Substituted 6-indole pyridine formyl oxime ester-containing derivative, application thereof and herbicide

Abstract

The invention relates to the technical field of compound synthesis, in particular to a substituted 6-indole-containing pyridine formyl oxime ester derivative, application thereof and a herbicide. The structural general formula of the substituted 6-indole-containing pyridine formyl oxime ester derivative is shown as a formula I or a formula II, and R is selected from any one of F, Cl and H; r1 is selected from any one of F, Cl and H, R2 is selected from phenyl, halogenated phenyl and the like, and R3 is selected from phenyl, halogenated phenyl and the like. The substituted 6-indole-containing pyridine formyl oxime ester derivative has a novel molecular skeleton, has excellent herbicidal activity on four broadleaf weeds such as amaranthus retroflexus, piemarker, alfalfa and quinoa and two grassy weeds such as barnyard grass and crab grass, and has good crop selectivity on wheat and rice.

Description

Technical Field

[0001] The invention relates to the technical field of compound synthesis, in particular to a substituted 6-indole-containing pyridine formyl oxime ester derivative and its application and herbicide. Background Art

[0002] Synthetic hormone (or auxin) herbicides are an important type of modern herbicide, with more than 20 products currently on the market. This type of herbicide exerts its weed control effect by simulating the effects of indoleacetic acid (IAA) and interfering with the growth regulation process of plants. After binding to the target site, they trigger a surge in physiological activity in plant cells, causing sensitive plants to grow out of control and eventually die. This type of herbicide usually has good absorption and conduction properties, similar symptoms, rapid onset, and is adaptable to a variety of farming systems. In addition, due to the complexity of its targets, as many as 6 target sites have been identified, so the risk of plant resistance is low.

[0003] The International Herbicide Resistance Action Committee (HRAC) classifies synthetic hormone herbicides (AUXIN MIMICS) as Group 4 (HRAC / WSSA Group 4) or Group "O" (HRAC Group O). Among them, fluazifop-butyl and clofopyralid are synthetic hormone herbicides with a completely new structure, belonging to the pyridine carboxylic acid class of compounds. Due to its unique structure, Corteva classifies it as a 6-arylpicolinate (6-AP) herbicide. Recently, Corteva announced the launch of its third-generation product, Indolauxipyr-cyanomethyl (Bexoveld TM ), the product shows good market prospects due to its wide herbicidal spectrum.

[0004] In order to develop more synthetic hormone herbicides, the present invention designs and synthesizes a class of substituted 6-indole pyridine carboxylic acid oxime ester derivatives, and explores their herbicidal activities. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a substituted 6-indole pyridine oxime ester derivative, its application and herbicide. The substituted 6-indole pyridine oxime ester derivative has a novel molecular skeleton, has excellent herbicidal activity against four broad-leaved weeds, namely, Amaranthus retroflexus, Abutilon, alfalfa and Chenopodium album, and two gramineous weeds, namely, Echinochloa crusgalli and Digitaria sanguinea, and has good crop selectivity for wheat and rice.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative, wherein the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative has a general structural formula as shown in Formula I or Formula II:

[0008]

[0009] Wherein, R is selected from any one of F, Cl and H;

[0010] R 1 Any one selected from F, Cl and H;

[0011] R 2 is selected from the group consisting of phenyl, halogenated phenyl, phenyl-C1~C4 alkyl, phenyl-C1~C4 alkoxy, 5-6 membered heterocyclic-C1~C6 alkyl, C1~C6 alkyl, C1~C6 halogenated alkyl, C3~C6 alkenyl, C3~C6 halogenated alkenyl, C3~C6 alkynyl, C3~C6 halogenated alkynyl, C1~C6 alkylcarbonyl, phenyl-C1~C6 alkylcarbonyl, C1~C6 alkoxycarbonyl, phenoxycarbonyl, phenyl-C1~C6 alkoxycarbonyl, cyano C1~C6 alkyl, C1~C6 alkylsulfinyl-C1~C6 alkyl, C1~C6 alkylsulfonyl-C1~C6 alkyl, C1~C6 alkylcarbonyl-C1~C6 Any one of C6 alkyl, C1~C6 alkylcarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C3~C6 alkenyl, C1~C6 alkoxycarbonyl-halogenated C3~C6 alkenyl, C1~C6 haloalkoxycarbonyl-C1~C6 alkyl, C3~C6 alkenyloxycarbonyl-C1~C6 alkyl, C3~C6 alkynyloxycarbonyl-C1~C6 alkyl, C1~C6 alkylamino-C1~C6 alkyl, C1~C6 alkylaminocarbonyl-C1~C6 alkyl and C3~C6 cycloalkyl-C1~C6 alkyl;

[0012] R 3is selected from the group consisting of phenyl, halogenated phenyl, phenyl-C1~C4 alkyl, phenyl-C1~C4 alkoxy, 5-6 membered heterocyclic-C1~C6 alkyl, C1~C6 alkyl, C1~C6 halogenated alkyl, C3~C6 alkenyl, C3~C6 halogenated alkenyl, C3~C6 alkynyl, C3~C6 halogenated alkynyl, C1~C6 alkylcarbonyl, phenyl-C1~C6 alkylcarbonyl, C1~C6 alkoxycarbonyl, phenoxycarbonyl, phenyl-C1~C6 alkoxycarbonyl, cyano C1~C6 alkyl, C1~C6 alkylsulfinyl-C1~C6 alkyl, C1~C6 alkylsulfonyl-C1~C6 alkyl, C1~C6 alkylcarbonyl-C1~C6 Any one of C6 alkyl, C1~C6 alkylcarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C3~C6 alkenyl, C1~C6 alkoxycarbonyl-halogenated C3~C6 alkenyl, C1~C6 haloalkoxycarbonyl-C1~C6 alkyl, C3~C6 alkenyloxycarbonyl-C1~C6 alkyl, C3~C6 alkynyloxycarbonyl-C1~C6 alkyl, C1~C6 alkylamino-C1~C6 alkyl, C1~C6 alkylaminocarbonyl-C1~C6 alkyl and C3~C6 cycloalkyl-C1~C6 alkyl.

[0013] Preferably, the R 2 Any one selected from CH2C6H5, CH2C6H4(4-F), CH2C6H4(2-F), CH2C6H4(4-CF3), CH2C6H4(2,4-diCl2), C6H5, CH3, CH2CH3, CH(CH3)2, (CH2)3CH3, C(CH3)3, CH2CH=CH2 and CH2CH=CHCl.

[0014] Preferably, the R 3 Selected from C6H5, C6H4(2-F), C6H4(3-F), C6H4(4-F), C6H4(2-Cl), C6H4(3-Cl), C6H4(4-Cl), C6H4(2-Br), C6H4(3-Br), C6H4(4-Br), C6H4 (2-CH3), C6H4(3-CH3), C6H4(4-CH3), C6H4(4-OCH3), C6H4(4-N(CH3CH2)2), C6H4(4-NO2), C6H4(4-CF3), C6H3(4-F-2-OCH3), C6H 10 , C 10 H 10 , C3H6 and C5H8.

[0015] The present invention also provides the use of the substituted 6-indole-containing pyridine formyl oxime ester derivatives described in the above technical solution in preventing and controlling weeds in crops.

[0016] Preferably, the crops include wheat and / or rice.

[0017] Preferably, the weeds include one or more of Amaranthus retroflexus, Ramie, alfalfa, Chenopodium album, Echinochloa crusgalli and Crabgrass.

[0018] Preferably, when the substituted 6-indole pyridine carboxylic acid oxime ester derivative contains R selected from Cl, R 1 Selected from H, R 2 Any one selected from CH2C6H4(4-CF3), CH2C6H4(2,4-diCl2), C6H5, CH(CH3)2, C(CH3)3 and CH2CH=CHCl, R 3 When selected from C6H4(4-N(CH3CH2)2), the weeds include alfalfa and / or Chenopodium album.

[0019] Preferably, when R in the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative is selected from Cl or F, R 1 Selected from H, R 3 When selected from C6H4(4-CF3), C5H8 or C3H6, the weeds include one or more of Amaranthus retroflexus, Ramie, alfalfa, Chenopodium album, Echinochloa crusgalli and Crabgrass.

[0020] Preferably, the application rate of the substituted 6-indolepyridinecarboxylic acid oxime ester derivative is 15 to 30 g ai / ha.

[0021] The present invention also provides a herbicide, characterized in that the herbicide comprises the substituted 6-indole-containing pyridine formyl oxime ester derivative described in the above technical solution.

[0022] Beneficial effects:

[0023] The substituted 6-indole-containing pyridine formyl oxime ester derivatives provided by the present invention have good weeding effects on weeds such as Amaranthus retroflexus, velvetleaf, alfalfa, quinoa, barnyard grass and crabgrass. In particular, the compounds 9a, 9b, 9c, 9d, 9h, 9m, 9n, 9p, 9q, 9r, 9u, 9v and 9w described later have excellent weeding effects on Amaranthus retroflexus, velvetleaf, alfalfa, quinoa, barnyard grass and crabgrass; the compounds 8a, 8b, 8c, 8g, 8h, 8j, 8l, 9e, 9f, 9g, 9i, 9j, 9k, 9l, 9s, 9t and 9x have excellent weeding effects on Amaranthus retroflexus, velvetleaf, alfalfa and quinoa; and the compounds 8d, 8e, 8f, 8i, 8k, 8m and 9o have excellent weeding effects on alfalfa and quinoa. Compounds 9q, 9u, 9v and 9w have particularly excellent herbicidal effects on Amaranthus retroflexus, Abutilon, alfalfa, Chenopodium album, Echinochloa crusgalli and Digitaria sanguinalis. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required to be used in the embodiments are briefly introduced below.

