WO2021031984A1 - 一种羧酸肟酯类化合物及用途 - Google Patents

一种羧酸肟酯类化合物及用途 Download PDF

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WO2021031984A1
WO2021031984A1 PCT/CN2020/109035 CN2020109035W WO2021031984A1 WO 2021031984 A1 WO2021031984 A1 WO 2021031984A1 CN 2020109035 W CN2020109035 W CN 2020109035W WO 2021031984 A1 WO2021031984 A1 WO 2021031984A1
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alkyl
cycloalkyl
alkoxy
general formula
halogenated
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PCT/CN2020/109035
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English (en)
French (fr)
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王刚
杨辉斌
马宏娟
王徵
商璐
连伟祥
郝泽生
英君伍
秦博
金守征
关云飞
李斌
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沈阳中化农药化工研发有限公司
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Priority claimed from CN201910756573.XA external-priority patent/CN112390725B/zh
Priority claimed from CN201910756575.9A external-priority patent/CN112390727B/zh
Application filed by 沈阳中化农药化工研发有限公司 filed Critical 沈阳中化农药化工研发有限公司
Publication of WO2021031984A1 publication Critical patent/WO2021031984A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/75—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/68—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with at least one of the esterifying carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

Definitions

  • the invention relates to a herbicidal compound, specifically a carboxylic oxime ester compound and its application.
  • One of the objectives of the present invention is to provide a carboxylic oxime ester compound with novel structure and safety to crops and its application as a herbicide.
  • R 1 is selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkyl, C 3- C 6 halogenated cycloalkyl, C 1 -C 6 alkoxy C 1 -C 6 alkyl, C 1 -C 6 halogenated alkoxy C 1 -C 6 alkyl, C 1- C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 6 cycloalkoxy, C 3 -C 6 halocycloalkoxy, C 3 -C 6 cycloalkyl
  • R 2 is selected from H or C 1 -C 12 alkyl
  • R 3 is selected from C 3 -C 12 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkyl, C 3- C 6 halogenated cycloalkyl or C 3 -C 6 cycloalkyl C 3 -C 6 cycloalkyl;
  • R 4 is selected from halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkane Group, C 1 -C 6 cycloalkyl C 1 -C 6 alkyl, C 1 -C 6 alkoxy C 1 -C 6 alkyl, C 1 -C 6 haloalkoxy C 1- C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 halogenated alkoxy, C 3 -C 6 cycloalkoxy, C 3 -C 6 halogenated cycloalkoxy or C 3 -C 6 cycloalkyl C 1 -C 6 alkoxy group.
  • R 1 is selected from a benzene ring, a 5- or 6-membered heterocyclic ring with 1-3 heteroatoms, a 5- or 6-membered heterocyclic ring with benzoic 1-3 heteroatoms, and the hydrogen on the benzene ring or heterocyclic ring may be Substituted by one or more R 4 that are the same or different;
  • R 2 is selected from H or C 1 -C 6 alkyl
  • R 3 is selected from C 3 -C 8 alkyl groups
  • R 4 is selected from halogen, nitro, cyano, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl.
  • R 1 is selected from benzene, furan, thiophene, pyrrole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, benzoxazole, benzothiazole, quinoxaline, quinazoline ,
  • the hydrogen on the ring may be substituted by one or more R 4 which are the same or different;
  • R 2 is selected from H or C 1 -C 3 alkyl
  • R 3 is selected from C 3 -C 6 alkyl groups
  • R 4 is selected from fluorine, chlorine, bromine, iodine, nitro, cyano, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl.
  • R 1 is selected from benzene, furan, thiophene, pyrrole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, benzoxazole, benzothiazole, quinoxaline, quinazoline ,
  • the hydrogen on the ring may be substituted by one or more R 4 which are the same or different;
  • R 2 is selected from H or methyl
  • R 3 is selected from C 3 -C 6 alkyl groups
  • R 4 is selected from fluorine, chlorine, bromine, nitro, cyano, methyl, difluoromethyl or trifluoromethyl.
  • reaction formula is as follows:
  • Suitable solvents are selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N,N-dimethylformamide or dimethylmethylene Sulfone etc.
  • the compounds of formula III are commercially available reagents or are prepared from their corresponding acids.
  • Table 1 lists the structure and physical properties of some compounds of general formula I.
  • the compound of general formula I of the present invention has herbicidal activity and can be used for the prevention and control of various weeds in agriculture.
  • the present invention also includes herbicidal compositions using compounds of general formula I as active ingredients.
  • the weight percentage of the active component in the herbicidal composition is 1-99%.
  • the herbicidal composition also includes an agriculturally acceptable carrier.
  • the herbicidal composition of the present invention with the compound of general formula I as the active ingredient can be applied in the form of various formulations.
  • the compound of the present invention is dissolved or dispersed in a carrier to prepare a formulation so as to be more easily dispersed when used as a herbicide.
  • these chemical agents can be made into wettable powders or emulsifiable concentrates. Therefore, in these compositions, at least one liquid or solid carrier is added, and it is usually necessary to add a suitable surfactant.
  • the present invention also provides a method for controlling weeds, which comprises applying a herbicidal effective amount of the herbicidal composition of the present invention with the compound of general formula I as an active ingredient to the weeds or the place where the weeds grow or On the surface of its growth medium.
  • a herbicidal effective amount of the herbicidal composition of the present invention with the compound of general formula I as an active ingredient to the weeds or the place where the weeds grow or On the surface of its growth medium.
  • the more suitable effective dose is 1 g to 1000 g per hectare, and the preferred effective dose is 10 g to 500 g per hectare.
  • one or more other herbicides can be added to the herbicidal composition of the present invention, which can produce additional advantages and effects.
  • the compound of general formula I of the present invention can be used alone or mixed with other known insecticides, fungicides, plant growth regulators or fertilizers.
  • the present invention also includes an application of the carboxylic oxime ester compound of the general formula I, and the application of the compound of the general formula I for preparing a bactericide shown in the general formula II:
  • R 5 is selected from a benzene ring, a 5- or 6-membered heterocyclic ring with 1-3 heteroatoms or a 5- or 6-membered heterocyclic ring with benzo and 1-3 heteroatoms, wherein the hydrogen on the benzene ring or the heterocyclic ring May be substituted by one or more same or different R 6 ;
  • R 6 is selected from halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkane Group, C 1 -C 6 cycloalkyl C 1 -C 6 alkyl, C 1 -C 6 alkoxy C 1 -C 6 alkyl, C 1 -C 6 haloalkoxy C 1- C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 halogenated alkoxy, C 3 -C 6 cycloalkoxy, C 3 -C 6 halogenated cycloalkoxy or C 3 -C 6 cycloalkyl C 1 -C 6 alkoxy;
  • the present invention also includes an oxime compound of general formula IV for preparing a carboxylic oxime ester compound of general formula I:
  • R 2 is selected from H or C 1 -C 12 alkyl
  • R 3 is selected from C 3 -C 12 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkyl, C 3- C 6 halogenated cycloalkyl or C 3 -C 6 cycloalkyl C 3 -C 6 cycloalkyl.
  • Table 2 lists the structure and physical properties of some compounds of general formula IV.
  • the present invention also includes an application of an oxime compound IV.
  • the compound of the general formula IV is used to prepare an oxime carboxylic acid compound represented by the general formula I.
  • the technical features of the present invention also include a method for preparing amide compound II.
  • the acid halide compound represented by general formula V and the oxime ester compound represented by general formula I undergo condensation reaction in a suitable solvent to obtain Amide compounds represented by formula II. Unless otherwise noted, each group in the reaction formula has the same definition as before.
