkoxyalkyl group, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl group, C2-C6Alkylcarbonyloxy, C2-C6Alkylcarbonylthio, C2-C6Alkylaminocarbonyl radical, C3-C8Dialkylaminocarbonyl and C3-C6A trialkylsilyl group; or phenyl or a 5 or 6 membered heteroaromatic ring, each of which is unsubstituted or substituted with at least one substituent independently selected from: c1-C6Alkyl radical, C1-C6Haloalkyl, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C6Cycloalkenyl, halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Halogenoalkylthio, C1-C4Haloalkylsulfinyl radical, C1-C4Haloalkylsulfonyl group, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C2-C4Alkoxyalkyl group, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl group, C2-C6Alkylcarbonyloxy, C2-C6Alkylcarbonylthio, C2-C6Alkylaminocarbonyl radical, C3-C8Dialkylaminocarbonyl and C3-C6A trialkylsilyl group;
each Z1Independently is a direct bond; or is a1 to 4 atom chain containing chain members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O, up to 2S and up to 2N, wherein up to 2 carbon atom chain members are independently selected from C (═ O) and C (═ S), and said sulfur atom chain members are independently selected from S (═ O)nEach chain of 1 to 4 atoms being unsubstituted or substituted by up to 4 atoms independently selected from R5Or when R is substituted5When halogen, is substituted with up to 9 halogens;
each X2Independently is O or S;
each Q1Independently is a 3 to 10 membered ring or a 7 to 11 membered ring system, each ring or ring system containing carbon selected fromA ring member of atoms and up to 4 heteroatoms independently selected from up to 2O, up to 2S and up to 4N, wherein up to 3 carbon atom ring members are independently selected from C (═ O) and C (═ S), and said sulfur atom ring members are independently selected from S (═ O)u(＝NR19)zEach ring or ring system is optionally substituted with up to 4 substituents independently selected from the group consisting of: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10、Si(R7)3And R11；
Each Q2Independently is phenyl or a 5 or 6 membered heteroaromatic ring, each of which is unsubstituted or substituted with up to 3 substituents independently selected from: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10、Si(R7)3And R11；
Each R is11Independently is C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkylalkyl or C3-C6Cycloalkenyl, each of which is unsubstituted or substituted with at least one substituent independently selected from: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Halogenoalkylthio, C1-C4Haloalkylsulfinyl group、C1-C4Haloalkylsulfonyl group, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C2-C4Alkoxyalkyl group, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl group, C2-C6Alkylcarbonyloxy, C2-C6Alkylcarbonylthio, C2-C6Alkylaminocarbonyl radical, C3-C8Dialkylaminocarbonyl and C3-C6A trialkylsilyl group; or phenyl or a 5 or 6 membered heteroaromatic ring, each of which is unsubstituted or substituted with at least one substituent independently selected from: c1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C6Cycloalkenyl, halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Halogenoalkylthio, C1-C4Haloalkylsulfinyl radical, C1-C4Haloalkylsulfonyl group, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C2-C4Alkoxyalkyl group, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl group, C2-C6Alkylcarbonyloxy, C2-C6Alkylcarbonylthio, C2-C6Alkylaminocarbonyl radical, C3-C8Dialkylaminocarbonyl and C3-C6A trialkylsilyl group;
each R is12Independently halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10、Si(R7)3Or Z1Q2；
Each R is13、R14And R15Independently is C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkylalkyl or C3-C6Cycloalkenyl, each of which is unsubstituted or at least one independently selected from R12Substituted with the substituent(s); or is Q2；
Each R is16、R17And R18Independently H, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkylalkyl or C3-C6Cycloalkenyl, each of which is unsubstituted or at least one independently selected from R12Substituted with the substituent(s); or is Q2；
Each R is19Independently is H, cyano, OCN, SCN, CHO, C (═ O) OH, C (═ O) NH2、C(＝S)NH2、SO2NH2、C(＝O)R13、C(＝O)OR13、NHR13、NR13R14、C(＝O)NR16R14、C(＝S)NR16R14、SO2NR16R14、OC(＝O)R16、OC(＝O)OR13、OC(＝O)NR16R14、N(R16)C(＝O)R16、N(R16)C(＝O)OR14、N(R16)C(＝O)NR16R17、OSO2R13、OSO2NR16R17、NR16SO2R13、NR16SO2NR16R17、Si(R13R14R15) Or Z1Q2(ii) a Or C1-C8Alkyl radical, C2-C8Alkenyl radical, C2-C8Alkynyl, C3-C10Cycloalkyl radical, C4-C10Alkyl cycloalkyl radical, C4-C10Cycloalkylalkyl radical, C6-C14Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C8Cycloalkenyl radical, C1-C8Alkoxy radical, C3-C8Cycloalkoxy, C4-C10Cycloalkylalkoxy radical, C2-C8Alkenyloxy radical, C2-C8Alkynyloxy, C1-C8Alkylthio radical, C1-C8Alkylsulfinyl radical, C1-C8Alkylsulfonyl radical, C3-C8Cycloalkylthio radical, C3-C8Cycloalkyl sulfinyl radical, C3-C8Cycloalkylsulfonyl radical, C4-C10Cycloalkylalkylthio radical, C4-C10Cycloalkyl alkylsulfinyl radical, C4-C10Cycloalkylalkylsulfonyl radical, C2-C8Alkenylthio radical, C2-C8Alkenylsulfinyl, C2-C8Alkenylsulfonyl radical, C2-C8Alkynylthio, C2-C8Alkynylsulfinyl or C2-C8Alkynylsulfonyl, each of which is unsubstituted or at least one independently selected from R12Substituted with the substituent(s);
each n is independently 0, 1 or 2; and is
u and z are in S (═ O)u(＝NR19)zIs independently 0, 1 or 2, provided that the sum of u and z is at S (═ O)u(＝NR19)zIs 0, 1 or 2 in each instance.
