Method for synthesizing n-thiobenzyl imine or its derivatives by bunte salt

A technology of thiobenzyl imine and derivatives, which is applied in the field of organic synthesis, can solve the problems of large environmental hazards, small substrate range, and raw material restrictions, and achieve the effects of reasonable process conditions, lower reaction temperature, simple and safe operation

Active Publication Date: 2021-09-28
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0012] There are some disadvantages in the above methods, such as the limited raw materials, the limited range of substrates, or the unavoidable use of thiophenols with bad smell. Even if disulfide is used as the sulfur source, the reaction process will generate thiophenols or Thiophenol pre-prepared reaction substrate
The use of various additives also increases the cost of the reaction, which is harmful to the environment and does not conform to the development direction of green chemistry.

Method used

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  • Method for synthesizing n-thiobenzyl imine or its derivatives by bunte salt
  • Method for synthesizing n-thiobenzyl imine or its derivatives by bunte salt
  • Method for synthesizing n-thiobenzyl imine or its derivatives by bunte salt

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047]Add 0.0428g (0.4mmol) benzylamine, 0.09g (0.6mmol) sodium methylthiosulfate, 0.0574g (0.4mmol) cuprous bromide and 2mL (25mmol) N,N- dimethylformamide. The reaction was stirred at 80°C for 10h. After the reaction, the reaction solution was diluted with 20 mL of water, extracted three times with 15 mL of ethyl acetate, the organic phases were combined, washed with saturated brine, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (the eluent was a mixture of petroleum ether and ethyl acetate, the volume ratio of which was 50:1) to obtain 0.0423 g of N-methylthiobenzyl imine with a yield of 70%.

[0048] N-methylthiobenzyl imine 1 H NMR diagram see figure 1 , N-Methylthiobenzimine 13 C NMR chart see figure 2 .

[0049] 1 H NMR (500MHz, Chloroform-d) δ8.31(s, 1H), 7.62(dd, J=7.8, 1.9Hz, 2H), 7.37(td, J=5.9, 2.8Hz, 3H), 2.76(s, 3H); ...

Embodiment 2

[0052] Add 0.0744g (0.4mmol) p-bromobenzylamine, 0.09g (0.6mmol) sodium methylthiosulfate, 0.0574g (0.4mmol) cuprous bromide and 2mL (25mmol) N to a 35mL thick-walled pressure-resistant tube, N-Dimethylformamide. The reaction was stirred at 80°C for 10h. After the reaction, the reaction solution was diluted with 20 mL of water, extracted three times with 15 mL of ethyl acetate, the organic phases were combined, washed with saturated brine, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (the eluent was a mixture of petroleum ether and ethyl acetate, the volume ratio of which was 30:1) to obtain 0.0614 g of N-methylthio-4-bromobenzyl imine with a yield of 67 %.

[0053] N-methylthio-4-bromobenzyl imine 1 H NMR diagram see image 3 , N-methylthio-4-bromobenzimine 13 C NMR diagram see Figure 4 .

[0054] 1 H NMR (500MHz, Chloroform-d) δ...

Embodiment 3

[0057] Add 0.07g (0.4mmol) 4-trifluoromethylbenzylamine, 0.09g (0.6mmol) sodium methylthiosulfate, 0.0574g (0.4mmol) cuprous bromide and 2mL ( 25mmol) N,N-dimethylformamide. The reaction was stirred at 80°C for 10h. After the reaction, the reaction solution was diluted with 20 mL of water, extracted three times with 15 mL of ethyl acetate, the organic phases were combined, washed with saturated brine, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (the eluent was a mixture of petroleum ether and ethyl acetate, and the volume ratio of the two was 10:1) to obtain 0.0569 g of N-methylthio-4-trifluoromethylbenzyl imine, producing The rate is 65%.

[0058] N-Methylthio-4-trifluoromethylbenzyl imine 1 H NMR diagram see Figure 5 , N-methylthio-4-trifluoromethylbenzyl imine 13 C NMR diagram see Image 6 , N-methylthio-4-trifluoromethylbenzyl ...

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Abstract

The invention discloses a method for synthesizing N-thiobenzyl imine or its derivatives from Bunte salt. The method uses benzylamine or benzylamine derivatives and Bunte salt as raw materials, uses cuprous bromide as a catalyst, and uses N,N-dimethylformamide as a solvent to fully react at 70 to 90°C. , the reaction solution is separated and purified to obtain N-thiobenzyl imine or its derivatives. The method of the invention is simple and safe, does not require the presence of oxidants and additives, adds cuprous bromide as a catalyst, reduces the reaction temperature, improves the reaction yield, avoids the use of raw materials such as mercaptan with bad smell, has less three wastes, and is environmentally friendly.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a method for synthesizing N-thiobenzyl imine or derivatives thereof from Bunte salt (organic thiosulfate). [0002] technical background [0003] N-thiobenzyl imine derivatives, also known as thioximes, are important synthetic intermediates in the field of organic synthesis, widely used in N-sulfinimide, N-sulfonimide, β-lactam , N-vinyl formamide and other bio-organic molecules in the synthesis. The sulfur sources used in the reported synthetic methods are mainly N-(thio)phthalimide, sulfenamide, thiophenol and disulfide. E.g: [0004] Document 1 (Jordi Burés, Carles Isart, and Jaume Vilarrasa, Efficient Preparation of N-Phenylsulfenyl Ketimines from Oximes or Nitro Compounds without Racemization of α-Stereocenters [J]. Organic letters, 2007, 9, 4635-4638.) uses oxime and N- (thio)phthalimide, with trimethylphosphine (PMe 3 ) as a reducing agent, using tetrahydrofuran...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C313/20
CPCC07C313/20
Inventor 易文斌刘帆敏赫五卷
Owner NANJING UNIV OF SCI & TECH
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