  • the molar ratio of the acyl halide compound represented by general formula V to the carboxylic oxime ester compound represented by general formula I is 1:0.8-1.5, in a suitable solvent at a temperature of -10°C to a suitable solvent boiling point.
  • the condensation reaction takes 0.5-8 hours to prepare the amide compound represented by the general formula II.
  • the solvent is selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, N,N-dimethylformaldehyde Amide or dimethyl sulfoxide.
  • the molar ratio of the acyl halide compound represented by general formula V to the carboxylic oxime ester compound represented by general formula I is 1:0.8-1.5, in a suitable solvent, at a temperature of -10°C to a suitable solvent boiling point, and pressure Under the pressure of -0.1MPa to -0.01MPa, the condensation reaction is carried out for 0.5-8 hours to prepare the amide compound represented by the general formula II.
  • the molar ratio of the acyl halide compound represented by general formula V to the carboxylic oxime ester compound represented by general formula I is 1:0.8-1.5, in a suitable solvent, at a temperature of -10°C to a suitable solvent boiling point, and pressure Under the pressure of -0.1 MPa to -0.01 MPa, a suitable acid is added and the condensation reaction is carried out for 0.5-8 hours to prepare an amide compound represented by the general formula II.
  • the acid is selected from hydrochloric acid, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid.
  • the molar ratio of the acyl halide compound represented by formula V to the carboxylic oxime ester compound represented by formula I is 1:0.9-1.2, in the presence of no acid binding agent, in a suitable solvent, at a temperature of 20°C to Within the boiling point range and under the pressure of -0.05MPa ⁇ -0.01MPa, add a suitable acid and carry out a condensation reaction for 0.5-4 hours to prepare amide compounds; wherein the solvent is selected from toluene or acetonitrile; The acid is selected from hydrochloric acid, sulfuric acid or p-methanesulfonic acid, and the molar ratio of the acid to the carboxylic oxime ester compound (II) is 0.01-0.5:1.
  • Alkyl refers to linear or branched form, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, N-hexyl and other groups. Cycloalkyl means to include cyclic chain forms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • Alkoxy refers to a group with an oxygen atom attached to the end of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, and t-butoxy.
  • Heteroatoms refer to N, O, S, etc.
  • the heterocyclic group refers to a cyclic group containing a hetero atom, such as furan, thiophene, pyrrole, pyrazole, oxazole, pyridine, piperidine, morpholine, pyrrolidine, oxolane and the like.
  • the compound of general formula I of the present invention has a carboxylic oxime ester structure with a novel structure, and the carboxylic oxime ester compound of the present invention has unexpectedly high herbicidal activity, and also has high herbicidal activity at lower doses, and is not only highly effective, Moreover, the use of pesticides is reduced, costs are reduced, and environmental pollution is reduced.
  • the compound of the general formula I of the present invention can also be used as an intermediate for the preparation of amide fungicides II, further expanding its application range.
  • the present invention prepares amide compound II by carboxylic oxime ester compound of general formula I. Compared with the original reaction of acid chloride and amine, this method avoids the use of aniline, which is expensive and not easily available as raw materials. Obviously reduce the cost, and avoid the use of acid binding agent, reduce environmental pollution and increase the safety of the reaction.
  • the reaction liquid of the previous step was transferred to an autoclave, a palladium-carbon catalyst (5.6 g, 10%) was added, and hydrogen was introduced, and the reaction was carried out at 2 MPa and 30° C. for 8 hours.
  • the reaction liquid was taken out, the catalyst was filtered off, water (200 g) was added, the methanol was evaporated, and the pH was adjusted to 6 with concentrated hydrochloric acid. A large amount of solids precipitated, filtered with suction, and dried to obtain 51.7g of 2-methyl-1,3-cyclohexanedione. Yield: 80% (calculated based on 1,3-cyclohexanedione). A purity of 97.5%.
  • the R 1 substituent is a substituted pyrazole ring, substituted pyridine ring, and substituted pyrazine ring.
  • test solution After the original drug is dissolved in acetone, use 1 ⁇ Tween 80 to stand still with tap water to prepare the test solution of the required concentration.
  • spray treatment spray pressure 1.95kg/cm 2 , spray volume 500L/hm 2 , crawler speed 1.48km/h
  • the test is set to be repeated 3 times. After treatment, the test materials are placed in the operation hall. After the liquid is naturally dried, it is placed in the greenhouse for management according to conventional methods. Observe and record the response of weeds to the drugs. After treatment, regularly visually observe the control effect of the test drugs on weeds. It is represented by 0-100%, with "0" representing no prevention and "100%” representing complete killing.
  • test results show that the compound of general formula I generally has a high control effect on broad-leaved weeds.
  • the dosage of compound I-79 is 600g ai/hm 2 , it has a good control effect on zinnia and abutilon, and the control effect is 100%.
  • reaction solution was cooled to room temperature, and then water (100 mL) and NaOH (16.8 g, 33%) aqueous solution were added, and the mixture was stirred at this temperature for 30 minutes and then separated into layers.
  • the oil layer was desolvated, and the residue was recrystallized with methanol and water to obtain 3-(difluoromethyl)-1-methyl-N-(2-methyl-3-(2-pentyloxy)phenyl)-1H- Pyrazole-4-carboxamide 25.9g, yield: 73.8%.
  • reaction solution was cooled to room temperature, and then water (100 mL) and NaOH (16.8 g, 33%) aqueous solution were added, and the mixture was stirred at this temperature for 30 minutes and then separated into layers.
  • the oil layer was desolvated, and the residue was recrystallized with methanol and water to obtain 3-(difluoromethyl)-1-methyl-N-(2-methyl-3-(2-pentyloxy)phenyl)-1H- Pyrazole-4-carboxamide 18.4g, yield: 52.4%.
  • reaction solution was cooled to room temperature, and then water (100 mL) and NaOH (16.8 g, 33%) aqueous solution were added, and the mixture was stirred at this temperature for 30 minutes and then separated into layers. The oil layer was desolvated, and the residue was recrystallized with methanol and water to obtain 3-(difluoromethyl)-1-methyl-N-(2-methyl-3-(2-pentyloxy)phenyl)-1H- Pyrazole-4-carboxamide 16.9 g, yield: 48.1%.
  • reaction solution was cooled to room temperature, and then NaOH (8.8 g) aqueous solution (120 mL) was added, and the mixture was stirred at this temperature for 30 min and then separated into layers.
  • the water layer was back-extracted with toluene (50 mL) to synthesize the oil layer and desolvate to obtain an oily product.
  • the product was recrystallized with methanol water (85%) twice the weight of the oily product to obtain 3-(difluoromethyl)-1-methyl-N-(2-methyl-3-(2-pentyloxy) (Phenyl)-1H-pyrazole-4-carboxamide 20.7 g, yield 56%.
  • reaction solution was cooled to room temperature, and then 100 mL of water and NaOH (16.8 g, 33%) aqueous solution were added, and the mixture was stirred at this temperature for 30 minutes and then separated into layers. The oil layer was desolvated, and the residue was recrystallized with methanol and water to obtain 3-(difluoromethyl)-1-methyl-N-(2-methyl-3-(2-pentyloxy)phenyl)-1H- Pyrazole-4-carboxamide was 21.8 g, yield: 62.1%.
  • reaction solution was cooled to room temperature, and then water (100 mL) and NaOH (16.8 g, 33%) aqueous solution were added, and the mixture was stirred at this temperature for 30 minutes and then separated into layers.
