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CN-122010769-A - Method for synthesizing diaryl hydrazine compounds by photocatalysis

CN122010769ACN 122010769 ACN122010769 ACN 122010769ACN-122010769-A

Abstract

The invention discloses a diaryl hydrazine compound and a preparation method thereof, wherein the preparation method comprises the following steps of mixing an azobenzene compound, an alkyl NHPI ester reagent, a photosensitizer, an alkaline reagent and a solvent, and reacting under the irradiation of visible light to obtain the diaryl hydrazine compound, wherein the photosensitizer is one or a mixture of two of 2,4,5, 6-tetra (carbazole-9-yl) -1, 3-dicyanobenzene, bis [2- (2, 4-difluorophenyl) -5-trifluoromethyl pyridine ] [2-2' -bis (4-tert-butylpyridine) ] iridium hexafluorophosphate, and the alkaline reagent is one or a mixture of more of N, N-diisopropylethylamine, potassium phosphate and 1, 8-diazabicyclo [5.4.0] undec-7-ene. The preparation method has the advantages of easily available raw materials, simple operation, mild reaction, wide substrate applicability and the like.

Inventors

  • YANG SHICHAO
  • YANG QI
  • LIN DONGHUI
  • ZHOU ZHENGYU
  • LI LU
  • Ge Feiyue
  • DING YONGLIANG
  • Sheng Chengyin
  • ZHANG NUO
  • HE JIAJUN
  • YANG JINGWEI
  • ZHOU FEIYANG

Assignees

  • 蚌埠学院

Dates

Publication Date
20260512
Application Date
20251226

Claims (10)

  1. 1. A method for synthesizing diaryl hydrazine compounds by photocatalysis is characterized by comprising the following steps of mixing an azobenzene compound, an alkyl NHPI ester reagent, a photosensitizer, an alkaline reagent and a solvent, and reacting under the irradiation of visible light to obtain the diaryl hydrazine compounds; Wherein the photosensitizer is one or two mixtures of 2,4,5, 6-tetra (carbazole-9-yl) -1, 3-dicyanobenzene and bis [2- (2, 4-difluorophenyl) -5-trifluoromethyl pyridine ] [2-2' -bis (4-tertiary butyl pyridine) ] iridium hexafluorophosphate, and the alkaline reagent is one or more mixtures of N, N-diisopropylethylamine, potassium phosphate and 1, 8-diazabicyclo [5.4.0] undec-7-ene; The structural formula of the azobenzene compound is as follows: ; The structural formula of the NHPI ester reagent of the alkyl is as follows: The structural formula of the diaryl hydrazine compound is as follows: ; Wherein R is selected from one or more of hydrogen, alkyl and halogen, and R 'is selected from one or more of cyclohexyl, adamantyl and 1- ([ 1,1' -biphenyl ] -4-yl) propane-1-ketone.
  2. 2. The method for photocatalytic synthesis of diarylhydrazine compounds according to claim 1, wherein the structural formula of the azobenzene compound is one of the following structural formulas: 、 、 。
  3. 3. the method for photocatalytic synthesis of diarylhydrazine compounds according to claim 1, wherein the structural formula of the alkyl NHPI ester reagent is one of the following structural formulas: 、 、 。
  4. 4. the method for synthesizing the diaryl hydrazine compound by photocatalysis according to claim 1, wherein the structural formula of the diaryl hydrazine compound is one of the following structural formulas: 、 、 ; Wherein R is selected from one or more of hydrogen, alkyl and halogen.
  5. 5. The method for synthesizing the diaryl hydrazine compound by photocatalysis according to claim 1 is characterized in that the molar ratio of the azobenzene compound to the NHPI ester reagent of the alkyl is 1:1-5, the molar ratio of the azobenzene compound to the photosensitizer is 1:0.01-0.10, and the molar ratio of the azobenzene compound to the alkaline reagent is 1:1-3.
  6. 6. The method for synthesizing the diaryl hydrazine compound by photocatalysis according to claim 1, wherein the solvent is at least one of tetrahydrofuran, acetonitrile, toluene, dichloroethane, methanol, N-dimethylformamide, chloroform, dioxane and dichloromethane.
  7. 7. The method for synthesizing the diaryl hydrazine compound by photocatalysis according to claim 1, wherein the wavelength of the visible light is 380-525 nm.
  8. 8. The method for synthesizing the diaryl hydrazine compound by photocatalysis according to claim 1, wherein the reaction temperature is 10 ℃ to 80 ℃ and the reaction time is 8h to 18h.
  9. 9. The method for synthesizing the diaryl hydrazine compound according to any one of claims 1 to 8, wherein the dosage ratio of the azobenzene compound and the solvent is 0.1 mmol/2 ml.
  10. 10. A diaryl hydrazine compound is characterized in that the structural formula is Or (b) 。