2. The compound of claim 1, wherein the compound of formula 1 is a compound of formula 1-1
a is 0, 1, 2 or 3.
3. The compound of claim 2, wherein
X and Y are O;
R2aand R2bIs H.
4. The compound of claim 3, wherein
Z is a direct bond; and is
R1Is phenyl or pyridyl, each of which is unsubstituted or substituted by up to 4 independently selected from R4Is substituted with the substituent(s).
5. The compound of claim 4, wherein
Q is
6. The compound of claim 5, wherein
R1Is phenyl, unsubstituted or substituted by up to 4 groups independently selected from R4Substituted with the substituent(s);
R3is F, Cl or CH3；
a is 0 or 1; and is
R6Is H, F, C1, Br, CH3、CHF2Or CF3。
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 abamectin, acephate, fenaminostrobin, acetamiprid, flupropathrin, pyriproxyfen, pyraclofen, sulfadimidine, amitraz, abamectin, azadir, oryzophos, prothioconazole, sulfolane, dimehypo, fenthion, fenpropathrin, fenthion, fenpropathrin, fenflurazophos, fenpropathrin, fenfluridone, fenpropathrin, fenfluridone, fenpropathrin, fenflurazocarb, fenflurazoate, fenflurazocarb, fenpropathrin, fenflurazocarb, fenpropathrin, fenthion, fenpropathrin, fenflurazocarb, fenthion, fenpropathrin, fenthion, fenpropathrin.
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, fluoropropylene, pyriproxyfen, amitraz, abamectin, azadirachtin, benfuracarb, thiofenthiobac, bifenthrin, 3-bromo-1- (3-chloro-2-pyridyl) -N- [ 4-cyano-2-methyl-6- [ (methylamino) carbonyl ] phenyl ] -1H-pyrazole-5-carboxamide, buprofezin, carbaryl, chlorantraniliprole, chlorfenapyr, chlorpyrifos, thiamethoxam, cyantraniliprole, cyclopromazine, cycloprothrin, cyfluthrin, β -cyfluthrin, lambda-cyhalothrin, gamma-cyfluthrin, cypermethrin, α -cypermethrin, zeta-cypermethrin, dimefluthrin, cypermethrin, dimehyporin, furfluthrin, dinotefuran, fenproxyfen, fenpropathrin, fenthiobac, flufenozide, flufenoxate, fenpropathrin, flufenoxafen, thifenthiobac, thifenprox, flufenoxafen, thifenfurazol, thifenprox, fenprox, flufenoxafen, flufenozide, flufenoxate, thifenfurazolidone, pyriproxyfen, thiobac, pyriproxyfen, thiobac, thifenproxyfen, thiobac, pyriproxyfen, thiobac, thifenproxyfen, thiobac, pyriproxyfen.
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 any one of claims 1-6.
11. A treated seed comprising the compound of any one of claims 1-6 in an amount of about 0.0001% to 1% by weight of the seed prior to treatment.
Technical Field
The present invention relates to certain mesoionic compounds, their N-oxides, salts and compositions suitable for agronomic and nonagronomic uses and methods for their use in controlling invertebrate pests such as arthropods in agronomic and nonagronomic environments.
Background
Control of invertebrate pests is extremely important in achieving high crop efficiency. Damage to growing and stored crops by invertebrate pests can cause significant reductions in productivity and thereby result in increased costs to consumers. Control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. For these purposes, many products are commercially available, but there is a continuing need for new compounds that are more effective, less costly, less toxic, environmentally safer, or have different sites of action.