  • the oil layer was desolvated, and the residue was recrystallized with methanol and water to obtain 3-(difluoromethyl)-1-methyl-N-(2-methyl-3-(2-pentyloxy)phenyl)-1H- Pyrazole-4-carboxamide 19.3g, yield: 55.0%.
  • reaction solution was cooled to room temperature, most of the acetonitrile was evaporated and dissolved in toluene, and then water (100 mL) and NaOH (16.8 g, 33%) aqueous solution were added, and the mixture was stirred at this temperature for 30 min and then separated. The oil layer was desolvated, and the residue was recrystallized with methanol and water to obtain 3-(difluoromethyl)-1-methyl-N-(2-methyl-3-(2-pentyloxy)phenyl)-1H- Pyrazole-4-carboxamide 25.3g, yield: 72.1%.
  • reaction solution was cooled to room temperature, and then water (100 mL) and NaOH (16.8 g, 33%) aqueous solution were added, and the mixture was stirred at this temperature for 30 minutes and then separated into layers.
  • the oil layer was desolvated, and the residue was recrystallized with methanol and water to obtain 1,3-dimethyl-5-chloro-N-(2-methyl-3-(2-pentyloxy)phenyl)-1H-pyrazole -4-formamide 18.2g, yield: 66.1%.
  • reaction solution was cooled to room temperature, and then water (100 mL) and NaOH (16.8 g, 33%) aqueous solution were added, and the mixture was stirred at this temperature for 30 minutes and then separated into layers.
  • the oil layer was desolvated, and the residue was recrystallized with methanol and water to obtain 1,3-dimethyl-5-chloro-N-(2-methyl-3-(2-hexyloxy)phenyl)-1H-pyrazole -4-formamide 18.6g, yield: 64.8%.
  • amide compounds represented by general formula II can be prepared.
  • Table 5 lists the structures of some compounds of general formula II.
  • the amide compound of formula II can be used as a bactericide.
  • Some compounds have been disclosed in the following patents: CN104649973A, CN105722828A, CN106187939A, CN106187893A, CN107108515A, CN108059613A, CN108069905A.

Abstract

一种羧酸肟酯类化合物及其作为除草剂、制备杀菌剂的应用，羧酸肟酯类化合物如通式I所示：

Description

一种羧酸肟酯类化合物及用途 技术领域
本发明涉及除草化合物，具体的说是一种羧酸肟酯类化合物及其应用。
背景技术
由于杂草种群的演替、变迁以及对化学农药抗药性的产生和迅速发展，人们对生态环境保护意识的不断加强，对化学农药污染、农药对非靶标生物影响的认识以及在农药生态环境中归宿问题的重视不断提高。随着世界耕地面积的逐渐减少、人口的不断增长及对粮食需求量的增加，迫使人们迅速发展农业生产技术、改进完善耕作制度，并需要不断发明新型的和改进的除草化合物和组合物。
现有技术中，结构如本发明通式I所示的羧酸肟酯类化合物及其除草活性未见报道。
发明内容
本发明的目的之一是提供一种结构新颖且对作物安全的羧酸肟酯类化合物及其作为除草剂的应用。
为实现上述目的，本发明的技术方案如下：
一种羧酸肟酯类化合物，如通式I所示：
Figure PCTCN2020109035-appb-000001
R 1选自C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基、C 3-C 6的环烷基C 1-C 6的烷氧基、苯环、具有1-3个杂原子的5或6元杂环、苯并具有1-3个杂原子的5或6元杂环，所述苯环或杂环上的氢可被一个或多个相同或不同的R 4取代；
R 2选自H或C 1-C 12的烷基；
R 3选自C 3-C 12的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基或C 3-C 6的环烷基C 3-C 6的环烷基；
R 4选自卤素、硝基、氰基、C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的卤代环烷基、C 1-C 6的环烷基C 1-C 6的烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基或C 3-C 6的环烷基C 1-C 6的烷氧基。
进一步的说，通式I中：
R 1选自苯环、具有1-3个杂原子的5或6元杂环、苯并具有1-3个杂原子的5或6元杂环，所述苯环或杂环上的氢可被一个或多个相同或不同的R 4取代；
R 2选自H或C 1-C 6的烷基；
R 3选自C 3-C 8的烷基；
R 4选自卤素、硝基、氰基、C 1-C 3的烷基或C 1-C 3的卤代烷基。
再进一步的说，通式I中：
R 1选自苯、呋喃、噻吩、吡咯、吡唑、噁唑、异噁唑、噻唑、吡啶、吡嗪、嘧啶、哒嗪、苯并噁唑、苯并噻唑、喹喔啉、喹唑啉，所述环上的氢可被一个或多个相同或不同的R 4取代；
R 2选自H或C 1-C 3的烷基；
R 3选自C 3-C 6的烷基；
R 4选自氟、氯、溴、碘、硝基、氰基、C 1-C 3的烷基或C 1-C 3的卤代烷基。
又进一步的说，通式I中：
R 1选自苯、呋喃、噻吩、吡咯、吡唑、噁唑、异噁唑、噻唑、吡啶、吡嗪、嘧啶、哒嗪、苯并噁唑、苯并噻唑、喹喔啉、喹唑啉，所述环上的氢可被一个或多个相同或不同的R 4取代；
R 2选自H或甲基；
R 3选自C 3-C 6的烷基；
R 4选自氟、氯、溴、硝基、氰基、甲基、二氟甲基或三氟甲基。
本发明技术特征还包括一种所述的通式I化合物的制备方法，除另有注明外，反应式中各基团定义同前。反应式如下：
Figure PCTCN2020109035-appb-000002
式中：
L离去基团；
通式III化合物与通式IV化合物在适宜的溶剂中，温度为-10℃到适宜溶剂的沸点下反应0.5-48小时制得化合物I。
适宜的溶剂选自二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙腈、四氢呋喃、二氧六环、N,N-二甲基甲酰胺或二甲基亚砜等。
通式III化合物为市售试剂或由其对应的酸制备而得。
通式IV化合物可参考下列文献制备：WO2007053755。
表1列出了部分通式I化合物的结构和物理性质。
表1部分通式I化合物的结构和物理性质
Figure PCTCN2020109035-appb-000003
Figure PCTCN2020109035-appb-000004
Figure PCTCN2020109035-appb-000005
Figure PCTCN2020109035-appb-000006
Figure PCTCN2020109035-appb-000007
Figure PCTCN2020109035-appb-000008
Figure PCTCN2020109035-appb-000009
部分化合物的 1H NMR(600MHz,CDCl 3)数据如下：
化合物I-70：8.84-8.85(m,1H),8.07-8.09(m,1H),7.55-7.57(m,1H),4.23-4.26(m,1H),2.65-2.67(m,2H),2.29-2.37(m,2H),1.84(s,3H),1.81-1.84(m,2H),1.34-1.59(m,4H),1.20(s,3H),0.93(t,3H).
化合物I-71：9.25-9.26(m,1H),8.80-8.81(m,1H),8.36-8.38(m,1H),7.44-7.46(m,1H),4.27-4.28(m,1H),2.76-2.78(m,2H),2.29-2.37(m,2H),1.87-2.10(m,3H),1.34-1.69(m,4H),1.22(s,3H),0.95(t,3H).
化合物I-73：8.52-8.53(m,1H),8.16-8.18(m,1H),8.34-8.37(m,1H),4.25-4.28(m,1H),2.73-2.74(m,2H),2.34-2.38(m,2H),1.91(s,3H),1.84-1.87(m,2H),1.39-1.66(m,4H),1.21(s,3H),0.94(t,3H).
