A mesoionic compound, its preparation and use

Abstract

The present application relates to a kind of mesoionic compound and its preparation method and application;Specifically, the present application relates to the mesoionic compound shown in formula (I) or the stereoisomer of the mesoionic compound shown in formula (I), nitroxide and its salt, and the preparation method of such mesoionic compound, and the use of such mesoionic compound and the composition comprising such mesoionic compound as insecticide in agriculture, and the method for preventing and treating pests using these compounds or compositions;Wherein, R 1 , R 2 , R 3 , R 4 , R 5 And R 6 It has the meaning described in the present application.

Description

Technical Field

[0001] This invention relates to the field of pesticides, and more specifically, to a mesoionic compound, a method for preparing the same, and the application of the mesoionic compound and compositions comprising the mesoionic compound as insecticides in the field of pesticides. Background Technology

[0002] Invertebrate pests cause widespread damage in agriculture, forestry, greenhouse crops, ornamental plants, nursery crops, stored food, livestock, housing, turf, wood products, and public health, resulting in significant economic losses and harm to public health. Due to increasing resistance to many commercially available pesticides, higher dosages are required to control pests, placing a heavy burden on the environment. Therefore, there is a continued need for novel compounds that are more effective, economical, less toxic, environmentally safer, or have different sites of action to control invertebrate pests.

[0003] WO2009099929, WO 2011017347 and WO2011017342 disclose the control efficacy of chain-substituted mesonotropic compounds against various pests, while the compounds involved in this invention are not disclosed. Summary of the Invention

[0004] This invention provides a mesoionic compound, a method for preparing the compound, the compound, and compositions and formulations containing the compound, and their application in pest control.

[0005] Specifically, in one aspect, the present invention provides a compound having the formula (I) or a stereoisomer of the compound having the formula (I), a nitrogen oxide or a salt thereof:

[0006]

[0007] in:

[0008] R 1 For hydrogen, C 1-8 Alkyl, Halogenated C 1-8 Alkyl, C 2-8 alkenyl, C 2-8 alkynyl group, C 3-8 cycloalkyl, C 3-8 cycloalkyl-C 1-3 Alkylene-, C 3-8 Cycloalkenyl or C 3-8 Cycloalkenyl-C 1-3 alkylene-; wherein, R 1 Optionally, one, two, or three groups are selected from halogen, hydroxyl, nitro, amino, carboxyl, cyano, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6Alkyl or halogenated C 1-6 Alkyl substitution;

[0009] Or, R 1 C 6-14 Aryl or 5-10 heteroaryl; wherein, R 1 Optionally, one, two, three, four, or five groups are selected from halogen, hydroxyl, nitro, amino, carboxyl, cyano, -CHO, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, Halogenated C 1-6 Alkoxy, C 1-6 Alkyl thiols, halogenated C 1-6 Alkylthio, C 2-6 alkenyl, C 2-6 alkenyloxy group, C 2-6 alkynyl group, C 2-6 Acryloxy group, C 3-8 cycloalkyl, C 3-8 Cycloalkyloxy, C 3-8 cycloalkyl-C 1-3 Alkylene-, -NHC 1-6 Alkyl, -N(C) 1-6 Alkyl)2、-C(=O)NHC 1-6 Alkyl, -C(=O)N(C) 1-6 Alkyl)2、-NH-C(=O)-C 1-6 Alkyl, -N(C) 1-6 alkyl)-C(=O)-C 1-6 Alkyl group, -NH-C(=O)-C 1-6 Alkoxy, -N(C) 1-6 alkyl)-C(=O)-C 1-6 Alkoxy group, -NH-S(=O)2-C 1-6 Alkyl, -N(C) 1-6 alkyl)-S(=O)2-C 1-6 Alkyl group, -OS(=O)2-C 1-6 Alkyl, C 1-6 Alkyl-C(=O)-, C 1-6 Alkoxy-C(=O)-, C 1-6 Alkyl-C(=O)-O-, (optionally surrounded by 1, 2, 3, 4 or 5 groups selected from halogen, hydroxyl, nitro, cyano, C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 1-6 alkoxy or halogenated C 1-6 Alkoxy-substituted) phenyl or (optionally substituted with 1, 2, 3, 4 or 5 groups selected from halogen, hydroxyl, nitro, cyano, C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C1-6 alkoxy or halogenated C 1-6 Alkyl-substituted) phenoxy-substituted;

[0010] Or, R 1 C 6-14 Aryl-C 1-3 alkylene- or 5-10 heteroaryl-C 1-3 alkylene-; wherein, R 1 Optionally, one, two, three, four, or five groups are selected from halogen, hydroxyl, nitro, amino, carboxyl, cyano, C 1-6 Alkyl, C 1-6 alkoxy-substituted C 1-6 Alkyl, hydroxyl substituted C 1-6 alkyl and cyano substituted C 1-6 Alkyl, nitro-substituted C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl or halogenated C 1-6 Alkyl substitution;

[0011] Or, R 1 for Among them, X, X2, X3, and X5 are each independently -CR 11 R 12 -, -O-, -S-, -S(=O)-, -S(=O)2- or -NR 13 -; X1 and X4 are each independently -CR 14 R 15 -;R 11 R 12 R 14 and R 15 Each is independently hydrogen, halogen, or C 1-6 Alkyl; R 13 It is hydrogen or C 1-6 alkyl;

[0012] R 2 and R 3 Each is independently hydrogen, halogen, or C 1-6 alkyl;

[0013] R 4 It is hydrogen, chlorine, bromine, iodine or C 1-6 alkyl;

[0014] R 5 R 6 Together with the nitrogen and carbon atoms bonded to it, it forms Among them, R a R b Rc and R d Each is independently hydrogen, cyano, nitro, halogen, C 1-6 Alkyl or C 1-6 Alkoxy;

[0015] Or, R 5 R 6 Together with the nitrogen and carbon atoms bonded thereto, they form the following rings: R-1, R-2, R-3, or R-4:

[0016]

[0017] Among them, ring R-1, ring R-2, ring R-3, and ring R-4 are optionally represented by 1, 2, or 3 groups selected from cyano, nitro, halogen, C 1-6 Alkyl or C 1-6 Alkyl-substituted.

[0018] In some implementation schemes, R 1 For hydrogen, C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 Alkylene-, C 3-6 Cycloalkenyl or C 3-6 Cycloalkenyl-C 1-3 alkylene-; wherein, R 1 Optionally, one, two, or three groups are selected from halogen, hydroxyl, nitro, amino, carboxyl, cyano, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkyl substitution;

[0019] Or, R 1 C 6-14 Aryl or 5-10 heteroaryl; wherein, R 1 Optionally, one, two, three, four, or five groups are selected from halogen, hydroxyl, nitro, amino, carboxyl, cyano, -CHO, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl, Halogenated C 1-4 Alkoxy, C 1-4 Alkyl thiols, halogenated C 1-4 Alkylthio, C 2-4 alkenyl, C 2-4 alkenyloxy group, C 2-4 alkynyl group, C 2-4 Acryloxy group, C 3-6cycloalkyl, C 3-6 Cycloalkyloxy, C 3-6 cycloalkyl-C 1-3 Alkylene-, -NHC 1-4 Alkyl, -N(C) 1-4 Alkyl)2、-C(=O)NHC 1-4 Alkyl, -C(=O)N(C) 1-4 Alkyl)2、-NH-C(=O)-C 1-4 Alkyl, -N(C) 1-4 alkyl)-C(=O)-C 1-4 Alkyl group, -NH-C(=O)-C 1-4 Alkoxy, -N(C) 1-4 alkyl)-C(=O)-C 1-4 Alkoxy group, -NH-S(=O)2-C 1-4 Alkyl, -N(C) 1-4 alkyl)-S(=O)2-C 1-4 Alkyl group, -OS(=O)2-C 1-4 Alkyl, C 1-4 Alkyl-C(=O)-, C 1-4 Alkoxy-C(=O)-, C 1-4 Alkyl-C(=O)O-, (optionally surrounded by 1, 2, 3, 4 or 5 groups selected from halogen, hydroxyl, nitro, cyano, C 1-4 Alkyl, Halogenated C 1-4 Alkyl, C 1-4 alkoxy or halogenated C 1-4 Alkoxy-substituted) phenyl or (optionally substituted with 1, 2, 3, 4 or 5 groups selected from halogen, hydroxyl, nitro, cyano, C 1-4 Alkyl, Halogenated C 1-4 Alkyl, C 1-4 alkoxy or halogenated C 1-4 Alkyl-substituted) phenoxy-substituted;

[0020] Or, R 1 C 6-14 Aryl-C 1-3 alkylene- or 5-10 heteroaryl-C 1-3 alkylene-; wherein, R 1 Optionally, one, two, three, four, or five groups are selected from halogen, hydroxyl, nitro, amino, carboxyl, cyano, C 1-4 Alkyl, C 1-4 alkoxy-substituted C 1-4 Alkyl, hydroxyl substituted C 1-4 alkyl and cyano substituted C 1-4 Alkyl, nitro-substituted C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C1-4 Alkyl or halogenated C 1-4 Alkyl substitution;

[0021] Or, R 1 for Among them, X, X2, X3, and X5 are each independently -CR 11 R 12 -, -O-, -S-, -S(=O)-, -S(=O)2- or -NR 13 -; X1 and X4 are each independently -CR 14 R 15 -;R 11 R 12 R 14 and R 15 Each is independently hydrogen, halogen, or C 1-4 Alkyl; R 13 It is hydrogen or C 1-4 alkyl.