Summary of The Invention
The present invention relates to compounds of formula 1 (including all geometric and stereoisomers), N-oxides, and salts thereof, and compositions containing them, and their use for controlling invertebrate pests:
wherein
X is O or S;
y is O or S;
a is a 5-, 6-or 7-membered ring containing a ring member selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2O, up to 2S and up to 3N, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and said sulfur atom ring members are independently selected from S (═ O)nEach ring being unsubstituted or substituted by up to 3 independently selected from R3Substituted with the substituent(s);
z is a direct bond; or a1 to 4 atom chain containing chain members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O, up to 2S and up to 2N, wherein up to 2 carbon atom chainsMembers are independently selected from C (═ O) and C (═ S), and said sulfur atom chain members are independently selected from S (═ O)nEach chain of 1 to 4 atoms being unsubstituted or substituted by up to 4 atoms independently selected from R5Or when R is substituted5When halogen, is substituted with up to 9 halogens;
R1is H or halogen; a 3 to 10 membered ring or a 7 to 11 membered ring system, each ring or ring system containing a ring member selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2O, up to 2S and up to 4N, wherein up to 3 carbon atom ring members are independently selected from C (═ O) and C (═ S), and said sulfur atom ring members are independently selected from S (═ O)u(＝NR19)zEach ring or ring system being unsubstituted or substituted by up to 8 groups independently selected from R4Substituted with the substituent(s); provided that when Z is a direct bond, R1Is not H or halogen;
R2aand R2bIndependently of one another H, halogen, cyano, C1-C3Alkyl radical, C2-C3Alkenyl or C2-C3An alkynyl group; or R2aAnd R2bTogether forming a 3 to 6 membered ring containing a ring member selected from carbon atoms and up to one heteroatom selected from O, N and S (O)n；
Q is a 5 or 6 membered heteroaromatic ring which is unsubstituted or substituted with up to 3 members independently selected from R6Substituted with the substituent(s);
each R is3Independently halogen, cyano, hydroxy, amino, nitro, C (═ O) OH, C (═ O) NH2、SO2NH2、C1-C4Alkyl radical, C1-C4Haloalkyl, C2-C4Alkenyl radical, C2-C4Haloalkenyl, C2-C4Alkynyl, C3-C7Cycloalkyl radical, C3-C7Halogenocycloalkyl, C4-C8Alkyl cycloalkyl radical, C4-C8Haloalkyl cycloalkyl, C4-C8Cycloalkylalkyl radical, C4-C8Halocycloalkylalkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C2-C6Alkoxycarbonyl group, C2-C6Halogenoalkoxycarbonyl, C2-C6Alkylcarbonyl or C2-C6A haloalkylcarbonyl group;
each R is4Independently halogen, cyano, hydroxy, amino, nitro, SF5、OCN、SCN、CHO、C(＝O)OH、C(＝O)NH2、C(＝S)NH2、SO2NH2、C(＝O)R13、C(＝O)OR13、NHR13、NR13R14、C(＝O)NR16R14、C(＝S)NR16R14、SO2NR16R14、OC(＝O)R16、OC(＝O)OR13、OC(＝O)NR16R14、N(R16)C(＝O)R16、N(R16)C(＝O)OR14、N(R16)C(＝O)NR16R17、OSO2R13、OSO2NR16R17、NR16SO2R13、NR16SO2NR16R17、Si(R13R14R15)、C(＝NR16)R17、C(＝NOR16)R17、C(＝NNR16R17)R18、C(＝NN(C(＝O)R14)R16)R17、C(＝NN(C(＝O)OR14)R16)R17、C(＝NN(C(＝O)NR16R17)R16)R17、C(＝NOR16)NR16R17、ON＝CR16R17、ONR16R17、S(＝O)(＝NR16)R17、SO2NR16C(＝O)NR17R18、P(＝X2)R13R14、OP(＝X2)R13R14、OP(＝X2)(OR13)R14、OP(＝X2)(OR13)OR14、N＝CR16R17、NR16N＝CR17R18、NR16NR17R18、NR16C(＝X2)NR17R18、NR16C(＝NR16)NR17R18、NR16NR16C(＝X2)NR17R18Or NR16NR16SO2NR17R18(ii) a Or
Each R is4Independently is C1-C8Alkyl radical, C2-C8Alkenyl radical, C2-C8Alkynyl, C3-C10Cycloalkyl radical, C4-C10Alkyl cycloalkyl radical, C4-C10Cycloalkylalkyl radical, C6-C14Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C8Cycloalkenyl radical, C1-C8Alkoxy radical, C3-C8Cycloalkoxy, C4-C10Cycloalkylalkoxy radical, C3-C10Cycloalkoxyalkyl radical, C3-C10Cycloalkoxy alkoxy, C2-C8Alkenyloxy radical, C2-C8Alkynyloxy, C1-C8Alkylthio radical, C1-C8Alkylsulfinyl radical, C1-C8Alkylsulfonyl radical, C3-C8Cycloalkylthio radical, C3-C8Cycloalkyl sulfinyl radical, C3-C8Cycloalkylsulfonyl radical, C4-C10Cycloalkylalkylthio radical, C4-C10Cycloalkyl alkylsulfinyl radical, C4-C10Cycloalkylalkylsulfonyl radical, C2-C8Alkenylthio radical, C2-C8Alkenylsulfinyl, C2-C8Alkenylsulfonyl radical, C2-C8Alkynylthio, C2-C8Alkynylsulfinyl or C2-C8Alkynylsulfonyl, each of which is unsubstituted or at least one independently selected from R12Substituted with the substituent(s); or
Each R is4Independently is Z1Q1(ii) a Or
Two R4The substituents together form a 5-to 7-membered carbocyclic or heterocyclic ring, each ring containing a ring member selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2O, up to 2S and up to 3N, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and said sulfur atom ring members are independently selected from S (═ O)nEach ring is optionally substituted with up to 3 substituents independently selected from the group consisting of: halogen, cyano, hydroxy, amino, nitro, C (═ O) OH, C (═ O) NH2、SO2NH2、C1-C4Alkyl radical, C1-C4Haloalkyl, C2-C4Alkenyl radical, C2-C4Haloalkenyl, C2-C4Alkynyl, C3-C7Cycloalkyl radical, C3-C7Halogenocycloalkyl, C4-C8Alkyl cycloalkyl radical, C4-C8Haloalkyl cycloalkyl, C4-C8Cycloalkylalkyl radical, C4-C8Halocycloalkylalkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C2-C6Alkoxycarbonyl group, C2-C6Halogenoalkoxycarbonyl, C2-C6Alkylcarbonyl group, C2-C6Halogenoalkylcarbonyl group, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl and C1-C4An alkylsulfonyl group;
