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CN-121990927-A - Preparation method of iminoaryl compound and intermediate

CN121990927ACN 121990927 ACN121990927 ACN 121990927ACN-121990927-A

Abstract

The invention belongs to the field of organic chemical synthesis, and in particular relates to a preparation method of an iminoaryl compound and an intermediate. The preparation of the intermediate comprises the following steps of carrying out selective dechlorination reaction on the compound III to obtain a compound IV, wherein the reaction formula is as follows: the intermediate compound IV is subjected to subsequent reaction to obtain the iminoaryl compound. The preparation method has the advantages of high yield, high product purity and easy industrial production.

Inventors

  • SHAO ZHUZHOU
  • PENG LIANG
  • HAN LONGKUN
  • LI YOU

Assignees

  • 山东清原农冠作物科学有限公司

Dates

Publication Date
20260508
Application Date
20241105

Claims (9)

  1. 1. The preparation method of the iminoaryl compound intermediate is characterized by comprising the following steps of: The compound III is subjected to selective dechlorination reaction to obtain a compound IV, and the reaction formula is as follows:
  2. 2. The preparation method of the iminoaryl compound is characterized by comprising the following steps of: (1) Carrying out selective dechlorination on the compound III to obtain a compound IV; (2) The compound IV reacts with chloroformate compound IV-a to obtain a compound V; (3) The compound V and the V-a1 are firstly cyclized and then methylated to obtain a compound VI, or the compound V and the V-a2 are cyclized to obtain the compound VI; (4) Reacting the compound VI to obtain a compound VII; (5) Reacting the compound VII with hydroxylamine hydrochloride to obtain a compound VIII; (6) Reacting the compound VIII with VIII-a to obtain an iminoaryl compound IX; The synthetic route is as follows: Wherein L represents halogen, R 1 is selected from alkyl or aryl, R 2 is selected from alkyl or aryl, and the aforementioned "aryl" is optionally substituted with at least one group selected from hydroxy, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio or alkylsulfonyl; Preferably, R 1 is selected from C1-C8 alkyl or aryl, R 2 is selected from C1-C8 alkyl or aryl, the foregoing "aryl" is optionally substituted with at least one group selected from hydroxy, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, haloC 1-C8 alkyl, haloC 2-C8 alkenyl, haloC 2-C8 alkynyl, C1-C8 alkoxy, haloC 1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio or C1-C8 alkylsulfonyl; More preferably, R 1 is selected from C1-C4 alkyl or phenyl, R 2 is selected from methyl, ethyl, isopropyl or phenyl, and the foregoing "phenyl" is optionally substituted with at least one group selected from hydroxy, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo C1-C6 alkyl, halo C2-C6 alkenyl, halo C2-C6 alkynyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio or C1-C6 alkylsulfonyl.
  3. 3. The method according to claim 1 or 2, wherein the dechlorination reaction is carried out in the presence of an alkali solution and a dechlorination catalyst, preferably at least one of the alkali solutions is selected from aqueous alkali metal hydroxide solutions, and/or the dechlorination catalyst is zinc or aluminum.
  4. 4. The process according to any one of claims 2 to 3, wherein the step (2) is carried out in the presence of a solvent, more preferably at least one solvent selected from acetonitrile, tetrahydrofuran, ethyl acetate, methylene chloride, 1, 2-dichloroethane, toluene, xylene, chlorobenzene or dichlorobenzene; The reaction temperature of the step (3) is 0-120 ℃, and/or the cyclization reaction is carried out in the presence of a solvent and a base, preferably, the solvent is at least one selected from acetonitrile, tetrahydrofuran, toluene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, 1, 3-dimethyl-2-imidazolone, sulfolane or N-methylpyrrolidone, the base is at least one selected from inorganic base or organic base, and/or the