WO2016070562A1 - 邻甲酰氨基苯甲酰胺类化合物及其应用 - Google Patents

邻甲酰氨基苯甲酰胺类化合物及其应用 Download PDF

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WO2016070562A1
WO2016070562A1 PCT/CN2015/075824 CN2015075824W WO2016070562A1 WO 2016070562 A1 WO2016070562 A1 WO 2016070562A1 CN 2015075824 W CN2015075824 W CN 2015075824W WO 2016070562 A1 WO2016070562 A1 WO 2016070562A1
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group
alkyl
alkoxy
acyl
alkylamino
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PCT/CN2015/075824
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English (en)
French (fr)
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冯美丽
李宏举
王春山
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江苏中旗作物保护股份有限公司
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Priority to CN201580058933.9A priority Critical patent/CN107001325B/zh
Publication of WO2016070562A1 publication Critical patent/WO2016070562A1/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings

Definitions

  • the present invention relates to the field of pesticides, and relates to an orthoformylbenzamide compound, an insecticide containing any of the compounds as an active ingredient, and uses thereof.
  • the problem of plant disease pests becoming resistant to insecticides is often a potential problem that plagues people, which is one of the most important reasons why pesticide researchers have been seeking to develop insecticides with special mechanisms of action. For many years, pesticide researchers have been working hard to find insecticides with special mechanisms of action.
  • the ortho-aminobenzamide compound developed by DuPont is a new type of compound that targets the nitinin receptor.
  • the representative compound chlorantraniliprole (RynaxypyrTM) exhibits excellent insecticidal activity. Evaluation results of activity and field effects, low toxicity to mammals, and good environmental compatibility.
  • Coragen Choinese name: Kang Kuan
  • a commercial product containing this compound as its main active ingredient was launched in 2008. In 2010, the sales of pesticide products containing this active ingredient will exceed US$100 million.
  • Patent CN 101298435 also discloses the following two compounds of the general formula, but no insecticidal activity is reported.
  • the object of the present invention is to provide a class of o-formylaminobenzamides which have excellent control effects against various pests, and which are characterized by high efficiency, safety and good environmental compatibility, so as to meet crop protection and to effectively and safely kill insects.
  • the demand for the agent In order to design and synthesize a new compound with high insecticidal activity, we introduced a piperidine ring and a piperazine ring into the (C) amide moiety, structurally modified the lead, and designed and synthesized a series of unreported reports. A new compound having the general structure. Although all of the disclosed compounds in the above patents (application) are similar to the compounds of the present invention, the structures are still significantly different.
  • Still another object of the invention is to provide the use of the above compounds in the preparation of insecticides.
  • the object of the invention can be achieved by the following measures:
  • R 1 represents halogen or -CN
  • R 2 represents -H.HCl or the following groups which may be substituted: C 1 -C 8 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, (C 1 -C 8 alkyl) An acyl group, a (C 1 -C 8 alkoxy) acyl group, a (C 1 -C 8 alkylamino) acyl group, an amide group, a morpholinyl group or a (C 1 -C 8 alkyl)sulfonyl group;
  • X represents C-H or N
  • R 3 represents -NH 2 ⁇ HCl or the following groups which may be substituted: C 1 -C 8 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, (C 1 -C 8 alkane) Amido group, (C 1 -C 8 alkoxy)amide group, (C 1 -C 8 alkylamino)amide group, (C 1 -C 8 alkylamino) acyl group, (C 1 -C 8- alkyl)sulfonylamino, ureido or morpholinamide;
  • R 4 represents halogen or -CN
  • R 2 or R 3 is selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or nitro.
  • R 1 represents Cl or -CN.
  • R 4 represents Cl or -CN.
  • R 2 represents -H.HCl or a group which may be substituted: (C 1 -C 8 alkyl) acyl, (C 1 -C 8 alkoxy) acyl, (C 1 a -C 8 alkylamino) acyl group, a morpholinyl group or a (C 1 -C 8 alkyl)sulfonyl group; the substituent is selected from halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • R 3 represents -NH 2 ⁇ HCl or a group which may be substituted: (C 1 -C 8 alkyl)amido, (C 1 -C 8 alkoxy)amide, (C 1 -C 8 alkylamino) amido, (C 1 -C 8 alkylamino) acyl methylene, ureido, (C 1 -C 8 alkyl)sulfonylamino or morpholinamide;
  • the substituent is selected from halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • R 2 represents -H.HCl or a group which may be substituted: (C 1 -C 4 alkyl) acyl, (C 1 -C 4 alkoxy) acyl, (C 1 a -C 4 alkylamino) acyl group, a morpholinyl group or a (C 1 -C 4 alkyl)sulfonyl group; the substituent is selected from halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • R 2 represents -H.HCl, tert-butoxycarbonyl, methylsulfonyl, morpholinyl, N-methylaminoacyl, N,N-dimethylamino, acetyl or methoxy Acyl group.
  • R 2 represents a (C 1 -C 4 alkoxy) acyl group or a (C 1 -C 4 alkylamino) acyl group; the substituent is selected from halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • R 3 represents -NH 2 ⁇ HCl or a group which may be substituted: (C 1 -C 4 alkyl)amido, (C 1 -C 4 alkoxy)amide, (C 1 -C 8 alkylamino) amido, (C 1 -C 8 alkylamino) acyl methylene, ureido, (C 1 -C 8 alkyl)sulfonylamino or morpholinamide;
  • the substituent is selected from halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • R 3 represents -NH 2 ⁇ HCl, 3-methylureido, acetamido, 3,3-dimethylureido, methanesulfonamide, methoxyamide, N-B Alkyl amide or tert-butoxyamide.
  • the compound of the formula (I) can be produced by the reaction formulae 1-1 and 1-2, and the compound of the formula (II) can be produced by the reaction formulas 2-1 and 2-2, wherein the substituents are as previously described unless otherwise specified. limited.
  • R 2 represents a C 1 -C 3 alkyl group which may be substituted, a C 3 -C 6 alkenyl group which may be substituted, a C 3 -C 6 alkynyl group which may be substituted, an alkoxy group which may be substituted.
  • the target compound (I) can be obtained by reacting (III) with (IV) in a suitable solvent at a temperature of from -20 ° C to the boiling point for 0.5 to 48 h.
  • Suitable solvents are selected from the group consisting of halogenated alkanes, acetone, benzene, toluene, ethyl acetate, acetonitrile, propionitrile, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, Or dimethyl sulfoxide and the like.
