Method for synthesizing 3-(methylthio) dibenzenamine by light/nickel concerted catalysis

A technology of methylthiodiphenylamine and methylthioaniline is applied in the field of synthesis of 3-methylthiodiphenylamine, a key intermediate of pyridazine drugs, and can solve the problems of expensive catalysts and ligands, and high industrial production costs. Achieve high coupling efficiency, shorten reaction time and reduce cost

Active Publication Date: 2018-08-17
SHAANXI NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The main disadvantage of this method is that the catalyst and l

Method used

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  • Method for synthesizing 3-(methylthio) dibenzenamine by light/nickel concerted catalysis
  • Method for synthesizing 3-(methylthio) dibenzenamine by light/nickel concerted catalysis
  • Method for synthesizing 3-(methylthio) dibenzenamine by light/nickel concerted catalysis

Examples

Experimental program
Comparison scheme
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Example Embodiment

[0034] Example 1

[0035] Under a nitrogen atmosphere, add 3-methylthioaniline (11.62g, 83.5mmol) and bromobenzene (8.74g, 55.7mmol) into a 250mL reaction flask containing 100mL N,N-dimethylformamide, and then add them sequentially NiBr 2 ·3H 2 O (0.30g, 1.114mmol), photocatalyst 1a (10.50mg, 0.011mmol), ethylene glycol dimethyl ether (0.10g, 1.114mmol), N,N-dimethylcyclohexylamine (12.76g, 100.26mmol) ), the reaction solution was raised to 50°C and reacted for 12 hours under blue light with a wavelength of 465 nm. After the reaction, the light and heating were stopped. After the reaction flask was cooled to room temperature, the reaction solution was distilled under reduced pressure to remove N,N-di Methylformamide, N,N-dimethylcyclohexylamine; add n-hexane to dilute the residue, filter to remove insoluble inorganic salts in the residue, concentrate the filtrate, and distill under reduced pressure to obtain 10.7g of 3-methylthiodiphenylamine. The yield was 89%.

Example Embodiment

[0036] Example 2

[0037] In this example, the photocatalyst 1a in Example 1 was replaced with an equimolar photocatalyst 1b, and the other steps were the same as in Example 1, to obtain 11.1 g of 3-methylthiodiphenylamine with a yield of 92.5%.

Example Embodiment

[0038] Example 3

[0039] In this example, the photocatalyst 1a in Example 1 was replaced with an equimolar photocatalyst 1c, and the other steps were the same as in Example 1, to obtain 10.4 g of 3-methylthiodiphenylamine with a yield of 87%.

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Abstract

The invention discloses a method for synthesizing 3-(methylthio) dibenzenamine by light/nickel concerted catalysis. According to the method, cheap 3-(methylthio) benzenamine and halogeno benzene are used as raw materials, a light/nickel concerted catalysis strategy is used for constructing C-N bonds for the first time, and pyridazines drug key intermediate 3-(methylthio) dibenzenamine is synthesized. The method has the advantages that 1) the use amount of a photocatalyst is low, and is 0.01-0.02% of the molar weight of the halogeno benzene; 2) nickel salt is directly used as a metal catalyst such as nickel bromide, and an external ligand is not required; 3) reaction conditions are gentle, and can be effectively carried out at the temperature of 40-50 DEG C; and 4) the product can be directly obtained by reduced pressure distillation and is easily separated. By the remarkable advantages, the method has good industrial application prospect.

Description

technical field [0001] The invention relates to the synthesis of 3-methylthiodiphenylamine, a key intermediate of pyridazine drugs, and provides an efficient and green new method and technology for its preparation. Background technique [0002] Nausea and vomiting caused by cancer chemotherapy are one of the serious adverse reactions, which are often unbearable for patients. Therefore, the demand for high-efficiency antiemetic drugs is increasing, and the drug molecule metoprenazine is a dopamine D 2 Receptor antagonist, has a strong antiemetic function. In addition, thioridazine can block dopamine receptors, M-receptors and α-receptors to act on the central nervous system, autonomic nervous system and endocrine system, and is an antipsychotic drug. Mesoridazine is a metabolite of thioridazine. Its antipsychotic effect is similar to that of chlorpromazine, but with less extrapyramidal reactions. It is mainly used for schizophrenia and neurosis. Levomepromazine is a phenot...

Claims

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Application Information

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IPC IPC(8): C07C319/20C07C323/36
Inventor 黄治炎解昆孟鸽马俊杰薛东杨俊
Owner SHAANXI NORMAL UNIV
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