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A kind of method of NFSI-catalyzed synthesis of asymmetric disulfide derivatives

A technology of disulfide and derivatives, which is applied in the field of NFSI catalytic synthesis of asymmetric disulfide derivatives, which can solve problems such as limited application, non-compliance with environmental protection, and unpleasant smell of mercaptans

Active Publication Date: 2022-07-26
CHANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There are two main methods for the preparation of asymmetric disulfides. The first method uses two different mercaptans as raw materials to synthesize asymmetric disulfides by oxidative dehydrogenation. The disadvantage of this method is that the mercaptans have an unpleasant smell. , at the same time, this type of reaction will undergo self-coupling to obtain a symmetrical disulfide; the second type uses a disulfide reagent to react with a nucleophile under the action of a transition metal catalyst to obtain the target product. The defect of this type of reaction mainly lies in the use of metal Catalyst, does not meet the characteristics of green environmental protection
In addition, the use of transition metal rhodium catalysts can also realize the exchange reaction between symmetrical disulfide compounds to synthesize asymmetric disulfide derivatives, but the application of this strategy is limited due to the use of expensive rhodium catalysts.

Method used

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  • A kind of method of NFSI-catalyzed synthesis of asymmetric disulfide derivatives
  • A kind of method of NFSI-catalyzed synthesis of asymmetric disulfide derivatives
  • A kind of method of NFSI-catalyzed synthesis of asymmetric disulfide derivatives

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Experimental program
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Embodiment 1

[0019] The reaction equation involved in Example 1 is as follows:

[0020]

[0021] General method for the synthesis of asymmetric disulfide derivatives: 1,2-dichloroethane (10 mL), symmetrical disulfide A (1.0 mmol), and symmetrical disulfide B ( 1.0 mmol) and NFSI (0.1 mmol), the inverse temperature was controlled at 50 degrees Celsius, and the reaction was vigorously stirred for 4 hours. After the reaction is completed, the reaction solution is concentrated and separated by column chromatography in sequence to obtain the asymmetric disulfide derivative.

[0022] 1. According to the above experimental conditions, a series of asymmetric disulfides were synthesized, and their structures and yields are as follows:

[0023]

[0024] 2. NMR and mass spectrometry data:

[0025] (1) Compound C1: 1 H NMR (300MHz, Chloroform-d) δ 7.53–7.48 (m, 2H), 6.92–6.87 (m, 2H), 3.80 (s, 3H), 2.45 (s, 3H). 13 C NMR (75MHz, Chloroform-d) δ 159.76, 132.16, 127.81, 114.77, 55.44, 22.94. M...

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Abstract

The invention belongs to the field of fine chemicals, and relates to a method for synthesizing asymmetric disulfide derivatives catalyzed by NFSI, comprising the following steps: adding NFSI, symmetric disulfide A and symmetric disulfide B into reaction solvents 1, 2 In the sealed tube of dichloroethane, react at 25~80 ℃, finish the reaction after 1~8 hours of reaction, and obtain the asymmetric disulfide derivative through separation and purification, wherein NFSI, symmetric disulfide A and the symmetric disulfide B in a molar ratio of 0.1:1.0:1.0. The method can efficiently synthesize asymmetric disulfide derivatives without using expensive rhodium metal catalysts and unpleasant thiols.

Description

technical field [0001] The invention belongs to the field of fine chemicals and relates to a method for catalyzing and synthesizing asymmetric disulfide derivatives by NFSI. Background technique [0002] Asymmetric disulfides are an important class of sulfur-containing organic compounds, which are widely found in various natural products, medicines, foods and materials with medicinal activity. Therefore, how to directly and efficiently synthesize such compounds has attracted great attention of chemists. There are two main methods for preparing asymmetric disulfides. The first one uses two different mercaptans as raw materials to synthesize asymmetric disulfides by oxidative dehydrogenation. The disadvantage of such methods is that the smell of mercaptans is unpleasant. At the same time, this type of reaction will self-coupling to obtain a symmetrical disulfide; the second uses a disulfanyl reagent to react with a nucleophile under the action of a transition metal catalyst t...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C323/20C07C323/09C07C321/20C07C319/24C07D277/78
CPCC07C319/24C07D277/78C07C323/20C07C323/09C07C321/20
Inventor 杨科胡倾月宋梦杰张菲杨李正义孙小强
Owner CHANGZHOU UNIV