[0025] Figure 1 The present invention provides a synthetic route for substituted 6-indole-containing pyridine carboxylic acid oxime ester derivatives. DETAILED DESCRIPTION

[0026] The present invention provides a substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative, wherein the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative has a general structural formula as shown in Formula I or Formula II:

[0027]

[0028] Wherein, R is selected from any one of F, Cl and H;

[0029] R 1 Any one selected from F, Cl and H;

[0030] R 2 is selected from the group consisting of phenyl, halogenated phenyl, phenyl-C1~C4 alkyl, phenyl-C1~C4 alkoxy, 5-6 membered heterocyclic-C1~C6 alkyl, C1~C6 alkyl, C1~C6 halogenated alkyl, C3~C6 alkenyl, C3~C6 halogenated alkenyl, C3~C6 alkynyl, C3~C6 halogenated alkynyl, C1~C6 alkylcarbonyl, phenyl-C1~C6 alkylcarbonyl, C1~C6 alkoxycarbonyl, phenoxycarbonyl, phenyl-C1~C6 alkoxycarbonyl, cyano C1~C6 alkyl, C1~C6 alkylsulfinyl-C1~C6 alkyl, C1~C6 alkylsulfonyl-C1~C6 alkyl, C1~C6 alkylcarbonyl-C1~C6 Any one of C6 alkyl, C1~C6 alkylcarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C3~C6 alkenyl, C1~C6 alkoxycarbonyl-halogenated C3~C6 alkenyl, C1~C6 haloalkoxycarbonyl-C1~C6 alkyl, C3~C6 alkenyloxycarbonyl-C1~C6 alkyl, C3~C6 alkynyloxycarbonyl-C1~C6 alkyl, C1~C6 alkylamino-C1~C6 alkyl, C1~C6 alkylaminocarbonyl-C1~C6 alkyl and C3~C6 cycloalkyl-C1~C6 alkyl;

[0031] R 3is selected from the group consisting of phenyl, halogenated phenyl, phenyl-C1~C4 alkyl, phenyl-C1~C4 alkoxy, 5-6 membered heterocyclic-C1~C6 alkyl, C1~C6 alkyl, C1~C6 halogenated alkyl, C3~C6 alkenyl, C3~C6 halogenated alkenyl, C3~C6 alkynyl, C3~C6 halogenated alkynyl, C1~C6 alkylcarbonyl, phenyl-C1~C6 alkylcarbonyl, C1~C6 alkoxycarbonyl, phenoxycarbonyl, phenyl-C1~C6 alkoxycarbonyl, cyano C1~C6 alkyl, C1~C6 alkylsulfinyl-C1~C6 alkyl, C1~C6 alkylsulfonyl-C1~C6 alkyl, C1~C6 alkylcarbonyl-C1~C6 Any one of C6 alkyl, C1~C6 alkylcarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C3~C6 alkenyl, C1~C6 alkoxycarbonyl-halogenated C3~C6 alkenyl, C1~C6 haloalkoxycarbonyl-C1~C6 alkyl, C3~C6 alkenyloxycarbonyl-C1~C6 alkyl, C3~C6 alkynyloxycarbonyl-C1~C6 alkyl, C1~C6 alkylamino-C1~C6 alkyl, C1~C6 alkylaminocarbonyl-C1~C6 alkyl and C3~C6 cycloalkyl-C1~C6 alkyl.

[0032] In the present invention, the R 2 Preferably, it is selected from any one of CH2C6H5, CH2C6H4(4-F), CH2C6H4(2-F), CH2C6H4(4-CF3), CH2C6H4(2,4-diCl2), C6H5, CH3, CH2CH3, CH(CH3)2, (CH2)3CH3, C(CH3)3, CH2CH=CH2 and CH2CH=CHCl. ​​In the present invention, the R 3 Preferably selected from C6H5, C6H4(2-F), C6H4(3-F), C6H4(4-F), C6H4(2-Cl), C6H4(3-Cl), C6H4(4-Cl), C6H4(2-Br), C6H4(3-Br), C6H4(4-Br), C6H4(2-CH3), C6H4(3-CH3), C6H4(4-CH3), C6H4(4-OCH3), C6H4(4-N(CH3CH2)2), C6H4(4-NO2), C6H4(4-CF3), C6H3(4-F-2-OCH3), C6H 10 , C 10 H 10 , C3H6 and C5H8.

[0033] In the present invention, the substituted 6-indole pyridine carboxylic acid oxime ester derivative is preferably prepared according to Figure 1The synthetic route shown was used to prepare it.

[0034] Reagents and conditions: (a) SOCl2, CH3OH, 65℃; (b) Selectfluor, CH3CN, 70℃; (c) LiOH, CH3OH / H2O, rt; (d) THF, -40℃; (e) B2pin2, PdCl2(dppf), KOAc, 1,4-dioxane, 110℃; (f) 2-or 2-(3,5,6-trichloropyridin-2-yl)oxy)acetic acid methyl ester, Pd[P(Ph3)2]Cl2, Na2CO3, DME / H2O, 60℃; (g) R 2 CH2ONH2 or R 3 CHNOH, PyBop, Et3N, DCM, rt.

[0035] 1) The synthesis method of compound 2 from compound 1 is as follows:

[0036] Preferably, the substituted picolinic acid 1 is dissolved in a methanol solution, and thionyl chloride is added to obtain compound 2 through an acylation reaction.

[0037] The acyl chloride used in the acylation reaction includes one or more of acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride and thionyl chloride, and thionyl chloride is preferably used as the acylating agent.

[0038] The amount of the acid chloride used in the acylation reaction is preferably 1 to 3 equivalents (molar ratio) relative to the amount of the compound 1 used, and more preferably 1.5 equivalents (molar ratio).

[0039] The temperature of the acylation reaction is preferably 25 to 70°C.

[0040] The acylation reaction time is preferably 2 to 12 hours.

[0041] 2) The synthesis method of compound 2b from compound 2c is as follows:

[0042] Preferably, compound 2c is reacted with a fluorine reagent Selectfluor in acetonitrile to obtain product 2b.

[0043] The solvent used in the above substitution reaction is preferably one or more of dichloromethane, chloroform, dimethyl sulfoxide, sulfolane, acetonitrile, etc., and acetonitrile is preferred as the solvent.

[0044] The amount of the fluorine reagent used in the substitution reaction is preferably 1 to 3 equivalents (molar ratio), more preferably 1.1 equivalents (molar ratio), relative to the amount of compound 2c.

[0045] The temperature of the substitution reaction is preferably 25 to 70°C.

[0046] The time for the substitution reaction is preferably 2 to 12 hours.

[0047] 3) The synthesis method of compound 1b from compound 2b is as follows:

[0048] Preferably, compound 2b is reacted with lithium hydroxide in methanol and water to obtain product 1b.

[0049] As the base used in the above hydrolysis reaction, one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide and the like are preferred, and lithium hydroxide is preferred as the solvent.

[0050] As the solvent used in the above hydrolysis reaction, one or more of water, methanol, ethanol, etc. are preferably used, and methanol is preferably used as the solvent.

[0051] The amount of the base used in the hydrolysis reaction is preferably 1 to 6 equivalents (molar ratio), more preferably 5 equivalents (molar ratio), relative to the amount of compound 2b used.

[0052] The temperature of the substitution reaction is preferably 25 to 40°C.

[0053] The time for the substitution reaction is preferably 2 to 12 hours.

[0054] 4) The synthesis method of compound 4 from compound 3 is as follows:

[0055] Preferably, compound 3 is reacted with vinylmagnesium bromide in tetrahydrofuran to obtain product 4.

[0056] The solvent used in the substitution reaction is preferably one or more of benzene, ethanol, diethyl ether, toluene, tetrahydrofuran, etc., and tetrahydrofuran is preferred as the solvent.

[0057] The amount of vinyl magnesium bromide used in the substitution reaction is preferably 1 to 5 equivalents (molar ratio) relative to the amount of compound 3 used, and more preferably 3 equivalents (molar ratio).

[0058] The temperature of the substitution reaction is preferably -60 to -20°C.

[0059] The time for the substitution reaction is preferably 1 to 6 hours.

[0060] 5) The synthesis method of compound 5 from compound 4 is as follows:

[0061] Preferably, compound 4 is coupled with B2pin2 under palladium catalysis conditions to obtain compound 5.

[0062] The amount of B2pin2 used in the coupling reaction is preferably 1 to 1.5 equivalents (molar ratio) relative to the amount of compound 4 used, and more preferably 1.05 to 1.2 equivalents (molar ratio).

[0063] The palladium catalyst used in the above coupling reaction is preferably various palladium catalysts known in the art, such as bis(triphenylphosphine)palladium dichloride, 1,1-bis(diphenylphosphine)diferropalladium dichloride, tetrakis(triphenylphosphine)palladium, palladium dichloride or palladium acetate.