化合物I-74：8.82-8.83(m,1H),8.12-8.14(m,1H),7.60-7.62(m,1H),4.25-4.28(m,1H),2.73-2.74(m,2H),2.31-2.38(m,2H),1.88(s,3H),1.82-1.84(m,2H),1.35-1.65(m,4H),1.21(s,3H),0.93(t,3H).
化合物I-75：8.88-8.89(m,1H),8.30-8.31(m,1H),7.53-7.55(m,1H),7.40(t,3H),4.26-4.29(m,1H),2.69-2.71(m,2H),2.33-2.39(m,2H),1.92(s,3H),1.84-1.86(m,2H),1.37-1.67(m,4H),1.21(s,3H),0.94(t,3H).
化合物I-76：9.42-9.43(m,1H),9.07(s,1H),7.53-7.55(m,1H),7.40(t,3H),4.26-4.29(m,1H),2.69-2.71(m,2H),2.33-2.39(m,2H),1.92(s,3H),1.84-1.86(m,2H),1.37-1.67(m,4H),1.21(s,3H),0.94(t,3H).
化合物I-77：9.05(s,1H),8.63(s,1H),8.17(s,1H),4.26-4.28(m,1H),2.76-2.78(m,2H),2.44(s,3H),2.36-2.39(m,2H),1.88(s,3H),1.62-1.63(m,2H),1.37-1.51(m,4H),1.21(s,3H),0.94(t,3H).
化合物I-78：8.80-8.81(m,2H),7.89-7.90(m,2H),4.27-4.28(m,1H),2.75-2.77(m,2H),2.34-2.41(m,2H),1.93(s,3H),1.87-1.90(m,2H),1.37-1.67(m,4H),1.21(s,3H),0.94(t,3H).
化合物I-79：9.03(s,1H),8.93(s,1H),7.66(s,1H),4.25-4.28(m,1H),2.62-2.64(m,2H),2.33-2.37(m,2H),1.87(s,3H),1.81-1.85(m,2H),1.35-1.64(m,4H),1.21(s,3H),0.93(t,3H).
化合物I-81：8.61-8.62(m,1H),8.51-8.52(m,1H),4.25-4.28(m,1H),2.87(s,3H),2.76-2.74(m,2H),2.32-2.39(m,2H),1.92(s,3H),1.84-1.86(m,2H),1.39-1.62(m,4H),1.21(s,3H),0.93(t,3H).
化合物I-87：7.98(s,1H),7.09(t,3H),4.24-4.27(m,1H),3.98(s,3H),2.67-2.70(m,2H),2.31-2.39(m,2H),1.90(s,3H),1.83-1.87(m,2H),1.35-1.64(m,4H),1.20(s,3H),0.93(t,3H).
化合物I-88：8.08(s,1H),4.23-4.26(m,1H),3.99(s,3H),2.68-2.70(m,2H),2.30-2.37(m,2H),1.90(s,3H),1.83-1.85(m,2H),1.34-1.49(m,4H),1.20(s,3H),0.93(t,3H)
本发明的通式I化合物具有除草活性，可用于农业上防治多种杂草。
本发明还包括以通式I化合物为活性组分的除草组合物。该除草组合物中活性组分的重量百分含量为1-99％。该除草组合物中还包括农业上可接受的载体。
本发明的以通式I化合物为活性组分的除草组合物可以多种制剂的形式施用。通常将本发明的化合物溶解或分散于载体中配制成制剂以便作为除草剂使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂或乳油等。因此，在这些组合物中，至少加入一种液体或固体载体，并且通常需要加入适当的表面活性剂。
本发明还提供了防治杂草的实施方法，该方法包括将除草有效量的本发明以通式I化合物为活性组分的除草组合物施于所述杂草或所述杂草生长的场所或其生长介质的表面上。较为适宜有效剂量为每公顷1克到1000克，优选有效剂量为每公顷10克到500克。对于某些应用，可在本发明的除草组合物中加入一种或多种其它的除草剂，由此可产生附加的优点和效果。
本发明通式I化合物既可以单独使用也可以和其它已知的杀虫剂、杀菌剂、植物生长调节剂或肥料等一起混合使用。
本发明还包括一种通式I所述的羧酸肟酯类化合物的应用，所述通式I化合物用于制备如通式II所示杀菌剂的应用：
Figure PCTCN2020109035-appb-000010
除另有注明外，反应式中各基团定义同前。式中：
L离去基团；
R 5选自苯环、具有1-3个杂原子的5或6元杂环或苯并具有1-3个杂原子的5或6元的杂环，其中，苯环或杂环上的氢可被一个或多个相同或不同的R 6取代；
R 6选自卤素、硝基、氰基、C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的卤代环烷基、C 1-C 6的环烷基C 1-C 6的烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基或C 3-C 6的环烷基C 1-C 6的烷氧基；
本发明还包括一种用于制备如通式I所示羧酸肟酯类化合物的通式IV所述的肟类化合物：
Figure PCTCN2020109035-appb-000011
式中：
R 2选自H或C 1-C 12的烷基；
R 3选自C 3-C 12的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基或C 3-C 6的环烷基C 3-C 6的环烷基。
通式IV化合物可参考下列文献制备：WO2007053755。
表2列出了部分通式IV化合物的结构和物理性质。
Figure PCTCN2020109035-appb-000012
表2部分通式IV化合物的结构和物理性质
Figure PCTCN2020109035-appb-000013
Figure PCTCN2020109035-appb-000014
Figure PCTCN2020109035-appb-000015
部分化合物的 1H NMR(600MHz,CDCl 3)数据如下：
化合物IV-23：9.36(brs,1H),4.12-4.17(m,1H),2.55-2.64(m,2H),2.22-2.33(m,2H),1.78-1.82(m,2H),1.82(s,3H),1.57-1.63(m,1H),1.34-1.49(m,3H),1.16(d,3H),0.92(t,3H).
