Synthetic method of 1,3,5-trithiane derivatives

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 popularization and use restrictions, environmental and human hazards, low reactivity, etc. problems, to achieve the effect of low synthesis cost, less side reactions, and low reaction temperature

Active Publication Date: 2018-05-15
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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  • Synthetic method of 1,3,5-trithiane derivatives
  • Synthetic method of 1,3,5-trithiane derivatives
  • Synthetic method of 1,3,5-trithiane derivatives

Examples

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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 propylene acetate and 200g ethylene glycol dimethyl ether into a 500ml four-necked flask (installed with a thermometer, a gas inlet tube and a gas outlet tube), slowly introduce 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 exported from the gas outlet pipe and absorbed by aqueous sodium hydroxide solution. After reacting for 6 h, the reaction solution was poured out, and the solvent and the generated acetic acid were recovered by distillation under reduced pressure at 42° C. to obtain a yellow solid. Then add 15g of activated carbon and 180ml of dichloromethane, heat to 50°C to dissolve the yellow solid and reflux for 30min, filter while hot to remove the activated carbon, cool the filtrate to 0°C, filter, and recycle the filtrate. The solid is vacuumed at 30°C (gauge pressure) ...

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, a gas inlet pipe and a gas outlet pipe), slowly introduce hydrogen sulfide gas (see formula 7) under mechanical stirring, and control the reaction temperature At 50°C, the pressure of the reactor was controlled at 20 atm, and the reaction was carried out for 1.5 hours under this condition, and the gas outlet was slowly opened, and the unreacted hydrogen sulfide gas was absorbed with aqueous sodium hydroxide solution to obtain sodium sulfide. Then, the solvent and the generated acetic acid were distilled under reduced pressure (gauge pressure 0.095 MPa) at 40° C. to obtain a yellow solid. Add 27g of molecular sieve and 350ml of petroleum ether, heat to 60°C to dissolve the yellow solid and reflux for 60min, filter while hot to remove the molecular sieve, cool the filtrate to 40°C...

Embodiment 3

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

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

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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 invention belongs to the field of organic synthesis, and relates to a new method for synthesizing compound 1,3,5-trithiacyclohexane derivatives, in particular, using unsaturated acetate to synthesize 1,3,5-trithiacyclohexane derivatives Methods. Background technique [0002] 1,3,5-Trithiacyclohexane derivatives are an important class of compounds, which are widely found in pork and beef, and also in fruits. They have a sulfur-like aroma and a nut-like aroma It is a kind of food and industrial spices with high safety announced by the United Nations Food Program, so it is widely used in food, essence, perfume, washing powder, liquid detergent and other fields. At present, 1,3,5-trithiane derivatives are mainly prepared by chemical reaction synthesis, but the existing synthesis methods have various deficiencies. So far, 1,3,5-trithiane derivatives mainly have the following synthetic methods: [0003] (1) Alkenyl ether method [0004] Korchevin, N....

Claims

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Application Information

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