[0064] The amount of the palladium catalyst used in the coupling reaction is preferably 0.3% to 5% equivalent (molar ratio) relative to the amount of compound 4 used, and more preferably 0.5% to 3% equivalent (molar ratio).

[0065] The solvent used in the coupling reaction is preferably one or more of ethylene glycol dimethyl ether, toluene, dioxane and tetrahydrofuran, and preferably ethylene glycol dimethyl ether or dioxane / water = 1 / 1 (volume ratio) as the solvent.

[0066] In the above coupling reaction, an acid binding agent is used, and the acid binding agent is well known in the art, such as one or more of sodium carbonate, potassium carbonate, potassium acetate, cesium carbonate and potassium phosphate.

[0067] The amount of the acid binding agent used in the coupling reaction is preferably 1 to 5 equivalents (molar ratio) relative to the amount of compound 4, and more preferably 2 to 3 equivalents (molar ratio).

[0068] The coupling reaction temperature is preferably 100 to 110°C.

[0069] The coupling reaction time is preferably 6 to 12 hours.

[0070] 6) The synthesis method of compound 6 obtained from compound 5 is as follows:

[0071] Preferably, under palladium catalysis conditions, compound 5 is coupled with compound 2 to obtain compound 6.

[0072] The amount of compound 2 used in the coupling reaction is preferably 1 to 1.5 equivalents (molar ratio) relative to the amount of compound 5 used, and more preferably 1.05 to 1.2 equivalents (molar ratio).

[0073] The palladium catalyst used in the above coupling reaction is preferably various palladium catalysts known in the art, such as bis(triphenylphosphine)palladium dichloride, 1,1-bis(diphenylphosphine)diferropalladium dichloride, tetrakis(triphenylphosphine)palladium, palladium dichloride or palladium acetate.

[0074] The amount of the palladium catalyst used in the coupling reaction is preferably 0.3% to 5% equivalent (molar ratio) relative to the amount of compound 5 used, and more preferably 0.5% to 3% equivalent (molar ratio).

[0075] The solvent used in the coupling reaction is preferably one or more of ethylene glycol dimethyl ether, toluene, dioxane and tetrahydrofuran, and dioxane is preferred as the solvent.

[0076] In the above coupling reaction, an acid binding agent is used, and the acid binding agent is well known in the art, such as one or more of sodium carbonate, potassium carbonate, cesium carbonate and potassium phosphate.

[0077] The amount of the acid binding agent used in the coupling reaction is preferably 1 to 5 equivalents (molar ratio) relative to the amount of compound 5 used, and more preferably 2 to 3 equivalents (molar ratio).

[0078] The coupling reaction temperature is preferably 40 to 80°C.

[0079] The coupling reaction time is preferably 6 to 12 hours.

[0080] 7) The synthesis method of compounds 8 and 9 from compound 7 is as follows:

[0081] Preferably, the substituted picolinic acid 7 reacts with an amine or aldoxime to generate compound 8 or 9 under the catalysis of a condensation agent.

[0082] The condensing agent used in the above condensation reaction includes one or more of PyBop, HATU, HOBt-EDCI, etc., and PyBop is preferably used as the acylating agent.

[0083] As the solvent for the above condensation reaction, one or more of dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide, toluene, xylene and tetrahydrofuran are preferred, and dichloromethane is preferred as the solvent.

[0084] The amount of the amine or aldoxime used in the condensation reaction is preferably 1 to 1.5 equivalents (molar ratio) relative to the amount of the compound 5 used, and more preferably 1.05 to 1.2 equivalents (molar ratio).

[0085] The temperature of the acylation reaction is preferably 15 to 30°C.

[0086] The acylation reaction time is preferably 2 to 12 hours.

[0087] The present invention also provides the use of the substituted 6-indole pyridine formyl oxime ester derivatives described in the above technical solution in preventing and controlling crop weeds. In the present invention, the crop preferably includes wheat and / or rice. In the present invention, the weeds preferably include one or more of Amaranthus retroflexus, Abutilon, alfalfa, Chenopodium album, Echinochloa crusgalli and Digitaria sanguinalis.

[0088] In the present invention, when R in the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative is preferably selected from Cl, R 1 Selected from H, R 2 Any one selected from CH2C6H4(4-CF3), CH2C6H4(2,4-diCl2), C6H5, CH(CH3)2, C(CH3)3 and CH2CH=CHCl, R 3 When selected from C6H4(4-N(CH3CH2)2), the weeds include alfalfa and / or Chenopodium album.

[0089] In the present invention, when R in the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative is preferably selected from Cl or F, R 1 Selected from H, R 3 When selected from C6H4(4-CF3), C5H8 or C3H6, the weeds include one or more of Amaranthus retroflexus, Ramie, alfalfa, Chenopodium album, Echinochloa crusgalli and Crabgrass.

[0090] In the present invention, when R in the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative is preferably selected from Cl or F, R 1 Select from H or F, R 3 When selected from any one of C6H5, C6H4(2-F), C6H4(3-F), C6H4(4-F), C6H4(2-Br), C6H4(4-CH3), C6H4(4-OCH3), C6H4(4-NO2), C6H4(4-CF3), C6H3(4-F-2-OCH3), C5H8 and C3H6, the weeds include one or more of Amaranthus retroflexus, Ramie, alfalfa, Chenopodium album, Echinochloa crusgalli and Crabgrass.

[0091] In the present invention, when R in the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative is preferably selected from Cl or H, R 1 Selected from H, R 2 Any one selected from CH2C6H5, CH2C6H4(4-F), CH2C6H4(2-F), CH3, CH2CH3, (CH2)3CH3 and CH2CH=CH2, R 3 Selected from C6H4(2-Cl), C6H4(3-Cl), C6H4(4-Cl), C6H4(3-Br), C6H4(4-Br), C6H4(2-CH3), C6H4(3-CH3), C6H10 , C 10 H 10 and any one of C3H6, the weeds include one or more of Amaranthus retroflexus, Ramie, alfalfa and Chenopodium album.

[0092] In the present invention, the application amount of the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative is preferably 15 to 30 gai / ha.

[0093] The present invention also provides a herbicide, characterized in that the herbicide comprises the substituted 6-indole pyridine oxime ester derivative described in the above technical solution. The present invention has no special limitation on the dosage form of the herbicide, and any dosage form acceptable to the substituted 6-indole pyridine oxime ester derivative can be used. The present invention has no special limitation on the preparation method of the herbicide, and it can be prepared by a conventional preparation method.

[0094] In order to further illustrate the present invention, the present invention is described in detail below in conjunction with embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0095] Unless otherwise specified, the chemical reagents used in the following examples were commercially available.

[0096] In the following examples, the nuclear magnetic resonance data were measured by using a Bruker ASCEND 400 (400 MHz) nuclear magnetic resonance instrument, and the mass spectrometry data were measured by using a Thermo Fisher Q Exactive mass spectrometer.

[0097] Reagents and conditions: (a) SOCl2, CH3OH, 65℃; (b) Selectfluor, CH3CN, 70℃; (c) LiOH, CH3OH / H2O, rt; (d) THF, -40℃; (e) B2pin2, PdCl2(dppf), KOAc, 1,4-dioxane, 110℃; (f) 2, Pd[P(Ph3)2]Cl2, Na2CO3, DME / H2O, 60℃; (g) R 2 CH2ONH2 or R 3 CHNOH, PyBop, Et3N, DCM, rt.

[0098] Example 1

[0099] This example is used to illustrate the preparation method of the substituted 6-indole pyridine carboxylic acid oxime ester derivatives of the present invention. The representative compound example includes the following steps:

[0100] (1) Synthesis of Compound 2:

[0101]

[0102] The substituted picolinic acid (10 mmol) was dissolved in 20 mL of methanol solution, and thionyl chloride (1.78 g, 15 mmol) was added dropwise at 0°C. After the addition was complete, the mixture was moved to 65°C for reaction for 12 h. After the reaction was complete, water was added dropwise, and the mixture was extracted three times with EtOAc. The organic phases were combined and dried over anhydrous Na2SO4, and concentrated under reduced pressure to obtain product 2.

[0103] (2) Synthesis of compounds 2b and 1b:

[0104]

[0105] 4-Amino-3,6-dichloropicolinic acid methyl ester (2.21 g, 10 mmol) was dissolved in 30 mL of acetonitrile, and then the fluorine reagent Selectfluor (3.90 g, 11 mmol) was added and reacted at 70°C overnight. After the reaction was completed, it was cooled to room temperature, extracted three times with EtOAc, the organic phases were combined and dried with anhydrous Na2SO4, and the raw material 2c was first separated by column chromatography, and then the mixture was separated by Shimadzu preparative liquid chromatograph LC-20AP (acetonitrile / water = 60%: 40%, flow rate 10 mL / min) to obtain compound 2b.

[0106] Compound 2b (478 mg, 2 mmol) was dissolved in methanol (10 mL), and 10 mL of water and LiOH (240 mg, 10 mmol) were added. After reacting at room temperature for 3 h, the mixture was acidified with 2M HCl to adjust the pH of the reaction solution to 2-3, and then filtered and dried to obtain product 1b.