  • the synthesis of the starting material (III) is carried out by a known method such as the method described in CN1541063A.
  • R 2 represents a (C 1 -C 8 )alkanoyl group which may be substituted, an aminoacyl group which may be substituted, a morpholinyl group which may be substituted, or a (C 1 -C 8 )alkylsulfonyl group
  • the reaction formula 1 is employed.
  • the object compound (I-2) is obtained by reacting the acid with a solvent in a solvent-free or a suitable solvent at a temperature of from -20 ° C to a boiling point for 0.5 to 48 h.
  • the acid is selected from inorganic acids such as hydrochloric acid, concentrated sulfuric acid, and the like; organic acids such as trifluoroacetic acid, p-toluenesulfonic acid, and the like.
  • Suitable solvents are selected from the group consisting of halogenated alkanes, acetone, benzene, toluene, acetonitrile, tetrahydrofuran, dioxane, and the like.
  • the synthesis route of the starting material (I-1) is shown in Reaction Scheme 1-1.
  • the compound (I-2) is reacted with an acylating agent (V) at a suitable temperature in a polar aprotic solvent under basic conditions to give a compound of the formula (I).
  • the base is an alkali metal hydroxide, an alkali metal carbonate, an alkali metal hydrogencarbonate or an organic base
  • the polar or non-polar aprotic solvent is a halogenated alkane, benzene, toluene, amide , nitrile solvent.
  • the alkali metal hydroxide is sodium hydroxide or potassium hydroxide
  • the alkali metal carbonate is sodium carbonate or potassium carbonate
  • the alkali metal hydrogencarbonate is sodium hydrogencarbonate or potassium hydrogencarbonate.
  • the organic base is pyridine, triethylamine, 4-dimethylaminopyridine or N-methylmorpholine;
  • the amide solvent is N,N-dimethylformamide, N,N-dimethyl
  • the nitrile solvent is acetonitrile or propionitrile.
  • the acylating agent (V) is R 2 -O-, R 2 -Cl or R 2 -Br.
  • the above suitable temperature is -10 to 30 ° C, preferably -5 to 0 ° C.
  • R 3 represents a C 1 -C 3 alkyl group which may be substituted, a C 3 -C 6 alkenyl group which may be substituted, a C 3 -C 6 alkynyl group which may be substituted, which may be substituted (C 1 -C 8 An alkyl group, an alkoxyamide group which may be substituted.
  • reaction conditions of (III) and (VI) are referred to the reaction conditions of Reaction Formula 1-1.
  • R 3 represents a H atom, an alkylamide group which may be substituted, a (C 1 -C 8 )alkylsulfonylamide group, an aminoamide group which may be substituted, a morpholinyl group which may be substituted, a reaction formula is employed 2-2 Preparation:
  • the synthesis conditions of (II-3) are referred to the reaction conditions of Reaction Formula 1-2.
  • the synthesis route of the starting material (II-1) is shown in Reaction Scheme 2-1.
  • Alkyl means a saturated aliphatic hydrocarbon group of 1 to 20 carbon atoms, including both straight-chain and branched-chain groups (the range of numbers referred to in this application, such as “1-20", refers to the group, In the case of an alkyl group, it may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 20 carbon atoms).
  • An alkyl group having 1 to 4 carbon atoms is referred to as a lower alkyl group. When the lower alkyl group has no substituent, it is referred to as an unsubstituted lower alkyl group.
  • the alkyl group is a medium size alkyl group having from 1 to 8 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, pentyl Base.
  • the alkyl group is a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl or t-butyl groups.
  • the alkenyl group having 2 to 6 carbon atoms is referred to as a lower alkenylene group.
  • the alkenyl group is a medium size alkyl group having from 3 to 6 carbon atoms.
  • Alkynyl means an unsaturated aliphatic hydrocarbon radical of from 2 to 20 carbon atoms containing at least one carbon carbon C ⁇ C, including both straight-chain and branched-chain groups (number ranges recited in this application, such as “1- 20” means the group, which may contain 2 carbon atoms, 3 carbon atoms, etc., up to 20 carbon atoms.
  • An alkynyl group having 2 to 6 carbon atoms is referred to as a lower alkynyl group.
  • the alkynyl group is a medium sized alkynyl group having from 3 to 6 carbon atoms.
  • (C 1 -C 8 alkyl) acyl means an acyl group having a substituted C 1 -C 8 alkyl group, wherein “C 1 -C 8 " represents 1 to 8 carbon atoms in the alkyl substituent For example, acetyl, n-propionyl, isopropionyl, n-butyryl and the like.
  • (C 1 -C 8 alkoxy)acyl means an acyl group having a substituted C 1 -C 8 alkoxy group, such as methoxy acyl, ethoxy acyl, n-propoxy acyl, isopropoxy acyl , n-butoxy acyl, tert-butoxy acyl and the like.
  • Alkoxy means an “alkyl-O-" group wherein alkyl is as defined above.
  • Alkylamino means an amine group having one or two alkyl substituents, such as an “alkyl-NH-” or “(alkyl) 2 N-” group, wherein alkyl is as defined above .
  • (C 1 -C 8 alkylamino) acyl represents an acyl group having a C 1 -C 8 alkylamino substituent.
  • morpholinyl means Group.
  • (C 1 -C 8 alkyl)sulfonyl means a “sulfonyl group having a C 1 -C 8 alkyl substituent”.
  • Sulfonylamino means an amino group having one or two sulfonyl substituents, such as.
  • (C 1 -C 8 alkyl)sulfonylamino means a sulfonylamino group having a C 1 -C 8 alkyl substituent on the sulfonyl group.
  • the ureido group in the present application is preferably a ureido group having a substituent, and the substituent may be an alkyl group or a lower alkyl group.
  • Halogen means a fluorine, chlorine, bromine or iodine group.
  • An orthoformylbenzamide derivative represented by the general formula (I) and (II) of the present invention or a pharmaceutically acceptable salt thereof can be used for the preparation of an insecticide, particularly an agronomic insecticide as an active ingredient.
  • an insecticide particularly an agronomic insecticide as an active ingredient.
  • Control various harmful insects such as agronomically harmful insects, stored grain harmful insects, hygienic harmful insects, nematodes, etc., which are harmful to rice, fruit trees, vegetables, other crops, flowers and ornamental plants, etc.