Description

Method for synthesizing diaryl hydrazine compounds by photocatalysis Technical Field The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing diaryl hydrazine compounds by photocatalysis. Background The diaryl hydrazine compounds are compounds which have important values in medicinal chemistry, functional materials and organic synthesis, and the derivatives thereof have good biological activity in the development of anticancer, anti-inflammatory, antidiabetic and other medicaments. However, there are still many limitations to the existing diaryl synthesis methods. The conventional method generally relies on coupling reaction of aryl halide and hydrazine reagent, or takes azo compound as raw material, and realizes reduction reaction by metal reducing agent (such as SnCl 2、NaBH4 and the like). In recent years, photocatalysis has been attracting attention in organic synthesis as a mild, green and controllable reaction means. The existing photo-catalytic reduction azo compounds report that although the conversion of certain systems can be realized, the existing photo-catalytic reduction azo compounds are limited to special substrates or require special catalytic systems, and the defects of high catalyst cost, limited substituent compatibility and the like still exist. Therefore, a novel photocatalysis method which has mild conditions and wide substrate range and can efficiently construct the diaryl hydrazine compounds is developed, and has important significance for expanding the synthesis strategy and application of the compounds. Disclosure of Invention The technical problem to be solved by the invention is how to construct the diaryl hydrazine compound efficiently. The invention solves the technical problems by the following technical means: mixing an azobenzene compound, an alkyl NHPI ester reagent, a photosensitizer, an alkaline reagent and a solvent, and reacting under the irradiation of visible light to obtain the diaryl hydrazine compound; Wherein the photosensitizer is one or two mixtures of 2,4,5, 6-tetra (carbazole-9-yl) -1, 3-dicyanobenzene, bis [2- (2, 4-difluorophenyl) -5-trifluoromethyl pyridine ] [2-2' -bis (4-tertiary butyl pyridine) ] iridium hexafluorophosphate, and the alkaline reagent is one or more mixtures of N, N-diisopropylethylamine, potassium phosphate and 1, 8-diazabicyclo [5.4.0] undec-7-ene DBU; The structural formula of the azobenzene compound is as follows: ; The structural formula of the NHPI ester reagent of the alkyl is as follows: The structural formula of the diaryl hydrazine compound is as follows: ; Wherein R is selected from one or more of hydrogen, alkyl and halogen, R 'is selected from cyclohexyl, adamantyl, 1- ([ 1,1' -biphenyl ] -4-yl) propane-1-keto ] ) One or more of the following. Preferably, the alkyl (including straight chain, branched chain and cycloalkyl) has one or more of 1-6 carbon atoms, and halogen is one or more of fluorine, chlorine, bromine and iodine. Preferably, the structural formula of the azobenzene compound is one of the following structural formulas: 、、。 Preferably, the structural formula of the NHPI ester reagent of alkyl is one of the following structural formulas: 、、。 Preferably, the structural formula of the diaryl hydrazine compound is one of the following structural formulas: 、、; Wherein R is selected from one or more of hydrogen, alkyl and halogen. Preferably, the molar ratio of the azobenzene compound to the NHPI ester reagent of the alkyl is 1:1-5, the molar ratio of the azobenzene compound to the photosensitizer is 1:0.01-0.10, and the molar ratio of the azobenzene compound to the alkaline reagent is 1:1-3. Preferably, the molar ratio of the azobenzene compound to the NHPI ester reagent of the alkyl is 1:2, the molar ratio of the azobenzene compound to the photosensitizer is 1:0.04, and the molar ratio of the azobenzene compound to the alkaline reagent is 1:2.5. Preferably, the solvent is at least one of tetrahydrofuran, acetonitrile, toluene, dichloroethane, methanol, N-dimethylformamide, chloroform, dioxane, and dichloromethane. Preferably, the wavelength of the visible light is 380-525 nm. Preferably, the wavelength band of the visible light is at least one of 380 nm to 390 nm, 420 nm to 430 nm, 450 nm to 455 nm and 520 nm to 525 nm. Preferably, the reaction temperature is 10-80 ℃ and the reaction time is 8-18 h. Preferably, the temperature of the reaction is room temperature. Preferably, the azobenzene compound and the solvent are used in an amount ratio of 0.1mmol to 2ml. Preferably, the reaction is carried out under the condition that the stirring speed is 300 rpm to 700 rpm. Preferably, the reaction product is separated and purified after the reaction is finished. Preferably, the specific operations of separation and purification comprise the steps of extracting a reaction product with dichloromethane, drying the reaction product by anhydrous Na 2SO4, distilling the reaction pr