[0107] (3) Synthesis of Compound 5:

[0108]

[0109] At -40°C, 2-fluoro-3-bromonitrobenzene (2.2 g, 10 mmol) was dissolved in tetrahydrofuran (THF, 20 mL), and then vinylmagnesium bromide (1M THF, 30 mL, 30 mmol) was added dropwise. After the addition was complete and the reaction was carried out at this temperature for 1 h, the reaction mixture was poured into saturated NH4Cl, extracted three times with EtOAc, the organic phases were combined and dried over anhydrous Na2SO4, and separated and purified by column chromatography to obtain compound 4a (compound 4b can be purchased directly).

[0110] PdCl2(dppf) (220 mg, 0.3 mmol), KOAc (2.85 g, 29 mmol) and B2pin2 (2.8 g, 11 mmol) were added to a solution of compound 4 (10 mmol) in 1,4-dioxane (60 mL) respectively. The mixture was reacted at 110°C for 2 h, then extracted with dichloromethane (DCM), the organic phases were combined and dried over anhydrous Na2SO4, and purified by column chromatography to obtain compound 5.

[0111] (4) Synthesis of compounds 6 and 7:

[0112]

[0113] Pd[P(Ph3)2]Cl2 (201 mg, 0.3 mmol), Na2CO3 (2.65 g, 25 mmol), 2 (11 mmol) and 5 (10 mmol) were added to the reaction bottle, and then DME / H2O (v / v=1:1) 40 mL was added and stirred. The reaction was continued overnight at 60°C, extracted three times with EtOAc, the organic phases were combined and dried with anhydrous Na2SO4, and purified by column chromatography to obtain compound 6. The synthesis of compound 7 is similar to that of compound 1b and is omitted here.

[0114] (5) Synthesis of compounds 7 and 8:

[0115]

[0116] At room temperature, the acid 7 (0.5 mmol) was dissolved in 5 mL of ultra-dry DCM, triethylamine (102 mg, 1 mmol) and PyBop (286 mg, 0.55 mmol) were added in sequence, and stirred at room temperature for 30 min. R 2 CH2ONH2(0.55mmol) or R 3 CHNOH (0.55 mmol), stirred at room temperature overnight, and purified by column chromatography to obtain compound 8 or 9.

[0117] The structural formula and molecular formula of target compounds 8 and 9 prepared in Example 1 of the present invention are shown in Table 1.

[0118]

[0119] Table 1 Chemical structures of substituted 6-indolepyridine carboxylic acid oxime ester derivatives

[0120]

[0121]

[0122] 8a: white solid, yield: 63%, melting point: 209-211°C. 1 H NMR (400MHz, DMSO-d6) δ11.72(s,1H),11.25(t,J=2.4Hz,1H),7.71-7.65(m,1H),7.61(d,J=8.2Hz,1H),7.49- 7.44(m,3H),7.43-7.34(m,3H),7.29(dd,J=8.3,1.5Hz,1H),6.85(s,2H),6.52-6.46(m,1H),4.94(s,2H). 13 CNMR (101MHz, DMSO-d6)δ162.6,154.8,149.0,148.0,136.2,135.7,131.0,129.4, 128.8,128.8,128.4,127.4,120.9,119.6,114.0,113.1,111.2,101.5,77.5. HRMS (ESI):calcd for C 21 H 17 C l2 N4O2[M+H] + 427.0723,found:427.0717.

[0123] 8b: white solid, yield: 56%, melting point: 163-165°C. 1 H NMR (400MHz, DMSO-d6) δ11.69(s,1H),11.24(t,J=2.4Hz,1H),7.70-7.64(m,1H),7.60(d,J=8.3Hz,1H),7.56-7.47(m,2H ),7.45(t,J=2.7Hz,1H),7.28(dd,J=8.2,1.6Hz,1H),7.24-7.16(m,2H),6.85(s,2H),6.51-6.45(m,1H),4.91(s,2H). 13 CNMR (101MHz, DMSO-d6) δ162.6,162.6(d,J=244.6Hz),154.8,149.0,147.9,135.7,132.5(d,J=3.2Hz),131.7 (d,J=8.4Hz),131.0,128.4,127.4,120.9,119.6,115.6(d,J=21.4Hz),114.0,113.1,111.2,101.5,76.6. 19 FNMR (377MHz,DMSO-d6)δ-113.8. HRMS (ESI):calcd for C21 H 16 Cl2FN4O2[M+H] + 445.0629,found:445.0627.

[0124] 8c: white solid, yield: 55%, melting point: 199-201°C. 1 H NMR (400MHz, DMSO-d6) δ11.74(s,1H),11.26(t,J=2.4Hz,1H),7.71-7.66(m,1H),7.61(d,J=8.3Hz,1H),7.56(td,J=7.5,1.8 Hz,1H),7.48-7.39(m,2H),7.30(dd,J=8.3,1.6Hz,1H),7.27-7.20(m,2H),6.85(s,2H),6.52-6.46(m,1H),5.01(s,2H). 13 CNMR (101MHz, DMSO-d6) δ162.7,161.3(d,J=246.9Hz),154.7,147.8,135.7,132.5(d,J=3.9Hz),131.3(d,J=8.3Hz),131.0,128.4 ,127.4,124.8(d,J=3.5Hz),123.0(d,J=14.8Hz),120.9,119.6,115.9,115.7,114.0,113.1,111.2,101.5,70.9(d,J=3.2Hz). 19 FNMR (377MHz,DMSO-d6)δ-117.9. HRMS (ESI):calcd for C 21 H 16 Cl2FN4O2[M+H] + 445.0628,found:445.0624.

[0125] 8d: white solid, yield: 48%, melting point: 186-188°C. 1 H NMR (400MHz, DMSO-d6) δ11.78(s,1H),11.25(t,J=2.3Hz,1H),7.76(d,J=8.1Hz,2H),7.73-7.66(m,3H),7.60(d,J =8.2Hz,1H),7.46(t,J=2.8Hz,1H),7.28(dd,J=8.3,1.6Hz,1H),6.86(s,2H),6.52-6.46(m,1H),5.05(s,2H). 13 CNMR(101MHz, DMSO-d6) δ162.7,154.8,149.0,147.8,141.0,135.7,131.0,129.8,129.2(q,J=31.5Hz),128 .4,127.4,125.6(q,J=3.7Hz),124.7(q,J=272.1Hz),120.8,119.6,114.0,113.1,111.2,101.5,76.5. 19 FNMR (377MHz,DMSO-d6)δ-61.0. HRMS (ESI):calcd for C 22 H 16 Cl2F3N4O2[M+H] + 495.0597,found:495.0592.

[0126] 8e: white solid, yield: 47%, melting point: 185-187°C. 1 H NMR (400MHz, DMSO-d6) δ11.76(s,1H),11.25(t,J=2.4Hz,1H),7.70-7.66(m,2H),7.62(dd,J=11.1,8.2H z,2H),7.50-7.43(m,2H),7.28(dd,J=8.2,1.6Hz,1H),6.86(s,2H),6.52-6.46(m,1H),5.04(s,2H). 13 CNMR (101MHz, DMSO-d6)δ162.7,154.7,149.0,147.7,135.7,134.7,134.3,133.2,132.9, 131.0,129.3,128.4,127.8,127.4,120.9,119.6,114.0,113.1,111.2,101.5,73.7. HRMS (ESI):calcd for C 21 H 15 Cl4N4O2[M+H] + 494.9944,found:494.9940.

[0127] 8f: white solid, yield: 55%, melting point: 181-183°C. 1 H NMR(400MHz, DMSO-d6) δ12.51(s,1H),11.27(s,1H),7.74(s,1H),7.62(d,J=8.3Hz,1H),7.47(t,J= 2.8Hz,1H),7.42-7.26(m,4H),7.15(d,J=8.0Hz,2H),7.09-6.91(m,4H),6.50(t,J=2.5Hz,1H). 13 CNMR (101MHz, DMSO-d6)δ163.1,159.9,155.0,149.2,147.4,135.7,131.0,130 .0,128.4,127.5,123.0,120.9,119.7,114.4,113.4,113.2,111.3,101.6. HRMS (ESI):calcd for C 20 H 15 Cl2N4O2[M+H] + 413.0567,found:413.0562.

[0128] 8g: yellow solid, yield: 65%, melting point: 135-137°C. 1 H NMR (400MHz, DMSO-d6) δ11.68(s,1H),11.24(t,J=2.8Hz,1H),7.69-7.64(m,1H),7.60(d,J=8.2Hz,1H ),7.46(t,J=2.8Hz,1H),7.28(dd,J=8.2,1.6Hz,1H),6.86(s,2H),6.51-6.45(m,1H),3.71(s,3H). 13 CNMR (101MHz, DMSO-d6) δ162.3,154.8,149.0,147.9,135.7,131.0,128.3,127.4,120.8,119.6,114.0,113.1,111.2,101.5,63.8. HRMS (ESI):calcd for C 15 H 12 Cl2N4O2Na[M+Na] + 373.0229,found:373.0221.