each R is5Independently halogen, cyano, nitro, C1-C3Alkyl radical, C1-C3Haloalkyl, C2-C3Alkenyl radical, C2-C3Haloalkenyl, C2-C3Alkynyl, C (═ O) OR8、C(＝O)NR9R10Or Z1Q2；
Each R is6Independently halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10Or Si (R)7)3(ii) a Or C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C6Cycloalkenyl radical, C2-C6Alkylcarbonyl or C2-C6Alkoxycarbonyl, each of which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10And Si (R)7)3；
Each R is7、R8、R9And R10Independently is C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkylalkyl or C3-C6Cycloalkenyl, each of which is unsubstituted or substituted with at least one substituent independently selected from: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Halogenoalkylthio, C1-C4Haloalkylsulfinyl radical, C1-C4Haloalkylsulfonyl group, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkyl radicalsAmino group, C2-C4Alkoxyalkyl group, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl group, C2-C6Alkylcarbonyloxy, C2-C6Alkylcarbonylthio, C2-C6Alkylaminocarbonyl radical, C3-C8Dialkylaminocarbonyl and C3-C6A trialkylsilyl group; or phenyl or a 5 or 6 membered heteroaromatic ring, each of which is unsubstituted or substituted with at least one substituent independently selected from: c1-C6Alkyl radical, C1-C6Haloalkyl, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C6Cycloalkenyl, halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Halogenoalkylthio, C1-C4Haloalkylsulfinyl radical, C1-C4Haloalkylsulfonyl group, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C2-C4Alkoxyalkyl group, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl group, C2-C6Alkylcarbonyloxy, C2-C6Alkylcarbonylthio, C2-C6Alkylaminocarbonyl radical, C3-C8Dialkylaminocarbonyl and C3-C6A trialkylsilyl group;
each Z1Independently is a direct bond; or a1 to 4 atom chain containing chain members selected from carbon atoms and up to 2 heteroatoms, saidHeteroatoms are independently selected from up to 2O, up to 2S and up to 2N, wherein up to 2 carbon atom chain members are independently selected from C (═ O) and C (═ S), and said sulfur atom chain members are independently selected from S (═ O)nEach chain of 1 to 4 atoms being unsubstituted or substituted by up to 4 atoms independently selected from R5Or when R is substituted5When halogen, is substituted with up to 9 halogens;
each X2Independently is O or S;
each Q1Independently is a 3 to 10 membered ring or a 7 to 11 membered ring system, each ring or ring system containing a ring member selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2O, up to 2S and up to 4N, wherein up to 3 carbon atom ring members are independently selected from C (═ O) and C (═ S) and the sulfur atom ring members are independently selected from S (═ O)u(＝NR19)zEach ring or ring system is optionally substituted with up to 4 substituents independently selected from the group consisting of: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10、Si(R7)3And R11；
Each Q2Independently is phenyl or a 5 or 6 membered heteroaromatic ring, each of which is unsubstituted or substituted with up to 3 substituents independently selected from: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10、Si(R7)3And R11；
Each R is11Independently is C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkylalkyl or C3-C6Cycloalkenyl, each of which is unsubstituted or substituted with at least one substituent independently selected from: halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Halogenoalkylthio, C1-C4Haloalkylsulfinyl radical, C1-C4Haloalkylsulfonyl group, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C2-C4Alkoxyalkyl group, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl group, C2-C6Alkylcarbonyloxy, C2-C6Alkylcarbonylthio, C2-C6Alkylaminocarbonyl radical, C3-C8Dialkylaminocarbonyl and C3-C6A trialkylsilyl group; or phenyl or a 5 or 6 membered heteroaromatic ring, each of which is unsubstituted or substituted with at least one substituent independently selected from: c1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C6Cycloalkenyl, halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio radical, C1-C4Alkylsulfinyl radical, C1-C4Alkylsulfonyl radical, C1-C4Halogenoalkylthio, C1-C4Haloalkylsulfinyl radical, C1-C4Haloalkylsulfonyl group, C1-C4Alkylamino radical, C2-C8Dialkylamino radical, C3-C6Cycloalkylamino, C2-C4Alkoxyalkyl group, C2-C4Alkylcarbonyl group, C2-C6Alkoxycarbonyl group, C2-C6Alkylcarbonyloxy, C2-C6Alkylcarbonylthio, C2-C6Alkylaminocarbonyl radical, C3-C8Dialkylaminocarbonyl and C3-C6A trialkylsilyl group;
each R is12Independently halogen, cyano, nitro, CHO, C (═ O) OH, C (═ O) NH2、C(＝O)R7、C(＝O)OR8、C(＝O)NR9R10、OR8、S(O)nR7、SO2NR9R10、Si(R7)3Or Z1Q2；
Each R is13、R14And R15Independently is C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkylalkyl or C3-C6Cycloalkenyl, each of which is unsubstituted or at least one independently selected from R12Substituted with the substituent(s); or is Q2；
Each R is16、RDoor with a door panelAnd R18Independently H, C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C8Cycloalkyl radical, C4-C8Alkyl cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C6-C10Cycloalkyl, C5-C10Alkyl cycloalkylalkyl or C3-C6Cycloalkenyl radicals, each of which is unsubstituted or substituted by at least oneSelected from R12Substituted with the substituent(s); or is Q2；