[0022] In other implementations, R 1 For hydrogen, C 1-4 Alkyl, Halogenated C 1-4 Alkyl, C 2-4 alkenyl, C 2-4 alkynyl group, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 Alkylene-, C 3-6 Cycloalkenyl or C 3-6 Cycloalkenyl-C 1-3 alkylene-; wherein, R 1 Optionally, one, two, or three groups are selected from halogen, hydroxyl, nitro, amino, carboxyl, cyano, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C 1-4 Alkyl substitution;

[0023] Or, R 1 It is phenyl, naphthyl, or thiophene; wherein, R 1 Optionally, one, two, three, four, or five groups are selected from halogen, hydroxyl, nitro, amino, carboxyl, cyano, -CHO, C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl, Halogenated C 1-4 Alkoxy, C 1-4 Alkyl thiols, halogenated C 1-4 Alkylthio, C 2-4 alkenyl, C 2-4 alkenyloxy group, C 2-4 alkynyl group, C2-4 Acryloxy group, C 3-6 cycloalkyl, C 3-6 Cycloalkyloxy, C 3-6 cycloalkyl-C 1-3 Alkylene-, -NHC 1-4 Alkyl, -N(C) 1-4 Alkyl)2、-C(=O)NHC 1-4 Alkyl, -C(=O)N(C) 1-4 Alkyl)2、-NH-C(=O)-C 1-4 Alkyl, -N(C) 1-4 alkyl)-C(=O)-C 1-4 Alkyl group, -NH-C(=O)-C 1-4 Alkoxy, -N(C) 1-4 alkyl)-C(=O)-C 1-4 Alkoxy group, -NH-S(=O)2-C 1-4 Alkyl, -N(C) 1-4 alkyl)-S(=O)2-C 1-4 Alkyl group, -OS(=O)2-C 1-4 Alkyl, C 1-4 Alkyl-C(=O)-, C 1-4 Alkoxy-C(=O)-, C 1-4 Alkyl-C(=O)-O-, (optionally surrounded by 1, 2, 3, 4 or 5 groups selected from halogen, hydroxyl, nitro, cyano, C 1-4 Alkyl, Halogenated C 1-4 Alkyl, C 1-4 alkoxy or halogenated C 1-4 Alkoxy-substituted) phenyl or (optionally substituted with 1, 2, 3, 4 or 5 groups selected from halogen, hydroxyl, nitro, cyano, C 1-4 Alkyl, Halogenated C 1-4 Alkyl, C 1-4 alkoxy or halogenated C 1-4 Alkyl-substituted) phenoxy-substituted;

[0024] Or, R 1 It is phenyl-C 1-3 alkylene-; wherein, R 1 Optionally, one, two, three, four, or five groups are selected from halogen, hydroxyl, nitro, amino, carboxyl, cyano, C 1-4 Alkyl, C 1-4 alkoxy-substituted C 1-4 Alkyl, hydroxyl substituted C 1-4 alkyl and cyano substituted C 1-4 Alkyl, nitro-substituted C 1-4 Alkyl, C 1-4 Alkoxy, halogenated C 1-4 Alkyl or halogenated C1-4 Alkyl substitution;

[0025] Or, R 1 for Among them, X, X2, X3, and X5 are each independently -CR 11 R 12 -, -O-, -S-, -S(=O)-, -S(=O)2- or -NR 13 -; X1 and X4 are each independently -CR 14 R 15 -;R 11 R 12 R 14 and R 15 Each is independently either hydrogen or halogen; R 13 It is hydrogen or C 1-4 alkyl.

[0026] In other implementation schemes, R 1 It can be hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -CH=CH2, -CH2CH=CH2, -C≡CH, -CH2C≡CH, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl-CH2-, cyclobutyl-CH2-, cyclopentyl-CH2- or cyclohexyl-CH2-;

[0027] Or, R 1 It is phenyl, naphth-1-yl, naphth-2-yl, or thiophen-3-yl; wherein, R 1 The radical can be selected from 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxyl, nitro, amino, carboxyl, cyano, -CHO, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -C(CH3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -CHF2, -CF3, -CH2CF3, -OCHF2, -OCF3, -OCH2CF3 -SCH3, -SCH2CH3, -SCF3, -SCH2CF3, (optionally substituted with 1, 2, 3, 4 or 5 substituted with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano, -CH3, -CF3, -OCH3 or -OCF3) phenyl or (optionally substituted with 1, 2, 3, 4 or 5 substituted with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano, -CH3, -CF3, -OCH3 or -OCF3) phenoxy;

[0028] Or, R 1 It is phenyl-CH2- or phenyl-CH2CH2-; wherein, R 1Optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxyl, nitro, amino, carboxyl, cyano, -CH3, -CH2CH3, -CH2OH, -CH2CN, -CH2NO2, -OCH3, -OCH2CH3, -CF3 or -OCF3;

[0029] Or, R 1 for Among them, X, X2, X3, and X5 are each independently -CR 11 R 12 -, -O-, -S-, -S(=O)-, -S(=O)2- or -NR 13 -; X1 and X4 are each independently -CR 14 R 15 -;R 11 R 12 R 14 and R 15 Each is independently either hydrogen or fluorine; R 13 It is hydrogen or -CH3.

[0030] In other implementation schemes, R 1 The following are substructures:

[0031]

[0032] In other implementation schemes, R 1 The following are substructures:

[0033]

[0034] In other implementation schemes, R 1 The following are substructures:

[0035]

[0036] This indicates the connection point between the structural formula and other parts of the molecule.

[0037] In some implementation schemes, R 2 and R 3 Each is independently hydrogen, halogen, or C 1-4 alkyl.

[0038] In other implementations, R 2 and R 3 Each can be independently hydrogen, fluorine, chlorine, bromine, iodine, -CH3 or -CH2CH3.

[0039] In some implementation schemes, R 4 It is hydrogen, chlorine, bromine, iodine or C 1-4alkyl.

[0040] In other implementations, R 4 It can be hydrogen, chlorine, bromine, iodine, -CH3 or -CH2CH3.

[0041] In some implementation schemes, R 5 R 6 Together with the nitrogen and carbon atoms bonded to it, it forms Among them, R a R b R c and R d Each is independently hydrogen, cyano, nitro, halogen, C 1-4 Alkyl or C 1-4 Alkoxy;

[0042] Or, R 5 R 6 Together with the nitrogen and carbon atoms bonded thereto, they form the following rings: R-1, R-2, R-3, or R-4:

[0043]

[0044] Among them, ring R-1, ring R-2, ring R-3, and ring R-4 are optionally represented by 1, 2, or 3 groups selected from cyano, nitro, halogen, C 1-4 Alkyl or C 1-4 Alkyl-substituted.

[0045] In other implementations, R 5 R 6 Together with the nitrogen and carbon atoms bonded to it, it forms Among them, R a R b R c and R d Each can be independently hydrogen, cyano, nitro, fluorine, chlorine, bromine, iodine, -CH3 or -OCH3;

[0046] Or, R 5 R 6 Together with the nitrogen and carbon atoms bonded thereto, they form the following rings: R-1, R-2, R-3, or R-4:

[0047]

[0048] In this embodiment, rings R-1, R-2, R-3, and R-4 are optionally substituted by 1, 2, or 3 of the following groups: cyano, nitro, fluorine, chlorine, bromine, iodine, -CH3, or -OCH3.

[0049] In some embodiments, the present invention provides a compound having the formula (IA) or a stereoisomer of the compound having the formula (IA), a nitride, or a salt thereof:

[0050]

[0051] Among them, R a R b R c R d R 1 R 2 R 3 and R 4 It has the meaning described in this invention.

[0052] In other embodiments, the present invention provides a compound having the formula (IA-1) or a stereoisomer of the compound having the formula (IA-1), a nitride, or a salt thereof:

[0053]

[0054] Among them, R 1 and R 4 It has the meaning described in this invention.

[0055] In other embodiments, the present invention provides a compound having the shape of a compound of formula (IB) or a stereoisomer of the compound of formula (IB), a nitride, or a salt thereof; or, the present invention provides a compound having the shape of a compound of formula (IC) or a stereoisomer of the compound of formula (IC), a nitride, or a salt thereof; or, the present invention provides a compound having the shape of a compound of formula (ID) or a stereoisomer of the compound of formula (ID), a nitride, or a salt thereof; or, the present invention provides a compound having the shape of a compound of formula (IE) or a stereoisomer of the compound of formula (IE), a nitride, or a salt thereof.

[0056]

[0057] Among them, R a R b R c and R d Each is independently a cyano, nitro, halogen, or C group. 1-6 Alkyl or C 1-6 Alkoxy;

[0058] R 1 R 2 R 3 and R 4 It has the meaning described in this invention.

[0059] In other embodiments, the present invention provides a compound having the shape of a compound of formula (IB) or a stereoisomer of the compound of formula (IB), a nitride, or a salt thereof; or, the present invention provides a compound having the shape of a compound of formula (IC) or a stereoisomer of the compound of formula (IC), a nitride, or a salt thereof; or, the present invention provides a compound having the shape of a compound of formula (ID) or a stereoisomer of the compound of formula (ID), a nitride, or a salt thereof; or, the present invention provides a compound having the shape of a compound of formula (IE) or a stereoisomer of the compound of formula (IE), a nitride, or a salt thereof.

[0060] Among them, R a R b R c and R d Each is independently a cyano, nitro, halogen, or C group. 1-4 Alkyl or C 1-4 Alkoxy;

[0061] R 1 R 2 R 3 and R 4 It has the meaning described in this invention.

[0062] In other embodiments, the present invention provides a compound having the shape of a compound of formula (IB) or a stereoisomer of the compound of formula (IB), a nitride, or a salt thereof; or, the present invention provides a compound having the shape of a compound of formula (IC) or a stereoisomer of the compound of formula (IC), a nitride, or a salt thereof; or, the present invention provides a compound having the shape of a compound of formula (ID) or a stereoisomer of the compound of formula (ID), a nitride, or a salt thereof; or, the present invention provides a compound having the shape of a compound of formula (IE) or a stereoisomer of the compound of formula (IE), a nitride, or a salt thereof.

