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A kind of preparation method of selectively synthesizing cis-4-n-pentyl cyclohexanethiol

A technology of n-pentylcyclohexanone and n-pentyl ring is applied in the field of selective synthesis of cis-4-n-pentylcyclohexanethiol, and can solve the problem of high difficulty in separation and purification, high cost of raw materials and great potential safety hazard. and other problems, to achieve the effect of high cis-product selectivity and simple operation

Active Publication Date: 2018-10-19
DALIAN JOIN KING FINE CHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the route (1), Grignard reagent is used to add sulfur powder in batches. During the scale-up production process, anaerobic conditions are not easy to achieve, and cyclohexanol derivatives are easily generated as oxidation by-products. This by-product is similar in nature to cyclohexanethiol. Purification is difficult and seriously affects subsequent reactions
The use of lithium aluminum hydride for deprotection in route (2) not only has high raw material costs, but also poses a greater safety hazard in the large-scale use of lithium aluminum hydride
[0003] In addition to the inconvenience in the operation of the reaction, there is no report on the route that can be used to synthesize cis or trans structure 1,4-cyclohexanethiol with high selectivity

Method used

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  • A kind of preparation method of selectively synthesizing cis-4-n-pentyl cyclohexanethiol

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] first step:

[0018] 22.2g (586.8mmol, 0.3eq) of sodium borohydride and 351.0g of tetrahydrofuran were added to a 2L four-necked flask, and 78.0g (4329.0mmol, 2.2eq) of water was added dropwise under mechanical stirring. After 20 minutes, the temperature of the kettle was basically maintained at 21°C. No significant changes. Then the four-necked bottle was placed in an ice machine and cooled to -5°C for use.

[0019] A solution prepared by 330.0 g of n-pentylcyclohexanone (1961.0 mmol, 1.0 eq) and 171.0 g of tetrahydrofuran was added dropwise, the temperature of the kettle was controlled at -5-5°C, the dropwise addition was completed in 1.5 h, and the stirring was continued for 1.0 h.

[0020] 308.4g (592.0mmol, 0.3eq, 7.0Wt.%) hydrochloric acid was added dropwise to quench the reaction, the temperature of the kettle was controlled at 5-20°C, dichloroethane was added for extraction twice, and the two oil phases were separated and combined. Water was added to wash unti...

Embodiment 2

[0031] first step:

[0032] 2.6g (69.2mmol, 0.3eq) of sodium borohydride and 41.2g of tetrahydrofuran were added to a 250mL four-necked bottle, and 9.1g (507.2mmol, 2.2eq) of water was added dropwise under mechanical stirring. After 20 minutes, the temperature of the kettle was basically maintained at 21°C. No significant changes. Then the four-necked bottle was placed in an ice machine and cooled to -5°C for use.

[0033] A solution prepared by 38.8g (230.6mmol, 1.0eq) of n-pentylcyclohexanone and 19.4g of tetrahydrofuran was added dropwise, the temperature of the kettle was controlled at -5-5°C, the dropwise addition was completed in 0.5h, and the stirring was continued for 1.0h.

[0034] 36.1 g of hydrochloric acid was added dropwise to quench the reaction, the temperature of the kettle was controlled at 5-20° C., dichloroethane was added to extract twice, and the two oil phases were separated and combined. Water was added to wash until neutral, and the oil layer was spin...

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Abstract

The invention relates to a preparation method for selectively synthesizing cis-4-n-amyl cyclohexylmereaptan, which belongs to the field of organic synthesis. The method comprises the following steps: 4-pentylcyclohexanone and sodium borohydride are added into a tetrahydrofuran water mixed solvent, the materials are subjected to a reduction reaction to obtain the 4-amylcyclohexanol; the 4-amylcyclohexanol and methylsulfonyl chloride are subjected to a methyl sulfonylation reaction in a dichloroethanes solvent, the 4-n-amyl cyclohexyl sulfonate with content of more than 98% can be obtained through crystallization; the 4-n-amyl cyclohexyl sulfonate and potassium thioacetate are subjected to a sulfur acetylation reaction in a N,N-dimethyl formamide solvent to obtain the thiolacetic acid-4-n-amyl cyclohexyl ring; the material is subjectd to a low-temperature saponification reaction in a methanol hydrosolvent to obtain the cis-4-n-amyl cyclohexylmereaptan, and the cis products selectivity is greater than 99%. The method has the advantages of short reaction time, simple operation, and high cis products selectivity.

Description

technical field [0001] The invention relates to a preparation method for selectively synthesizing cis-4-n-pentylcyclohexanethiol, which belongs to the field of fine chemical intermediate synthesis. Background technique [0002] 4-Alkylcyclohexanethiol is an important fine chemical intermediate. The main synthesis methods are: (1) Grignard reagent prepared by cyclohexyl halide and reacted with sulfur powder to prepare cyclohexanethiol (see: US20030224298,2003 ); (2) Reaction of cyclohexyl methanesulfonate with potassium thioacetate, and then deprotection using lithium aluminum hydride to obtain cyclohexanethiol (see: J.Phys.Chem.C 2012, 116, 13559). In the route (1), Grignard reagent is used to add sulfur powder in batches. During the scale-up production process, anaerobic conditions are not easy to achieve, and cyclohexanol derivatives are easily generated as oxidation by-products. This by-product is similar in nature to cyclohexanethiol. The purification is difficult and s...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/02C07C321/22
CPCC07C29/143C07C303/28C07C319/02C07C327/22C07C321/22C07C35/08C07C309/66
Inventor 戴耀梁全德赵丹阳刘玲玲王维新王荣良
Owner DALIAN JOIN KING FINE CHEM CO LTD
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