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Synthetic method for 1,4-dithioalkyl benzene and halide thereof

A technology of disulfide benzene and benzene dithiol, which is applied in the preparation of hydrogenated polysulfides/polysulfides, mercaptans, and sulfides, and can solve the problem of high production costs and the flammability and explosion of tert-butyllithium , many reaction steps, etc., to achieve the effect of large-scale industrial production, good safety and controllability

Inactive Publication Date: 2017-02-08
XIANGTAN UNIV
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Problems solved by technology

But the biggest disadvantage of this method is that tert-butyllithium must be used, and tert-butyllithium is extremely flammable and explosive, so it is difficult to apply in industrial production; (2) 1,4-dibromobenzene reacts with n-butyllithium , and then react with dimethyl disulfide, and then use metal sodium to remove the methyl group at a high temperature of 130 ° C, and obtain 1,4-benzenedithiol after acidification. This reaction requires the use of highly toxic dimethyl disulfide Sulfur, and many reaction steps, high production cost

Method used

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  • Synthetic method for 1,4-dithioalkyl benzene and halide thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0013] Feed ratio: 4-bromothiophenol: potassium carbonate: 1-bromo-2-hexyldecane=1:1.5:1 (molar ratio), N,N-dimethylformamide is used as an organic solvent, and its consumption is 4 -5 times that of bromothiophenol.

[0014] Add 10 g (52.89 mmol) of 4-bromothiophenol, 100 mL of N, N-dimethylformamide, and 10.94 g (79.33 mmol) of anhydrous potassium carbonate into a 250 mL three-necked flask equipped with a magnetic stirrer and a reflux condenser. Under argon protection, stirred at room temperature for 30 minutes, 1-bromo-2-hexyldecane 16.2mL (52.89mmol) was added dropwise into the reaction system with a constant pressure dropping funnel, and the reaction temperature was gradually raised to 85°C. React for 24 hours. After the reaction was completed, cool to room temperature, pour the reaction solution into 150 mL of ice water, stir for 10 minutes, then extract petroleum ether as the extractant 3 times, 100 mL each time, combine the organic phases, and wash the organic phases w...

Embodiment 2

[0020] Feed ratio: 4-bromothiophenol: n-butyllithium: sulfur powder=1:2:1 (molar ratio), tetrahydrofuran is used as an organic solvent, and its dosage is 5 times that of 4-bromothiophenol.

[0021] In a 50mL three-necked flask equipped with a magnetic stirrer, 1.037g (5.48mmol) of 4-bromothiophenol was fully dissolved in 5mL of anhydrous tetrahydrofuran, cooled to -78°C under the protection of argon, and then 4.4mL (2.5 mol / L, 10.96mmol) n-butyllithium solution, after dripping, continue to react at -78°C for 2 hours, add sulfur powder 0.175g (5.48mmol) at low temperature, continue to react for 3 hours, add 10 % hydrochloric acid solution 10mL, stirred and reacted for 1 hour, after the reaction was completed, dichloromethane was used as the extractant, extracted 3 times, 15mL each time, the organic phase was combined, and the organic phase was washed 3 times with distilled water, 20mL each time. The organic phase was dried with anhydrous sodium sulfate, filtered with suction, a...

Embodiment 3

[0028] 2,5-dibromo-1,4-bis(2-hexyldecylthio)benzene preparation ratio is: 1,4-bis(2-hexyldecylthio)benzene: liquid bromine=1:2.5 (molar ratio), dichloromethane is used as an organic solvent, and its consumption is 5 times of 1,4-bis(2-hexyldecylthio)benzene.

[0029] Add 2.4g (4.06mmol) 1,4-(2-hexyldecylthio)benzene and 25mL dichloromethane into a 100mL two-necked flask equipped with a magnetic stirrer and a constant pressure dropping funnel, stir well, and then add iodine Elemental substance 0.026g (0.1mmol), and liquid bromine 0.52mL (10.15mmol) was slowly added dropwise to the reaction solution with a constant pressure dropping funnel under ice bath. After the reaction was completed, the reaction solution was poured into 50 mL of sodium thiosulfate aqueous solution, stirred for 10 minutes, and then extracted three times with petroleum ether, 25 mL each time, the organic phases were combined, and the organic phase was washed with water 3 times, 30 mL each time. The organic ...

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Abstract

The invention relates to a synthetic method for 1,4-dithioalkyl benzene and halide thereof. According to the method, 4-bromothiophenol is used as a raw material and reacts with alkyl bromide to synthesize 4-bromo-1-thioalkyl benzene, and then a reaction is carried out to synthesize 1,4-dithioalkyl benzene; or 4-bromothiophenol successively reacts with n-butyl lithium, sulfur powder and acid to synthesize 1,4-benzenedithiol, and then1,4-benzenedithiol reacts with alkyl bromide to synthesize 1,4-dithioalkyl benzene; and 1,4-dithioalkyl benzene can be further halogenated. The synthetic method provided by the invention does not need flammable and combustible t-butyl lithium, so the synthetic method has better security and controllability, is favorable for large-scale industrial production, reduces production cost and is environment friendly.

Description

technical field [0001] The invention belongs to the field of organic chemical synthesis and relates to a method for synthesizing 1,4-disulfanylbenzene and its halides. Background technique [0002] In the existing method, the synthetic method of 1,4-disulfanylbenzene is usually to adopt 1,4-benzenedithiol and bromoalkane and potassium carbonate to prepare under high temperature conditions, yet, 1,4-benzenedithiol The price of mercaptan is expensive, the unit price is close to 800 yuan / gram, so it is difficult to realize industrial application. There are two ideas to solve this problem: one is to reduce the production cost of 1,4-benzenedithiol; the other is not to use 1,4-benzenedithiol to prepare 1,4-disulfanylbenzene. [0003] At present, there are two synthetic methods for 1,4-benzenedithiol: (1) 1,4-dibromobenzene reacts with tert-butyllithium, and then reacts with sulfur and acid successively to obtain 1,4-benzenedithiol Mercaptans. But the biggest disadvantage of th...

Claims

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Application Information

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IPC IPC(8): C07C319/22C07C321/28
CPCC07C319/02C07C319/14C07C319/22C07C323/09C07C321/26C07C321/28
Inventor 赵斌刘海路黄美华唐博
Owner XIANGTAN UNIV
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