methylation reagent is at least one selected from methyl iodide, methyl chloride, methyl bromide, dimethyl sulfate or dimethyl carbonate; The step (4) is carried out in the presence of a halogenating reagent, a catalyst and a solvent, wherein the solvent is preferably at least one selected from acetonitrile, tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, carbon tetrachloride, methylene dichloride, 1, 2-dichloroethane, chloroform, acetonitrile, ethyl acetate, isopropyl acetate or benzene, the halogenating reagent is preferably at least one selected from N-bromosuccinimide, dibromo-sea-buckthorn, N-chlorosuccinimide, dichloro-sea-buckthorn, chlorine, bromine, hydrogen peroxide/hydrobromic acid or sodium bromide/sodium bromate/sulfuric acid, and/or the catalyst is preferably at least one selected from azodiisobutyronitrile or benzoyl peroxide; the step (5) is carried out in the presence of a solvent, preferably an alcohol; The step (6) is performed in the presence of a base and a polar solvent, preferably at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate, and/or the polar solvent is at least one of acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, sulfolane or N-methylpyrrolidone, and more preferably the base is in a powder form.
  5. 5. The process according to any one of claims 1 to 4, wherein the compound III is obtained by reduction of a compound II with a hydrogenation reagent, the reaction formula being as follows: preferably, the reduction reaction is carried out in the presence of a hydrogenation solvent and a hydrogenation catalyst, more preferably the hydrogenation solvent is selected from at least one of methanol, ethanol, isopropanol or water, and/or the hydrogenation catalyst is selected from at least one of iron powder, copper powder, raney nickel, palladium on carbon, platinum on carbon or ferric trichloride.
  6. 6. The preparation method according to claim 5, wherein the compound II is obtained by nitration of the compound I with nitric acid, and the reaction formula is as follows: Preferably, the nitration is carried out in the presence of a nitration solvent and a nitration catalyst, more preferably the nitration solvent is selected from at least one of dichloromethane, dichloroethane, chloroform, water, acetic acid or trifluoroacetic acid, and/or the nitration catalyst is selected from at least one of concentrated sulfuric acid, acetic anhydride or trifluoroacetic anhydride.
  7. 7. The preparation method according to claim 5, wherein the compound II is obtained by performing nitration reaction of the compound I 'with nitric acid and then performing fluorination reaction of the compound I' with fluoride, and the reaction formula is as follows: Preferably, the nitration is carried out in the presence of a nitration solvent and a nitration catalyst, more preferably, the nitration solvent is selected from at least one of dichloromethane, dichloroethane, chloroform, water, acetic acid or trifluoroacetic acid, and/or the nitration catalyst is selected from at least one of concentrated sulfuric acid, acetic anhydride or trifluoroacetic anhydride; Preferably, the fluorination reaction is performed in the presence of a fluorination catalyst and a fluorination solvent, more preferably the fluorination catalyst is selected from at least one of a quaternary phosphonium salt phase transfer catalyst, a quaternary ammonium salt phase transfer catalyst, a crown ether, CNC + , or PNC + , the fluorination solvent is selected from at least one of acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone, sulfolane, or N-methylpyrrolidone, and preferably the fluoride salt is selected from at least one of potassium fluoride, sodium fluoride, cesium fluoride, amine fluoride, or tetrabutylammonium fluoride.
  8. 8. The process according to any one of claims 1 to 7, wherein the carbon atom to which the L group of step (6) is attached is in the R configuration, which is of the formula:
  9. 9. an intermediate compound of formula III according to claim 1 or formula II according to claim 5.