[0063] Among them, R a R b R c and R d Each can be independently cyano, nitro, fluorine, chlorine, bromine, iodine, -CH3, or -OCH3;

[0064] R 1 R 2 R 3 and R 4 It has the meaning described in this invention.

[0065] In other embodiments, the present invention provides a compound having the formula (IB-1) or a stereoisomer of the compound having the formula (IB-1), a nitride, or a salt thereof; or, the present invention provides a compound having the formula (IC-1) or a stereoisomer of the compound having the formula (IC-1), a nitride, or a salt thereof; or, the present invention provides a compound having the formula (ID-1) or a stereoisomer of the compound having the formula (ID-1), a nitride, or a salt thereof; or, the present invention provides a compound having the formula (IE-1) or a stereoisomer of the compound having the formula (IE-1), a nitride, or a salt thereof.

[0066]

[0067] Among them, R a R b R c and R d Each is independently a cyano, nitro, halogen, or C group. 1-6 Alkyl or C 1-6 Alkoxy;

[0068] R 1 and R 4 It has the meaning described in this invention.

[0069] In other embodiments, the present invention provides a compound having the formula (IB-1) or a stereoisomer of the compound having the formula (IB-1), a nitride, or a salt thereof; or, the present invention provides a compound having the formula (IC-1) or a stereoisomer of the compound having the formula (IC-1), a nitride, or a salt thereof; or, the present invention provides a compound having the formula (ID-1) or a stereoisomer of the compound having the formula (ID-1), a nitride, or a salt thereof; or, the present invention provides a compound having the formula (IE-1) or a stereoisomer of the compound having the formula (IE-1), a nitride, or a salt thereof.

[0070] Among them, R a R b R c and R d Each is independently a cyano, nitro, halogen, or C group. 1-4 Alkyl or C 1-4 Alkoxy;

[0071] R 1 and R 4 It has the meaning described in this invention.

[0072] In other embodiments, the present invention provides a compound having the formula (IB-1) or a stereoisomer of the compound having the formula (IB-1), a nitride, or a salt thereof; or, the present invention provides a compound having the formula (IC-1) or a stereoisomer of the compound having the formula (IC-1), a nitride, or a salt thereof; or, the present invention provides a compound having the formula (ID-1) or a stereoisomer of the compound having the formula (ID-1), a nitride, or a salt thereof; or, the present invention provides a compound having the formula (IE-1) or a stereoisomer of the compound having the formula (IE-1), a nitride, or a salt thereof.

[0073] Among them, R a R b R c and R d Each can be independently cyano, nitro, fluorine, chlorine, bromine, iodine, -CH3, or -OCH3;

[0074] R 1 and R 4 It has the meaning described in this invention.

[0075] In some embodiments, the present invention provides a compound having one of the following structures, or a stereoisomer, nitride, or salt thereof having one of the following structures:

[0076]

[0077]

[0078]

[0079]

[0080]

[0081] On the other hand, the present invention provides a composition comprising the compound described herein and at least one pesticide adjuvant commonly used in agronomy.

[0082] Furthermore, commonly used adjuvants in pesticide science include surfactants and carriers.

[0083] On the other hand, the present invention provides the use of the compounds or compositions described herein in agriculture, forestry or horticulture.

[0084] On the other hand, the present invention provides the use of the compounds or compositions described herein as insecticides.

[0085] Furthermore, the present invention provides the use of the compounds or compositions described herein as pesticides in agriculture, forestry, or horticulture.

[0086] On the other hand, the present invention provides the application of the compounds or compositions described herein as pest control agents.

[0087] Furthermore, the pests described in this invention are preferably Lepidoptera and / or Hemiptera pests.

[0088] Furthermore, the pests described in this invention are preferably armyworms, whiteflies, alfalfa aphids, and / or brown planthoppers.

[0089] Detailed Description of the Invention

[0090] Definitions and general terms

[0091] Certain embodiments of the invention will now be described in detail, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover all alternatives, modifications, and equivalents, all of which are included within the scope of the invention as defined in the claims. Those skilled in the art will recognize that many similar or equivalent methods and materials can be used to practice the invention. The invention is by no means limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ from or contradict this application (including, but not limited to, defined terminology, application of terminology, described techniques, etc.), this application shall prevail.

[0092] It should be further appreciated that certain features of the invention, for clarity, have been described in multiple independent embodiments, but may also be provided in combination in a single embodiment. Conversely, various features of the invention, for brevity, have been described in a single embodiment, but may also be provided individually or in any suitable sub-combination.

[0093] Unless otherwise stated, all technical terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. All patents and publications related to this invention are incorporated herein by reference in their entirety.

[0094] Unless otherwise stated, the following definitions as used in this invention shall apply. For the purposes of this invention, chemical elements are consistent with the periodic table (CAS edition) and the Handbook of Chemistry and Physics, 75th edition, 1994. Furthermore, general principles of organic chemistry can be found in "Organic Chemistry," Thomas Sorrell, University Science Books, Sausalito: 1999, and "March's Advanced Organic Chemistry" by Michael B. Smith and Jerry March, John Wiley & Sons, New York: 2007, the entire contents of which are incorporated herein by reference.

[0095] Unless otherwise stated or there is an obvious conflict in the context, the articles “a,” “an,” and “described” as used in this invention are intended to include “at least one” or “one or more.” Therefore, these articles as used in this invention refer to articles for one or more (i.e., at least one) objects. For example, “a component” refers to one or more components, meaning that more than one component may be considered for use or employed in the embodiments described.

[0096] The term "comprising" is an open-ended expression, meaning it includes the contents specified in this invention, but does not exclude other aspects.

[0097] "Stereoisomers" are compounds that have the same chemical structure but whose atoms or groups are arranged differently in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotational isomers), geometric isomers (cis / trans) isomers, and hindered isomers, etc.

[0098] "Enantiomers" refer to two non-overlapping but mirror-image isomers of a compound.

[0099] A diastereomer is a stereoisomer that has two or more chiral neutral molecules that are not mirror images of each other. Diastereomers possess different physical properties, such as melting point, boiling point, spectral properties, and reactivity. Mixtures of diastereomers can be separated using high-resolution analytical techniques such as electrophoresis and chromatography, for example, HPLC.

[0100] The stereochemical definitions and rules used in this invention generally follow the descriptions in S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984), McGraw-Hill Book Company, New York; and Eliel, E. and Wilen, S., “Stereochemistry of Organic Compounds”, John Wiley & Sons, Inc., New York, 1994.

[0101] Many organic compounds exist in an optically active form, meaning they possess the ability to rotate the plane of plane-polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to indicate the absolute configuration of the molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are symbols used to specify the plane-polarized light rotation caused by the compound, where (-) or l indicates that the compound is levorotatory. Compounds with the prefix (+) or d are dextrorotatory. A specific stereoisomer is an enantiomer, and a mixture of such isomers is called an enantiomeric mixture. A 50:50 mixture of enantiomers is called a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.

[0102] Any asymmetric atom (e.g., carbon, etc.) in the compounds disclosed in this invention can exist in a racemic or enantiomerically enriched form, such as in (R)-, (S)-, or (R,S)- configurations. In some embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R)- or (S)- configuration.

[0103] Depending on the choice of starting materials and methods, the compounds of this invention can exist as one or a mixture of possible isomers, such as racemic mixtures and mixtures of non-corresponding isomers (depending on the number of asymmetric carbon atoms). Optically active (R)- or (S)- isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituents may be E or Z configurations; if the compound contains a disubstituted cycloalkyl group, the cycloalkyl substituents may be cis or trans configurations.

[0104] Any mixture of stereoisomers obtained can be separated into pure or substantially pure geometric isomers, enantiomers, and diastereomers based on differences in the physicochemical properties of the components, for example, by chromatography and / or fractional crystallization.

[0105] Racemic derivatives of any resulting end product or intermediate can be separated into optical enantiomers using known methods familiar to those skilled in the art, such as by separating the obtained diastereomeric salts. Racemic products can also be separated by chiral chromatography, such as high-performance liquid chromatography (HPLC) using chiral adsorbents. In particular, enantiomers can be prepared via asymmetric synthesis.

[0106] As described in this invention, the compounds of this invention may optionally be substituted with one or more substituents, such as the general formula compounds above, or as the specific examples, subclasses, and classes of compounds included in this invention. It should be understood that the term "optionally substituted" is used interchangeably with the terms "substituted or unsubstituted" and "optionally substituted with...". Generally, the term "substituted" means that one or more hydrogen atoms in the given structure are substituted by a specific substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substituted position of the group. When more than one position in the given structural formula can be substituted by one or more substituents selected from a specific group, the substituents may be substituted at the same or different positions. Specifically, examples of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The substituents described therein can be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclic alkoxy, arylalkoxy, heteroarylalkoxy, heterocyclic alkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkylacyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclic, heterocyclic alkyl, heterocyclic acyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amide, sulfonyl, aminosulfonyl, etc.

[0107] Additionally, it should be noted that, unless otherwise explicitly stated, the descriptive terms “each…independently is”, “…each independently is”, and “…independently is” used in this invention are interchangeable and should be interpreted broadly. They can mean that the specific options expressed by the same symbols in different groups do not affect each other, or that the specific options expressed by the same symbols in the same group do not affect each other.

[0108] In various parts of this specification, the substituents of the compounds disclosed herein are disclosed according to the type or scope of the groups. In particular, this invention includes every independent secondary combination of the various members of these group types and scopes. For example, the terms "C1-C6 alkyl" or "C..." 1-6 "Alkyl" specifically refers to independently disclosed methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.