Each R is19Independently is H, cyano, OCN, SCN, CHO, C (═ O) OH, C (═ O) NH2、C(＝S)NH2、SO2NH2、C(＝O)R13、C(＝O)OR13、NHR13、NR13R1414、C(＝O)NR16R14、C(＝S)NR16R14、SO2NR16R14、OC(＝O)R16、OC(＝O)OR13、OC(＝O)NR16R14、N(R16)C(＝O)R16、N(R16)C(＝O)OR14、N(R16)C(＝O)NR16R17、OSO2R13、OSO2NR16R17、NR16SO2R13、NR16SO2NR16R17、Si(R13R14R15) Or Z1Q2(ii) a Or C1-C8Alkyl radical, C2-C8Alkenyl radical, C2-C8Alkynyl, C3-C10Cycloalkyl radical, C4-C10Alkyl cycloalkyl radical, C4-C10Cycloalkylalkyl radical, Cé-C14Cycloalkyl, C5-C10Alkyl cycloalkyl alkyl, C3-C8Cycloalkenyl radical, C1-C8Alkoxy radical, C3-C8Cycloalkoxy, C4-C10Cycloalkylalkoxy radical, C2-C8Alkenyloxy radical, C2-C8Alkynyloxy, C1-C8Alkylthio radical, C1-C8Alkylsulfinyl radical, C1-C8Alkylsulfonyl radical, C3-C8Cycloalkylthio radical, C3-C8Cycloalkyl sulfinyl radical, C3-C8Cycloalkylsulfonyl radical, C4-C10Cycloalkylalkylthio radical, C4-C10Cycloalkyl alkylsulfinyl radical, C4-C10Cycloalkylalkylsulfonyl radical, C2-C8Alkenylthio radical, C2-C8Alkenylsulfinyl, C2-C8Alkenylsulfonyl radical, C2-C8Alkynylthio, C2-C8Alkynylsulfinyl or C2-C8Alkynylsulfonyl, each of which is unsubstituted or at least one independently selected from R12Substituted with the substituent(s);
each n is independently 0, 1 or 2; and is
u and z are in S (═ O)u(＝NR19)zIs independently 0, 1 or 2, provided that the sum of u and z is at S (═ O)u(＝NR19) Each instance of Z is 0, 1 or 2.
The present invention also provides a composition comprising a compound of formula 1, an N-oxide or a salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent. In one embodiment, the present invention also provides a composition for controlling an invertebrate pest comprising a compound of formula 1, an N-oxide or a salt thereof and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, the composition optionally further comprising at least one additional biologically active compound or agent.
The present invention provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g., in the form of a composition described herein). The present invention also relates to methods wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, the composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent.
The present invention also provides a method for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g., in the form of a composition described herein). The invention also relates to treated seeds. The present invention also provides a method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g., in the form of a composition described herein). The present invention also provides the use of a compound of formula 1, an N-oxide, or a salt thereof (e.g., in the form of a composition described herein) for protecting an animal from an invertebrate pest.
The present invention also provides a method of increasing the vigor of a crop plant comprising contacting the crop plant, a seed in which the crop plant is growing, or the locus of the crop plant (such as a growth medium) with a biologically effective amount of a compound of formula 1 (e.g., in the form of a composition described herein).
Detailed Description
As used herein, the terms "comprises," "comprising," "includes," "including," "has," "containing," "characterized by," or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process, or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, or method.
The conjunctive phrase "consisting of …" excludes any unspecified elements, steps or components. If in the claims, such phrases are intended to claim as closed, such that it does not include materials other than those described, except for impurities normally associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims, rather than the immediately preceding clause, it is limited only to the elements mentioned in that clause; other elements are not excluded from the claims as a whole.
The conjoint phrase "consisting essentially of …" is used to define a composition or method that includes materials, steps, features, components or elements in addition to those literally disclosed, provided that such additional materials, steps, features, components or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of …" is intermediate between "comprising" and "consisting of …".
While applicants have defined the invention, or a portion thereof, in open-ended terms such as "comprising," then it should be readily understood (unless otherwise indicated) that the specification should be interpreted to describe such invention also using the term "consisting essentially of …" or "consisting of ….
Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not to an exclusive "or". For example, condition a or B is satisfied by any one of: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).
Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and the singular forms of an element or component also include the plural unless the numerical value clearly indicates the singular.
As referred to in this disclosure, the term "invertebrate pest" includes arthropods, gastropods, nematodes and helminths of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, coccidia and symphytum (symphylan). The term "gastropod" includes snails, slugs and other anomalas. The term "nematode" includes members of the phylum nematoda, such as phytophagous nematodes and helminth nematodes parasitic to animals. The term "helminths" includes all parasites, such as roundworms (phylum nematoda), heartworms (phylum nematoda, class cytopenias), flukes (phylum platyphylla, class trematoda), echinoderms (phylum echinoderma) and cestodes (phylum platyphylla, class cestoda).