  • Insecticidal effects such as against lepidopteran pests, including cotton bollworm, beet armyworm, diamondback moth, cabbage caterpillar, rice leaf roller and stem borer, and homopteran pests such as spider mites, planthoppers, aphids , whitefly, etc., diptera pests such as housefly, leaf miner, mosquitoes, etc., Orthoptera and coleoptera and other pests.
  • the compounds of the present invention are useful as insecticides for protecting plants such as agriculture, horticulture and the like.
  • the pests to which the compounds of the present invention are controll are not limited to the scope of the above examples.
  • the o-methylaminobenzamide derivative of the present invention or a pharmaceutically acceptable salt thereof is an active ingredient, and an agriculturally acceptable carrier can be used as an insecticidal composition, and the weight percentage of the active ingredient in the composition It is 0.1-99.5%.
  • the agrochemical agent of the present invention is generally prepared into a conventional dosage form in accordance with a common agrochemical preparation method.
  • the o-formylaminobenzamide derivative represented by (I) and (II) or a salt thereof and an optional auxiliary agent are blended in an appropriate ratio with a suitable inert carrier, by dissolving, dispersing, suspending, Mixing, dipping, adsorbing or adhering to form suitable dosage forms such as suspensions, emulsifiable concentrates, soluble concentrates, wettable powders, granules, powders, tablets, sachets, and the like.
  • the inert carrier which can be used in the present invention can be either a solid or a liquid.
  • a raw material usable as a solid carrier soybean powder, cereal flour, wood flour, bark powder, sawdust, tobacco stem powder, walnut shell powder, alfalfa, cellulose powder, vegetable extract residue, and synthesis can be exemplified.
  • Polymer or resin powder Polymer or resin powder, clay (such as kaolin, bentonite and acid clay), talc (such as talc and pyrophyllite), silica powder or flakes (such as diatomaceous earth, silica sand, mica and white carbon (synthetic high dispersion)
  • Silicic acid also known as finely pulverized hydrated silica or hydrated silicic acid, some commercially available products containing calcium silicate as the main component
  • activated carbon sulfur powder, pumice, calcined diatomaceous earth, ground Brick, fly ash, sand, calcium carbonate, calcium phosphate and other inorganic or mineral powders
  • plastic carriers such as polyethylene, polypropylene and polyvinylidene chloride
  • chemical fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, Ammonium chloride
  • compost can be used alone or as a mixture.
  • the material which can be used as the liquid carrier is selected from materials which are inherently soluble or which, although not soluble, are capable of dispersing the active ingredient compound by means of an adjuvant.
  • liquid carriers such as water; organic solvents such as toluene, xylene, cyclohexane, methanol, butanol, ethylene glycol, acetone, dimethylformamide, diethyl ether, dimethyl sulfoxide, animal and vegetable oils and fatty acids;
  • Surfactants such as emulsifiers and dispersants include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants; other auxiliaries such as wetting agents, thickeners and the like.
  • the compound of the present invention represented by the general formulae (I) and (II) or a salt thereof is used as an active ingredient in an insecticide
  • the content in the insecticide may be selected in the range of 0.1% to 99.5%, and the appropriate active ingredient content may be determined according to the formulation form and the application method.
  • the aqueous emulsion contains 5% to 50% by weight of the active ingredient, preferably in an amount of 10% to 40%; in the microemulsion, 5% to 50% of the active ingredient, preferably The content is from 10% to 30%; from 1% to 90% of the active ingredient in the cream, preferably from 10% to 80%.
  • the compound of the present invention as an active ingredient can be uniformly mixed with an auxiliary agent such as a solvent and a surfactant, and can be diluted with water to a specified concentration during use.
  • the wettable powder can be prepared by mixing and pulverizing the compound of the present invention, a solid carrier, a surfactant, and the like as an active ingredient, and diluting with water at the time of use.
  • the processing method of the preparation is by no means limited to the above. A person skilled in the art can select an appropriate method depending on the active ingredient, the purpose of use, and the like.
  • the insecticide of the present invention may contain other insecticides, acaricides, fungicides, insect growth regulators, plant growth, in addition to the compounds represented by the general formulae (I) and (II) as active ingredients. Any suitable active ingredient such as a regulator and a soil amendment.
  • the insecticide of the present invention conventional application methods such as stem and leaf spray, surface application, soil treatment, and seed treatment can be selected.
  • stem and leaf spray surface application
  • soil treatment soil treatment
  • seed treatment seed treatment
  • the compound represented by the general formulae (I) and (II) as an active ingredient may be used in an aqueous emulsion, microemulsion or emulsifiable concentrate having a concentration ranging from 1 to 1000 ppm, preferably at a concentration of 1 to 500ppm.
  • novel o-formylaminobenzamide compound disclosed by the invention has excellent control effect on harmful insects, and therefore the compound can be used for preparing insecticides in the fields of agriculture, horticulture and the like, and has the advantages of high efficiency, low toxicity and environmental friendliness.
  • the compound 2-8 was used as a raw material, and the synthesis procedure was carried out in the same manner as in Example 2 to obtain 5.69 g of a pale yellow solid, yield 96.8%.
  • Test Example 1 Insecticidal effect on Plutella xylostella
  • the 3rd instar larvae were selected and the insecticidal effect test was carried out by using the leaf-fed feeding method.
  • the compounds of the examples of the present invention were each made into an insecticide.
  • the obtained insecticide emulsifiable concentrate is diluted with purified water and uniformly mixed to obtain a liquid medicine of a desired concentration.
  • Select amaranth, wash and dry, use a puncher to make a leaf dish, dip in the liquid for 10 seconds, and then dry it naturally and put it into the dish.
  • Ten dishes of the third instar larvae of Plutella xylostella were introduced into each dish and repeated three times. The number of dead insects on the 1st, 2nd and 3d days was investigated, the mortality was counted, and the insecticidal effect was evaluated.