[0109] As used in this invention, the term "alkyl" or "alkyl group" refers to a saturated straight-chain or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted by one or more substituents described in this invention. Unless otherwise specified, the alkyl group contains 1 to 20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in another embodiment, the alkyl group contains 1 to 8 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 6 carbon atoms; in still another embodiment, the alkyl group contains 1 to 4 carbon atoms; and in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.

[0110] Examples of alkyl groups include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), n-propyl (n-Pr, -CH2CH2CH3), isopropyl (i-Pr, -CH(CH3)2), n-butyl (n-Bu, -CH2CH2CH2CH3), isobutyl (i-Bu, -CH2CH(CH3)2), sec-butyl (s-Bu, -CH(CH3)CH2CH3), tert-butyl (t-Bu, -C(CH3)3), and so on. Pentyl (-CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), etc.

[0111] The term "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group containing 2-12 carbon atoms, with at least one unsaturated site, i.e., one carbon-carbon sp. 2 The double bond, wherein the alkenyl group may optionally be substituted by one or more substituents described in this invention, including the orientation of "cis" and "tans", or the orientation of "E" and "Z". In one embodiment, the alkenyl group comprises 2-8 carbon atoms; in another embodiment, the alkenyl group comprises 2-6 carbon atoms; in yet another embodiment, the alkenyl group comprises 2-4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), propenyl (CH3-CH=CH-), oxobutenyl (CH3-C(=O)-CH=CH-), etc.

[0112] The term "alkynyl" refers to a straight-chain or branched monovalent hydrocarbon group containing 2-12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl group may optionally be substituted by one or more substituents described in this invention. In one embodiment, the alkynyl group contains 2-10 carbon atoms; in another embodiment, the alkynyl group contains 2-8 carbon atoms; in yet another embodiment, the alkynyl group contains 2-6 carbon atoms; and in still another embodiment, the alkynyl group contains 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C≡CH, -C≡CCH3, -CH2-C≡CH, -CH2-C≡CCH3, -CH2CH2-C≡CH, -CH2-C≡CCH2CH3, -CH2CH2-C≡CCH3, etc.

[0113] The term "alkoxy" indicates that an alkyl group is attached to the rest of the molecule by an oxygen atom, wherein the alkyl group has the meaning as described in this invention. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH3), ethoxy (EtO, -OCH2CH3), 1-propoxy (n-PrO, n-propoxy, -OCH2CH2CH3), 2-propoxy (i-PrO, i-propoxy, -OCH(CH3)2), etc.

[0114] The term "alkylthio" indicates that an alkyl group is attached to the rest of the molecule via a sulfur atom, wherein the alkyl group has the meaning as described in this invention. Examples of alkylthio groups include, but are not limited to, -SCH3, -SCH2CH3, -SCH2CH2CH3, -SCH(CH3)2, etc.

[0115] The term "cycloalkyl" refers to a monovalent or polyvalent saturated monocyclic, bicyclic, or tricyclic system containing 3-12 carbon atoms. In one embodiment, the cycloalkyl group comprises 3-10 carbon atoms; in another embodiment, it comprises 3-8 carbon atoms; and in yet another embodiment, it comprises 3-6 carbon atoms. The cycloalkyl group may optionally be substituted by one or more substituents described in this invention. Examples of such substituents include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, etc.

[0116] The term "cycloalkyl-alkylene-" indicates that the cycloalkyl group is attached to the rest of the molecule via an alkylene group, wherein the alkylene and cycloalkyl groups have the meanings as described in this invention.

[0117] The term "cycloalkyloxy group" means that a cycloalkyl group is attached to the rest of the molecule by an oxygen atom, wherein the cycloalkyl group has the meaning as described in this invention.

[0118] The term "cycloalkenyl" refers to a monovalent or polyvalent monocyclic, bicyclic, or tricyclic system containing 3-12 carbon atoms, comprising at least one carbon-carbon double bond, wherein the cyclic system is non-aromatic. In one embodiment, the cycloalkenyl group comprises 3-10 carbon atoms; in another embodiment, it comprises 3-8 carbon atoms; and in yet another embodiment, it comprises 3-6 carbon atoms. The cycloalkenyl group may optionally be substituted by one or more substituents described in this invention. Examples of such substituents include, but are not limited to, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, etc.

[0119] The term "cycloalkenyl-alkylene-" indicates that the cycloalkenyl group is attached to the rest of the molecule via an alkylene group, wherein the alkylene and cycloalkenyl groups have the meanings as described in this invention.

[0120] The term "aryl" refers to a monocyclic, bicyclic, or tricyclic carbocyclic system containing 6-14, 6-12, or 6-10 ring atoms, wherein at least one ring system is aromatic, and each ring system comprises a ring of 3-7 atoms with one or more attachment sites connected to the remainder of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring." Examples of aryl groups may include phenyl, indenyl, naphthyl, and anthraceneyl. The aryl group may optionally be substituted by one or more substituents described in this invention.

[0121] The term "aryl-alkylene-" indicates that the aryl group is attached to the rest of the molecule via an alkylene group, wherein the aryl group and the alkylene group have the meanings as described in this invention. Examples of such examples include, but are not limited to, benzyl (phenyl-CH2-), phenyl ethylene (phenyl-CH2CH2-), etc.

[0122] The term "alkylene" refers to a saturated divalent hydrocarbon group obtained by removing two hydrogen atoms from a saturated straight-chain or branched hydrocarbon. Unless otherwise specified, the alkylene group contains 1-12 carbon atoms. In one embodiment, the alkylene group contains 1-8 carbon atoms; in another embodiment, the alkylene group contains 1-6 carbon atoms; in yet another embodiment, the alkylene group contains 1-4 carbon atoms; in still another embodiment, the alkylene group contains 1-3 carbon atoms; and in yet another embodiment, the alkylene group contains 1-2 carbon atoms. Examples of such groups include methylene (-CH2-), ethylene (-CH2CH2-), and so on.

[0123] The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0124] The term "heteroaryl" refers to a monocyclic, bicyclic, or tricyclic system containing 5-12, 5-10, or 5-6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5-7 atoms and has one or more attachment sites connected to the remainder of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound." The heteroaryl group may optionally be substituted by one or more substituents described in this invention. In one embodiment, the 5-10 atom heteroaryl group comprises 1, 2, 3, or 4 heteroatoms independently selected from O, S, and N.

[0125] Examples of heteroaryl groups include, but are not limited to, 2-furanyl, 3-furanyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl), and triazolyl (e.g., 2-triazolyl). And 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-triazolyl, 1,2,3-thiodiazolyl, 1,3,4-thiodiazolyl, 1,2,5-thiodiazolyl, pyrazinyl, 1,3,5-triazinyl, pyrimidinoneyl, pyridinoneyl; also including, but not limited to, the following bicyclic groups: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (such as 2-indolyl), benzopiperidinyl, etc.

[0126] The terms "5-12-membered heteroaryl", "5-10-membered heteroaryl", or "5-6-membered heteroaryl" typically describe the number of ring atoms in a molecule. For example, pyrrole, pyrazolyl, imidazolyl, thiophene, isothiazolyl, thiazolyl, furanyl, isoxazolyl, and oxazolyl are 5-membered heteroaryl groups, while pyridinyl, pyrimidinyl, pyrazinyl, and pyridazinyl are 6-membered heteroaryl groups.

[0127] The term "heteroaryl-alkylene-" indicates that the heteroaryl group is attached to the rest of the molecule via an alkylene group, wherein the alkylene and heteroaryl groups have the meanings as described in this invention.

[0128] The term “halogenated alkyl” means that an alkyl group is replaced by one or more halogen atoms. Examples of such substitutions include, but are not limited to, -CF3, -CHF2, -CH2Cl, -CH2CF3, -CH2CHF2, -CH2CH2CF3, etc.

[0129] The term “haloalkoxy” means that the alkoxy group is replaced by one or more halogen atoms. Examples of such substitutions include, but are not limited to, -OCF3, -OCHF2, -OCHCl2, -OCH2CHF2, -OCH2CHCl2, -OCH(CH3)CHF2, etc.

[0130] The term “haloalkylthio” means that the alkylthio group is replaced by one or more halogen atoms. Examples of such substitutions include, but are not limited to, -SCF3, -SCH2CF3, etc.

[0131] The term "alkenyloxy group" means that an alkenyl group is attached to the rest of the molecule by an oxygen atom, wherein the alkenyl group has the meaning as described in this invention.

[0132] The term "alkynyl group" means that the alkynyl group is attached to the rest of the molecule by an oxygen atom, wherein the alkynyl group has the meaning as described in this invention.

[0133] The term "cyano" refers to -CN.

[0134] The term "hydroxyl group" refers to -OH.

[0135] The term "nitro" refers to -NO2.

[0136] The term "carboxyl group" refers to -COOH.

[0137] The term "amino" refers to -NH2.

[0138] The compounds involved in this invention are methanogenic inner salts. "Inner salts," known in the art as "zwitterions," are electrically neutral molecules, but according to valence bond theory, they carry formal positive and negative charges in each valence bond structure on different atoms. The molecular structure of the compound of formula (I) can be represented by the following six valence bond structures, each carrying formal positive and negative charges on different atoms. Due to this resonance, the compound of formula (I) is also described as a "methanion." Although for brevity, the molecular structure of the compound of formula (I) is described as the single valence bond structure shown in this invention, this specific valence bond structure should be understood as representative of all six valence bond structures involved in the intramolecular linkage of the compound of formula (I). Therefore, unless otherwise specified, reference to formula (I) of this invention refers to all six applicable valence bond structures as well as other structures (e.g., those based on molecular orbital theory).