In the context of the present disclosure, "invertebrate pest control" refers to inhibiting invertebrate pest development (including mortality, reduced feeding, and/or mating disruption), and related expression is defined in a similar manner.
The term "agronomic" refers to the production of field crops, such as for food and fiber, and includes the growth of maize or corn, soybeans and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, and rice), leafy vegetables (e.g., lettuce, cabbage, and other cabbage crops), fruit vegetables (e.g., tomatoes, peppers, eggplants, crucifers, and cucurbits), potatoes, sweet potatoes, grapes, cotton, woody fruits (e.g., pomes, stone fruits (stones), and citrus), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflower, and olives).
The term "non-agronomic" refers to applications other than field crops, such as horticultural crops (e.g., greenhouses, nurseries or ornamentals that do not grow in the field), residential, agricultural, commercial and industrial structures, turf (e.g., grasslands, rangelands, golf courses, lawns, sports fields, etc.), wood products, storage products, agroforestry and vegetation management, public health (i.e., human), and animal health (e.g., domesticated animals such as pets, livestock and poultry, non-domesticated animals such as wildlife).
The term "crop vigor" refers to the growth rate or biomass accumulation of a crop plant. By "increase in vigor" is meant an increase in growth or biomass accumulation in crop plants relative to untreated control crop plants. The term "crop yield" refers to the return on both quantity and quality of crop material obtained after harvesting a crop plant. By "increase in crop yield" is meant an increase in crop yield relative to untreated control crop plants.
The term "biologically effective amount" refers to an amount of a biologically active compound (e.g., a compound of formula 1) that is sufficient to produce a desired biological effect when applied to (i.e., contacted with) the invertebrate pest or its environment to be controlled, or the plant, the seed from which the plant is grown, or the locus of the plant (e.g., a growth medium) to protect the plant from the invertebrate pest or for other desired effects (e.g., increase plant vigor).
In the structure of formula 1, the variable A is defined as containing a carbon atom selected from the group consisting ofA 5-, 6-or 7-membered ring of a ring member of up to 3 heteroatoms independently selected from up to 2O, up to 2S and up to 3N, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and said sulfur atom ring members are independently selected from S (═ O)nEach ring being unsubstituted or substituted by up to 3 independently selected from R3Is substituted with the substituent(s). These 5-, 6-and 7-membered rings comprise the imidazolium nitrogen and carbon atoms to which the a ring members are attached to form said ring, as shown in the following structure, wherein R represents a ring member selected from the group as defined above, and a is 0, 1, 2 or 3.
In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl", includes straight-chain or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, or the different butyl, pentyl, or hexyl isomers. "alkenyl" includes straight or branched chain alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "alkenyl" also includes polyalkenes such as 1, 2-allenyl and 2, 4-hexadienyl. "alkynyl" includes straight or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl, pentynyl and hexynyl isomers. "alkynyl" may also include moieties made up of multiple triple bonds, such as 2, 5-hexadiynyl.
"alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and the different butoxy, pentoxy, and hexoxy isomers. "alkylthio" includes branched or straight chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio, and hexylthio isomers.
"cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "halogen", alone or in compound words such as "haloalkyl", or when in the description such as "taken with halogenWhen used in "substituted alkyl" groups include fluoro, chloro, bromo or iodo. Further, when used in compound words such as "haloalkyl", or when used in describing words such as "alkyl substituted with halogen", the alkyl may be partially or fully substituted with halogen atoms (which may be the same or different). Examples of "haloalkyl" or "alkyl substituted with halo" include F3C-、ClCH2-、CF3CH2And CF3CCl2-. The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio", "haloalkenyl" and the like are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF3O-、CCl3CH2O-、HCF2CH2CH2O-and CF3CH2O-is formed. Examples of "haloalkylthio" include CCl3S-、CF3S-、CCl3CH2S-and ClCH2CH2CH2S-。
The chemical abbreviations S (O) and S (═ O) as used herein represent sulfinyl moieties. Chemical abbreviation SO as used herein2、S(O)2And S (═ O)2Represents a sulfonyl moiety. The chemical abbreviations C (O) and C (═ O) as used herein represent carbonyl moieties. Chemical abbreviation CO as used herein2C (O) O and C (═ O) O represent oxycarbonyl moieties. "CHO" refers to formyl.
The total number of carbon atoms in the substituents being represented by "Ci-Cj"prefix" indicates. E.g. C1-C6Alkyl represents methyl, ethyl and the various propyl, butyl, pentyl and hexyl isomers.
When a compound is substituted with a substituent bearing a subscript indicating that the number of substituents can be greater than 1, the substituents (when they are greater than 1) are independently selected from the group of defined substituents. Further, the subscripts indicate the range (e.g., (R)i-j) When so, then the number of substituents can be selected from the integers between i and j inclusive. When a group contains a substituent which may be hydrogen, then when the substituent is hydrogen, this is considered to correspond to the group being unsubstituted. When one on the radicalOne or more positions are described as "unsubstituted" or "unsubstituted," and a hydrogen atom may be attached to occupy any free valence.
