Synthesis method for 1,3,5-trithio heterocyclic hexane derivative

A technology for cyclohexane and derivatives, which is applied in the field of synthesizing 1,3,5-trithiacyclohexane derivatives by using unsaturated acetate, which can solve the problems of low reactivity, restrictions on promotion and use, environmental and human hazards, etc. problems, to achieve the effect of low reaction temperature, less side reactions, and environmental protection in the production process

Active Publication Date: 2016-08-10
HEBEI UNIVERSITY OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the low chemical reactivity of divinyl sulfide, this method requires the use of HgCl 2 as catalyst, while HgCl 2 It is a highly toxic mercury chemical, which is very harmful to the environment and human body, so the promotion and use of this method is greatly restricted

Method used

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  • Synthesis method for 1,3,5-trithio heterocyclic hexane derivative
  • Synthesis method for 1,3,5-trithio heterocyclic hexane derivative
  • Synthesis method for 1,3,5-trithio heterocyclic hexane derivative

Examples

Experimental program
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Effect test

Embodiment 1

[0041] Example 1, Synthesis of 2,4,6-triethyl-1,3,5-trithiocyclohexane.

[0042] Add 98.0g of propylene acetate and 200g of ethylene glycol dimethyl ether into a 500ml four-necked flask (equipped with a thermometer, gas inlet tube and gas outlet tube), slowly pass hydrogen sulfide gas (see formula 6) under mechanical stirring, and react The temperature is controlled at 20°C, and the unreacted hydrogen sulfide gas is led out from the gas outlet pipe and absorbed by sodium hydroxide aqueous solution. After reacting for 6 hours, the reaction solution was poured out, and the solvent and the produced acetic acid were recovered by distillation under reduced pressure at 42° C. to obtain a yellow solid. Then add 15g activated carbon and 180ml dichloromethane, heat to 50℃ to dissolve the yellow solid and reflux for 30min, filter to remove the activated carbon while hot, cool the filtrate to 0℃, filter, and circulate the filtrate. The solid is vacuumed at 30℃ (gauge pressure) 0.095MPa) an...

Embodiment 2

[0046] Example 2. Synthesis of 2,4,6-triethyl-1,3,5-trithiocyclohexane.

[0047] Add 200.0g of propylene acetate and 380g of dichloroethane into a 1000ml pressure reactor (installed with a thermometer, gas inlet pipe and gas outlet pipe), slowly pass in hydrogen sulfide gas under mechanical stirring (see formula 7), and control the reaction temperature At 50°C, the pressure of the reactor is controlled at 20atm, and the reaction is carried out for 1.5h under this condition, the gas outlet is slowly opened, and the unreacted hydrogen sulfide gas is absorbed by sodium hydroxide aqueous solution to obtain sodium sulfide. Then, the solvent and the generated acetic acid were recovered by distillation under reduced pressure (gauge pressure 0.095MPa) at 40°C to obtain a yellow solid. Add 27g molecular sieve and 350ml petroleum ether, heat to 60℃ to dissolve the yellow solid and reflux for 60min, filter to remove the molecular sieve while hot, cool the filtrate to 40℃, filter, and circul...

Embodiment 3

[0051] Example 3. Synthesis of 2,4,6-triethyl-1,3,5-trithiocyclohexane.

[0052] Add 98.0g of propylene acetate, 150g of tetrahydrofuran and 60g of water into a 500ml four-necked flask (equipped with a thermometer, gas inlet pipe and gas outlet pipe), slowly pass hydrogen sulfide gas under mechanical stirring (see formula 8), and control the reaction temperature At 23°C, the unreacted hydrogen sulfide gas was led out from the gas outlet pipe and absorbed by the sodium hydroxide aqueous solution. After reacting for 35 hours, the reaction liquid was poured out, and the solvent and the generated acetic acid were distilled at 60° C. under reduced pressure (gauge pressure 0.095 MPa) to obtain a yellow solid. Then add 19g diatomaceous earth and 190ml tetrahydrofuran, heat to 40℃ to dissolve the yellow solid and reflux for 50min, filter to remove the diatomaceous earth while hot, cool the filtrate to 30℃, filter, and recycle the filtrate. The solid is vacuumed at 25℃ ( Gauge pressure (...

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Abstract

The invention discloses a method for synthesizing a 1,3,5-trithio heterocyclic hexane derivative through a chemical reaction with unsaturated acetate and hydrogen sulfide as main raw materials. The method includes the operating steps that unsaturated acetate and a solvent are added to a reactor, hydrogen sulfide is slowly added, the reaction is conducted for 0.1-30 h at the internal pressure (gage pressure) of the reactor being 1-20 atm and the temperature of -30-150 DEG C, a catalyst is filtered away, filtrate is subjected to reduced pressure (gage pressure is 0.1-0.095 MPa) distillation, a solvent and generated acetic acid are recycled, and a solid product is obtained. Then the obtained solid product is dissolved in a preset solvent, a decoloring agent is added, stirring is conducted for 0.1-35 h at the temperature of 20-100 DEG C, a decoloring agent is filtered away, filtrate is cooled to 0-40 DEG C, filtering is conducted, and the colorless or light yellow solid 1,3,5-trithio heterocyclic hexane derivative is obtained. According to the method for synthesizing the 1,3,5-trithio heterocyclic hexane derivative, the raw materials are low in price and easy to obtain, the technological process is simple, the product yield is 85% or above, and the production process is safer and more reliable.

Description

Technical field [0001] The present invention belongs to the field of organic synthesis, and relates to a new method for synthesizing 1,3,5-trithiacyclohexane derivatives, especially the synthesis of 1,3,5-trithiacyclohexane derivatives using unsaturated acetates Methods. Background technique [0002] 1,3,5-Trithiacyclohexane derivatives are an important class of compounds, which are widely found in pork and beef, as well as in fruits. They have a sulfur-like aroma and a nut-like aroma. And taste is a kind of highly safe edible and industrial spices announced by the United Nations Food Program, so it is widely used in food, flavor, perfume, washing powder, liquid detergent and other fields. At present, 1,3,5-trithiane derivatives are mainly prepared by chemical reaction synthesis methods, but the existing synthesis methods have various deficiencies. So far, 1,3,5-trithiacyclohexane derivatives mainly have the following synthesis methods: [0003] (1) Alkenyl ether method [0004] ...

Claims

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Application Information

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IPC IPC(8): C07D341/00
CPCC07D341/00
Inventor李军章张志伟冯娟
OwnerHEBEI UNIVERSITY OF SCIENCE AND TECHNOLOGY