[0129] 8h: White solid, yield: 56%, melting point: 110-112°C. 1 H NMR(400MHz, DMSO-d6) δ11.55(s,1H),11.24(t,J=2.3Hz,1H),7.69-7.65(m,1H),7.60(d,J=8.2Hz,1H),7.46(t,J=2.8 Hz,1H),7.28(dd,J=8.2,1.5Hz,1H),6.85(s,2H),6.52-6.46(m,1H),3.94(q,J=7.1Hz,2H),1.21(t,J=7.0Hz,3H). 13 CNMR (101MHz, DMSO-d6) δ162.5,154.8,149.0,148.2,135.7,131.1,128.3,127.4,120.8,119.6,113.9,113.1,111.1,101.5,71.3,14.0. HRMS (ESI):calcd for C 16 H 15 Cl2N4O2[M+H] + 365.0567,found:365.0562.

[0130] 8i: white solid, yield: 57%, melting point: 219-221°C. 1 H NMR (400MHz, DMSO-d6) δ11.39(s,1H),11.25(t,J=2.3Hz,1H),7.70-7.65(m,1H),7.60(d,J=8.2Hz,1H),7.46(t,J=2 .7Hz,1H),7.29(dd,J=8.2,1.6Hz,1H),6.85(s,2H),6.52-6.46(m,1H),4.20-4.08(m,1H),1.21(d,J=6.2Hz,6H). 13 CNMR (101MHz, DMSO-d6) δ162.8,154.8,148.9,148.6,135.7,131.1,128.3,127.4,120.8,119.6,113.9,113.1,111.0,101.5,77.2,21.1. HRMS (ESI):calcd forC 17 H 17 Cl2N4O2[M+H] + 379.0723,found:379.0721.

[0131] 8j: light brown solid, yield: 57%, melting point: 198-200°C. 1 H NMR(400MHz, CH3OH-d4)δ7.6-7.6(m,1H),7.6(dd,J=8.2,0.7Hz,1H),7.3(d,J=3.1Hz,1H),7.3(dd,J=8.2,1.5Hz ,1H),6.5(dd,J=3.1,0.9Hz,1H),4.0(t,J=6.6Hz,2H),1.7-1.6(m,2H),1.5-1.4(m,2H),1.0(t,J=7.4Hz,3H). 13 CNMR (101MHz, CH3OH-d4) δ163.5,155.6,149.1,146.3,135.6,130.6,128.5,125.9,120.0,119.1,114.7,112.1,111.6,101.0,75.9,29.8,18.7,12.8. HRMS (ESI):calcdfor C 18 H 18 Cl2N4O2Na[M+Na] + 415.0699,found:415.0692.

[0132] 8k: white solid, yield: 58%, melting point: 229-231℃. 1 H NMR (400MHz, DMSO-d6) δ11.25(t,J=2.3Hz,1H),10.98(s,1H),7.71-7.65(m,1H),7.60(d,J=8.2Hz,1H ),7.45(t,J=2.7Hz,1H),7.29(dd,J=8.2,1.6Hz,1H),6.83(s,2H),6.51-6.45(m,1H),1.25(s,9H). 13 CNMR (101MHz, DMSO-d6) δ163.9,154.8,149.1,148.9,135.7,131.2,128.3,127.4,120.8,119.6,113.7,113.1,110.9,101.5,82.0,27.0. HRMS (ESI):calcd for C 18 H 19 Cl2N4O2[M+H] + 393.0880,found:393.0875.

[0133] 8l: white solid, yield: 54%, melting point: 210-212℃. 1 H NMR(400MHz, DMSO-d6) δ11.63(s,1H),11.24(t,J=2.3Hz,1H),7.70-7.64(m,1H),7.60(d,J=8.3Hz,1H),7.46(t,J=2.7Hz,1H),7.28(dd,J= 8.3,1.6Hz,1H),6.85(s,2H),6.51-6.45(m,1H),6.06-5.91(m,1H),5.43-5.33(m,1H),5.32-5.24(m,1H),4.42(dt,J=6.0,1.3Hz,2H). 13 CNMR (101MHz, DMSO-d6) δ162.6,154.8,149.0,148.0,135.7,133.3,131.0,128.3,127.4,120.8,119.9,119.6,114.0,113.1,111.2,101.5,76.5. HRMS (ESI):calcd for C 17 H 15 Cl2N4O2[M+H] + 377.0567,found:377.0567.

[0134] 8m: light brown solid, yield: 56%, melting point: 182-184°C. 1 H NMR (400MHz, CH3OH-d4) δ7.64(d,J=1.5Hz,1H),7.60(d,J=8.2Hz,1H),7.32(d,J=3.1Hz,1H),7.26(dd,J=8.2,1.6Hz ,1H),6.54(dt,J=13.3,1.3Hz,1H),6.49(dd,J=3.2,0.9Hz,1H),6.23-6.11(m,1H),4.46(dd,J=7.2,1.2Hz,2H). 13 CNMR (101MHz, CH3OH-d4) δ163.7,155.6,149.1,146.0,135.6,130.6,128.6,127.6,125.9,124.5,120.1,119.2,114.7,112.1,111.6,101.0,73.6. HRMS (ESI):calcd for C 17 H 13 Cl3N4O2Na[M+Na] + 432.9996,found:432.9991.

[0135] 9a: white solid, yield: 59%, melting point: 174-176°C. 1 H NMR (400MHz, DMSO-d6) δ11.25(t,J=2.4Hz,1H),8.88(s,1H),7.84-7.76(m,2H),7.69-7.65(m,1H),7.6 4-7.49(m,4H),7.46(t,J=2.8Hz,1H),7.26(dd,J=8.3,1.6Hz,1H),7.06(s,2H),6.52-6.45(m,1H). 13 CNMR (101MHz, DMSO-d6) δ162.9,159.2,155.5,149.3,145.0,135.7,132.6,130.8, 130.2,129.6,128.8,128.4,127.5,120.7,119.7,114.9,113.0,111.3,101.6. HRMS (ESI):calcd forC 21 H 15 Cl2N4O2[M+H] + 425.0567,found:425.0565.

[0136] 9b: white solid, yield: 46%, melting point: 103-105°C. 1 H NMR (400MHz, DMSO-d6) δ11.25(t,J=2.3Hz,1H),8.93(s,1H),7.88(td,J=7.6,1.6Hz,1H),7.69-7.59(m,3H) ,7.46(t,J=2.8Hz,1H),7.42-7.33(m,2H),7.27(dd,J=8.2,1.6Hz,1H),7.07(s,2H),6.52-6.46(m,1H). 13 CNMR (101MHz, DMSO-d6) δ162.7,161.3(d,J=254.7Hz),155.5,153.7(d,J=2.5Hz),149.3,144.8,135.7,134.8(d,J=8.7Hz),130.8,129.3( d,J=2.1Hz),128.5,127.5,125.7(d,J=3.4Hz),120.7,119.7,117.9(d,J=10.9Hz),117.0(d,J=20.4Hz),114.9,113.0,111.4,101.6. 19 FNMR (377MHz,DMSO-d6)δ-114.6. HRMS (ESI):calcd for C21 H 14 Cl2FN4O2[M+H] + 443.0472,found:443.0465.

[0137] 9c: white solid, yield: 42%, melting point: 188-190°C. 1 H NMR (400MHz, DMSO-d6)δ11.25(t,J=2.2Hz,1H),8.91(s,1H),7.70-7.53(m,5H),7 .49-7.38(m,2H),7.26(dd,J=8.2,1.6Hz,1H),7.07(s,2H),6.52-6.46(m,1H). 13 CNMR (101MHz, DMSO-d6) δ162.7,162.6(d,J=244.9Hz),158.3(d,J=2.9Hz),155.5,149.3,144.7,135.7,132.5(d,J=8.1Hz),131.9(d,J=8 .3Hz), 130.8, 128.4, 127.5, 125.1 (d, J = 2.9Hz), 120.7, 119.7, 119.5 (d, J = 21.1Hz), 115.3, 115.0 (d, J = 9.1Hz), 113.0, 111.4, 101.6. 19 FNMR (377MHz,DMSO-d6)δ-111.9. HRMS (ESI):calcd for C 21 H 14 Cl2FN4O2[M+H] + 443.0472,found:443.0468.

[0138] 9d: white solid, yield: 51%, melting point: 175-177°C. 1 H NMR (400MHz, DMSO-d6) δ11.25(t,J=2.2Hz,1H),8.89(s,1H),7.91-7.81(m,2H),7.69-7.65(m,1H),7.61(d,J=8. 2Hz,1H),7.49-7.43(m,1H),7.43-7.32(m,2H),7.26(dd,J=8.2,1.6Hz,1H),7.06(s,2H),6.52-6.46(m,1H). 13 CNMR(101MHz, DMSO-d6)δ164.7(d,J=250.4Hz),162.8,158.1,155.5,149.3,144.9,135.7,131.4(d,J=9.1Hz), 130.8,128.4,127.5,126.8(d,J=3.2Hz),120.7,119.7,116.9(d,J=22.3Hz),114.9,113.0,111.3,101.6. 19 FNMR (377MHz,DMSO-d6)δ-107.2. HRMS (ESI):calcd for C 21 H 14 Cl2FN4O2[M+H] + 443.0472,found:443.0476.