Unless otherwise indicated, a "ring" or "ring system" (e.g., substituent R) as a component of formula 11) Is carbocyclic or heterocyclic. The term "ring system" denotes two or more fused rings. The terms "bicyclic ring system" and "fused bicyclic ring system" refer to a ring system consisting of two fused rings, which may be "ortho fused", "bridged bicyclic" or "spirobicyclic". An "ortho-fused bicyclic ring system" refers to a ring system in which two component rings share two adjacent atoms. A "bridged bicyclic ring system" is formed by the attachment of a fragment of one or more atoms to a non-adjacent ring member of a ring. A "spirobicyclic ring system" is formed by binding fragments of two or more atoms to the same ring member of a ring. The term "fused heterobicyclic ring system" denotes a fused bicyclic ring system wherein at least one ring atom is not carbon. The term "ring member" refers to an atom or other moiety (e.g., C (═ O), C (═ S), S (O), or S (O)) that forms the backbone of a ring or ring system2)。
The term "carbocyclic ring", "carbocyclic ring" or "carbocyclic ring system" denotes a ring or ring system in which the atoms forming the ring skeleton are selected from carbon only. The term "heterocyclic ring", "heterocyclic ring" or "heterocyclic ring system" denotes a ring or ring system wherein at least one of the atoms forming the ring backbone is not carbon (e.g. nitrogen, oxygen or sulfur). Typically, the heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs. Unless otherwise indicated, the carbocyclic or heterocyclic ring may be a saturated or unsaturated ring. "saturated" refers to a ring having a backbone consisting of atoms connected to each other by single bonds; unless otherwise indicated, the remaining atomic valences are occupied by hydrogen atoms. Unless otherwise indicated, an "unsaturated ring" may be partially unsaturated or fully unsaturated. The expression "fully unsaturated ring" means a ring of atoms in which the bonds between the atoms in the ring are single or double bonds according to valence bond theory and furthermore the bonds between the atoms in the ring comprise as many double bonds as possible without cumulative double bonds (i.e. without C ═ C or C ═ N). The term "partially unsaturated ring" means a ring comprising at least one ring member bonded to an adjacent ring member by a double bond, and conceptually may accommodate a number of non-cumulative double bonds (i.e., in its fully unsaturated counterpart) between adjacent ring members greater than the number of double bonds present (i.e., in its partially unsaturated form).
Unless otherwise indicated, heterocycles and ring systems may be attached through any available carbon or nitrogen via a hydrogen substituted on that carbon or nitrogen.
By "aromatic" is meant that each ring atom is substantially in the same plane and has a p-orbital perpendicular to the plane of the ring, and wherein (4n +2) pi electrons (where n is a positive integer) are associated with the ring to comply with the Huckel rule. The term "aromatic ring system" denotes a carbocyclic or heterocyclic ring system in which at least one ring in said ring system is aromatic. When a fully unsaturated carbocyclic ring satisfies the huckel rule, then the ring is also referred to as "aromatic ring" or "aromatic carbocyclic ring".
The term "aromatic carbocyclic ring system" refers to a carbocyclic ring system in which at least one ring of the ring system is aromatic. When a fully unsaturated heterocyclic ring satisfies the huckel rule, then the ring is also referred to as a "heteroaryl ring," aromatic heterocyclic ring, "or" heterocyclic aromatic ring. The term "aromatic heterocyclic ring system" refers to heterocyclic ring systems in which at least one ring in the ring system is aromatic. The term "non-aromatic ring system" denotes a carbocyclic or heterocyclic ring system which may be fully saturated as well as partially or fully unsaturated, provided that no ring in the ring system is aromatic. The term "non-aromatic carbocyclic ring system" denotes a carbocyclic ring in which no ring in the ring system is aromatic. The term "non-aromatic heterocyclic ring system" refers to heterocyclic ring systems in which no ring in the ring system is aromatic.
The term "optionally substituted" in relation to a heterocycle refers to a group that is unsubstituted or has at least one non-hydrogen substituent that does not eliminate the biological activity possessed by the unsubstituted analog. As used herein, the following definitions will apply unless otherwise indicated. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un) substituted". Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of each other.
When the substituent is a 5 or 6 membered nitrogen containing heterocycle, it may be attached to the remainder of formula 1 through any available carbon or nitrogen ring atom, unless otherwise specified. As indicated above, R1May be (especially) phenyl optionally substituted with one or more substituents selected from the group of substituents as defined in the summary of the invention. Examples of the phenyl group optionally substituted with one to five substituents are rings as shown in U-1 in example 1, wherein R isvIs as in the summary of the invention for R1R as definedxAnd r is an integer from 0 to 5.
As indicated above, R1May be (inter alia) a 5-or 6-membered heterocyclic aromatic ring, optionally substituted with one or more substituents selected from the group of substituents as defined in the summary of the invention. Examples of the 5-or 6-membered unsaturated aromatic heterocyclic ring optionally substituted with one or more substituents include rings U-2 to U-61 shown in example 1, wherein R isvIs as in the summary of the invention for R1Any substituents defined, and r is an integer from 0 to 4, limited by the number of available positions on each U group. Since U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42, and U-43 have only one position available, for these U groups R is limited to the integer 0 or 1, and R is 0 means that the U group is unsubstituted and hydrogen is present in the group consisting of (R-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42, and U-43)v)rAt the indicated position.