[0139]

[0140] Salts of the compounds described in this invention include those derived from alkali metals or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and those having the chemical formula N. + (R AA R BB R CC R DD The ammonium cation of ) where R AA R BB R CC and R DDThe compounds are independently selected from hydrogen, C1-C6 alkyl, and C1-C6 hydroxyalkyl. Salts of the compounds of the present invention can be prepared by treating the compounds of the present invention with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine).

[0141] When the compounds of the present invention contain a base moiety, the acceptable salts can be formed from organic and inorganic acids, such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, and similarly known acceptable acids.

[0142] Compositions and formulations of the compounds of the present invention

[0143] The compounds of the present invention can generally be used as insecticidal active ingredients in compositions and formulations, and usually also include adjuvants commonly used in pesticide science, including surfactants and / or carriers.

[0144] The surfactants mentioned above can be various surfactants known in the field of pesticide formulation, and the present invention is preferably one or more of emulsifiers, dispersants and wetting agents.

[0145] Other carriers besides the surfactants mentioned above can be any type of carrier known in the field of pesticide formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, examples include: silica, kaolin, diatomaceous earth, clay, talc, organobentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust, urea, amine fertilizer, mixtures of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, mixtures of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and mixtures of anhydrous sodium carbonate and anhydrous sodium bicarbonate, or one or more of these.

[0146] The emulsifier mentioned above can be any emulsifier known in the field of pesticide formulation. Specifically, the emulsifier can be one or more of the following: calcium dodecylbenzenesulfonate, triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct, polyol fatty acid ester and its ethylene oxide adduct, styrene-based phenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrene-based phenol formaldehyde resin polyoxyethylene polyoxypropylene ether, and castor oil polyoxyethylene ether.

[0147] The dispersant mentioned above can be any dispersant known in the field of pesticide formulation. Specifically, the dispersant is one or more of the following: sodium salt of acrylic acid homopolymer, disodium salt of maleate, sodium salt of naphthalene sulfonate formaldehyde condensate, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and sodium salt of p-hydroxyphenyl lignin sulfonate.

[0148] The aforementioned wetting agent can be any wetting agent known in the field of pesticide formulation. Specifically, the wetting agent can be one or more of sodium dodecyl sulfate, sodium secondary alkyl sulfate, sodium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl naphthalene sulfonate, and alkylphenol resin polyoxyethylene ether sulfate.

[0149] According to the insecticide composition of the present invention, the insecticide composition may further contain various formulation adjuvants commonly used in the field of pesticide formulation. Specifically, the formulation adjuvant may be one or more of solvents, cosolvents, thickeners, antifreeze agents, encapsulating materials, protectants, defoamers, disintegrants, stabilizers, preservatives, and binders.

[0150] The solvents mentioned above can be various solvents known in the field of pesticide formulations. Specifically, the solvent can be one or more of organic solvents, vegetable oils, mineral oils, solvent oils, and water.

[0151] The organic solvent includes one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethyldecylamide, N,N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1,4-dioxane, and cyclohexanone.

[0152] The vegetable oils include one or more of the following: methylated vegetable oils, rosin-based vegetable oils, turpentine oil, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil, and pine nut oil.

[0153] The mineral oil includes one or more of liquid wax, engine oil, kerosene, and lubricating oil.

[0154] In addition, the above solvents can also be used as cosolvents.

[0155] The antifreeze agent mentioned above can be any antifreeze agent known in the field of pesticide formulation, and the present invention preferably includes one or more of ethylene glycol, propylene glycol, glycerin and urea.

[0156] The aforementioned thickener can be any thickener known in the field of pesticide formulation. Specifically, the thickener can be one or more of xanthan gum, polyvinyl alcohol, polyacryl alcohol, polyethylene glycol, silica, diatomaceous earth, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose, and organobentonite.

[0157] The aforementioned encapsulating material can be any of the encapsulating materials known in the field of pesticide formulations, and the present invention preferably uses one or more of polyurethane, polyurea, and urea-formaldehyde resin.

[0158] The aforementioned protective agent can be any of the protective agents known in the field of pesticide formulation, and the present invention preferably uses polyvinyl alcohol and / or polyethylene glycol.

[0159] The defoamer mentioned above can be any defoamer known in the field of pesticide formulations. The present invention preferably includes one or more of organosiloxanes, tributyl phosphate and silicones.

[0160] The stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin, and acetic anhydride.

[0161] The above-mentioned preservatives are selected from one or more of benzoic acid, sodium benzoate, 1,2-benzisothiazolin-3-one (BIT), Kathon and potassium sorbate.

[0162] This invention also provides a formulation prepared from the above-described insecticide composition, wherein the formulation is in the form of an emulsifiable concentrate, an emulsion, a microemulsion, a soluble liquid, an aqueous suspension, a suspension emulsion, an ultra-low volume spray, an oil suspension, a microcapsule suspension, a water-spreading oil, a wettable powder, a water-dispersible granule, a dry suspension, a soluble powder, a soluble granule, an emulsifiable powder, an emulsifiable granule, granules, a solid microcapsule formulation, an effervescent tablet, an effervescent granule, a water-floating dispersible granule, or a seed coating agent. All of the above formulations can be prepared by conventional methods in the art.

[0163] The preparation method of the above-mentioned emulsifiable concentrate formulation may include, for example, mixing and stirring the active components, solvent, cosolvent and emulsifier to form a uniform and transparent oil phase, thereby obtaining the emulsifiable concentrate formulation.

[0164] The above-mentioned method for preparing water-in-water emulsions may include, for example, mixing active ingredients, emulsifiers, co-solvents, and solvents to form a homogeneous oil phase; or mixing water, thickeners, antifreeze, etc., to form a homogeneous aqueous phase. Under high-speed shearing, the aqueous phase is added to the oil phase or the oil phase is added to the aqueous phase to form a well-dispersible water-in-water emulsion.

[0165] The preparation method of the above-mentioned microemulsion may include, for example, mixing and stirring the active ingredient, emulsifier, and solvent to form a homogeneous and transparent oil phase. Under stirring conditions, water is gradually added to form a homogeneous and transparent microemulsion.

[0166] The preparation method of the above-mentioned water / oil suspension is as follows: For example, water or oil can be used as the medium. The active component, surfactant, and other additives are added to a sand mill and ground to a certain particle size, then filtered. A metered thickener is then added to the ground mother liquor and sheared to disperse it evenly. This produces an oil suspension or a water suspension.

[0167] The preparation methods of the above-mentioned water-dispersible granules and soluble granules are as follows: For example, the active components, dispersants, wetting agents, carriers, etc. are mixed evenly, then pulverized to a certain particle size by airflow, water is added and kneaded, and finally added to a granulator for granulation. After drying, water-dispersible granules or soluble granules can be obtained.

[0168] The preparation methods of the above-mentioned soluble powders and wettable powders include, for example, thoroughly mixing each active component, various additives and other carriers and fillers, and then pulverizing them using an ultrafine pulverizer.

[0169] The insecticide composition of the present invention can be provided as a finished formulation, i.e., the substances in the composition have been mixed; or it can be provided as a separate formulation, which can be mixed in a bucket or can before use and selectively diluted with water according to the desired concentration of active substances.

[0170] For further information related to the formulation field, see T.S. Woods, “The Formulator’s Toolbox – Product Forms for Modern Agriculture,” Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and TR. Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120–133. See also US 3,235,361, column 6, lines 16-7, line 19 and Examples 10-41; U.S. 3,309,192, column 5, lines 43-7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; US 2,891,855, column 3, lines 66-5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; Hance et al., Weed Control Handbook, 8th edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB. Publications, Richmond, UK, 2000.

[0171] Application of the compounds and compositions of the present invention

[0172] The compounds and / or compositions of the present invention are suitable for controlling pests in useful plants, such as arthropods, gastropods, and nematodes, including but not limited to:

[0173] Hemiptera: Planthoppers (Delphacidae) such as the brown planthopper (Nilaparvatalugens) and the small gray planthopper (Laodelphax striatellus); leafhoppers (Deltecephalidae) such as the green rice leafhopper (Nephotettix cincticeps); aphids (Aphididae) such as the cotton aphid (Aphisgossypii) and the alfalfa aphid (Aphis craccivora Koch); stink bugs (Pentatomidae) such as the green stink bug (Nezaraantennata); whiteflies (Aleyrodidae) such as the greenhouse whitefly (Trialeurodes vaporariorum); scale insects (Coccidae) such as the California red scale (Calformia red scale) (Aonidiella). aurantii); Tingidae; Homoptera, Psyllidea;

[0174] Lepidoptera: Pyralidae moths such as the rice stem borer (Chilo suppressalis); Noctuidae moths such as the fall armyworm (Spodoptera litura), armyworm (Pseudaletia separata), *Heliothis* spp., and *Helicoverpa* spp.; Pieridae butterflies such as the cabbage white butterfly (Pierisrapae); Tortricidae moths such as the brown-banded leafroller (Adoxophyes); Gracillariidae moths such as the tea leafroller (Caloptilia theivora) and the apple leafroller (Phyllonorycter ringoneella); Carposinidae moths such as the peach leafroller (Carposina niponensis); Lyonetiidae moths such as the genus *Lyonetia*. spp.); tussock moths (Lymantriidae) such as the genera *Lymantria* spp. and *Euproctis* spp.; nest moths (Yponomeutidae) such as the diamondback moth (*Plutella xylostella*); wheat moths (Gelechiidae) such as the red boll moth (*Pectinophora gossypiella*) and the potato moth (*Phthorimaea operculella*); light moths (Arctiidae) such as the fall webworm (*Hyphantria cunea*); and grain moths (Tineidae) such as the clothes moth (*Tinea translucens*) and the curtain grain moth (*Tineola bisselliella*);