[0139] 9e: pale yellow solid, yield: 53%, melting point: 170-172°C. 1 H NMR (400MHz, DMSO-d6) δ11.25(t,J=2.3Hz,1H),9.00(s,1H),7.97-7.90(m,1H),7.70-7.64(m,1H),7 .64-7.57(m,3H),7.53-7.43(m,2H),7.26(dd,J=8.2,1.5Hz,1H),7.07(s,2H),6.52-6.46(m,1H). 13 CNMR (101MHz, DMSO-d6) δ162.7,155.9,155.5,149.3,144.7,135.7,134.5,134.1,130 .8,130.8,129.1,128.4,127.9,127.5,120.7,119.7,115.0,113.0,111.4,101.6. HRMS (ESI):calcd forC 21 H 14 Cl3N4O2[M+H] + 459.0177,found:459.0174.

[0140] 9f: white solid, yield: 48%, melting point: 182-184°C. 1 H NMR(400MHz, DMSO-d6) δ11.25(t,J=2.3Hz,1H),8.90(s,1H),7.82(t,J=1.8Hz,1H),7.77(dt,J=7.8,1.4Hz,1 H),7.69-7.53(m,4H),7.46(t,J=2.8Hz,1H),7.26(dd,J=8.2,1.5Hz,1H),7.07(s,2H),6.52-6.46(m,1H). 13 CNMR (101MHz, DMSO-d6) δ162.6,158.1,155.5,149.4,144.7,135.7,134.3,132.3,132.3, 131.6,130.8,128.5,128.4,127.5,127.2,120.7,119.7,115.0,113.0,111.4,101.6. HRMS (ESI):calcd for C 21 H 14 Cl3N4O2[M+H] + 459.0177,found:459.0176.

[0141] 9g: white solid, yield: 55%, melting point: 168-170℃. 1 H NMR (400MHz, DMSO-d6) δ11.25(t,J=2.3Hz,1H),8.90(s,1H),7.85-7.77(m,2H),7.69-7.64(m,1 H),7.64-7.56(m,3H),7.49-7.43(m,1H),7.30-7.23(m,1H),7.07(s,2H),6.52-6.46(m,1H). 13 CNMR (101MHz, DMSO-d6) δ162.7,158.2,155.5,149.3,144.8,137.3,135.7,130.8, 130.5,129.8,129.1,128.4,127.5,120.7,119.7,114.9,113.0,111.4,101.6. HRMS (ESI):calcd for C 21 H 14 Cl3N4O2[M+H] + 459.0177,found:459.0172.

[0142] 9h: Gray solid, yield: 51%, melting point: 162-164°C. 1 H NMR(400MHz, DMSO-d6) δ11.25(t,J=2.3Hz,1H),8.94(s,1H),7.96-7.88(m,1H),7.83-7.75(m,1H),7.69-7.66(m,1H),7.61 (d,J=8.2Hz,1H),7.57-7.49(m,2H),7.46(t,J=2.7Hz,1H),7.26(dd,J=8.2,1.6Hz,1H),7.08(s,2H),6.52-6.45(m,1H). 13 CNMR (101MHz, DMSO-d6)δ162.7,157.9,155.5,149.4,144.7,135.7,134.2,134.0,130.8, 129.5,129.3,128.9,128.5,127.5,124.6,120.7,119.7,115.0,113.0,111.4,101.6. HRMS (ESI):calcd for C 21 H 14 BrCl2N4O2[M+H] + 502.9672, found:502.9673.

[0143] 9i: pale yellow solid, yield: 48%, melting point: 183-185°C. 1 H NMR (400MHz, DMSO-d6) δ11.26(t,J=2.2Hz,1H),8.89(s,1H),7.96(t,J=1.8Hz,1H),7.85-7.75(m,2H),7.69-7.65 (m,1H),7.61(d,J=8.2Hz,1H),7.53-7.44(m,2H),7.26(dd,J=8.2,1.6Hz,1H),7.08(s,2H),6.52-6.46(m,1H). 13 CNMR (101MHz, DMSO-d6) δ162.6,158.0,155.5,149.4,144.7,135.7,135.2,132.6,131.8, 131.4,130.8,128.4,127.5,127.5,122.7,120.7,119.7,115.0,113.0,111.4,101.6. HRMS (ESI):calcd for C 21 H 14 BrCl2N4O2[M+H] + 502.9672,found:502.9670.

[0144] 9j: pale yellow solid, yield: 47%, melting point: 168-170°C. 1 H NMR (400MHz, DMSO-d6) δ11.25(t,J=2.3Hz,1H),8.89(s,1H),7.74(s,4H),7.68-7.66(m,1H),7.61(d, J=8.3Hz,1H),7.46(t,J=2.7Hz,1H),7.26(dd,J=8.2,1.6Hz,1H),7.06(s,2H),6.52-6.46(m,1H). 13 CNMR (101MHz, DMSO-d6)δ162.7,158.3,155.5,149.3,144.8,135.7,132.7,130.8, 130.7,129.4,128.4,127.5,126.2,120.7,119.7,114.9,113.0,111.4,101.6. HRMS (ESI):calcd forC 21 H 14 BrCl2N4O2[M+H] + 502.9672,found:502.9671.

[0145] 9k: light grey solid, yield: 68%, melting point: 165-167°C. 1 H NMR (400MHz, DMSO-d6) δ11.25(t,J=2.5Hz,1H),9.00(s,1H),7.76(dd,J=8.1,1.5Hz,1H),7.70-7.64(m,1H),7.61(d,J=8.2 Hz,1H),7.49-7.40(m,2H),7.36-7.29(m,2H),7.27(dd,J=8.3,1.6Hz,1H),7.06(s,2H),6.52-6.46(m,1H),2.44(s,3H). 13 CNMR (101MHz, DMSO-d6) δ163.3,158.3,155.5,149.3,145.4,139.1,135.7,132.2,131.7,130 .8,129.1,128.6,128.4,127.5,126.8,120.7,119.7,114.7,113.0,111.1,101.6,20.3. HRMS (ESI):calcd for C 22 H 17 Cl2N4O2[M+H] +439.0723,found:439.0721.

[0146] 9l: Light grey solid, yield: 63%, melting point: 178-180°C. 1 H NMR (400MHz, DMSO-d6) δ11.26(t,J=2.3Hz,1H),8.84(s,1H),7.70-7.65(m,1H),7.65-7.56(m,3H),7.48-7. 45(m,1H),7.44-7.36(m,2H),7.27(dd,J=8.3,1.5Hz,1H),7.07(s,2H),6.52-6.46(m,1H),2.37(s,3H). 13 CNMR (101MHz, DMSO-d6)δ162.8,159.2,155.5,149.3,145.0,139.0,135.7,133.3,130.8,130 .1,129.5,129.0,128.4,127.5,126.2,120.7,119.7,114.9,113.0,111.3,101.6,21.3. HRMS (ESI):calcd for C 22 H 17 Cl2N4O2[M+H] + 439.0723,found:439.0721.

[0147] 9m: white solid, yield: 55%, melting point: 111-113°C. 1 H NMR (400MHz, DMSO-d6) δ11.26(t,J=2.3Hz,1H),8.83(s,1H),7.69(d,J=8.2Hz,3H),7.61(d,J=8.2Hz,1H),7.46(t, J=2.7Hz,1H),7.34(d,J=8.1Hz,2H),7.27(dd,J=8.2,1.5Hz,1H),7.06(s,2H),6.51-6.47(m,1H),2.37(s,3H). 13 CNMR (101MHz, DMSO-d6) δ162.9,159.0,155.5,149.3,145.1,142.8,135.7,130.8,130 .2,128.8,128.4,127.5,127.4,120.7,119.7,114.8,113.0,111.3,101.6,21.7. HRMS (ESI):calcd for C 22 H 17Cl2N4O2[M+H] + 439.0723,found:439.0723.

[0148] 9n: white solid, yield: 38%, melting point: 169-171°C. 1 H NMR (400MHz, DMSO-d6) δ11.26(t,J=2.3Hz,1H),8.79(s,1H),7.78-7.70(m,2H),7.67(s,1H),7.61(d,J=8.2Hz,1 H),7.46(t,J=2.8Hz,1H),7.27(dd,J=8.3,1.6Hz,1H),7.12-7.01(m,4H),6.49(t,J=2.8Hz,1H),3.83(s,3H). 13 CNMR (101MHz, DMSO-d6)δ163.0,162.8,158.6,155.5,149.3,145.2,135.7,130.8,130 .7,128.4,127.5,122.4,120.7,119.7,115.2,114.8,113.0,111.2,101.6,55.9. HRMS (ESI):calcd for C 22 H 17 Cl2N4O3[M+H] + 455.0672,found:455.0668.

[0149] 9o: white solid, yield: 40%, melting point: 182-184℃. 1 H NMR (400MHz, DMSO-d6) δ11.25(t,J=2.3Hz,1H),8.58(s,1H),7.70-7.64(m,1H),7.61(d,J=8.2Hz,1H),7.59-7.50(m,2H),7.49-7.43(m ,1H),7.27(dd,J=8.2,1.6Hz,1H),7.03(s,2H),6.78-6.69(m,2H),6.52-6.46(m,1H),3.40(q,J=7.0Hz,4H),1.11(t,J=7.0Hz,6H). 13 CNMR (101MHz, DMSO-d6) δ163.2,158.6,155.4,150.6,149.2,145.6,135.7,130.9,130.6 ,128.4,127.5,120.7,119.7,115.5,114.6,113.0,111.5,111.1,101.6,44.2,12.8.HRMS (ESI):calcd for C 25 H 24 Cl2N5O2[M+H] + 496.1302, found:496.1306.