本发明还包括一种肟类化合物IV的应用，所述通式IV化合物用于制备如通式I所示羧酸肟酯类化合物的应用。
本发明技术特征还包括一种酰胺类化合物II的制备方法，通式V所示的酰卤化合物与通式I所示羧酸肟酯类化合物于适宜的溶剂中，进行缩合反应，制得通式II所示的酰胺类化合物。除另有注明外，反应式中各基团定义同前。
Figure PCTCN2020109035-appb-000016
进一步的说，
通式V所示的酰卤化合物与通式I所示羧酸肟酯类化合物加料摩尔比为1：0.8-1.5，于适宜的溶剂中、温度为-10℃至适宜溶剂沸点范围内，进行缩合反应0.5-8个小时，制得通式II所示的酰胺类化合物。
所述的溶剂选自二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙腈、四氢呋喃、二氧六环、丙酮、丁酮、N,N-二甲基甲酰胺或二甲基亚砜。
再进一步的说，
通式V所示的酰卤化合物与通式I所示羧酸肟酯类化合物加料摩尔比为1：0.8-1.5，于适宜的溶剂中、温度为-10℃至适宜溶剂沸点范围内、压力为-0.1MPa～-0.01MPa压力下，进行缩合反应0.5-8个小时，制得通式II所示的酰胺类化合物。
更进一步的说，
通式V所示的酰卤化合物与通式I所示羧酸肟酯类化合物加料摩尔比为1：0.8-1.5，于适宜的溶剂中、温度为-10℃至适宜溶剂沸点范围内、压力为-0.1MPa～-0.01MPa压力下，加入适宜的酸，进行缩合反应0.5-8个小时，制得通式II所示的酰胺类化合物。
所述的酸选自盐酸、硫酸、甲磺酸或对甲苯磺酸。
再更进一步的说，
通式V所示的酰卤化合物与通式I所示羧酸肟酯类化合物加料摩尔比为1：0.9-1.2，在无缚酸剂存在下、于适宜的溶剂中、温度为20℃至沸点范围内、压力为-0.05MPa～-0.01MPa压力下，加入适宜的酸，进行缩合反应0.5-4个小时，制得酰胺类化合物；其中所述的溶剂选自甲苯或乙腈；所述的的酸选自盐酸、硫酸或对甲磺酸，所述的酸与羧酸肟酯类化合物(II)加料摩尔比为0.01-0.5：1。
上面给出的通式I，II，III，IV，V化合物的定义中，汇集所用术语定义如下：
烷基是指直链或支链形式，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、特丁基、正戊基、异戊基、正己基等基团。环烷基是指包括环状链形式，例如环丙基、环丁基、环戊基、环己基等基团。烷氧基是指烷基末端连有氧原子的基团，例如甲氧基、乙氧基、正丙氧基、异丙氧基、特丁氧基等。杂原子是指N、O、S等。杂环基是指含有杂原子的环基，例如呋喃、噻吩、吡咯、吡唑、噁唑、吡啶、哌啶、吗啉、吡咯烷、氧杂环戊烷等。
应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。
本发明所具有的优点：
本发明通式I化合物为羧酸肟酯类结构，结构新颖，并且本发明的羧酸肟酯类化合物具有意想不到的高除草活性，在较低剂量下也具有高的除草活性，不仅高效，而且减少了农药的使用量，降低了成本，减少了对环境的污染。同时，本发明化合物通式I化合物还可以用作制备酰胺类杀菌剂II的中间体，进一步拓展了其应用范围。
本发明通过羧酸肟酯类通式I化合物制备酰胺类化合物II的方法，该方法与原有的酰氯与胺的反应相比，避免了高价格、且原料不易得的苯胺的使用，起到了明显的降低成本的作用，并避免了缚酸剂的使用，降低了对环境的污染并增加反应的安全性。
具体实施方式
下列合成实施例可用来进一步说明本发明，但不意味着限制本发明。
合成实施例
实施例1
2-甲基-3-(戊烷-2-氧基)环己-2-烯-1-酮肟(化合物IV-23)的合成
(1)2-[(二甲基氨基)亚甲基]-1,3-环己二酮的合成
Figure PCTCN2020109035-appb-000017
往带有机械搅拌装置的三口烧瓶中加入甲醇(200.0g)，二甲胺溶液(112.8g，40％)和1,3-环己二酮(56.0g)，室温搅拌30min，降温至0-10℃，将甲醛溶液(88.3g，37％)缓慢滴入，搅拌5h，得到2-[(二甲基氨基)亚甲基]-1,3-环己二酮的合成，直接用于下一步。
(2)2-甲基-1,3-环己二酮的合成
Figure PCTCN2020109035-appb-000018
将上步反应液转移至高压反应釜，加入钯碳催化剂(5.6g，10％)，通入氢气，在2MPa、30℃条件下反应8h。取出反应液，滤除催化剂，加入水(200g)，蒸除甲醇，用浓盐酸调至pH值为6。有大量固体析出，抽滤，干燥，得到2-甲基-1,3-环己二酮51.7g，收率：80％(以1,3-环己二酮计算)，经液相检测归一纯度为97.5％。
(3)2-甲基-3-(2-戊氧基)环己-2-烯-1-酮的合成
Figure PCTCN2020109035-appb-000019
往带有分水装置的三口烧瓶中加入2-甲基-1,3-环己二酮(12.9g)、甲苯(200mL)、2-戊醇(72.1g)、对甲苯磺酸一水合物(2.0g)，升温至回流温度反应4h。降温至室温后，加入NaHCO 3(11.2g)饱和水溶液，分层。油层进行减压脱溶。得到中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮18.1g，收率：90％(以2-甲基-1,3-环己二酮计算)。
(4)2-甲基-3-(戊烷-2-氧基)环己-2-烯-1-酮肟(化合物IV-23)的合成
Figure PCTCN2020109035-appb-000020
向反应瓶内加入2-甲基-3-(2-戊氧基)环己-2-烯-1-酮(19.6g)、盐酸羟胺(13.9g)、醋酸钠(32.8g)、无水甲醇200mL、水20mL，升温至80℃反应4h。再将反应液降至10℃以下，再加入水(200mL)。此时有大量固体析出，进行过滤，滤饼用冰水淋洗，烘干。得到中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟11.6g，定量含量98％，收率：54％(以2-甲基-3-(2-戊氧基)环己-2-烯-1-酮计算)。
实施例2
2-甲基-3-(己烷-2-氧基)环己-2-烯-1-酮肟(化合物IV-25)的合成
(1)2-甲基-3-(2-己氧基)环己-2-烯-1-酮的合成
Figure PCTCN2020109035-appb-000021
往带有分水装置的三口烧瓶中加入2-甲基-1,3-环己二酮(12.9g，合成方法见实施例1)、甲苯(200mL)、2-己醇(83.6g)、对甲苯磺酸一水合物(2.0g)，升温至回流温度反应4h。降温至室温后，加入NaHCO 3(11.2g)饱和水溶液，分层。油层进行减压脱溶。得到2-甲基-3-(2-己氧基)环己-2-烯-1-酮16.2g，收率：75.3％(以2-甲基-1,3-环己二酮计算)。
(2)2-甲基-3-(己烷-2-氧基)环己-2-烯-1-酮肟(化合物IV-25)的合成
Figure PCTCN2020109035-appb-000022
向反应瓶内加入2-甲基-3-(2-己氧基)环己-2-烯-1-酮(21.0g)、盐酸羟胺(13.9g)、醋酸钠(32.8g)、无水甲醇(200mL)、水(20mL)，升温至80℃反应4h。再将反应液降至10℃以下，再加入水(200mL)。此时有大量固体析出，进行过滤，滤饼用冰水淋洗，烘干。得到2-甲基-3-(2-己氧基)环己-2-烯-1-酮肟10.8g，定量含量98％，收率：48％(以2-甲基-3-(2-己氧基)环己-2-烯-1-酮计算)。
实施例3
2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-乙酰肟(化合物I-65)的合成
Figure PCTCN2020109035-appb-000023
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟(21.1g)、三乙胺(10.1g)、甲苯(200mL)，向其中滴加乙酰氯(7.9g)，滴毕室温搅拌3h。将反应液降温至室温，再加入水(100mL)，并在此温度下搅拌30min后分层。油层脱溶得到2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-乙酰肟24.8g，收率：98％(以2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟计算)。
实施例4
2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-特戊酰肟(化合物I-67)的合成
Figure PCTCN2020109035-appb-000024
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟(21.1g)、三乙胺(10.1g)、甲苯(200mL)，向其中滴加特戊酰氯(12.1g)，滴毕室温搅拌3h。将反应液降温至室温，再加入水(100mL)，并在此温度下搅拌30min后分层。油层脱溶得到2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-特戊酰肟28.4g，收率：96％(以2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟计算)。
实施例5
2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-苯甲酰肟(化合物I-68)的合成