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Abstract

本发明公开了一种邻甲酰氨基苯甲酰胺类化合物及其应用，该化合物为由通式(I)或(II)代表的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，本发明的新型邻甲酰氨基苯甲酰胺类化合物对有害昆虫具有优良的防治效果，其可用制备农业、园艺等领域的杀虫剂，具有高效、低毒、环境友好的优点。

Description

邻甲酰氨基苯甲酰胺类化合物及其应用 技术领域
本发明属于农药领域，涉及邻甲酰氨基苯甲酰胺类化合物、含有任意所述化合物作为活性成分的杀虫剂和它们的用途。
背景技术
植物病害虫对杀虫剂产生抗性的问题，常常是一个困扰人们的潜在问题，这也是为什么农药科研工作者一直寻求开发具有特殊作用机制的杀虫剂的最重要的原因之一。多年来农药科研工作者都在为发现特殊作用机制的杀虫剂而努力。其中由杜邦公司研发的邻甲酰氨基苯甲酰胺类化合物就是一类新型的以鱼尼丁受体为作用靶标的化合物，代表化合物氯虫酰胺(chlorantraniliprole，RynaxypyrTM)表现出了综合优异的杀虫活性和田间效果、对哺乳动物毒性低及环境相容性良好等评价结果。以该化合物为主要活性成分的商品化品种Coragen(中文名：康宽)已于2008年上市，2010年含该有效成分的杀虫剂产品销售额将超过1亿美元。
通过对大量已报道邻甲酰氨基苯甲酰胺类结构的总结，该类物质的通式可表示如下：(式1-1)即(A)桥基部分、(B)酰胺部分和(C)酰胺部分。其中对(C)酰胺部分修饰的工作较多。
Figure PCTCN2015075824-appb-000001
式1-1邻甲酰氨基苯甲酰胺类化合物的结构通式
专利US 2004192731、WO 2007043677和WO 2007024833中分别公开了如下通式(A)、(B)和(C)具有杀虫活性的化合物：
Figure PCTCN2015075824-appb-000002
专利WO 2007043677公开了双酰肼结构的化合物见下图中的结构1；WO 2007006670和WO 2013024008(巴斯夫公司)公开了以N＝S双键结构的化合物(结 构2-1、2-2、2-3)；CN 101570535公开了不同取代基的双酰肼结构的化合物；CN 101298435公开了酰肼取代基的化合物(结构3)；CN 101337959公开了N-含氧取代的酰胺类化合物(结构4)；
Figure PCTCN2015075824-appb-000003
专利CN 101298435还公开了以下两个通式化合物，但没有报道杀虫活性。
Figure PCTCN2015075824-appb-000004
发明内容
本发明的目的是提供针对各种害虫具有优良防治效果，并具有高效、安全、环境相容性好等特点的一类邻甲酰氨基苯甲酰胺类化合物，以满足作物保护对高效安全杀虫剂的需求。为设计并合成具有高效杀虫活性的新化合物，我们将取代哌啶环和哌嗪环引入到(C)酰胺部分，对先导物进行结构修饰，设计并合成了一系列未见任何文献报道的具有通式结构的新化合物。虽然以上专利(申请)中所有公开的化合物虽与本发明化合物有相似之处，但结构仍存在显著不同。
本发明还有一个目的是提供上述化合物在制备杀虫剂方面的用途。
本发明的目的可以通过以下措施达到：
一类由通式(I)或(II)代表的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，
Figure PCTCN2015075824-appb-000005
其中，
R1代表卤素或-CN；
R2代表-H·HCl或可被取代的下述基团：C1-C8烷基、C3-C6烷烯基、C3-C6炔基、(C1-C8烷基)酰基、(C1-C8烷氧基)酰基、(C1-C8烷胺基)酰基、酰胺基、吗啉酰基或(C1-C8烷基)磺酰基；
X代表C-H或N；
R3代表-NH2·HCl或可被取代的下述基团：C1-C8烷基、C3-C6烷烯基、C3-C6炔基、(C1-C8烷基)酰胺基、(C1-C8烷氧基)酰胺基、(C1-C8烷胺基)酰胺基、(C1-C8烷胺基)酰烷基、(C1-C8烷基)磺酰胺基、脲基或吗啉酰胺基；
R4代表卤素或-CN；
R2或R3中的取代基选自卤素、C1-C4烷基、C1-C4烷氧基或硝基。
在一种技术方案中，R1代表Cl或-CN。
在一种技术方案中，R4代表Cl或-CN。
在一种技术方案中，R2代表-H·HCl或可被取代的下述基团：(C1-C8烷基)酰基、(C1-C8烷氧基)酰基、(C1-C8烷胺基)酰基、吗啉酰基或(C1-C8烷基)磺酰基；其取代基选自卤素、C1-C4烷基或C1-C4烷氧基。
在一种技术方案中，R3代表-NH2·HCl或可被取代的下述基团：(C1-C8烷基)酰胺基、(C1-C8烷氧基)酰胺基、(C1-C8烷胺基)酰胺基、(C1-C8烷胺基)酰基亚甲基、脲基、(C1-C8烷基)磺酰胺基或吗啉酰胺基；其取代基选自卤素、C1-C4烷基或C1-C4烷氧基。
在一种优选方案中，R2代表-H·HCl或可被取代的下述基团：(C1-C4烷基)酰基、(C1-C4烷氧基)酰基、(C1-C4烷胺基)酰基、吗啉酰基或(C1-C4烷基)磺酰基；其取代基选自卤素、C1-C4烷基或C1-C4烷氧基。
在一种优选方案中，R2代表-H·HCl、叔丁氧酰基、甲磺酰基、吗啉酰基、N-甲基胺酰基、N,N-二甲基胺酰基、乙酰基或甲氧酰基。
在一种优选方案中，R2代表(C1-C4烷氧基)酰基或(C1-C4烷胺基)酰基；其取代基选自卤素、C1-C4烷基或C1-C4烷氧基。
在一种优选方案中，R3代表-NH2·HCl或可被取代的下述基团：(C1-C4烷基)酰胺基、(C1-C4烷氧基)酰胺基、(C1-C8烷胺基)酰胺基、(C1-C8烷胺基)酰基亚甲基、脲基、(C1-C8烷基)磺酰胺基或吗啉酰胺基；其取代基选自卤素、C1-C4烷基或C1-C4烷氧基。
在一种优选方案中，R3代表-NH2·HCl、3-甲基脲基、乙酰胺基、3,3-二甲基脲基、甲磺酰胺基、甲氧酰胺基、N-乙基胺酰基亚乙基或叔丁氧酰胺基。
下表1列出了部分通式(I)和(II)化合物的结构和物理性质。
表1部分通式(I)和(II)化合物的结构和物理性质
Figure PCTCN2015075824-appb-000006
Figure PCTCN2015075824-appb-000007
