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Method for preparing trinexapac-ethyl

A technology of trinexapac-ethyl and diethyl maleate, which is applied in the field of preparation of cyclohexanedicarboxylic acid high-efficiency plant growth regulator trinexapac-ethyl, can solve the problem of high toxicity of metal cyanide, increase of production cost, and unfavorable environmental protection and other problems, to achieve the effect of good product purity, reduced production cost, and mild reaction

Inactive Publication Date: 2006-10-25
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In method one, the hydrogen pressure when 3,5-dihydroxybenzoic acid is reduced to 3,5-cyclohexanedione-1-carboxylic acid needs to reach 95.28 atm, and the yield is also low, and expensive DMAP needs to be used as heavy Catalyst discharge increases the production cost; the metal cyanide in the second method is highly toxic, which is not conducive to environmental protection

Method used

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  • Method for preparing trinexapac-ethyl

Examples

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Embodiment 1

[0017] 1) Preparation of 2-acetonyl-1,4-diethyl succinate

[0018] Diethyl maleate (34.4g, 0.2mol), acetone (95.3g, 1.64mol) and dimethylamine (1.8g, 0.04mol) were dropped into a 500ml autoclave, heated to 150°C, and the pressure in the kettle was 10atm, and the temperature was kept React for 21 hours, cool to room temperature, remove low boilers at normal pressure, then distill under reduced pressure, collect fractions at 155-160°C / 5mmHg to obtain 39.8g of light yellow liquid with a yield of 86.5% and a content of more than 99%.

[0019] 2) Preparation of ethyl 3,5-cyclohexanedione-1-carboxylate

[0020] Drop into 40ml of 28% methanol solution of sodium methylate (10.8g, 0.056mol) in the reaction bottle, add dropwise 2-acetonyl-1,4-diethyl succinate (12g, 0.052mol), and heat to reflux after the dropwise addition After reacting for 5 hours, the reaction solution was cooled, concentrated to recover methanol, 80ml of water was added to the residue, extracted twice with 50ml of ...

Embodiment 2

[0024] 1) Preparation of 2-acetonyl-1,4-diethyl succinate

[0025] Diethyl maleate (34.4g, 0.2mol), acetone (95.3g, 1.64mol) and trimethylamine (2.4g, 0.041mol) were put into a 500ml autoclave, heated to 140°C, the pressure in the kettle was 15atm, and the reaction After 18 hours, cool to room temperature, remove low boilers at normal pressure, and then distill under reduced pressure to collect fractions at 155-160°C / 5mmHg to obtain 39.6g of light yellow liquid with a yield of 86.1% and a content of more than 99%.

[0026] 2) Preparation of ethyl 3,5-cyclohexanedione-1-carboxylate

[0027] Drop into 40ml of 15% sodium ethylate (25g, 0.055mol) ethanol solution in the reaction bottle, add dropwise 2-acetonyl-1,4-diethyl succinate (12g, 0.052mol), and heat to reflux after the dropwise addition After 5 hours, the reaction solution was cooled, concentrated to recover ethanol, 80ml of water was added to the residue, extracted twice with 50ml of dichloroethane to remove impurities, ...

Embodiment 3

[0031] 1) Preparation of 2-acetonyl-1,4-diethyl succinate

[0032] Diethyl maleate (34.4g, 0.2mol), acetone (95.3g, 1.64mol) and diethylamine (2.9g, 0.04mol) were put into a 500ml autoclave, heated to 160°C, the pressure in the kettle was 6atm, and the temperature was kept React for 24 hours, cool to room temperature, remove low boilers at normal pressure, then distill under reduced pressure, collect fractions at 155-160°C / 5mmHg to obtain 38.9g of light yellow liquid with a yield of 84.6% and a content of more than 99%. Preparation of ethyl 3,5-cyclohexanedione-1-carboxylate

[0033] 40ml of 10% sodium tert-butoxide (51.8g, 0.054mol) in tert-butanol solution was dropped into the reaction flask, and 2-acetonyl-1,4-diethyl succinate (12g, 0.052mol) was added dropwise. After completion, the reaction was heated under reflux for 5 hours, the reaction solution was cooled, concentrated to recover tert-butanol, 80ml of water was added to the residue, and 50ml of dichloroethane was us...

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Abstract

This invention discloses anti inverse ester preparation method. 2-acetonyl-1, 4 diethyl succiante is high pressure condensed by diethyl maleate and acetone under organic amine condition. Then it cycles to get 3, 5-dioxygen hexahydrobenzoic acid ethyl esterunder sodium alcoholate condition, finally anti inverse ester is got by reacting with ring third formic anhydride under alkali condition. The operation is simple, reaction is wild, material is easy to get, yield is high, product purity is high, and generating cost is reduced, so it is propitious to industrial manufacure.

Description

technical field [0001] The invention relates to a preparation method of trinexapac-ethyl, a high-efficiency plant growth regulator of cyclohexanedicarboxylic acids. Background technique [0002] The main preparation methods of existing trinexapac-ethyl are: method one (US 4,693,745, JP 59,163,346) is that starting material is 3,5-dihydroxybenzoic acid, obtains 3,5-cyclohexanedione-1-formic acid through hydrogenation reduction , and then esterified to obtain 3,5-cyclohexanedione-1-ethyl carboxylate, which was acylated with cyclopropanecarbonyl chloride to obtain 3-ethoxycarbonyl-5-oxocyclohex-1-enol ring Propionate, rearrangement reaction occurs under the catalysis of DMAP to obtain the target product trinexapac-ethyl. Method 2 (EP 0126713, US4803268) uses diethyl maleate and acetone as starting materials, and prepares 2-acetonyl-butyric acid diethyl ester through addition, and then condenses to form a ring in the presence of sodium ethoxide. Obtain 3,5-cyclohexanedione-1-f...

Claims

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Application Information

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IPC IPC(8): C07C67/347C07C69/757
Inventor 戴立言王晓钟陈英奇
Owner ZHEJIANG UNIV
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