Figure PCTCN2020109035-appb-000025
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟(21.1g)、三乙胺(10.1g)、甲苯(200mL)，向其中滴加苯甲酰氯(14.1g)，滴毕室温搅拌3h。将反应液降温至室温，再加入水(100mL)，并在此温度下搅拌30min后分层。油层脱溶得到2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-苯甲酰肟31.2g，收率：99％。
实施例6
2-甲基-3-(戊烷-2-氧基)环己-2-烯-1-酮O-(3-(三氟甲基)异烟酰胺基)肟(化合物I-79)的合成
Figure PCTCN2020109035-appb-000026
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟(0.28g)、三乙胺(0.13g)、二氯甲烷(20mL)，向其中滴加2-三氟甲基异烟酰氯(0.30g)，滴毕室温搅拌3h。反应结束，加入二氯甲烷和水萃取，柱层析，得到2-甲基-3-(戊烷-2-氧基)环己-2-烯-1-酮O-(3-(三氟甲基)异烟酰胺基)肟0.24g，收率：39.8％。
实施例7
2-甲基-3-(戊烷-2-氧基)环己-2-烯-1-酮-O-(3-甲基吡嗪-2-羰基)肟(化合物I-81)的合成
Figure PCTCN2020109035-appb-000027
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟(0.39g)、三乙胺(0.18g)、二氯甲烷(20mL)，向其中滴加2-甲基吡嗪酰氯(0.30g)，滴毕室温搅拌3h。反应结束，加入二氯甲烷和水萃取，柱层析，得到2-甲基-3-(戊烷-2-氧基)环己-2-烯-1-酮-O-(3-甲基吡嗪-2-羰基)肟0.55g，收率：76.0％。
实施例8
2-甲基-3-(戊烷-2-氧基)环己-2-烯-1-酮O-(3-(二氟甲基)-1-甲基-1H-吡唑-4-羰基)肟(化合物I-87)的合成
Figure PCTCN2020109035-appb-000028
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟(0.31g)、三乙胺(0.14g)、二氯甲烷(20mL)，向其中滴加3-(二氟甲基)-1-甲基-1H-吡唑-4-碳酰氯(0.32g)，滴毕室温搅拌3h。反应结束，加入二氯甲烷和水萃取，柱层析，得到2-甲基-3-(戊烷-2-氧基)环己-2-烯-1-酮O-(3-(二氟甲基)-1-甲基-1H-吡唑-4-羰基)肟0.35g，收率：46.2％。
实施例9
2-甲基-3-(戊烷-2-氧基)环己-2-烯-1-酮O-(3-(二氟甲基)-1-甲基-1H-吡唑-4-羰基)肟(化合物I-87)的合成
Figure PCTCN2020109035-appb-000029
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟(21.1g)、三乙胺(10.1g)、甲苯(200mL)，向其中滴加1-甲基-3-二氟甲基-1H-吡唑-4-酰氯(19.5g)， 滴毕室温搅拌1h。将反应液降温至室温，再加入水(100mL)，并在此温度下搅拌30min后分层。油层脱溶得到中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-(1-甲基-3-二氟甲基-1H-吡唑-4-羧酸)肟36.0g，收率：97％(以2-甲基-3-(2-戊氧基)环己-2-烯-1-酮肟计算)。
实施例10
2-甲基-3-(2-己氧基)环己-2-烯-1-酮-O-苯甲酰肟(化合物I-100)的合成
Figure PCTCN2020109035-appb-000030
向反应瓶内加入中间体2-甲基-3-(2-己氧基)环己-2-烯-1-酮肟(22.5g)、三乙胺(10.1g)、甲苯(200mL)，向其中滴加苯甲酰氯(14.1g)，滴毕室温搅拌3h。将反应液降温至室温，再加入水(100mL)，并在此温度下搅拌30min后分层。油层脱溶得到中间体2-甲基-3-(2-己氧基)环己-2-烯-1-酮-O-苯甲酰肟30.8g，收率：94％(以2-甲基-3-(2-己氧基)环己-2-烯-1-酮肟计算)。
按照上述记载的方式将原料进行替换即可获得通式I所示的其它化合物，本发明通式化合物中R 1取代基为取代吡唑环，取代吡啶环，取代吡嗪环时均具有一定的除草效果等，现以化合物I-79为例进一步对此类化合物的活性进行测试验证。
生物活性测定实施例
实施例11
除草活性的测定
将阔叶杂草(百日草、苘麻)或禾本科杂草(狗尾草、稗草)种子分别播于直径为7cm的装有营养土的纸杯中，播后覆土1cm，镇压、淋水后在温室按常规方法培养，待杂草2-3叶期后茎叶喷雾处理。
原药用丙酮溶解后，按试验要求用1‰的吐温80静置自来水配制所需浓度的待测液。按试验设计剂量，在履带式作物喷雾机(英国Engineer Research Ltd.设计生产)上进行喷雾处理(喷雾压力1.95kg/cm 2，喷液量500L/hm 2，履带速度1.48km/h)。试验设3次重复。试材处理后置于操作大厅，待药液自然阴干后，放于温室内按常规方法管理，观察并记录杂草对药剂的反应情况，处理后定期目测供试药剂对杂草的防除效果，用0～100％来表示，以“0”代表无防效和“100％”代表完全杀死。
试验结果表明，通式I化合物对阔叶杂草普遍具有较高防效。部分供试的化合物中，如化合物I-79用剂量为600g a.i./hm 2时对百日草、苘麻均具有较好防效，防效均为100％。
按照以上测试方法，选取部分通式I化合物进行防除苘麻的活性试验，结果见表3。
表3：通式I部分化合物防除苘麻活性(苗后，防效％)
Figure PCTCN2020109035-appb-000031
按照以上测试方法，选取部分通式I化合物进行防除百日草的活性试验，结果见表4。
表4：通式I部分化合物防除百日草活性(苗后，防效％)
Figure PCTCN2020109035-appb-000032
制备杀菌剂(通式II)实施例
实施例12
3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺(化合物II-315)的合成
Figure PCTCN2020109035-appb-000033
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-苯甲酰肟(31.5g，合成方法见实施例5)，向此反应液中开始快速滴加3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰氯(20.4g)的甲苯溶液(100mL)，加入甲基磺酸(1.0g)，将反应液缓慢升温至110℃并抽真空至-0.04MPa，并在此温度下反应4h。将反应液降温至室温，再加入水(100mL)和NaOH(16.8g，33％)水溶液，并在此温度下搅拌30min后分层。油层脱溶，残余物再用甲醇水重结晶得3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺25.9g，收率：73.8％。
实施例13
3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺(化合物II-315)的合成
Figure PCTCN2020109035-appb-000034
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-特戊酰肟(29.5g，合成方法见实施例4)，向此反应液中开始快速滴加3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰氯(20.4g)的甲苯溶液(100mL)，加入甲基磺酸(1.0g)，将反应液缓慢升温至110℃并抽真空至-0.04MPa，并在此温度下反应4h。将反应液降温至室温，再加入水(100mL)和NaOH(16.8g，33％)水溶液，并在此温度下搅拌30min后分层。油层脱溶，残余物再用甲醇水重结晶得3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺18.4g，收率：52.4％。
实施例14
3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺(化合物II-315)的合成
Figure PCTCN2020109035-appb-000035
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-乙酰肟(25.3g，合成方法见实施例3)，向此反应液中开始快速滴加3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰氯(20.4g)的甲苯溶液(100mL)，加入甲基磺酸(1.0g)，将反应液缓慢升温至110℃并抽真空至-0.04MPa，并在此温度下反应4h。将反应液降温至室温，再加入水(100mL)和NaOH(16.8g，33％)水溶液，并在此温度下搅拌30min后分层。油层脱溶，残余物再用甲醇水重结晶得3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺16.9g，收率：48.1％。
实施例15