部分化合物的1HNMR(DMSO-d6，300MHz)数据如下表2所示。
表2部分化合物的1HNMR数据
Figure PCTCN2015075824-appb-000008
Figure PCTCN2015075824-appb-000009
Figure PCTCN2015075824-appb-000010
本发明的典型制备方法如下，但是它决不在于以任何方式限制本发明的范围。
通式化合物(I)可以通过反应式1-1和1-2制备，通式化合物(II)的可以通过反应式2-1和2-2制备，其中取代基除特别指明外均如前所限定。
通式化合物(I)的制备：
反应式1-1：
Figure PCTCN2015075824-appb-000011
R2代表可被取代的C1-C3烷基、可被取代的C3-C6烷烯基、可被取代的C3-C6炔基、可被取代的烷氧酰基。
(III)与(IV)在适宜的溶剂中、温度为-20℃至沸点下反应0.5-48h得到目标化合物(I)。
适宜的溶剂选自卤代烷烃、丙酮、苯、甲苯、乙酸乙酯、乙腈、丙腈、四氢呋喃、二氧六环、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、或二甲亚砜等。原料(III)的合成采用已知方法，例如CN1541063A所述的方法。
当R2代表可被取代的(C1-C8)烷酰基、可被取代的氨酰基、可被取代的吗啉酰基、(C1-C8)烷基磺酰基时，采用反应式1-2制备：
反应式1-2：
Figure PCTCN2015075824-appb-000012
(I-1)与酸在无溶剂或合适的溶剂中、温度为-20℃至沸点下反应0.5-48h得到目标化合物(I-2)。酸选自无机酸如盐酸、浓硫酸等；有机酸如三氟乙酸、对甲基苯磺酸等。合适的溶剂选自卤代烷烃、丙酮、苯、甲苯、乙腈、四氢呋喃、二氧六环等。原料(I-1)合成路线见反应式1-1。
在碱性条件下、极性非质子溶剂中，在适当温度下，化合物(I-2)与酰化剂(V)反应得到通式化合物(I)。其中：所述的碱为碱金属氢氧化物、碱金属碳酸盐、碱金属碳酸氢盐或有机碱；所述的极性或非极性非质子溶剂为卤代烷烃、苯、甲苯、酰胺类、腈类溶剂。所述的碱金属氢氧化物是氢氧化钠或氢氧化钾，所述的碱金属碳酸盐是碳酸钠或碳酸钾，所述的碱金属碳酸氢盐是碳酸氢钠或碳酸氢钾，所述的有机碱是吡啶、三乙胺、4-二甲氨基吡啶或N-甲基吗啉；所述的酰胺类溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲亚砜或N-甲基吡咯烷酮；所述的腈类溶剂是乙腈或丙腈。其中酰化剂(V)为R2-O-、R2-Cl或R2-Br。上述合适的温度为-10-30℃，优选为-5-0℃。
通式化合物(II)的制备：
反应式2-1：
Figure PCTCN2015075824-appb-000013
R3代表可被取代的C1-C3烷基、可被取代的C3-C6烷烯基、可被取代的C3-C6炔基、可被取代的(C1-C8)烷基、可被取代的烷氧酰胺基。
(III)与(VI)的反应条件参照反应式1-1的反应条件。
当R3代表H原子、可被取代的烷基酰胺基、(C1-C8)烷基磺酰基酰胺基、可被取代的氨基酰胺基、可被取代的吗啉酰基时，采用反应式2-2制备：
反应式2-2：
Figure PCTCN2015075824-appb-000014
(II-3)的合成条件参照反应式1-2的反应条件。原料(II-1)合成路线见反应式2-1。
除非另外说明，在说明书和权利要求中使用的以下术语具有下面讨论的含义：
“烷基”表示1-20个碳原子的饱和的脂烃基，包括直链和支链基团(本申请书中提到的数字范围，例如“1-20”，是指该基团，此时为烷基，可以含1个碳原子、2个碳原子、3个碳原子等，直至包括20个碳原子)。含1－4个碳原子的烷基称为低级烷基。当低级烷基没有取代基时，称其为未取代的低级烷基。更优选的是，烷基是有1-8个碳原子的中等大小的烷基，例如甲基、乙基、丙基、2-丙基、正丁基、异丁基、叔丁基、戊基等。最好是，烷基为有1-4个碳原子的低级烷基，例如甲基、乙基、丙基、2-丙基、正丁基、异丁基或叔丁基等。
“烷烯基”表示2-20个碳原子的含有至少一个碳碳双键C＝C的不饱和的脂烃基，包括直链和支链基团(本申请书中提到的数字范围，例如“2-20”，是指该基团，此时可以含2个碳原子、3个碳原子等，直至包括20个碳原子)。含2－6个碳原子的烷烯基称为低级烷烯基。当低级烷烯基没有取代基时，称其为未取代的低级烷烯基。更优选的是，烷烯基是有3-6个碳原子的中等大小的烷基。
“炔基”表示2-20个碳原子的含有至少一个碳碳C≡C的不饱和的脂烃基，包括直链和支链基团(本申请书中提到的数字范围，例如“1-20”，是指该基团，此时可以含2个碳原子、3个碳原子等，直至包括20个碳原子)。含2－6个碳原子的炔基称为低级炔基。当低级炔基没有取代基时，称其为未取代的低级炔基。更优选的是，炔基是有3-6个碳原子的中等大小的炔基。
“酰基”表示-(C＝O)-基团或-(C＝O)H基团。
“(C1-C8烷基)酰基”表示具有取代基C1-C8烷基的酰基，其中“C1-C8”表示烷基取代基中的碳原子数为1个至8个，例如乙酰基、正丙酰基、异丙酰基、正丁酰基等。
“(C1-C8烷氧基)酰基”表示具有取代基C1-C8烷氧基的酰基，例如甲氧基酰基、乙氧基酰基、正丙氧基酰基、异丙氧基酰基、正丁氧基酰基、叔丁氧基酰基等。
“烷氧基”表示“烷基-O-”基团，其中烷基的定义如上所述。
“烷胺基”表示具有一个或两个烷基取代基的胺基基团，如“烷基-NH-”或“(烷基)2N-”基团，其中烷基的定义如上所述。
“(C1-C8烷胺基)酰基、”表示具有C1-C8烷胺基取代基的酰基。
“酰胺基”表示“H(C＝O)-NH-”基团。
“吗啉酰基”表示
Figure PCTCN2015075824-appb-000015
基团。
“磺酰基”表示“-S(＝O)2-”基团。
“(C1-C8烷基)磺酰基”表示“具有C1-C8烷基取代基的磺酰基”基团。
“酰烷基”表示“-(C＝O)-烷基-”或“H(C＝O)-烷基-”基团。其中烷基的定义如上所述，在该基团中的烷基优选低级烷基，特别是亚甲基或亚乙基。
“磺酰胺基”表示具有一个或两个磺酰基取代基的胺基基团，如。
“(C1-C8烷基)磺酰胺基”表示磺酰基上具有C1-C8烷基取代基的磺酰胺基基团。
“脲基”表示“-NH-C(＝O)-NH2”或“-NH-C(＝O)-NH-”基团。本申请中的脲基优选是具有取代基的脲基，其取代基可以为烷基或低级烷基。
