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Preparation method of beta-dione compound

A compound and diketone technology, which is applied in the field of preparation of β-diketone compounds, can solve the problems of low yield and unsafety of β-diketone compounds, and achieve the effect of high yield

Active Publication Date: 2017-11-07
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] The purpose of the present invention is to overcome the low yield and unsafe defects of prior art preparation of β-diketone compounds, and provide a preparation method of β-diketone compounds

Method used

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Examples

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preparation example Construction

[0018] The present invention provides a method for preparing a β-diketone compound represented by formula (4), wherein the method comprises: in the presence of a solvent represented by formula (3) and an alkali metal potassium alkoxide, formula (1) ) The methyl carboxylate shown in ) reacts with the ketone shown in formula (2);

[0019] CH 3 O-CO-CR 1 R 2 R 3 Formula 1);

[0020] CH 3 -CO-CR 1 R 2 R 3 Formula (2);

[0021] R 4 O-(CH 2 (CH 2 ) n O) m -R 4 Formula (3);

[0022] R 3 R 2 R 1 C-CO-CH 2 -CO-CR 1 R 2 R 3 Formula (4);

[0023] Among them, R 1 , R 2 and R 3 each independently hydrogen or C 1 -C 4 Alkyl groups, such as R 1 , R 2 and R 3 Can each independently be one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl; preferably, R 1 , R 2 and R 3 each independently hydrogen or C 1 -C 2 The alkyl groups, for example, can be independently hydrogen, methyl or ethyl; more preferably, the methy...

Embodiment 1

[0039]Add 135g (1.2mol) potassium tert-butoxide (purchased from Sinopharm Group Chemical Reagent Co., Ltd., referred to as "Sinopharm", the same below) and 104.5g (1.16mol) ethylene glycol dimethyl ether ( (purchased from Sinopharm Corporation) and heated to reflux under stirring with a mechanical stirrer to raise the temperature to 20°C. Then, a liquid mixture consisting of 319g (3.6mol) methyl propionate (purchased from Japan TCI Company) and 86.5g (1.2mol) methyl ethyl ketone (purchased from Sinopharm Corporation) was added at a constant speed through the constant pressure dropping funnel, and the dropping time for 20 minutes, then stirred at 75°C for another 4.5 hours, cooled to 40°C, added 120g of ice water, and adjusted the pH to 6 with concentrated hydrochloric acid. Then filter with a suction filter bottle to remove potassium chloride, the filtrate is separated into layers, and the organic layer and the water layer are separated. Gas chromatography analysis of the org...

Embodiment 2

[0041] Add 13.6g (0.12mol) of potassium tert-butoxide (purchased from Sinopharm) and 40mL (0.28mol) of diethylene glycol dimethyl ether into a 250ml three-neck flask, heat and reflux to 60° C. under stirring with a mechanical stirrer. Then, a liquid mixture composed of 39mL (0.41mol) methyl propionate (purchased from Japan TCI Company) and 9mL (0.1mol) butanone (purchased from Sinopharm Corporation) was added at a constant speed through a constant pressure dropping funnel, and the dropping time was 40min, then stirred at 60°C for another 4.5 hours, cooled to 40°C, added 20g of ice water, and adjusted the pH to 6 with concentrated hydrochloric acid. Then filter with a suction filter bottle to remove potassium chloride, the filtrate is separated into layers, and the organic layer and the water layer are separated. The gas chromatographic analysis of the organic layer showed that the yield of 3,5-heptanedione was 64.3% (calculated as butanone).

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Abstract

The invention relates to the field of compound preparation, and discloses a preparation method of a beta-dione compound. The method comprises: in the presence of a solvent and alkali metal potassium alcoholate, reacting methyl carboxylate with ketone. The method is high in yield, is safe, and is suitable for industrial application. Particularly, when 3,5-heptadione is prepared through the method, the yield of 3,5-heptadione can reach more than 60%, wherein the yield is far more higher than that in the prior art by taking DMF as a solvent.

Description

technical field [0001] The invention relates to the field of compound preparation, in particular to a preparation method of β-diketone compounds. Background technique [0002] β-diketone compounds are a class of compounds with special structures, which are widely used in the fields of catalysts, thermal stabilizers and luminescent materials. [0003] It is well known that the ester ketone condensation method is a common method for the preparation of β-diketone compounds. For example, the journal literature J.Org.chem (Vol.50.No26.1985.5598-5604) reports that in the presence of sodium hydride, tetrahydrofuran is used as a solvent, and ethyl propionate is reacted with methyl ethyl ketone to prepare 3,5-heptanedione. The rate is 48.3%. [0004] In the journal literature Zhurnal Obshchei Khimii (1958, 28, 2845-2846), malonyl chloride was used to react with Grignard reagent EtMgBr to synthesize 3,5-heptanedione with a yield of 51%. The reaction condition is -70°C, and it is di...

Claims

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Application Information

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IPC IPC(8): C07C49/12C07C45/68
CPCC07C45/68C07C49/12
Inventor 谢伦嘉滕征远贺黎明冯再兴王瑞璞曾佳
Owner CHINA PETROLEUM & CHEM CORP