[0175] Thysanoptera: Western flower thrips (Frankliniella occidentalis), palm thrips (Thrips palmi), yellow hard thrips (Scirtothrips dorsalis), tobacco thrips (Thrips tabaci), beautiful flower thrips (Frankliniella intonsa), and potato thrips (Frankliniella fusca);

[0176] Diptera: Housefly (Musca domestica), Culex popienspallens, Tabanus trigonus, Onion fly (Hylemya anitqua), Grey ground fly (Hylemyaplatura), Anopheles sinensis, Japanese rice leafminer (Agromyza oryzae), Rice leafminer (Hydrellia griseola), Rice straw fly (Chlorops oryzae), Melon fruit fly (Dacus cucurbitae), Mediterranean fruit fly (Ceratitis capitata), and Clover leafminer (Liriomyza trifolii);

[0177] Coleoptera: *Epilachna vigintioctopunctata*, *Phyllotreta striolata*, *Oulema oryzae*, *Echinocnemus squameus*, *Lissorhoptrus oryzophilus*, *Anthonomus grandis*, *Callosobruchus chinensis*, *Sphenophorus venatus*, *Popillia japonica*, *Anomala cuprea*, *Diabrotica spp.*, *Leptinotarsa ​​decemlineata*, *Agriotes spp.*, *Lasioderma serricorne*, *Anthrenus* The species include verbasci, Tribolium castaneum, Lyctus brunneus, Anoplophora malasiaca, and Tomicus piniperda.

[0178] Orthoptera: Locusta migratoria, Gryllotalpaafficana, Oxya yezoensis, and Oxya japanica;

[0179] Hymenoptera: Xinjiang cabbage bee (Athalia rosae), leafcutter ant (Acromyrmex spp.), and fire ant (Solenopsis spp.);

[0180] Nematodes: Rice stem tip nematode (Aphelenchoides besseyi), strawberry bud nematode (Nothotylenchus acris), soybean cyst nematode (Heterodera glycines), southern root-knot nematode (Meloidogyne incognita), short-bodied nematode (Pratylenchus penetrans), and abnormal pearl nematode (Nacobbus aberrans);

[0181] Blattariae: German cockroach (Blattella germanica), black-breasted cockroach (Periplaneta fulliginosa), American cockroach (Periplaneta Americana), brown-spotted cockroach (Periplaneta brunnea), and oriental cockroach (Blatta orientalis);

[0182] Order Acarina: Tetranychidae (e.g., Tetranychus cinnabarinus, Tetranychusurticae, Panonychus citri, and Oligoychus spp.)); Eriophyidae (e.g., Aculops pelekassi)); Tarsonemidae; Tenuipalpidae; Tuckerellidae; Tuckerellidae Acaridae; Pyroglyphidae (e.g., Dermatophagoides farinae and Dermatophagoides ptrenyssnus)); Cheyletidae; Cheyletus malaccensis and Cheyletus moorei; and Dermanyssidae.

[0183] Within the scope of this invention, useful plants include the following plant species: cereals (wheat, barley, rye, oats, rice, corn, sorghum, and related species); sugar beets (sugar beets and forage sugar beets); pome fruits, stone fruits, and soft fruits (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, and blackberries); legumes (lentils, beans, peas, soybeans); oil crops (rapeseed, mustard, olives, sunflowers, coconuts, castor oil plants, cocoa beans, peanuts, or soybeans); and cucurbits (pumpkins, cucumbers, melons). ; fiber plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruits, tangerines); vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, red peppers); laurel plants (avocados, camphor, camphor) or plants such as tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, bananas, and natural rubber plants, along with turf, ornamental and forest plants such as flowers, shrubs, broad-leaved trees or evergreen trees such as conifers, and plant propagation materials.

[0184] The term “plant propagation material” should be understood to refer to the reproductive parts of the plant, such as seeds, which can be used for the propagation of the plant, as well as nutrient materials, such as cuttings or tubers (e.g., potatoes).

[0185] The compounds and / or compositions of the present invention can kill pests with an effective amount of active substance. The pest control effect is better when the effective amount of the compounds of the present invention is within 10g-5kg per hectare.

[0186] The present invention also relates to a method for controlling pests, said method by applying the compounds or compositions of the present invention to seeds, plants or plant parts, fruits or the soil in which plants grow. Application can be carried out before and after the seeds, plants or plant parts, fruits or the soil in which plants grow are infected by pests.

[0187] The term "effective amount" as used refers to the amount of the compound or composition of the present invention sufficient to control pests on cultivated plants or in the protection of materials without causing significant damage to the treated plants. This amount can vary over a wide range and depends on various factors such as the pest species, the cultivated plant or material being treated, climatic conditions, and the specific compound used.

[0188] The method of using the compounds and / or compositions of the present invention is simple: apply the compounds and / or compositions of the present invention to the pests or their growth media. The dosage of the compounds and / or compositions of the present invention varies depending on weather conditions, formulation, timing of application, method of application, area covered, target disease, and target crop.

[0189] General Synthesis Process

[0190] In this specification, if there are any differences between chemical names and chemical structures, the structure is preferred. Generally, the compounds of the present invention can be prepared by the methods described herein, unless further specified. Unless otherwise specified, the preparation of the compounds of the present invention is carried out at room temperature. "Room temperature" means a temperature of approximately 10°C-35°C, approximately 20°C-30°C, approximately 23°C-28°C, or approximately 25°C. In the context of this invention, all figures disclosed herein, whether or not the words "approximately" or "about," are approximate values.

[0191] The testing conditions for the proton NMR spectrum of this invention are: room temperature, a Bruker 400MHz or 600MHz NMR spectrometer, with CD13, d 6 -DMSO, CD3OD or d 6 - Acetone is used as the solvent (reported in ppm), with TMS (0 ppm) or chloroform (7.26 ppm) as reference standards. When multiplets are observed, the following abbreviations will be used: s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), br (broadened), dd (doublet of doublets), dt (doublet of triplets). The coupling constant is expressed in Hertz (Hz).

[0192] The mass spectrometry analysis methods used in this invention are: Agilent 1260 HPLC; Agilent 6120 ESI.

[0193] Phase A: Water (containing 0.1% formic acid); Phase B: Acetonitrile (containing 0.1% formic acid).

[0194] Gradient elution: 0-3 min, 5-100% B; 3-6 min, 100% B.

[0195] Flow rate: 0.6 mL / min.

[0196] Detection wavelength: 254nm.

[0197] MS parameters: ESI positive scan, collision-induced ionization: 70V.

[0198] Dry nitrogen: 12 L / min, atomizing gas pressure: 40 psi, gas temperature: 350 °C.

[0199] Synthesis scheme

[0200] Synthesis Scheme 1

[0201]

[0202]

[0203] The compound shown in formula (A) can be prepared by synthetic scheme one. The compound shown in formula (a) reacts with oxalyl chloride to obtain the compound, which then reacts with 2,4,6-trichlorophenol to obtain the compound shown in formula (b); the compound shown in formula (b) reacts with the compound shown in formula (c) in toluene at 50°C to 150°C to obtain the compound shown in formula (A).

[0204] Synthesis Scheme 2

[0205]

[0206] The compound shown in formula (A) can also be prepared by synthetic scheme two. The compound shown in formula (a) and the compound shown in formula (c) undergo a condensation reaction in an inert organic solvent (such as dichloromethane) in the presence of a condensing agent (such as dicyclohexylcarbodiimide) to obtain the compound shown in formula (A).

[0207] In the above synthesis scheme, R 1 R 2 R 3 and R 4 It has the meaning described in this invention;

[0208] A 1 A 2 A 3 and A 4 Each is independently a nitrogen atom or -CR x -, where R x It is hydrogen, cyano, nitro, halogen, C 1-6 Alkyl or C 1-6 Alkyl group. Example

[0209] Preparation of intermediate Z1: N-(2,2-difluoroethyl)pyridine-2-amine

[0210]

[0211] Step 1: Preparation of tert-butyl pyridine-2-ylaminocarbamate

[0212]

[0213] 2-Aminopyridine (4.70 g, 0.05 mol), di-tert-butyl dicarbonate (14.17 g, 0.65 mol), and triethylamine (7.55 g, 0.075 mol) were sequentially added to dichloromethane (45 mL), and the mixture was stirred at room temperature for 12 hours. The mixture was filtered, and the filtrate was concentrated under reduced pressure. The concentrate was extracted with ethyl acetate (30 mL × 3), washed with saturated brine (30 mL × 3), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 5 / 1] to give 4.62 g of the title compound as a white solid, yield: 48.0%.

[0214] Step 2: Preparation of N-(2,2-difluoroethyl)pyridine-2-amine

[0215]

[0216] At 0°C, tert-butyl pyridinium-2-ylaminocarbamate (1.29 g, 6.64 mmol) was added to a 100 mL single-necked flask, and tetrahydrofuran (40 mL) was added to dissolve it. Sodium hydride (60% by mass, 0.4 g, 9.96 mmol) was slowly added in portions to the reaction solution at 0°C. After the addition was complete, the mixture was stirred at 0°C for 30 minutes. The mixture was then cooled to room temperature, and 1,1-difluoro-2-iodoethane (1.27 g, 6.64 mmol) was added. The reaction was continued at room temperature for 12 hours. Ice water (30 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (50 mL × 3). The organic phases were combined, dried over anhydrous sodium sulfate for 1 hour, filtered, and the filtrate was concentrated by vacuum distillation to obtain a brown oily substance.