“吗啉酰胺基”表示”
Figure PCTCN2015075824-appb-000016
”基团或”
Figure PCTCN2015075824-appb-000017
”基团。
“卤素”表示氟、氯、溴或碘基团。
含有本发明由通式(I)和(II)代表的邻甲酰氨基苯甲酰胺衍生物或其药学上可接受的盐可以制备杀虫剂，特别是作为活性成分的农艺杀虫剂用于控制各种有害昆虫，例如农艺有害昆虫、储存谷物有害昆虫、卫生有害昆虫、线虫等，这些对稻谷、果树、蔬菜、其他作物、花卉和观赏植物等是有害的，它们具有显 著的杀虫效果，例如对鳞翅目害虫，包括棉铃虫、甜菜夜蛾、小菜蛾、菜青虫、稻纵卷叶螟和二化螟等，同翅目害虫如叶蝉、飞虱、蚜虫、粉虱等，双翅目害虫如家蝇、潜叶蝇、蚊类等，直翅目和鞘翅目等害虫等。因而本发明的化合物可用作保护农业、园艺等植物的杀虫剂。当然，本发明的化合物可防治的有害生物不限于上述举例的范围。本发明的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐为活性组分，以及农业上可接受的载体可制成杀虫组合物，组合物中活性组分的重量百分含量为0.1-99.5％。
一般按照普通的农用化学品制备方法将本发明的农艺杀剂制成常用的剂型。
也就是说，将(I)和(II)代表的邻甲酰氨基苯甲酰胺衍生物或其盐和可选的助剂按适当比例与适合的惰性载体掺合，通过溶解、分散、悬浮、混合、浸渍、吸附或附着作用，制成适合的剂型，例如悬液、乳油、可溶性浓缩物、可湿性粉剂、颗粒剂、粉剂、片剂、药包等。
可用于本发明的惰性载体既可以是固体也可以是液体。作为可用作固体载体的原料，可供例证的是大豆粉、谷物粉、木粉、树皮粉、锯屑、烟草茎粉、胡桃壳粉、糠、纤维素粉、蔬菜提取残余物、合成聚合物或树脂粉、粘土(例如高岭土、膨润土和酸性粘土)、滑石(例如滑石和叶蜡石)、二氧化硅粉或薄片(例如硅藻土、硅沙、云母和白炭(合成的高分散性硅酸，也称微细粉碎的水合二氧化硅或水合硅酸，有些商业上可得到的产品含有硅酸钙作为主要组分)、活性炭、硫磺粉、浮石、煅烧硅藻土、磨碎的砖、飞灰、沙子、碳酸钙、磷酸钙和其他无机或矿物粉末、塑料载体(如聚乙烯、聚丙烯和聚偏氯乙烯)、化学肥料(例如硫酸铵、磷酸铵、硝酸铵、尿素、氯化铵)和堆肥。这些载体可以单独使用，或者作为混合物使用。
可用作液体载体的材料选自这样的材料，它们本身具有溶解性，或者虽然没有溶解性但是能够借助助剂分散活性成分化合物。常用的液体载体，如水；有机溶剂如甲苯、二甲苯、环己烷、甲醇、丁醇、乙二醇、丙酮、二甲基甲酰胺、乙醚、二甲亚砜、动物和植物油及脂肪酸；常用的表面活性剂如乳化剂和分散剂，包括阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂和两性表面活性剂；其它助剂，如湿润剂、增稠剂等。
由通式(I)和(II)表示的本发明的化合物或其盐用作杀虫剂中的活性成 分时，在所述杀虫剂中的含量可在0.1％至99.5％的范围内进行选择，并可根据制剂形式和施用方法确定适当的活性成分含量。通常，在水乳剂中含有5％至50％(重量百分比，下同)所述的活性成分，优选其含量为10％至40％；在微乳剂中含有5％至50％的活性成分，优选其含量为10％至30％；在乳油中含有1％至90％的活性成分，优选其含量为10％至80％。
例如，对于所述水乳剂、微乳剂，可将作为活性成分的本发明化合物与溶剂和表面活性剂等助剂进行均匀混合而制成，使用时可用水稀释到指定浓度。对于所述可湿性粉剂，可将作为活性成分的本发明化合物、固体载体和表面活性剂等混合并进行粉碎而制成，使用时用水进行稀释。当然，制剂的加工方法绝不限于上述内容。本领域的技术人员可根据所述活性成分和使用目的等，选择合适的方法。
除了作为活性成分的由通式(I)和(II)表示的所述化合物之外，本发明的杀虫剂可包含其它杀虫剂、杀螨剂、杀菌剂、昆虫生长调节剂、植物生长调节剂和土壤改良剂等任何适用的活性成分。
对于本发明的杀虫剂的使用，可选择常用的施药方法，如茎叶喷雾、水面施用、土壤处理和种子处理等。例如，当采用茎叶喷雾时，作为活性成分的由通式(I)和(II)表示的化合物的可使用浓度范围为1至1000ppm的水乳剂、微乳剂或乳油，优选其浓度为1至500ppm。
本发明公开的新型邻甲酰氨基苯甲酰胺类化合物对有害昆虫具有优良的防治效果，因此该化合物可用制备农业、园艺等领域的杀虫剂，具有高效、低毒、环境友好的优点。
具体实施方式
为了便于对本发明的进一步了解，下面提供的实施例对其做了更详细的说明，但它们不应被视为是对本发明范围的限制。
实施例1：
化合物1-1：4-(2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺基)-5-氯-3-甲基苯甲酰胺基)哌啶-1-甲酸叔丁酯的合成
将4.50g(10mmol)的2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基)-6-氯-8-甲基-4H-3，1-苯并恶嗪-4-酮(通式III，R1＝Cl)溶于30ml的N,N-二甲 基甲酰胺，室温下，30min内将2.00g(10mmol)4-氨基哌啶-1-甲酸叔丁酯的20ml N,N-二甲基甲酰胺溶液滴入上述溶液中，滴毕后继续搅拌反应30min。将反应液倾入60ml水中，过滤，干燥得白色固体6.30g，收率：96.6％。
实施例2：
化合物1-8：3-溴-N-(4-氯-2-甲基-6-(哌啶-4-甲酰胺基)苯基)-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺盐酸盐的合成
将3.00g(4.6mmol)的4-(2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺基)-5-氯-3-甲基苯甲酰胺基)哌啶-1-甲酸叔丁酯(化合物1-1)与20ml二氯甲烷混合后，冷却至0℃，5min内将10ml三氟乙酸滴入上述混合液中，滴毕后，自然升至室温反应2h后，加入10ml浓盐酸后，脱溶，得到2.58g淡黄色粉末状固体，收率95.2％。
实施例3：
化合物1-2：3-溴-N-(4-氯-2-甲基-6-((1-甲磺酰基)哌啶-4-甲酰胺基)苯基)-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺的合成
