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Synthetic method of plant growth regulator trinexapac-ethyl intermediate 3-carbethoxy-5-oxo-cyclohexane-1-enol cyclopropanecarboxylate

A kind of technology of enol cyclopropanecarboxylate and ethoxycarbonyl, which is applied to the synthesis of plant growth regulator trinexapac-ethyl intermediate 3-ethoxycarbonyl-5-oxocyclohex-1-enol cyclopropanecarboxylate It can solve the problems of high product yield, increased material loss, environmental pollution, etc., and achieve the effects of short reaction time, easy operation and process safety.

Active Publication Date: 2015-04-08
JIANGSU YOUJIA CHEM +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This not only increases material loss, but also causes environmental pollution, and the highest product yield is only 82%.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] (1) Preparation of 2-acetonyl-butyric acid diethyl ester

[0029] Diethyl maleate (344g, 2mol), acetone (953g, 16.4mol) and diethylamine (29g, 0.4mol) were put into a 2L autoclave, heated to 155°C, and the pressure inside the kettle was 1MPa, kept for 20h, cooled After reaching room temperature, remove low boilers under normal pressure and distill under reduced pressure, collect fractions at 155°C~160°C (5mmHg) to obtain 398g of light yellow liquid with a yield of 86.5%.

[0030] (2) Synthesis of 3-ethoxycarbonyl-5-oxocyclohex-1-enol-cyclopropanecarboxylate

[0031] Put 52g of solid sodium methoxide and 1000g of toluene into a dry four-necked bottle; start stirring, raise the temperature to 50°C, add 200g of 2-acetonyl-butyric acid diethyl ester obtained in step (1) dropwise, after the dropwise addition, keep warm for 1hr . After the heat preservation is completed, 50 g of methanol is added and the temperature is lowered to 0-10° C., 100 g of N,N-dimethylaniline is ad...

Embodiment 2

[0035] (1) The preparation of 2-acetonyl-butyric acid diethyl ester is the same as in Example 1.

[0036] (2) Synthesis of 3-ethoxycarbonyl-5-oxocyclohex-1-enol-cyclopropanecarboxylate

[0037] Put 65g of solid sodium ethoxide and 800g of toluene into a dry four-necked bottle; start stirring, raise the temperature to 90°C, add 200g of 2-acetonyl-butyric acid diethyl ester obtained in step (1) dropwise, after the dropwise addition, keep warm for 1hr . After the heat preservation is completed, add 100g of ethanol and cool down to 0~10°C, add 100g of N,N-dimethylaniline, and dropwise add 100g of cyclopropionic acid chloride. After dropping, keep warm for 5hr. The post-processing operation is the same as Example 1. Receive 1000g oil layer, analysis content is 20.38%, and yield is 93%;

[0038] (3) Synthesis of trinexapac-ethyl

[0039]The 3-ethoxycarbonyl-5-oxocyclohex-1-enol-cyclopropylcarboxylate toluene solution obtained in the previous step was heated up to 60°C, 6g of DM...

Embodiment 3

[0041] Synthesis of 3-ethoxycarbonyl-5-oxocyclohex-1-enol-cyclopropanecarboxylate

[0042] Put 75g of solid sodium tert-butoxide and 1,000g of toluene into a dry four-necked flask; start stirring, raise the temperature to 90°C, add 200g of commercially available 2-acetonyl-butyric acid diethyl ester dropwise, and keep the temperature for 1 hr. After the heat preservation is completed, 100 g of tetrahydrofuran was added, and the temperature was lowered to 0-10° C., 88 g of triethylamine was added, and 100 g of cyclopropionic acid chloride was added dropwise. After dropping, keep warm for 5hr. The post-processing operation is the same as Example 1. Obtain 1200g oil layer, analysis content is 16.76%, and yield is 91.8%.

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Abstract

The invention provides a synthetic method of plant growth regulator trinexapac-ethyl intermediate 3-carbethoxy-5-oxo-cyclohexane-1-enol cyclopropanecarboxylate. The synthetic method comprises the following steps: (1) carrying out annulation reaction on 2-acetonyl-1,4-diethyl succinate and organic alkaline at the temperature of 20-120 DEG C for 0.5-5 hours in a non-polarity organic solvent to obtain 3,5-cyclohexanedione-1-ethyl formate; and (2) adding organic amine and cyclopropanecarboxylic acid chloride, and carrying out acylation reaction at the temperature of minus 5-50 DEG C, so as to obtain 3-ethoxycarbonyl-5-oxo-cyclohexane-1-enol cyclopropanecarboxylate in the presence of micromolecular alcohol, ether, ketone and nitrile the carbon atoms of which are below C8 and are used as additives. According to the method, special additives are added before acylation so that cyclopropanecarboxylic acid chloride can directly react with intermediate-state 3-ethoxycarbonyl-5-oxo-cyclohexane-1-enol sodium salt to obtain the trinexapac-ethyl precursor 3-ethoxycarbonyl-5-oxo-cyclohexane-1-enol cyclopropanecarboxylate, thereby shortening reaction time, simplifying synthesis process and improving yield; and the product is directly rearranged without purification so as to obtain the final product trinexapac-ethyl.

Description

technical field [0001] The invention relates to a method for preparing a plant growth regulator trinexapac-ethyl synthetic key intermediate 3-ethoxycarbonyl-5-oxocyclohex-1-enol cyclopropanecarboxylate. Background technique [0002] Trinexapac-ethyl is a cyclohexane carboxylic acid compound. It is an excellent plant growth regulator and herbicide. Post-emergence application on cereals and rapeseed crops can prevent crop lodging and improve harvest yield. Use on lawns can reduce the number of pruning , application of pesticides to sugarcane can promote maturation. [0003] Early literature reports use 2-acetonyl-butyric acid diethyl ester as a raw material to form a ring under the action of sodium hydride, and directly react with cyclopropanecarbonyl chloride without separating the intermediate to obtain the product 3-ethoxycarbonyl-5-oxocyclohexyl -1-enol cyclopropanecarboxylate, the process is relatively simple, but the process safety is not high, and the use of dangerous ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C69/757C07C67/343
Inventor 戚明珠冯广军孙迎东花越如吴春中
Owner JIANGSU YOUJIA CHEM
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