[0150] 9p: pale yellow solid, yield: 51%, melting point: 175-177°C. 1 H NMR (400MHz, DMSO-d6) δ11.26(t,J=2.3Hz,1H),9.07(s,1H),8.41-8.33(m,2H),8.10-8.02(m,2H),7.70-7.65(m, 1H),7.61(d,J=8.3Hz,1H),7.47(t,J=2.8Hz,1H),7.27(dd,J=8.2,1.6Hz,1H),7.09(s,2H),6.52-6.46(m,1H). 13 CNMR (101MHz, DMSO-d6) δ162.5,157.7,155.5,149.7,149.4,144.5,136.3,135.7, 130.8,130.1,128.4,127.5,124.7,120.7,119.7,115.1,113.0,111.5,101.6. HRMS (ESI):calcd for C 21 H 13 Cl2N5O4Na[M+Na] + 492.0237,found:492.0235.

[0151] 9q: white solid, yield: 57%, melting point: 176-178°C. 1 H NMR (400MHz, DMSO-d6) δ11.26(d,J=2.3Hz,1H),9.02(s,1H),8.05-7.98(m,2H),7.91(d,J=8.7Hz,2H),7.71-7.65 (m,1H),7.62(d,J=8.2Hz,1H),7.50-7.43(m,1H),7.27(dd,J=8.2,1.6Hz,1H),7.09(s,2H),6.52-6.46(m,1H). 13 CNMR(101MHz, DMSO-d6) δ162.6,158.1,155.5,149.4,144.7,135.7,134.2,132.1(d,J=32.1Hz),130.8,129 .6,128.4,127.5,126.5(q,J=3.8Hz),124.3(q,J=272.6Hz),120.7,119.7,115.0,113.0,111.5,101.6. 19 FNMR (377MHz,DMSO-d6)δ-61.5. HRMS (ESI):calcd for C 22 H 13 Cl2F3N4O2Na[M+Na] + 515.0260,found:515.0255.

[0152] 9r: white solid, yield: 55%, melting point: 183-185°C. 1 H NMR (400MHz, DMSO-d6) δ11.26(t,J=2.2Hz,1H),8.81(s,1H),7.84(dd,J=8.7,6.8Hz,1H),7.71-7.65(m,1H),7.61(d,J=8.3Hz,1H),7.46(t,J=2. 8Hz,1H),7.27(dd,J=8.2,1.6Hz,1H),7.11(dd,J=11.3,2.4Hz,1H),7.05(s,2H),6.92(td,J=8.5,2.4Hz,1H),6.52-6.46(m,1H),3.87(s,3H). 13 CNMR (101MHz, DMSO-d6) δ166.2(d,J=250.3Hz),162.9,160.7(d,J=11.1Hz),155.5,153.9,149.3,145.0,135.7,130.8,129.6(d,J=11.0 Hz), 128.4, 127.5, 120.7, 119.7, 114.8, 114.6 (d, J = 3.1Hz), 113.0, 111.3, 108.6 (d, J = 22.5Hz), 101.6, 101.1 (d, J = 26.1Hz), 57.0. 19 FNMR (377MHz,DMSO-d6)δ-103.9. HRMS (ESI):calcd for C 22 H 16 Cl2FN4O3[M+H] + 473.0578,found:473.0576.

[0153] 9s: white solid, yield: 48%, melting point: 197-199°C. 1 H NMR (400MHz, DMSO-d6) δ11.26(t,J=2.3Hz,1H),7.67(s,1H),7.60(d,J=8.2Hz,1H),7.46(t,J=2.8Hz,1H),7.26(dd,J=8.3,1.6Hz, 1H),7.00(s,2H),6.49(t,J=2.5Hz,1H),2.54(t,J=6.0Hz,2H),2.35(t,J=6.3Hz,2H),1.70(p,J=5.8Hz,2H),1.65-1.52(m,4H). 13 CNMR (101MHz, DMSO-d6)δ171.5,163.1,155.4,149.2,145.8,135.7,130.8,128.4,1 27.5,120.7,119.7,114.6,113.0,110.9,101.6,31.8,27.0,26.9,25.9,25.1. HRMS (ESI):calcd for C 20 H 19 Cl2N4O2[M+H] + 417.0880,found:417.0883.

[0154] 9t: white solid, yield: 65%, melting point: 194-196°C. 1 H NMR (400MHz, DMSO-d6) δ11.26(t,J=2.2Hz,1H),7.99(dd,J=8.0,1.4Hz,1H),7.72-7.67(m,1H),7.61(d,J=8.2Hz,1H),7.49-7.40( m,2H),7.36-7.25(m,3H),7.04(s,2H),6.52-6.46(m,1H),2.89(t,J=6.5Hz,2H),2.78(t,J=6.0Hz,2H),1.81(p,J=6.4Hz,2H). 13 CNMR (101MHz, DMSO-d6)δ163.8,162.9,155.4,149.3,145.6,142.1,135.7,131.7,130.8,129.6,12 8.5,128.4,127.5,127.1,125.3,120.7,119.7,114.7,113.1,111.1,101.6,29.1,25.8,21.3. HRMS(ESI):calcd forC 24 H 19 Cl2N4O2[M+H] + 465.0880,found:465.0875.

[0155] 9u: white solid, yield: 52%, melting point: 193-195℃. 1 HNMR(400MHz,CHCl3-d)δ8.70(s,1H),7.63(d,J=8.2Hz,1H),7.60(s,1H),7.41(dd,J=8.3,1.5Hz,1H) ,7.22(t,J=2.8Hz,1H),6.50(t,J=2.6Hz,1H),5.30(s,2H),2.57(t,J=7.1Hz,4H),1.83-1.70(m,4H). 13 CNMR (101MHz,CHCl3-d)δ177.4,162.9,155.4,147.6,144.9,135.4,131.0,128.5,126.0, 121.1,119.9,115.8,112.7,112.6,102.3,31.5,29.8,25.1,24.5.HRMS(ESI):calcd forC 19 H 17 Cl2N4O2[M+H] + 403.0723,found:403.0718.

[0156] 9v: white solid, yield: 48%, melting point: 205-207℃. 1 H NMR (400MHz, DMSO-d6) δ11.25(s,1H),7.69-7.64(m,1H),7.60(d,J=8.2Hz,1H),7.48-7.43(m ,1H),7.26(dd,J=8.2,1.6Hz,1H),6.99(s,2H),6.51-6.45(m,1H),2.02(d,J=9.1Hz,6H). 13 CNMR (101MHz, DMSO-d6) δ167.1,162.9,155.3,149.2,145.8,135.7,130.8,128.4,127.5,120.7,119.7,114.6,113.1,110.9,101.5,21.8,17.4. HRMS (ESI):calcd for C 17 H 15 Cl2N4O2[M+H] +377.0567,found:377.0563.

[0157] 9w: light brown solid, yield: 71%, melting point: 88-90℃. 1 H NMR (400MHz, CHCl3-d)δ8.75(s,1H),7.45(d,J=8.2Hz,1H),7.31-7.27(m,1H),7.25(d,J=7.7H z,1H),6.57(q,J=2.9Hz,1H),4.93(s,2H),2.60(dt,J=14.0,7.3Hz,4H),1.85-1.73(m,5H). 13 CNMR (101MHz, CHCl3-d) δ177.3,162.5,148.3,147.3,145.8,144.7,143.2(d,J=4.8Hz),139.9(dd,J=14.1,1.7Hz),132.6(d,J=5.9Hz ), 126.3, 124.1 (d, J = 13.1Hz), 121.8, 116.5 (d, J = 3.5Hz), 114.8 (d, J = 1.5Hz), 113.7 (dd, J = 10.5, 4.4Hz), 31.5, 29.8, 25.2, 24.5. 19 FNMR (377MHz,CHCl3-d)δ-135.2(d,J=34.1Hz),-137.7(d,J=33.8Hz). HRMS (ESI):calcd forC 19 H 16 ClF2N4O2[M+H] + 405.0924,found:405.0922.

[0158] 9v: light green solid, yield: 52%, melting point: 146-148°C. 1 H NMR (400MHz, CHCl3-d)δ8.89(t,J=2.3Hz,1H),7.81(d,J=1.4Hz,1H),7.62-7.50(m,2H),7.15(t,J=2.8 Hz,1H),6.94(s,1H),6.44(t,J=2.7Hz,1H),4.83(s,2H),2.55(q,J=6.8Hz,4H),1.81-1.67(m,4H). 13 CNMR(101MHz,CHCl3-d)δ177.6,163.9,156.8,150.5,147.5,136.1,131.7,128. 8,126.3,120.5,118.6,112.6,110.4,107.5,102.1,31.5,29.8,25.1,24.5. HRMS (ESI):calcd forC 19 H 18 ClN4O2[M+H] + 369.1113, found:369.1106.

[0159] Example 2

[0160] The post-emergence herbicidal activities of the target compounds against Amaranthus retroflexus, Ramulus velutipes, Alfalfa, Chenopodium album, Echinochloa crusgalli and Digitaria sanguinalis are shown in Table 2.