将1.00g(1.7mmol)的3-溴-N-(4-氯-2-甲基-6-(哌啶-4-甲酰胺基)苯基)-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺盐酸盐(化合物1-8)溶于10ml干燥的N,N-二甲基甲酰胺中，加入0.35g(3.4mmol)的三乙胺，冷却至-5℃，10min内将0.19g(1.7mmol)甲磺酰氯的10ml，N-二甲基甲酰胺溶液滴入上述溶液中，滴毕，自然升温至室温后继续搅拌反应2h后，将反应液倾入40ml水中，过滤，干燥得白色固体0.99g，收率92.5％。
实施例4：
化合物1-4：4-(2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺基)-5-氯-3-甲基苯甲酰胺基)哌啶-1-N,N-二甲基甲酰胺的合成
将1.50g(2.6mmol)的3-溴-N-(4-氯-2-甲基-6-(哌啶-4-甲酰胺基)苯基)-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺盐酸盐(化合物1-8)加入15ml干燥的乙腈中，加入0.79g(7.8mmol)的三乙胺，冷却至-5℃，10min内将0.34g(3.1mmol)N,N-二甲基氨基甲酰氯的15ml乙腈溶液滴入上述溶液中，滴毕，再在-5℃继续搅拌反应4h后，将反应液倾入80ml水中，过滤，干燥得白色固体1.44g，收率89.0％。
按本例的方法采用不同的原料分别制备化合物1-5和1-6。
实施例5：
化合物1-9：4-(2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺基)-5-氰基-3-甲基苯甲酰胺基)哌啶-1-甲酸叔丁酯的合成
将2.10g(5mmol)的2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基)-6-氰基-8-甲基-4H-3，1-苯并恶嗪-4-酮(通式III，R1＝CN)溶于20ml的四氢呋喃中，室温下，10min内将1.50g(7.5mmol)4-氨基哌啶-1-甲酸叔丁酯的15ml四氢呋喃溶液滴入上述溶液中，滴毕后，升温至回流继续搅拌反应2h。将反应液倾入40ml水中，过滤，干燥得白色固体3.09g，收率：96.1％。
按本例的方法采用不同的原料分别制备化合物1-3和1-7。
实施例6：
化合物1-10：3-溴-N-(4-氰基-2-甲基-6-(哌啶-4-甲酰胺基)苯基)-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺盐酸盐的合成
合成过程参照实施例2，得淡黄色固体2.64g，收率99.1％。
实施例7：
化合物1-11：4-(2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺基)-5-氰基-3-甲基苯甲酰胺基)哌啶-1-N,N-二甲基甲酰胺的合成
将1.27g(2.2mmol)的3-溴-N-(4-氰基-2-甲基-6-(哌啶-4-甲酰胺基)苯基)-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺盐酸盐(化合物1-10)加入15ml干燥的丙酮中，加入0.61g(6mmol)的三乙胺，室温下5min内将0.42g(2.0mmol)N,N-二甲基氨基甲酰氯的15ml丙酮溶液滴入上述溶液中，滴毕，再在室温下继续搅拌反应2h后，将反应液倾入50ml水中，过滤，干燥得白色固体1.44g，收率89.0％。
实施例8：
化合物2-8：1-(2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺基)-5-氯-3-甲基苯甲酰胺基)哌啶-4-氨基甲酸叔丁酯
将4.50g(10mmol)的2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基)-6-氯-8-甲基-4H-3，1-苯并恶嗪-4-酮(通式III，R1＝Cl)加入30ml的二氯甲烷中，室温下，30min内将2.00g(10mmol)哌啶-4-氨基甲酸叔丁酯的20ml二 氯甲烷溶液滴入上述溶液中，滴毕后，升温至回流，继续搅拌反应2h。将反应液倾入60ml水中，过滤，干燥得白色固体6.04g，收率：92.6％。
实施例9：
化合物2-1：N-(2-(4-氨基哌啶-1-羰基)-4-氯-6-甲基苯基)-3-溴-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺盐酸盐
以化合物2-8为原料，合成过程参照实施例2，得淡黄色固体5.69g，收率96.8％。
实施例10：
化合物2-6：N-(2-(4-甲酰胺基哌啶-1-羰基)-4-氯-6-甲基苯基)-3-溴-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺
将1.30g(2.2mmol)的N-(2-(4-氨基哌啶-1-羰基)-4-氯-6-甲基苯基)-3-溴-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺盐酸盐(化合物2-1)加入15ml干燥的三氯甲烷中，加入0.61g(6mmol)的三乙胺，0℃下5min内将0.22g(2.0mmol)乙酸酐的15ml三氯甲烷溶液滴入上述混合液中，滴毕，再在室温下继续搅拌反应4h后，将反应液倾入50ml水中，过滤，干燥得白色固体1.28g，收率98.0％。
按本例的方法采用不同的原料分别制备化合物2-2、2-3、2-4和2-5。
实施例11：
化合物2-7：3-溴-N-(4-氯-2-(1-(2-(乙胺基)-2-氧代乙基)哌嗪-4-羰基)-6-甲基苯基)-1-(3-氯-2-吡啶基)-1H-5-吡唑甲酰胺
将4.50g(10mmol)的2-(3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-基)-6-氯-8-甲基-4H-3，1-苯并恶嗪-4-酮(通式III，R1＝Cl)加入30ml的N,N-二甲基乙酰胺中，室温下，30min内将1.71g(10mmol)2-(1-哌嗪基)-N-乙基乙酰胺的20ml N,N-二甲基乙酰胺溶液滴入上述溶液中，滴毕后，升温至回流，继续搅拌反应4h。将反应液倾入60ml水中，过滤，干燥得白色固体6.02g，收率：96.6％。