Description

Preparation method of iminoaryl compound and intermediate Technical Field The invention belongs to the field of organic chemical synthesis, and in particular relates to a preparation method of an iminoaryl compound and an intermediate. Background In recent years, the development of agricultural chemicals in China is rapid, the types of herbicides are more and more, and the iminoaryl compounds are novel herbicides disclosed by CN113105405A, and have the characteristics of wide herbicide controlling spectrum, high activity, high weeding speed, environmental friendliness and the like. However, the synthesis process still has the problems of low product purity, low reaction yield, high cost and the like, and scientists are still required to further develop the synthesis process which is more suitable for industrial production. Disclosure of Invention In order to solve the problems in the prior art, the invention provides a preparation method of an iminoaryl compound and an intermediate. The technical scheme adopted by the invention is as follows: a preparation method of an iminoaryl compound intermediate comprises the following steps: The compound III is subjected to selective dechlorination reaction to obtain a compound IV, and the reaction formula is as follows: the application also discloses a preparation method of the iminoaryl compound, which comprises the following steps: (1) Carrying out selective dechlorination on the compound III to obtain a compound IV; (2) The compound IV reacts with chloroformate compound IV-a to obtain a compound V; (3) The compound V and the V-a1 are firstly cyclized and then methylated to obtain a compound VI, or the compound V and the V-a2 are cyclized to obtain the compound VI; (4) Reacting the compound VI to obtain a compound VII; (5) Reacting the compound VII with hydroxylamine hydrochloride to obtain a compound VIII; (6) Reacting the compound VIII with VIII-a to obtain an iminoaryl compound IX; The synthetic route is as follows: Wherein L represents halogen, R 1 is selected from alkyl or aryl, R 2 is selected from alkyl or aryl, and the foregoing "aryl" is optionally substituted with at least one group selected from hydroxy, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio or alkylsulfonyl. Preferably, R 1 is selected from C1-C8 alkyl or aryl, R 2 is selected from C1-C8 alkyl or aryl, and the foregoing "aryl" is optionally substituted with at least one group selected from hydroxy, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, haloC 1-C8 alkyl, haloC 2-C8 alkenyl, haloC 2-C8 alkynyl, C1-C8 alkoxy, haloC 1-C8 alkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, or C1-C8 alkylsulfonyl. More preferably, R 1 is selected from C1-C4 alkyl or phenyl, R 2 is selected from methyl, ethyl, isopropyl or phenyl, and the foregoing "phenyl" is optionally substituted with at least one group selected from hydroxy, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo C1-C6 alkyl, halo C2-C6 alkenyl, halo C2-C6 alkynyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio or C1-C6 alkylsulfonyl. In a specific embodiment, the dechlorination reaction is performed in the presence of an alkali solution and a dechlorination catalyst, more preferably, the alkali solution is selected from at least one of an aqueous alkali metal hydroxide solution (such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous lithium hydroxide solution, etc.), and/or the dechlorination catalyst is zinc or aluminum. In a specific embodiment, the step (2) is performed in the presence of a solvent, preferably at least one solvent selected from acetonitrile, tetrahydrofuran, ethyl acetate, dichloromethane, 1, 2-dichloroethane, toluene, xylene, chlorobenzene or dichlorobenzene. Wherein, in the step (2), high yield can be realized without adding alkali. In a specific embodiment, the reaction temperature in the step (3) is between 0 ℃ and 120 ℃. In a specific embodiment, the cyclization reaction of step (3) is performed in the presence of a solvent, a base, preferably at least one of acetonitrile, tetrahydrofuran, toluene, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, 1, 3-dimethyl-2-imidazolidinone, sulfolane or N-methylpyrrolidone, the base is selected from at least one of an inorganic base (such as K2CO3、Na2CO3、Cs2CO3、NaHCO3、KF、CsF、K3PO4、NaOH、KOH、NaH、KH, etc.) or an organic base (such as AcOK, acONa, t-BuONa, meONa, etONa, DMAP, pyrazole, triethylamine, DIEA, etc.), and/or the methylating agent is selected from at least one of methyl iodide, methyl chloride, methyl bromide, dimethyl sulfate or dimethyl carbonate. In a specific embodiment, the step (4) is performed in the presence of a halogenating agent, a catalyst and a solvent, preferably the solvent is selected from at least one of acetonitrile, tetrahydrofuran, 1, 4-dioxane, ethylene glyco