3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺(化合物II-315)的合成
Figure PCTCN2020109035-appb-000036
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-(1-甲基-3-二氟甲基-1H-吡唑-4-羧酸)肟(36.0g，合成方法见实施例8)，向此反应液中开始快速滴加3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰氯(19.5g)的甲苯溶液(100mL)，加入甲基磺酸(1.0g)，将反应液缓慢升温至100℃并抽真空至-0.03MPa，并在此温度下反应2h，去掉真空继续反应2h。将反应液降温至室温，再加入NaOH(8.8g)水溶液(120mL)，并在此温度下搅拌30min后分层。水层再用甲苯(50mL)反萃，合成油层并脱溶得到油状产品。产品再用2倍油状产品重量的甲醇水(85％)重结晶，得到3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺20.7g，收率56％。
实施例16
3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺(化合物II-315)的合成
Figure PCTCN2020109035-appb-000037
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-苯甲酰肟(31.5g，合成方法见实施例5)，向此反应液中开始快速滴加3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰氯(20.4g)的甲苯溶液(100mL)，加入甲基磺酸(1.0g)，将反应液缓慢升温至80℃并抽真空至-0.05MPa，并在此温度下反应4h。将反应液降温至室温，再加入水100mL和NaOH(16.8g，33％)水溶液，并在此温度下搅拌30min后分层。油层脱溶，残 余物再用甲醇水重结晶得3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺21.8g，收率：62.1％。
实施例17
3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺(化合物II-315)的合成
Figure PCTCN2020109035-appb-000038
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-苯甲酰肟(31.5g，合成方法见实施例5)，向此反应液中开始快速滴加3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰氯(20.4g)的甲苯溶液(100mL)，加入甲基磺酸(1.0g)，将反应液缓慢升温至80℃并抽真空至-0.01MPa，并在此温度下反应4h。将反应液降温至室温，再加入水(100mL)和NaOH(16.8g，33％)水溶液，并在此温度下搅拌30min后分层。油层脱溶，残余物再用甲醇水重结晶得3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺19.3g，收率：55.0％。
实施例18
3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺(化合物II-315)的合成
Figure PCTCN2020109035-appb-000039
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-苯甲酰肟(31.5g，合成方法见实施例5)，向此反应液中开始快速滴加3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰氯(20.4g)的乙腈溶液(100mL)，加入甲基磺酸(1.0g)，将反应液缓慢升温至110℃并抽真空至-0.04MPa，并在此温度下反应4h。将反应液降温至室温，蒸出绝大部分乙腈后用甲苯溶解，再加入水(100mL)和NaOH(16.8g，33％)水溶液，并在此温度下搅拌30min后分层。油层脱溶，残余物再用甲醇水重结晶得3-(二氟甲基)-1-甲基-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺25.3g，收率：72.1％。
实施例19
1,3-二甲基-5-氯-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺(化合物II-317)的合成
Figure PCTCN2020109035-appb-000040
向反应瓶内加入中间体2-甲基-3-(2-戊氧基)环己-2-烯-1-酮-O-苯甲酰肟(24.8g，合成方法见实施例5)，向此反应液中开始快速滴加1,3-二甲基-5-氯-1H-吡唑-4-甲酰氯(15.2g)的甲苯溶液(100mL)，加入甲基磺酸(0.8g)，将反应液缓慢升温至110℃并抽真空至-0.04MPa，并在此温度下反应4h。将反应液降温至室温，再加入水(100mL)和NaOH(16.8g，33％)水溶液，并在此温度下搅拌30min后分层。油层脱溶，残余物再用甲醇水重结晶得1,3-二甲基-5-氯-N-(2-甲基-3-(2-戊氧基)苯基)-1H-吡唑-4-甲酰胺18.2g，收率：66.1％。
实施例20
1,3-二甲基-5-氯-N-(2-甲基-3-(2-己氧基)苯基)-1H-吡唑-4-甲酰胺(化合物II-353)的合成
Figure PCTCN2020109035-appb-000041
向反应瓶内加入中间体2-甲基-3-(2-己氧基)环己-2-烯-1-酮-O-苯甲酰肟(26.0g，合成方法见实施例10)，向此反应液中开始快速滴加1,3-二甲基-5-氯-1H-吡唑-4-甲酰氯(15.2g)的甲苯溶液(100mL)，加入甲基磺酸(0.8g)，将反应液缓慢升温至110℃并抽真空至-0.04MPa，并在此温度下反应4h。将反应液降温至室温，再加入水(100mL)和NaOH(16.8g，33％)水溶液，并在此温度下搅拌30min后分层。油层脱溶，残余物再用甲醇水重结晶得1,3-二甲基-5-氯-N-(2-甲基-3-(2-己氧基)苯基)-1H-吡唑-4-甲酰胺18.6g，收率：64.8％。
按照本发明所提供的方法可制备通式II所示酰胺类化合物，表5列出部分通式II化合物的结构。
表5.部分通式II化合物的结构
Figure PCTCN2020109035-appb-000042
Figure PCTCN2020109035-appb-000043
Figure PCTCN2020109035-appb-000044
Figure PCTCN2020109035-appb-000045
Figure PCTCN2020109035-appb-000046
Figure PCTCN2020109035-appb-000047
Figure PCTCN2020109035-appb-000048
Figure PCTCN2020109035-appb-000049
Figure PCTCN2020109035-appb-000050
Figure PCTCN2020109035-appb-000051
Figure PCTCN2020109035-appb-000052
Figure PCTCN2020109035-appb-000053
Figure PCTCN2020109035-appb-000054
Figure PCTCN2020109035-appb-000055
Figure PCTCN2020109035-appb-000056
Figure PCTCN2020109035-appb-000057
Figure PCTCN2020109035-appb-000058
Figure PCTCN2020109035-appb-000059
通式II酰胺化合物可作为杀菌剂使用。部分化合物已在如下专利中公开：CN104649973A，CN105722828A，CN106187939A，CN106187893A，CN107108515A，CN108059613A，CN108069905A。

Claims (16)

  1. 一种羧酸肟酯类化合物，如通式I所示：
    Figure PCTCN2020109035-appb-100001
    式中：
    R 1选自C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基、C 3-C 6的环烷基C 1-C 6的烷氧基、苯环、具有1-3个杂原子的5或6元杂环、苯并具有1-3个杂原子的5或6元杂环，所述苯环或杂环上的氢可被一个或多个相同或不同的R 4取代；
    R 2选自H或C 1-C 12的烷基；
    R 3选自C 3-C 12的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基或C 3-C 6的环烷基C 3-C 6的环烷基；
    R 4选自卤素、硝基、氰基、C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的卤代环烷基、C 1-C 6的环烷基C 1-C 6的烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基或C 3-C 6的环烷基C 1-C 6的烷氧基。