下面将叙述以本发明化合物为活性成分的制剂例，所述的制剂例可用作农业、园艺和花卉栽培领域的杀虫剂。但是，本发明的实施方式并不限于以下内容。
制剂实施例1:水乳剂
本发明化合物20份、甲苯12份、环氧乙烷-环氧丙烷嵌段共聚物6份、黄原胶6份，乙二醇/丙二醇复合防冻剂8.5份，有机硅0.8份，水46.7份，一起均匀混合得到活性成分为20％的水乳剂。
制剂实施例2:微乳剂：
本发明化合物20份、三苯乙烯苯酚聚氧乙烯醚10份、烷基苯磺酸钙盐5份、丙酮5份，异丙醇10份，聚氧乙烯醚甲酰胺3份，水47份，一起均匀混合得到活性成分为20％的微乳剂。
制剂实施例3:乳油
将本发明化合物10份溶于由40份丙酮和35份二甲基甲酰胺组成的混合溶剂中，然后加入乳化剂15份，搅拌并均匀混合得到活性成分为10％的乳油。
下面将叙述以本发明化合物为活性成分的杀虫剂的试验例。但是，本发明的实施方式并不限于以下内容。
试验例1:对小菜蛾的杀虫效果
选择3龄幼虫，采用浸叶饲喂法进行杀虫效果测试。根据制剂实施例3的组成方式，将本发明实施例的化合物分别制成杀虫剂。用纯净水将所得到的杀虫剂乳油进行稀释，均匀混合得到所需浓度的药液。选取苞菜，清洗并晾干，用打孔器做成叶碟，在药液中浸10秒钟取出，待自然晾干后装入培养皿内。每皿接入小菜蛾3龄幼虫10头，重复3次，调查第1d、2d和3d的死亡虫数，统计死亡率，评价其杀虫效果。
校正的死亡率(％)＝害虫死亡数÷害虫总数×100％
判断标准：
A---死亡率100％
B---死亡率99-90％
C---死亡率89-80％
D---死亡率79-50％
E---死亡率49-0％
部分测试结果如下：
药液浓度为100ppm时，实施例的各个化合物对小菜蛾的杀虫活性达到C级及以上；药液浓度达到50ppm和10ppm时，测试结果见下表3。
表3 50ppm和10ppm下部分对小菜蛾的杀虫活性测试结果
Figure PCTCN2015075824-appb-000018

Claims (10)

  1. 由通式(I)或(II)代表的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，
    Figure PCTCN2015075824-appb-100001
    其中，
    R1代表卤素或-CN；
    R2代表-H·HCl或可被取代的下述基团：C1-C8烷基、C3-C6烷烯基、C3-C6炔基、(C1-C8烷基)酰基、(C1-C8烷氧基)酰基、(C1-C8烷胺基)酰基、酰胺基、吗啉酰基或(C1-C8烷基)磺酰基；
    X代表C-H或N；
    R3代表-NH2·HCl或可被取代的下述基团：C1-C8烷基、C3-C6烷烯基、C3-C6炔基、(C1-C8烷基)酰胺基、(C1-C8烷氧基)酰胺基、(C1-C8烷胺基)酰胺基、(C1-C8烷胺基)酰烷基、(C1-C8烷基)磺酰胺基、脲基或吗啉酰胺基；
    R4代表卤素或-CN；
    R2或R3中的取代基选自卤素、C1-C4烷基、C1-C4烷氧基或硝基。
  2. 根据权利要求1所述的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，其中R1代表Cl或-CN；R4代表Cl或-CN。
  3. 根据权利要求1所述的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，其中R2代表-H·HCl或可被取代的下述基团：(C1-C8烷基)酰基、(C1-C8烷氧基)酰基、(C1-C8烷胺基)酰基、吗啉酰基或(C1-C8烷基)磺酰基；R3代表-NH2·HCl或可被取代的下述基团：(C1-C8烷基)酰胺基、(C1-C8烷氧基)酰胺基、(C1-C8烷胺基)酰胺基、(C1-C8烷胺基)酰基亚甲基、脲基、(C1-C8烷基)磺酰胺基或吗啉酰胺基；R2或R3中的取代基选自卤素、C1-C4烷基或C1-C4烷氧基。
  4. 根据权利要求3所述的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，其中R2代表-H·HCl或可被取代的下述基团：(C1-C4烷基)酰基、(C1-C4烷氧基)酰基、(C1-C4烷胺基)酰基、吗啉酰基或(C1-C4烷基)磺酰基；R3代表-NH2·HCl或可被取代的下述基团：(C1-C4烷基)酰胺基、(C1-C4烷氧基)酰胺基、(C1-C8烷胺基)酰胺基、(C1-C8烷胺基)酰基亚甲基、脲基、(C1-C8烷基)磺酰胺基或吗啉酰胺基；其取代基选自卤素、C1-C4烷基或C1-C4烷氧基。
  5. 根据权利要求4所述的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，其中R2代表-H·HCl、叔丁氧酰基、甲磺酰基、吗啉酰基、N-甲基胺酰基、N,N-二甲基胺酰基、乙酰基或甲氧酰基。
  6. 根据权利要求4所述的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，其中R3代表-NH2·HCl、3-甲基脲基、乙酰胺基、3,3-二甲基脲基、甲磺酰胺基、甲氧酰胺基、N-乙基胺酰基亚乙基或叔丁氧酰胺基。
  7. 根据权利要求4所述的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，其中R2代表(C1-C4烷氧基)酰基或(C1-C4烷胺基)酰基；其取代基选自卤素、C1-C4烷基或C1-C4烷氧基。
  8. 根据权利要求1～7中任一项所述的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐，其中化合物选自：
    Figure PCTCN2015075824-appb-100002
    Figure PCTCN2015075824-appb-100003
  9. 权利要求1～7中任一项所述的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐在制备杀虫剂方面的用途。
  10. 一种杀虫组合物，其含有权利要求1～7中任一项所述的邻甲氨基苯甲酰胺衍生物或其药学上可接受的盐为活性组分，以及农业上可接受的载体，组合物中活性组分的重量百分含量为0.1-99.5％。
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