[0161] Post-emergence herbicidal activity was determined by spraying two representative grass weeds, barnyard grass and crabgrass, and four representative broadleaf weeds, velvetleaf, amaranth, alfalfa, and quinoa. Common synthetic hormone herbicides with broad-spectrum herbicidal activity, haloxifen-methyl and Indolauxipyr, were used as positive controls. The target compound was dissolved in N,N-dimethylformamide to prepare a high-concentration mother solution, which was then diluted to the required concentration with 0.1% Tween-80 water. The spray dose (active ingredient, g ai / ha) was calculated by dividing the mass of the sprayed inhibitor by the upper surface area of ​​the flower pot. Before planting, a flower pot with a diameter of 7 cm was selected, and about 6 to 10 weed seeds were sown and covered with 0.5 cm of soil. During the experiment, the temperature in the greenhouse was maintained at 25 to 28 °C, and the air humidity was maintained at about 50 to 75%. Post-emergence herbicidal activity: Monocotyledonous weeds and broadleaf weeds at the 2-3 leaf stage were treated with diluted inhibitor emulsions, and the inhibitor-free solvent (N,N-dimethylformamide + Tween-80) was directly used as the negative control group. Each treatment was repeated three times. The results of the herbicidal activity were visually evaluated 14 days after the application.

[0162] Table 2 Post-emergence herbicidal activity of substituted 6-indolepyridine carboxylic acid oxime ester derivatives

[0163]

[0164]

[0165] As shown in Table 2, at a dosage of 30 g / ha, most compounds had 100% inhibitory activity against four broadleaf weeds: Amaranthus retroflexus, Ramulus velutipes, Alfalfa and Chenopodium album. Their herbicidal activity against the grass weed Echinochloa crusgalli was better than that of Digitaria sanguinalis. The herbicidal activity of Compound 9 was significantly better than that of Compound 8. 3When the substituted groups on the benzene ring are different, 9b (2-F), 9c (3-F), 9d (4-F) and 9q (4-CF3) have higher herbicidal activity. Meanwhile, compound 9u (C5H8) has a 100% control effect on four broadleaf weeds and a 90% herbicidal activity on barnyard grass and crabgrass. Therefore, 9u analogs 9w and 9x were synthesized, and the herbicidal activity of these compounds was further tested at a dose of 15 g / ha. The experimental results showed that at a concentration of 15 g ai / ha, the inhibition rates of 9u and 9w on the four broadleaf weeds were both 100%, which was comparable to the positive control agents fluclopyralid and Indolauxipyr, and better than compound 9x. At the same time, 9w (100%) had a better control effect on barnyard grass than 9x (90%).

[0166] Example 3

[0167] Crop safety testing of target compounds

[0168] The greenhouse spray method used in Example 2 was adopted to conduct safety evaluation on six crops including wheat, rice, peanut, corn, soybean and cotton at an application dosage of 30 g ai / ha.

[0169] Table 3 Post-emergence crop selectivity of substituted 6-indolepyridine carboxylic acid oxime ester derivatives

[0170]

[0171]

[0172] As shown in Table 3, compounds 9u and 9w showed high sensitivity to peanut, soybean and cotton at a dosage of 30 g ai / ha, and moderate sensitivity to corn. In contrast, these compounds showed low sensitivity to rice and wheat at this dosage, which was comparable to the positive control agents halochloridone and Indolauxipyr. The experimental results showed that compounds 9u and 9w could be used as potential herbicides for controlling broadleaf weeds and some grass weeds in rice and wheat fields at a dosage of 30 g ai / ha.

[0173] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative, characterized in that: The general structural formula of the substituted 6-indole-containing pyridine formyl oxime ester derivative is as shown in Formula I or Formula II: Wherein, R is selected from any one of F, Cl and H; R 1 Any one selected from F, Cl and H; R 2 is selected from the group consisting of phenyl, halogenated phenyl, phenyl-C1~C4 alkyl, phenyl-C1~C4 alkoxy, 5-6 membered heterocyclic-C1~C6 alkyl, C1~C6 alkyl, C1~C6 halogenated alkyl, C3~C6 alkenyl, C3~C6 halogenated alkenyl, C3~C6 alkynyl, C3~C6 halogenated alkynyl, C1~C6 alkylcarbonyl, phenyl-C1~C6 alkylcarbonyl, C1~C6 alkoxycarbonyl, phenoxycarbonyl, phenyl-C1~C6 alkoxycarbonyl, cyano C1~C6 alkyl, C1~C6 alkylsulfinyl-C1~C6 alkyl, C1~C6 alkylsulfonyl-C1~C6 alkyl, C1~C6 alkylcarbonyl-C1~C6 Any one of C6 alkyl, C1~C6 alkylcarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C3~C6 alkenyl, C1~C6 alkoxycarbonyl-halogenated C3~C6 alkenyl, C1~C6 haloalkoxycarbonyl-C1~C6 alkyl, C3~C6 alkenyloxycarbonyl-C1~C6 alkyl, C3~C6 alkynyloxycarbonyl-C1~C6 alkyl, C1~C6 alkylamino-C1~C6 alkyl, C1~C6 alkylaminocarbonyl-C1~C6 alkyl and C3~C6 cycloalkyl-C1~C6 alkyl; R 3 is selected from the group consisting of phenyl, halogenated phenyl, phenyl-C1~C4 alkyl, phenyl-C1~C4 alkoxy, 5-6 membered heterocyclic-C1~C6 alkyl, C1~C6 alkyl, C1~C6 halogenated alkyl, C3~C6 alkenyl, C3~C6 halogenated alkenyl, C3~C6 alkynyl, C3~C6 halogenated alkynyl, C1~C6 alkylcarbonyl, phenyl-C1~C6 alkylcarbonyl, C1~C6 alkoxycarbonyl, phenoxycarbonyl, phenyl-C1~C6 alkoxycarbonyl, cyano C1~C6 alkyl, C1~C6 alkylsulfinyl-C1~C6 alkyl, C1~C6 alkylsulfonyl-C1~C6 alkyl, C1~C6 alkylcarbonyl-C1~C6 Any one of C6 alkyl, C1~C6 alkylcarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyloxy-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C1~C6 alkyl, C1~C6 alkoxycarbonyl-C3~C6 alkenyl, C1~C6 alkoxycarbonyl-halogenated C3~C6 alkenyl, C1~C6 haloalkoxycarbonyl-C1~C6 alkyl, C3~C6 alkenyloxycarbonyl-C1~C6 alkyl, C3~C6 alkynyloxycarbonyl-C1~C6 alkyl, C1~C6 alkylamino-C1~C6 alkyl, C1~C6 alkylaminocarbonyl-C1~C6 alkyl and C3~C6 cycloalkyl-C1~C6 alkyl.

2. The substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative according to claim 1, characterized in that: The R 2 Any one selected from CH2C6H5, CH2C6H4(4-F), CH2C6H4(2-F), CH2C6H4(4-CF3), CH2C6H4(2,4-diCl2), C6H5, CH3, CH2CH3, CH(CH3)2, (CH2)3CH3, C(CH3)3, CH2CH=CH2 and CH2CH=CHCl.

3. The substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative according to claim 1, characterized in that: The R 3 Selected from C6H5, C6H4(2-F), C6H4(3-F), C6H4(4-F), C6H4(2-Cl), C6H4(3-Cl), C6H4(4-Cl), C6H4(2-Br), C6H4(3-Br), C6H4(4-Br), C6H4 (2-CH3), C6H4(3-CH3), C6H4(4-CH3), C6H4(4-OCH3), C6H4(4-N(CH3CH2)2), C6H4(4-NO2), C6H4(4-CF3), C6H3(4-F-2-OCH3), C6H 10 , C 10 H 10 , C3H6 and C5H8.

4. Use of the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative according to any one of claims 1 to 3 in controlling weeds in crops.

5. The use according to claim 4, characterized in that: The crops include wheat and / or rice.

6. The use according to claim 4, characterized in that: The weeds include one or more of Amaranthus retroflexus, Abutilon, alfalfa, Chenopodium album, Echinochloa crusgalli and Crabgrass.

7. The use according to claim 6, characterized in that: When R in the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative is selected from Cl, R 1 Selected from H, R 2 Any one selected from CH2C6H4(4-CF3), CH2C6H4(2,4-diCl2), C6H5, CH(CH3)2, C(CH3)3 and CH2CH=CHCl, R 3 When selected from C6H4(4-N(CH3CH2)2), the weeds include alfalfa and / or lambsquarters.

8. The use according to claim 6, characterized in that: When R in the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative is selected from Cl or F, R 1 Selected from H, R 3 When selected from C6H4(4-CF3), C5H8 or C3H6, the weeds include one or more of Amaranthus retroflexus, Ramie, alfalfa, Chenopodium album, Echinochloa crusgalli and Crabgrass.

9. The use according to any one of claims 4 to 8, characterized in that: The application amount of the substituted 6-indole pyridine carboxylic acid oxime ester derivative is 15-30 g ai / ha.

10. A herbicide, characterized in that: The herbicide comprises the substituted 6-indole-containing pyridine carboxylic acid oxime ester derivative according to any one of claims 1 to 3.

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