Synthetic method of cis-4-methoxycyclohexyl-1-carbamic acid

A methoxycyclohexyl and cis-4-technology, applied in the field of synthesis of carbamic acid chemicals, can solve problems such as few synthesis research reports, unsuitability for industrial production, lack of optimization of proportional equipment and process parameters, etc., and achieve improvement Effects of reaction yield, ease of operation, and shortened reaction time

Inactive Publication Date: 2019-05-24
NANTONG JIANGSHAN AGROCHEM & CHEM LIMITED LIABILITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] cis -4-Methoxycyclohexyl-1-carbamic acid is an important intermediate for the synthesis of spirotetramat, and its chiral intermediate is also the core part of the insecticidal activity of spirotetramat, but the synthesis research reports related to it are relatively There are mainly two types: the first 、 Yes cis -8-Methoxy-1,3-diazaspiro[4,5]decane-2,4-dione, alkaline hydrolysis in an autoclave to obtain the target product, the product obtained by this method has more The cis product is convenient for the separation of the following configurations, and is more suitable for industrial production; the second method 、 Methoxycyclohexanone reacts with ammonium chloride and sodium cyanide, and the obtained product is hydrolyzed under acidic conditions to obtain the target product, but the target cis product obtained by this method has only 50% content, so it is necessary to obtain a relatively pure product It also needs to go through a complicated separation process, which is not suitable for industrial production
[0003] The synthesis and optimization of cis-4-methoxycyclohexyl-1-carbamic acid published in the October 2018 issue of "Pesticides" lacks an optimal plan for the ratio of raw materials, equipment used, and process parameters, etc.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Step a: add ethanol 640g in autoclave, p-hydroxyanisole 200g (99%), catalyzer RaneyNi33g, feed finishes, seal autoclave, replace 3 times with nitrogen, hydrogen is discharged nitrogen, logical hydrogen reaction, temperature is controlled at 70°C~80°C, keep the pressure at about 1.5 MPa, react for 6h, cool down to remove hydrogen, filter to remove ethanol, and get 208.7g of 4-methoxy-1-hydroxy-cyclohexane (content 94.5%), yield 95.0%. Ethanol and catalyst RaneyNi are recovered and reused.

[0026] Step b: Preparation of acidification solution: Add 673.78 g of water into a three-necked flask, stir and add 160.87 g of chromic anhydride with a content of 99%, add 268.56 g of 30% sulfuric acid dropwise, control the reaction temperature at 60°C, and add water after the dropwise addition 224.59 g, cooled to 25°C to obtain an acidified solution.

[0027] In the three-necked flask, add 208.7g of 94.5% 3-methoxy-1-hydroxy-cyclohexane (intermediate 1), stir and add the above aci...

Embodiment 2

[0034] Step a: add ethanol 640g in autoclave, p-hydroxyanisole 200g (99%), catalyzer RaneyNi33g, feed finishes, seal autoclave, replace 3 times with nitrogen, hydrogen is discharged nitrogen, logical hydrogen reaction, temperature is controlled at 60℃~70℃, keep the pressure at about 0.5 MPa, react for 6h, cool down to remove hydrogen, filter to remove ethanol, and get 208.7g of 4-methoxy-1-hydroxy-cyclohexane (content 94.5%), yield 95.0%. Recycling and reuse of ethanol and catalyst RaneyNi.

[0035] Step b: Preparation of acidification solution: Add 654.51 g of water into a three-necked flask, stir and add 156.28 g of chromic anhydride with a content of 99%, add 242.62 g of 30% sulfuric acid dropwise, and control the reaction temperature at 60°C. 224.59 g of water was added, and the temperature was lowered to 25° C. to obtain an acidified solution.

[0036] The acidification solution and intermediate 1 (208.7 g) with a content of 94.5% were fed into the microreactor at the s...

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PUM

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Abstract

The invention provides a synthetic method of cis-4-methoxycyclohexyl-1-carbamic acid. The synthetic method includes the steps of catalytic hydrogenation, oxidative reaction, replacement reaction and hydrolytic reaction; the hydrolytic reaction is carried out in a microreactor, with a Jones reagent acting as an oxidant; barium hydroxide octahydrate is used as an alkaline material in the hydrolyticreaction. The synthetic method has few steps and shorter reaction time; the salt content in reaction wastewater is low, the content of heavy metals is low, and discharged waste is little; the finishedproduct has the content of 98% and above; the total reaction yield is 45% and above.

Description

technical field [0001] The invention relates to a synthesis method of carbamic acid chemicals. Background technique [0002] cis -4-Methoxycyclohexyl-1-carbamic acid is an important intermediate for the synthesis of spirotetramat, and its chiral intermediate is also the core part of the insecticidal activity of spirotetramat, but the synthesis research reports related to it are relatively There are mainly two types: the first 、 yes cis -8-Methoxy-1,3-diazaspiro[4,5]decane-2,4-dione, alkaline hydrolysis in an autoclave to obtain the target product, the product obtained by this method has more The cis product is convenient for the separation of the following configurations, and is more suitable for industrial production; the second method 、 Methoxycyclohexanone reacts with ammonium chloride and sodium cyanide, and the obtained product is hydrolyzed under acidic conditions to obtain the target product, but the target cis product obtained by this method has only 50% content,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C269/00C07C271/02
Inventor 杜辉于春红秦欢郭磊
Owner NANTONG JIANGSHAN AGROCHEM & CHEM LIMITED LIABILITY
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