  2. 按照权利要求1所述的化合物，其特征在于，通式I中：
    R 1选自苯环、具有1-3个杂原子的5或6元杂环、苯并具有1-3个杂原子的5或6元杂环，所述苯环或杂环上的氢可被一个或多个相同或不同的R 4取代；
    R 2选自H或C 1-C 6的烷基；
    R 3选自C 3-C 8的烷基；
    R 4选自卤素、硝基、氰基、C 1-C 3的烷基或C 1-C 3的卤代烷基。
  3. 按照权利要求2所述的化合物，其特征在于，通式I中：
    R 1选自苯、呋喃、噻吩、吡咯、吡唑、噁唑、异噁唑、噻唑、吡啶、吡嗪、嘧啶、哒嗪、苯并噁唑、苯并噻唑、喹喔啉、喹唑啉，所述环上的氢可被一个或多个相同或不同的R 4取代；
    R 2选自H或C 1-C 3的烷基；
    R 3选自C 3-C 6的烷基；
    R 4选自氟、氯、溴、碘、硝基、氰基、C 1-C 3的烷基或C 1-C 3的卤代烷基。
  4. 按照权利要求3所述的化合物，其特征在于，通式I中：
    R 1选自苯、呋喃、噻吩、吡咯、吡唑、噁唑、异噁唑、噻唑、吡啶、吡嗪、嘧啶、哒嗪、苯并噁唑、苯并噻唑、喹喔啉、喹唑啉，所述环上的氢可被一个或多个相同或不同的R 4取代；
    R 2选自H或甲基；
    R 3选自C 3-C 6的烷基；
    R 4选自氟、氯、溴、硝基、氰基、甲基、二氟甲基或三氟甲基。
  5. 一种按照权利要求1所述的通式I化合物的制备方法，其特征在于：反应式如下：
    Figure PCTCN2020109035-appb-100002
    式中：
    L离去基团；
    R 1选自C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基、C 3-C 6的环烷基C 1-C 6的烷氧基、苯环、具有1-3个杂原子的5或6元杂环、苯并具有1-3个杂原子的5或6元杂环，所述苯环或杂环上的氢可被一个或多个相同或不同的R 4取代；
    R 2选自H或C 1-C 12的烷基；
    R 3选自C 3-C 12的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基或C 3-C 6的环烷基C 3-C 6的环烷基。
    R 4选自卤素、硝基、氰基、C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的卤代环烷基、C 1-C 6的环烷基C 1-C 6的烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基或C 3-C 6的环烷基C 1-C 6的烷氧基。
  6. 一种按照权利要求1所述的羧酸肟酯类化合物的应用，其特征在于：所述通式I化合物用于控制杂草中的应用。
  7. 一种除草组合物，其特征在于：除草组合物为活性物质和农业上可接受的载体，活性组分为权利要求1所述的通式I化合物，组合物中活性组分的重量百分含量为1-99％。
  8. 一种按照权利要求7所述的除草组合物的控制杂草的方法，其特征在于：向杂草或杂草的生长介质或地点上施用除草有效剂量的如权利要求7所述的除草组合物。
  9. 一种按照权利要求1所述的羧酸肟酯类化合物的应用，其特征在于：所述通式I化合物用于制备如通式II所示酰胺类化合物的应用；反应式为
    Figure PCTCN2020109035-appb-100003
    式中：
    L离去基团；
    R 1选自C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基、C 3-C 6的环烷基C 1-C 6的烷氧基、苯环、具有1-3个杂原子的5或6元杂环、苯并具有1-3个杂原子的5或6元杂环，所述苯环或杂环上的氢可被一个或多个相同或不同的R 4取代；
    R 2选自H或C 1-C 12的烷基；
    R 3选自C 3-C 12的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基或C 3-C 6的环烷基C 3-C 6的环烷基；
    R 4选自卤素、硝基、氰基、C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的卤代环烷基、C 1-C 6的环烷基C 1-C 6的烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基或C 3-C 6的环烷基C 1-C 6的烷氧基；
    R 5选自苯环、具有1-3个杂原子的5或6元杂环或苯并具有1-3个杂原子的5或6元的杂环，其中，苯环或杂环上的氢可被一个或多个相同或不同的R 6取代；
    R 6选自卤素、硝基、氰基、C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的卤代环烷基、C 1-C 6的环烷基C 1-C 6的烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基或C 3-C 6的环烷基C 1-C 6的烷氧基。
  10. 一种酰胺类化合物(II)的制备方法，其特征在于：通式(V)所示的酰卤化合物与羧酸肟酯类化合物(I)于适宜的溶剂中，进行缩合反应，制得通式(II)所示的酰胺类化合物；
    反应式如下：
    Figure PCTCN2020109035-appb-100004
    式中：
    L离去基团；
    R 1选自C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基、C 3-C 6的环烷基C 1-C 6的烷氧基、苯环、具有1-3个杂原子的5或6元杂环、苯并具有1-3个杂原子的5或6元杂环，所述苯环或杂环上的氢可被一个或多个相同或不同的R 4取代；
    R 2选自H或C 1-C 12的烷基；
    R 3选自C 3-C 12的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基或C 3-C 6的环烷基C 3-C 6的环烷基；
    R 4选自卤素、硝基、氰基、C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的卤代环烷基、C 1-C 6的环烷基C 1-C 6的烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基或C 3-C 6的环烷基C 1-C 6的烷氧基；
    R 5选自苯环、具有1-3个杂原子的5或6元杂环或苯并具有1-3个杂原子的5或6元的杂环，其中，苯环或杂环上的氢可被一个或多个相同或不同的R 6取代；
    R 6选自卤素、硝基、氰基、C 1-C 6的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的卤代环烷基、C 1-C 6的环烷基C 1-C 6的烷基、C 1-C 6的烷氧基C 1-C 6的烷基、C 1-C 6的卤代烷氧基C 1-C 6的烷基、C 1-C 6的烷氧基、C 1-C 6的卤代烷氧基、C 3-C 6的环烷氧基、C 3-C 6的卤代环烷氧基或C 3-C 6的环烷基C 1-C 6的烷氧基。
  11. 按照权利要求10所述的制备方法，其特征在于：通式V所示的酰卤化合物与通式I所示的羧酸肟酯类化合物加料摩尔比为1：0.8-1.5，于适宜的溶剂中、温度为-10℃至适宜溶剂沸点范围内，进行缩合反应0.5-8个小时，制得通式II所示的酰胺类化合物。
  12. 按照权利要求11所述的制备方法，其特征在于：通式V所示的酰卤化合物与通式I所示的羧酸肟酯类化合物加料摩尔比为1：0.8-1.5，于适宜的溶剂中、温度为-10℃至适宜溶剂沸点范围内、压力为-0.1MPa～-0.01MPa压力下，进行缩合反应0.5-8个小时，制得通式II所示的酰胺类化合物。
  13. 按照权利要求12所述的制备方法，其特征在于：通式V所示的酰卤化合物与通式I所示的羧酸肟酯类化合物加料摩尔比为1：0.8-1.5，于适宜的溶剂中、温度为-10℃至适宜溶剂沸点范围内、压力为-0.1MPa～-0.01MPa压力下，加入适宜的酸，进行缩合反应0.5-8个小时，制得通式II所示的酰胺类化合物。
  14. 按照权利要求13所述的制备方法，其特征在于：通式(V)所示的酰卤化合物与通式I所示的羧酸肟酯类化合物加料摩尔比为1：0.9-1.2，在无缚酸剂存在下、于适宜的溶剂中、温度为20℃至沸点范围内、压力为-0.05MPa～-0.01MPa压力下，加入适宜的酸，进行缩合反应0.5-4个小时，制得通式II所示的酰胺类化合物。
  15. 一种用于制备通式I的中间体肟类化合物，其特征在于：中间体肟类化合物如通式IV所示：
    Figure PCTCN2020109035-appb-100005
    式中：
    R 2选自H或C 1-C 12的烷基；
    R 3选自C 3-C 12的烷基、C 1-C 6的卤代烷基、C 3-C 6的环烷基、C 3-C 6的环烷基C 1-C 6烷基、C 3-C 6的卤代环烷基或C 3-C 6的环烷基C 3-C 6的环烷基。
  16. 一种按照权利要求15所述的中间体化合物肟类化合物的应用，其特征在于：所述通式IV化合物用于制备如通式I所示羧酸肟酯类化合物的应用。
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