[0217] Dichloromethane (20 mL) and trifluoroacetic acid (2.05 g, 18 mmol) were added to the brown oily substance, and the reaction was carried out at 40 °C for 12 hours. The reaction solution was concentrated under reduced pressure, and the pH was adjusted to 8 by adding saturated potassium carbonate aqueous solution. Dichloromethane (50 mL × 3) was added for extraction, and the organic phases were combined. The organic phases were dried with anhydrous sodium sulfate for 1 hour, filtered, and the filtrate was concentrated by distillation under reduced pressure to give 0.84 g of the title compound. The obtained title compound was a colorless oily substance, with a yield of 80.1%.

[0218] 1 H NMR (400MHz, CDCl3) δ (ppm): 8.10 (d, J = 4.9Hz, 1H), 7.49–7.32 (m, 1H), 6.69–6.59 (m, 1H), 6.46 ( d,J=8.4Hz,1H),5.97(tt,J=56.6,4.3Hz,1H),4.86(s,1H),3.77(tdd,J=14.6,6.4,4.3Hz,2H).

[0219] MS(ES-API,pos.ion)m / z:158.97[M+1] + .

[0220] Using the corresponding starting materials (such as pyrazin-2-amine, pyrimidine-2-amine, 5-methoxypyridine-2-amine, 5-nitropyridine-2-amine, 4-methoxypyridine-2-amine, 4-fluoropyridine-2-amine, 3-methylpyridine-2-amine) as raw materials, the intermediate compounds in Table 1 can be obtained by referring to the preparation method of intermediate Z1 above.

[0221] Table 1

[0222]

[0223]

[0224] By replacing the 1,1-difluoro-2-iodoethane with 1-chloro-1,1-difluoro-2-iodoethane and 2,2-difluoro-1-iodopropane in the second step of preparing intermediate Z1, and using 2-aminopyridine as the starting material, the intermediate compound in Table 2 can be obtained by referring to the preparation method of intermediate Z1.

[0225] Table 2

[0226]

[0227] The structures of 2-aminopyridine, pyrazin-2-amine, pyrimidine-2-amine, 5-methoxypyridine-2-amine, 5-nitropyridine-2-amine, 4-methoxypyridine-2-amine, 4-fluoropyridine-2-amine, 3-methylpyridine-2-amine, 1-chloro-1,1-difluoro-2-iodoethane, and 2,2-difluoro-1-iodopropane are detailed in Table 3.

[0228] Table 3

[0229]

[0230]

[0231] Preparation of intermediate N1: bis(2,4,6-trichlorophenyl)2-(3-(trifluoromethyl)phenyl)malonate

[0232]

[0233] Step 1: Preparation of methyl 2-(3-(trifluoromethyl)phenyl)acetate

[0234]

[0235] 4.08 g (20 mmol) of 3-trifluoromethylphenylacetic acid was dissolved in 60 mL of methanol, and 2 mL of concentrated sulfuric acid was added. The reaction mixture was heated to 60 °C and stirred for 10 hours. The reaction system was concentrated under reduced pressure, and the residue was dissolved in 100 mL of ethyl acetate, washed with water (30 mL × 3), and the organic phase was dried over anhydrous sodium sulfate for 1 hour. After filtration, the residue was concentrated and separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 30 / 1] to give 4.0 g of the title compound. The title compound was a colorless liquid, with a yield of 91.7%.

[0236] Step 2: Preparation of dimethyl 2-(3-(trifluoromethyl)phenyl)malonate

[0237]

[0238] At room temperature, methyl 2-(3-(trifluoromethyl)phenyl)acetate (2.9 g, 13.3 mmol) was dissolved in tetrahydrofuran (40 mL), followed by the addition of sodium hydride (60% by mass, 1.70 g, 42 mmol) in portions. After the addition was complete, the mixture was stirred at room temperature for 30 minutes. Then, dimethyl carbonate (8.1 g, 90 mmol) was added dropwise to the reaction mixture. After the addition was complete, the reaction system was heated to 60 °C and refluxed for 18 hours. The reaction was quenched by adding 15 mL of saturated ammonium chloride solution, and the mixture was extracted with ethyl acetate (50 mL × 3). The organic phases were combined and dried over anhydrous sodium sulfate for 1 hour. The mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 10 / 1] to give 3.0 g of the title compound as a colorless liquid, yield: 75.8%.

[0239] Step 3: Preparation of 2-(3-(trifluoromethyl)phenyl)malonic acid

[0240]

[0241] Dimethyl 2-(3-(trifluoromethyl)phenyl)malonate (5.52 g, 20.00 mmol) was added to a 100 mL reaction flask, and an aqueous solution of sodium hydroxide (4.00 g, 100.00 mmol) (40 mL) was slowly added. The resulting mixture was heated to 60 °C and refluxed for 3 hours. The reaction solution was then transferred to 0 °C and stirred, and concentrated hydrochloric acid (10 mL) was slowly added to adjust the pH to 1. Ethyl acetate (50 mL × 3) was added for extraction. The organic phases were combined and dried over anhydrous sodium sulfate for 1 hour. The mixture was filtered, and the filtrate was distilled under reduced pressure to give 4.41 g of the title compound as a yellow solid, yield: 90%.

[0242] Step 4: Preparation of bis(2,4,6-trichlorophenyl)2-(3-(trifluoromethyl)phenyl)malonate

[0243]

[0244] 2-(3-(trifluoromethyl)phenyl)malonic acid (4.41 g, 18.00 mmol), N,N-dimethylformamide (1 mL), and dichloromethane (50 mL) were added to a 250 mL single-necked flask. Oxaloyl chloride (8 mL, 95 mmol) was slowly added dropwise to the reaction solution at 0 °C. After the addition was complete, the reaction solution was placed at room temperature and stirred for 6 hours. Then, 2,4,6-trichlorophenol (8 g, 40.00 mmol) was added to the reaction solution, and the reaction was continued at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure, and methanol (40 mL) was added. After standing at room temperature for 3 hours, a large amount of white precipitate formed in the reaction solution. The precipitate was filtered, and the filter cake was washed with methanol (20 mL) to give 6.64 g of the title compound. The title compound was a white solid, yield: 61%.

[0245] 1 H NMR (400MHz, CDCl3) δ (ppm): 7.94 (s, 1H), 7.87 (d, J = 7.8Hz, 1H), 7.73 (d, J = 7.8Hz, 1H), 7.62 (t, J = 7.8Hz, 1H), 7.49 (s, 2H), 7.41 (s, 2H), 5.40 (s, 1H).

[0246] MS(ES-API,pos.ion)m / z:607.85[M+1] + .

[0247] Using the corresponding phenylacetic acid derivative as the starting material, and referring to the preparation method of intermediate N1, the intermediate compounds in Table 4 can be obtained.

[0248] Table 4

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258] Example 1: Preparation of 1-(2,2-difluoroethyl)-3-(1-(4-fluorophenyl)-2-nitroethyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onium-2-olate

[0259]

[0260] Step 1: Preparation of (E)-1-fluoro-4-(2-nitrovinyl)benzene

[0261]

[0262] 4-Fluorobenzaldehyde (6.20 g, 50 mmol) and nitromethane (7.32 g, 120 mmol) were dissolved in methanol (15 mL) and stirred at -8 °C. A solution of sodium hydroxide (4.00 g, 100 mmol) in water (15 mL) was added dropwise, keeping the temperature below 15 °C. The reaction was allowed to proceed for 15 minutes after the addition was complete. 50 mL of ice water was added, and the mixture was stirred at 0 °C for 20 minutes. The mixture was then slowly added to a solution of 6 M HCl (30 mL) and zinc chloride (1.5 g), controlling the dropping rate. The addition was completed over 45 minutes, followed by stirring at 0 °C for 45 minutes, resulting in a yellow precipitate. The precipitate was filtered, washed with ice water, and then ethanol (40 mL) was added. The mixture was heated until the precipitate dissolved, cooled to 0 °C, and crystallized. The crystals were filtered, washed with ice water, and dried to give 7.02 g of the title compound as a yellow solid, with a yield of 84%.

[0263] Step 2: Preparation of dimethyl 2-(1-(4-fluorophenyl)-2-nitroethyl)malonic acid

[0264]

[0265] (E)-1-fluoro-4-(2-nitrovinyl)benzene (5.01 g, 30 mmol) and dimethyl malonate (7.92 g, 60 mmol) were dissolved in toluene (35 mL), and triethylamine (6.06 g, 101 mmol) was added. The mixture was reacted at room temperature for 8 hours. After the reaction was complete, 50 mL of water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic phases were combined and dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The residue was separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 4 / 1] to give 2.93 g of the title compound as a yellow oil, yield: 58%.

[0266] Step 3: Preparation of 2-(1-(4-fluorophenyl)-2-nitroethyl)malonic acid

[0267] Using the compound 2-(1-(4-fluorophenyl)-2-nitroethyl)malonic acid dimethyl ester obtained in the second step reaction as a starting material, and following the preparation method of the third step of intermediate N1, the title compound was obtained after preparation. The title compound was a yellow solid.

[0268]

[0269] Step 4: Preparation of bis(2,4,6-trichlorophenyl)2-(1-(4-fluorophenyl)-2-nitroethyl)malonate

[0270]

[0271] Using the compound 2-(1-(4-fluorophenyl)-2-nitroethyl)malonic acid obtained in step 3 as a raw material, and following the preparation method in step 4 of intermediate N1, the title compound was obtained after preparation. The title compound was a white solid.

[0272] MS(ES-API,pos.ion)m / z:630.87[M+1] + .

[0273] Step 5: Preparation of 1-(2,2-difluoroethyl)-3-(1-(4-fluorophenyl)-2-nitroethyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-olate

[0274]

[0275] Intermediate Z1 (N-(2,2-difluoroethyl)pyridine-2-amine) (0.079 g, 0.5 mmol) and di(2,4,6-trichlorophenyl)2-(1-(4-fluorophenyl)-2-nitroethyl)malonate (0.32 g, 0.5 mmol) were dissolved in 15 mL of toluene and reacted at 110 °C for 12 hours. The reaction mixture was concentrated, and the residue was separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 1 / 3] to give 87 mg of the target compound as a yellow solid, yield: 37%.

