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Method for preparing alpha, beta-unsaturated carbonyl compounds

A carbonyl compound, unsaturated technology, applied in the alpha field, can solve problems such as limited application, and achieve the effects of simple operation, high yield and short synthesis route

Active Publication Date: 2014-07-23
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Through people's continued research, it is found that α, β-unsaturated carbonyl compounds with certain structures can also be constructed through Suzuki coupling reaction and Heck coupling reaction [see: (a) Andersson, C.-M.; Hallberg, A.J.Org .Chem.1988,53,4257.Eddarir,S.;(b)Cotelle,N.;Bakkour,Y.;Rolando,C.Tetrahed.Lett.2003,44,5359.;(c)Wu,X.- F.;Neumann,H.;Beller,M.Angew.Chem.,Int.Ed.2010,49,5284.], but this type of reaction requires a special reaction substrate, which limits the application of the reaction

Method used

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  • Method for preparing alpha, beta-unsaturated carbonyl compounds
  • Method for preparing alpha, beta-unsaturated carbonyl compounds
  • Method for preparing alpha, beta-unsaturated carbonyl compounds

Examples

Experimental program
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Effect test

Embodiment 1

[0036] Example 1: Synthesis of (E)-1-(4-acetylphenyl)-3-phenylprop-2-en-1-one (3a) Accurately weigh 4-bromoacetophenone (99.5mg, 0.5mmol), hydrogen Potassium oxide (84.2mg, 1.5mmol), palladium chloride (4.4mg, 0.025mmol), and triphenylphosphine (26.2mg, 0.1mmol) were successively added to a 25mL autoclave, and after three times of nitrogen replacement, the Under nitrogen protection, 3 mL of tetrahydrofuran and phenylacetylene (102.1 mg, 1.0 mmol) were added. Fill the autoclave with CO to a pressure of 30atm, and stir at 60°C for 48h. After the reaction, add 10 mL of water to the reaction solution, extract 3 times with 3×10 mL of ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate for 1 h, remove the solvent under reduced pressure, and use petroleum ether / ethyl acetate as the eluent Reagent, silica gel column separation, (E)-1-(4-acetylphenyl)-3-phenylprop-2-en-1-one yield is 84%. 1 H NMR (400MHz, CDCl 3 )δ8.07(s,4H),7.82(d,J=15.6Hz,1H),7.67–7.64(m,2...

Embodiment 2

[0037] Example 2: Synthesis of (E)-1-(4-acetylphenyl)-3-(4-methoxyphenyl)prop-2-en-1-one (3b)

[0038] Accurately weigh 4-bromoacetophenone (99.5mg, 0.5mmol), sodium carbonate (159.0mg, 1.5mmol), palladium chloride (8.9mg, 0.05mmol), 1,4-bis(diphenylphosphino) Butane (42.6mg, 0.1mmol) was successively added into a 25mL autoclave. After three times of nitrogen replacement, 3mL of tetrahydrofuran and 4-methoxyphenylacetylene (132.2mg, 1.0mmol) were added under nitrogen protection. Fill the autoclave with CO until the pressure is 20atm, check whether there is air leakage after sealing, and stir at 150°C for 48h. After the reaction, add 10 mL of water to the reaction solution, extract 3 times with 3×10 mL of ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate for 1 h, remove the solvent under reduced pressure, and use petroleum ether / ethyl acetate as the eluent Reagent, silica gel column separation, (E)-1-(4-acetylphenyl)-3-(4-methoxyphenyl)prop-2-en-1-on...

Embodiment 3

[0039] Example 3: Synthesis of (E)-1-(4-acetylphenyl)-3-(p-tolyl)prop-2-en-1-one (3c) Accurately weigh 4-bromoacetophenone (99.5 mg, 0.5mmol), bis(triphenylphosphine)palladium dichloride (17.5mg, 0.05mmol), 1,5-bis(diphenylphosphine)pentane (44.0mg, 0.1mmol), and added to 25mL of In the autoclave, after three times of nitrogen replacement, 3 mL of anhydrous dimethyl sulfoxide, 4-methylphenylacetylene (174.2 mg, 1.5 mmol), and triethylamine (202.4 mg, 2.0 mmol) were added under nitrogen protection. Fill the autoclave with CO until the pressure is 20atm, check for air leakage after sealing, and stir at 100°C for 48h. After the reaction, add 10 mL of water to the reaction solution, extract 3 times with 3×10 mL of ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate for 1 h, remove the solvent under reduced pressure, and use petroleum ether / ethyl acetate as the eluent Reagent, silica gel column separation, (E)-1-(4-acetylphenyl)-3-(p-tolyl)prop-2-en-1-one ...

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Abstract

The invention belongs to a pharmaceutical chemical intermediate and the related technical field of chemistry, and relates to a novel method for preparing alpha, beta-unsaturated carbonyl compounds. The method is characterized by comprising the following steps of: reacting aryl halide and a derivative thereof which are taken as a raw material with carbon monoxide and an alkyne compound in a high-pressure kettle under the action of a metal catalyst and alkali, and performing column chromatography separation to obtain the alpha, beta-unsaturated carbonyl compounds. The method for preparing the alpha, beta-unsaturated carbonyl compounds is simple and convenient to operate, the raw material is cheap, and reaction conditions are mild; and the yield and purity of obtained products are high, the products fully meet the quality requirements when the products are taken as medicinal intermediates, and favorable conditions are provided for the industrialized production of the products.

Description

technical field [0001] The invention belongs to the field of pharmaceutical and chemical intermediates and related chemical technologies, and relates to a novel preparation method of α, β-unsaturated carbonyl compounds. Background technique [0002] α, β-unsaturated carbonyl compounds widely exist in many aspects of the chemical field. As a skeleton structure, they often appear in molecular structures closely related to people's daily necessities, such as natural products, biological activities, medicines, and agricultural chemicals. In particular, chalcones exhibit good biological activities in terms of anti-cancer, anti-oxidation, pain relief and anti-inflammation. [0003] The traditional method of synthesizing α, β-unsaturated carbonyl compounds is to use the Claisen-Schmidt reaction of aldehydes and ketones [see: (a) Krishnakumar, B.; Velmurugan, R.; Swaminathan, M. Catal. Commun. 2011, 12, 375 .;(b) B. Krishnakumar, M. Swaminathan, J. Mol. Catal. A: Chem. 2011, 350, 1...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B41/06C07C49/796C07C49/84C07C49/86C07C45/49C07C255/56C07C253/30
Inventor 包明冯秀娟于晓强王良广
Owner DALIAN UNIV OF TECH
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