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Preparation method of trinexapac-ethyl and intermediate thereof

An intermediate, trinexapac-ethyl technology, which is applied in the field of preparation of trinexapac-ethyl and its intermediates, can solve the problems of affecting the quality of trinexapac-ethyl, increasing the cost of purification, and low reaction efficiency, so as to avoid high-temperature and high-pressure reactions and by-products Less, good reaction selectivity effect

Active Publication Date: 2015-11-25
MAX RUDONG CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Not only high requirements on equipment, but also low reaction efficiency
In addition, the catalyst diethylamine will have a secondary reaction with the product to generate by-products, which will increase the cost of purification and affect the quality of trinexapac-ethyl

Method used

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  • Preparation method of trinexapac-ethyl and intermediate thereof
  • Preparation method of trinexapac-ethyl and intermediate thereof
  • Preparation method of trinexapac-ethyl and intermediate thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] 1) Preparation of ethyl 4-oxopentane-1,2-dicarboxylate-3-tert-butyl carboxylate

[0029] Add 200 g of tert-butyl acetoacetate and 228 g of diethyl maleate to a 1 L three-neck equipped with a mechanical stirrer, a thermometer and a drying tube. 1.4 g of potassium tert-butoxide were added with stirring. After the addition, the stirring reaction was continued for 5h. Add 400 mL of chloroform, 100 g of water and 7.06 g of industrial hydrochloric acid, separate the layers, and desolventize the organic phase to obtain 410 g of ethyl 4-oxopentane-1,2-dicarboxylate-3-tert-butyl carboxylate. MS: m / z = 330.1 ([M+1]+).

[0030] 2) Preparation of 2-acetonyl-1,4-diethyl succinate

[0031] Add 410g of 4-oxopentane-1,2-dicarboxylate ethyl-3-tert-butylcarboxylate to the reaction flask, add 1000mL of toluene, 21.6g of p-toluenesulfonic acid, and stir for 2h. After successively washing with 200 mL of water and 200 mL of 5% sodium bicarbonate solution, 256 g of diethyl 2-acetonyl-1,4-...

Embodiment 2

[0039] 1) Preparation of ethyl 4-oxopentane-1,2-dicarboxylate-3-isopropyl carboxylate

[0040] Add 137 g of isopropyl acetoacetate and 172 g of diethyl maleate to a 1 L three-neck equipped with a mechanical stirrer, thermometer and drying tube. 3 g of potassium hydroxide were added with stirring. After the addition, the stirring reaction was continued for 5h. Add 300 mL of chloroform, 100 g of water and 5 g of industrial hydrochloric acid, separate the layers, and desolventize the organic phase to obtain 306 g of ethyl 4-oxopentane-1,2-dicarboxylate-3-isopropyl carboxylate.

[0041] 2) Preparation of 2-acetonyl-1,4-diethyl succinate

[0042] Add 306g of ethyl 4-oxopentane-1,2-dicarboxylate-3-isopropyl carboxylate to the reaction flask, add 800mL of toluene and 15.3g of p-toluenesulfonic acid, and stir for 2h. After successively washing with 150 mL of water and 150 mL of 5% sodium bicarbonate solution, 200 g of diethyl 2-acetonyl-1,4-butanedioate was obtained by precipitatio...

Embodiment 3

[0050] 1) Preparation of ethyl 4-oxopentane-1,2-dicarboxylate-3-isopropyl carboxylate

[0051] Add 165 g of isopropyl acetoacetate and 206 g of diethyl maleate to a 1 L three-neck equipped with a mechanical stirrer, a thermometer and a drying tube. 6.5 g of potassium hydroxide was added with stirring. After the addition, the stirring reaction was continued for 6h. Add 800mL of toluene, 200g of water and 6.3g of industrial hydrochloric acid, separate the layers, and the organic phase containing the crude product is directly used in the next reaction.

[0052] 2) Preparation of 2-acetonyl-1,4-diethyl succinate

[0053] Add the above-mentioned toluene solution and 12 g of trifluoroacetic acid into the reaction flask, stir for 2 h, wash with 200 mL of water and 200 mL of 5% sodium bicarbonate solution in turn, and desolvate under reduced pressure to obtain 230 g of 2-acetonyl-1,4-butanedioic acid diethyl ester.

[0054] 3) Preparation of ethyl 3,5-cyclohexanedione-1-carboxylat...

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Abstract

The invention discloses a preparation method of trinexapac-ethyl and an intermediate thereof. The method comprises the following steps: under the action of an alkali, reacting acetoacetic ester (I) with diethyl maleate to obtain an intermediate (II), continuing reaction under the action of an acid to obtain diethyl 2-acetonyl-1,4-succinate; cyclizing the diethyl 2-acetonyl-1,4-succinate in the presence of an alkali, and acidifying to obtain ethyl 3,5-cyclohexyldione-formate; esterifying the ethyl 3,5-cyclohexyldione-formate and cyclopropyl formyl chloride in the presence of an acid-binding agent to obtain ethyl 4-cyclopropylformacyl-3,5-dione cyclohexane-carboxylate; and carrying out reaction on the end product under the actions of an organic alkali and a catalyst to obtain the trinexapac-ethyl. The technique has the advantages of favorable reaction selectivity, high yield and fewer byproducts, and is beneficial to obtaining the high-quality trinexapac-ethyl product. The method does not have high requirements for equipment, and avoids high-temperature high-pressure reaction. The method has the advantages of simple technique and mild reaction conditions, and is suitable for industrialization.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of trinexapac-ethyl and its intermediate. Background technique [0002] Trinexapac-ethyl is a cyclohexane carboxylic acid compound, which is an excellent plant growth regulator. It can show growth inhibitory effect on cereal crops, castor, rice, sunflower and lawn, and it can prevent lodging when applied after plant emergence. . [0003] Early patent US4693745 discloses a synthetic method of trinexapac-ethyl. The method uses 3,5-dihydroxybenzoic acid as a starting material, and undergoes Pd / C catalytic hydrogenation reduction, esterification, cyclization, esterification and transposition to obtain the target product trinexapac-ethyl. In this process, the reduction reaction needs to be carried out under high pressure (96atm), which has strict requirements on equipment, high safety risks, and difficult production implementation. [0004] Patents ...

Claims

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Application Information

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IPC IPC(8): C07C69/757C07C67/313C07C69/716
CPCC07C67/31C07C67/313C07C67/333C07C67/347C07C69/716C07C69/757
Inventor 盛秋菊陈玲刘伟平覃小龙苏叶华虞小华蔡国平陈邦池
Owner MAX RUDONG CHEM
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