[0276] MS(ES-API,pos.ion)m / z:394.10[M+1] + .

[0277] 1H NMR (400MHz, CDCl3) δ (ppm): 9.50–9.38 (m, 1H), 8.16 (ddd, J = 8.8, 7.2, 1.6Hz, 1H), 7.63 (t, J = 8.6Hz, 1H), 7.58 (dd, J = 8.6, 5.4Hz, 2H), 7.42 (t, J = 6.9Hz, 1H),7.06–6.94(m,2H),6.35–5.98(m,1H),5.58(dd,J=12.4,8.8Hz,1H),5. 32–5.24(m,1H),5.16(dd,J=12.4,7.0Hz,1H),4.61(td,J=12.7,4.6Hz,2H).

[0278] Example 2: Preparation of 1-(2,2-difluoroethyl)-3-methyl-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-olate

[0279]

[0280] Intermediate Z1 (N-(2,2-difluoroethyl)pyridine-2-amine) (0.079 g, 0.5 mmol) and 2-methylmalonic acid (0.12 g, 1.0 mmol) were dissolved in 20 mL of dichloromethane. Dicyclohexylcarbodiimide (0.41 g, 2.0 mmol) was added, and the mixture was reacted at room temperature for 24 hours. The mixture was filtered, the filtrate was concentrated, and the residue was separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 1 / 3] to give 0.065 g of the target compound as a yellow solid, yield: 39%.

[0281] MS(ES-API,pos.ion)m / z:241.07[M+1] + .

[0282] 1 H NMR (400MHz, CDCl3) δ (ppm): 9.52 (dd, J=6.8, 1.3Hz, 1H), 8.12 (ddd, J=8.8, 7.1, 1.6Hz, 1H), 7.66 (d ,J=9.0Hz,1H),7.41(t,J=6.9Hz,1H),6.40–6.02(m,1H),4.68(td,J=12.7,4.7Hz,2H),2.16(s,3H).

[0283] Example 3: Preparation of 1-(2,2-difluoroethyl)-3-(3-fluoro-5-(trifluoromethyl)phenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-olate

[0284]

[0285] Intermediate Z1 (N-(2,2-difluoroethyl)pyridine-2-amine) (0.079 g, 0.5 mmol), intermediate N2 (bis(2,4,6-trichlorophenyl)2-(3-fluoro-5-(trifluoromethyl)phenyl)malonate) (0.31 g, 0.5 mmol), and toluene (20 mL) were added to a 50 mL single-necked flask and heated to 110 °C for 12 hours. After the reaction was complete, the solvent was removed by vacuum distillation, and the residue was separated by silica gel column chromatography [methanol / dichloromethane (v / v) = 1 / 20] to give 0.078 g of the target compound as a yellow oil, yield: 40.2%.

[0286] MS(ES-API,pos.ion)m / z:389.07[M+1] + .

[0287] 1 H NMR (400MHz, CDCl3) δ (ppm): 9.63–9.53 (m, 1H), 8.29–8.18 (m, 1H), 8.03 (s, 1H), 7.85 (d, J = 10.5Hz, 1H), 7.73 (d, J = 8 .9Hz,1H),7.49(t,J=7.0Hz,1H),7.21(d,J=8.4Hz,1H),6.25(tt,J=56.1,4.7Hz,1H),4.71(td,J=12.6,4.7Hz,2H).

[0288] Using any one of intermediate compounds Z1 to Z8 and any one of intermediate compounds N1 to N43 as reactants, the target compounds in Table 5 can be prepared by referring to the preparation method in step 5 of Example 1 or the preparation method in Example 3.

[0289] Table 5

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308] Activity test

[0309] Preparation method of the drug: Weigh a certain mass of the original drug using an analytical balance (0.0001g), dissolve it in acetone to make a mother liquor of 10000ppm, and then dilute it with a certain volume of distilled water containing 1‰ Tween-80 emulsifier for later use.

[0310] 1) Experimental Method - Test Target: Armyworm

[0311] Leaf immersion method: Soak an appropriate amount of corn leaves thoroughly in the prepared solution, then allow them to air dry naturally. Place the leaves in a petri dish lined with filter paper, and attach 10 mid-3rd instar larvae of the corn cress per dish. Incubate in a 24–27℃ observation room, and investigate the results after 72 hours. Touch the insects with a paintbrush; no reaction indicates a dead insect.

[0312] The experimental results showed that at a test concentration of 100 mg / L, the mortality rate of armyworms in Examples 3, 4, 9, 13, 14, 15, 17, 19, 20, 21, 42, 43, 44, 51, 53, 63, and 76 was ≥70%.

[0313] 2) Experimental Methods - Test Target: Whitefly

[0314] Spraying method: Place eggplant seedlings with uniform growth into a whitefly rearing cage. After 24 hours, transfer the egg-laying plants to an insect-free cage for normal cultivation. When the nymphs reach the first instar, use a 12mm diameter punch to take samples. Place the sampled leaf discs in a 9cm petri dish (moisturized with agar). Count the total number of insects under a stereomicroscope. Then, use a potter sprayer to treat the insects with the prepared pesticide solution in descending order of concentration (the pesticide concentration can be 200mg / L, 100mg / L, 50mg / L, etc.). After air-drying naturally, place the plants in an artificial climate chamber. Observe under a stereomicroscope after 3 days. Touch the insects with a brush; if the insects do not move, they are dead. Count the total number of insects and the number of dead insects, and calculate the mortality rate.

[0315] The experimental results showed that at a test concentration of 50 mg / L, the mortality rate of whiteflies in Examples 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 19, 20, 23, 24, 25, 26, 27, 76, and 78 was ≥90%.

[0316] 3) Experimental Method - Target Specimen: Alfalfa Aphid

[0317] Spraying method: Select cowpea leaves of uniform growth and make leaf discs using a perforator, two leaf discs per dish. Place a damp sponge block in the petri dish, place the leaf discs on the sponge, and add water until it is level with the leaf discs. Inoculate 2nd-3rd instar alfalfa aphids (raised indoors) onto the prepared leaf discs, at least 15 aphids per disc. Use a spray tower for treatment, spraying 0.5 mL of pesticide solution per treatment. Place the treated materials in an observation room and observe the results after 2 days. Touch the insects with a brush; no reaction indicates dead insects.

[0318] The experimental results showed that at a test concentration of 100 mg / L, the mortality rate of alfalfa aphids in Examples 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 14, 17, 19, 20, 21, 23, 24, 25, 26, 27, 33, 34, 40, 42, 44, 45, 70, 72, and 73 was ≥70%.

[0319] Even at reduced concentrations, the compounds of this invention still exhibit excellent control efficacy (mortality rate) against alfalfa aphids. Specific test results are shown in Table 6.

[0320] Table 6

[0321]

[0322] The test results show that the compound of the present invention still has excellent control efficacy (mortality rate) against alfalfa aphids after the concentration is reduced: at the test concentration of 10 mg / L, the mortality rate of alfalfa aphids in Examples 4 and 9 is ≥80%.

[0323] 4) Experimental Methods - Test Target: Brown Planthopper

[0324] Spraying method: Rice seedlings inoculated with rice brown planthoppers (15 2nd-3rd instar larvae) were sprayed under a Potter spray tower. After treatment, the rice brown planthoppers were placed in an observation room at 24-27℃ for cultivation. The results were investigated after 72 hours. The insects were touched with a brush. If the insects did not move, they were considered dead. The mortality rate was calculated.

[0325] The experimental results showed that at a test concentration of 100 mg / L, the mortality rate of brown planthoppers in Examples 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 17, 18, 19, 20, 21, 22, 25, 32, 35, 38, 39, 40, 44, 49, 50, 52, 53, 59, 73, 74, 76, 77, 78, and 79 was ≥70%.

[0326] The test results showed that at a test concentration of 20 mg / L, the mortality rate of brown planthoppers in Examples 4, 5, 8, 9, and 10 was ≥90%.

[0327] The test results show that the compound of the present invention still has excellent control efficacy (mortality rate) against brown planthoppers after the concentration is reduced: at the test concentration of 10 mg / L, the mortality rate of brown planthoppers in Examples 4, 5, 8 and 10 is ≥80%, while the mortality rate of compound 7 in patent CN101939302A against brown planthoppers is only 40% at the test concentration of 10 mg / L.

[0328] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

Claims

1. A compound having one of the following structures or a salt thereof: (1)、 (2)、 (3)、 (4)、 (5)、 (6)、 (7)、 (8)、 (9)、 (10)、 (11)、 (12)、 (13)、 (14)、 (15)、 (17)、 (18)、 (19)、 (20)、 (21)、 (22)、 (23)、 (24)、 (25)、 (26)、 (27)、 (32)、 (33)、 (34)、 (35)、 (38)、 (39)、 (40)、 (42)、 (43)、 (44)、 (45)、 (49)、 (50)、 (51)、 (52)、 (53)、 (59)、 (63)、 (70)、 (72)、 (73)、 (74)、 (76)、 (77)、 (78)、 (79)。 2. A composition comprising the compound of claim 1 and at least one pesticide adjuvant commonly used in agronomy, wherein, The commonly used auxiliary agents include surfactants and / or carriers.

3. The use of the compound of claim 1 or the composition of claim 2 as an insecticide in agriculture, forestry, or horticulture, wherein, The insecticide is used to control armyworms, whiteflies, alfalfa aphids and / or brown planthoppers.

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