Example 1
Although R is shown in structures U-1 through U-61vGroups, it should be noted, however, that they need not be present because they are optional substituents. It should be noted that when R isvWhen attached to an atom, this is as if the atom is unsubstituted. The nitrogen atom to be substituted to fill its valence is substituted by H or RvAnd (4) substitution. It should be noted that when (R)v)rWhen the point of attachment to the U group is shown to be floating, (R)v)rAny available carbon or nitrogen atom that can be attached to the U group. It should be noted that when the point of attachment on the U group is shown as floating, the U group may be attached to the remainder of formula 1 through any available carbon or nitrogen of the U group via replacement of a hydrogen atom. It should be noted that some U groups can only be substituted by less than 4RvSubstituted (e.g., U-2 to U-5, U-7 to U-48, and U-52 to U-61).
Various synthetic methods are known in the art to enable the preparation of aromatic and non-aromatic heterocycles and ring systems; for an extensive review see the eight-volume complex Heterocyclic Chemistry, A.R. Katritzky and C.W.Rees eds, Pergamon Press, Oxford [ Pegman Press, Oxford ], 1984 and the twelve-volume complex Heterocyclic Chemistry II, A.R. Katritzky, C.W.rees and E.F.V. Scriviven eds, Pergamon Press, Oxford, 1996.
The compounds of the present invention may exist as one or more stereoisomers. Stereoisomers are isomers that are identical in composition but differ in the arrangement of their atoms in space, and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about a single bond, where the rotational energy barrier is high enough to allow separation of isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to one or more other stereoisomers, or when separated from one or more other stereoisomers. In addition, the skilled artisan knows how to isolate, enrich and/or selectively prepare the stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Stereochemistry of Organic Compounds [ Organic compound Stereochemistry ] of ErnestL.Eliel and Samuel H.Wilen, John Wiley & Sons [ John Willi-Ginko, 1994.
The present invention includes all stereoisomers, conformers and mixtures thereof in all proportions and in isotopic forms, such as deuterated compounds.
Those skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides because the nitrogen requires an available lone pair to oxidize to the oxide; those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines are capable of forming N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art and include the oxidation of heterocycles and tertiary amines using peroxy acids such as peracetic acid and 3-chloroperoxybenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for preparing N-oxides have been widely described and reviewed in the literature, see for example: T.L.Gilchrist, Comprehensive Organic Synthesis, Vol.7, pp.748-; tisler and b.stanovnik, Comprehensive Heterocyclic Chemistry, volume 3, pages 18-20, edited by a.j.boulton and a.mckillop, Pergamon Press; M.R.Grimett and B.R.T.Keene, Advances in heterocyclic chemistry [ Advances in heterocycle chemistry ], Vol.43, p.149-161, edited by A.R.Katritzky, Academic Press [ Academic Press ]; M.Tisler and B.Stanovnik, Advances in Heterocyclic Chemistry, Vol.9, p.285-291, edited by A.R.Katritzky and A.J.Boulton, Academic Press; and g.w.h.cheeseman and e.s.g.werstink, Advances in Heterocyclic Chemistry, vol 22, p 390-.
One skilled in the art recognizes that salts share the biological utility of non-salt forms, as salts of compounds are in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions. Thus, various salts of the compounds of formula 1 are useful for controlling invertebrate pests. Salts of the compounds of formula 1 include acid addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acid. When the compound of formula 1 contains an acidic moiety such as a carboxylic acid or phenol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention includes compounds selected from formula 1, N-oxides and suitable salts thereof.
Compounds selected from formula 1, stereoisomers, tautomers, N-oxides and salts thereof, typically exist in more than one form, and formula 1 thus includes all crystalline and non-crystalline forms of the compounds represented by formula 1. Non-crystalline forms include embodiments that are solids, such as waxes and gums, and embodiments that are liquids, such as solutions and melts. Crystalline forms include embodiments that represent substantially single crystal types and embodiments that represent mixtures of polymorphs (i.e., different crystalline types). The term "polymorph" refers to a particular crystalline form of a compound that can crystallize in different crystalline forms having different molecular arrangements and/or conformations in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound within the crystal lattice. Polymorphs can differ in such chemical, physical, and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate, and bioavailability. One skilled in the art will appreciate that a polymorph of a compound represented by formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or mixture of polymorphs of the same compound represented by formula 1. The preparation and isolation of specific polymorphs of a compound represented by formula 1 can be achieved by methods known to those skilled in the art, including, for example, crystallization using selected solvents and temperatures. The compounds of the present invention may exist as one or more crystalline polymorphs. The present invention includes both individual polymorphs and mixtures of polymorphs, including mixtures enriched in one polymorph relative to the others. For a comprehensive discussion of Polymorphism, see Polymorphism Pharmaceutical Industry, edited by R.Hilfiker, Wiley-VCH, Weinheim, 2006.
Embodiments of the invention as described in the summary of the invention include those described below. In the following embodiments, references to "a compound of formula 1" include the definitions of the substituents set forth in the summary of the invention, unless otherwise defined in the embodiments.
Embodiment 1. compounds of formula 1 wherein a is a 5 or 6 membered ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2O, up to 2S and up to 3N, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and said sulfur atom ring members are independently selected from S (═ O)nEach ring being unsubstituted or substituted by up to 3 independently selected from R3Is substituted with the substituent(s).