Method for preparing alpha-alkylated ketone by coupling alcohol with alpha-methyl/methylene ketone

A technology for coupling and alkylating ketones with methylene ketones is applied in the preparation of carbon-based compounds, chemical instruments and methods, and the preparation of organic compounds. It can solve the problems of complex reaction products, long reaction time and high reaction temperature. To achieve the effect of good selectivity, short reaction time and high activity

Active Publication Date: 2014-03-05
盐城盐西幸福产业发展有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Studies on such reactions have been reported for a long time, but there are certain limitations
In 2002, Cho's group used RuCl2(PPh3) (Tetrahedron Letters 2002, 43, 7987–7989) as a catalyst to synthesize α-alkyl ketones, but the reaction It is necessary to add a hydrogen acceptor such as dodecene or decene; in 2005, they used Pd/C (Journal of Molecular Catalysis A: Chemical 240 (2005) 55–60) as a catalyst to synthesize α-alkyl ketone, but the reaction needs 40h to complete; in 2003, the Ishii group used [Ir(cod)Cl]2/PPh3 (J. Am. Chem. Soc . 2004, 126,72-73) as a catalyst also synthesized the substance, but the reaction requires nitrogen protection; i

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] Example 1 A method for preparing α-alkylated ketones by coupling alcohols with α-methyl / methylene ketones, the method refers to sequentially adding α-methyl / methylene ketones and alcohols into the reaction solvent, and then add 2 mol% catalyst RhCl(CO)(PPh 3 ) 2 , finally add inorganic base, react at 90°C, track the whole reaction process with thin layer chromatography: that is, take samples every 5 minutes, use a capillary to drip the reaction solution on the silica gel plate to spot the sample, the raw material solution α-formazine base / methylene ketone compound and alcohol compound, and the three spots are on the same straight line, and then put the silica gel plate into a mixture of petroleum ether and ethyl acetate with a volume ratio of 10mL: 1 mL in the exhibition bottle. After the plate movement is completed, put the silica gel plate under an ultraviolet lamp or an iodine bottle for observation. If there is no point flush with the raw material liquid α-methyl / ...

Embodiment 2

[0020] Example 2 A method for preparing α-alkylated ketones by coupling alcohols with α-methyl / methylene ketones, the method refers to sequentially adding α-methyl / methylene ketones and alcohols into the reaction solvent, and then add 2 mol% catalyst RhCl(CO)(PPh 3 ) 2 , add inorganic base at last, carry out reaction at 85 ℃, obtain reaction solution after reaction is complete, whole reaction process is tracked with embodiment 1 with thin-layer chromatography; This reaction solution is filtered by the method for embodiment 1, concentrated, column After analysis and separation, 3-phenyl-1-(4-methylphenyl)-1-propanone was obtained with a yield of 91%.

[0021] Among them: the molar ratio of catalyst to α-methyl / methylene ketone compound is 2:100, the molar ratio of α-methyl / methylene ketone compound to alcohol compound is 1:1.5, and the ratio of inorganic base to α - The molar ratio of the methyl / methylene ketone compound is 2:1, and the amount of the reaction solvent used is ...

Embodiment 3

[0026] Example 3 A method for preparing α-alkylated ketones by coupling alcohols with α-methyl / methylene ketones, the method refers to sequentially adding α-methyl / methylene ketones and alcohols into the reaction solvent, and then add 2 mol% catalyst RhCl(CO)(PPh 3 ) 2 , add inorganic base at last, carry out reaction at 100 ℃, obtain reaction solution after reaction is complete, whole reaction process is tracked with embodiment 1 with thin-layer chromatography; This reaction solution is filtered by the method for embodiment 1, concentrated, column After analysis and separation, 3-phenyl-1-(4-bromophenyl)-1-propanone was obtained with a yield of 82%.

[0027] Among them: the molar ratio of catalyst to α-methyl / methylene ketone compound is 2:100, the molar ratio of α-methyl / methylene ketone compound to alcohol compound is 1:1.5, and the ratio of inorganic base to α - The molar ratio of the methyl / methylene ketone compound is 2:1, and the amount of the reaction solvent used is ...

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Abstract

The invention relates to a method for preparing alpha-alkylated ketone by coupling alcohol with alpha-methyl/methylene ketone. The method comprises the following steps: sequentially adding alpha-methyl/methylene ketone compounds and alcohol compounds into a reaction solvent, then, adding 2mol% of catalyst bistriphenylphosphine rhodium carbonyl chloride (RhCl (CO) (PPh3) 2), finally adding an inorganic alkali, and reacting at 50-100 DEG C to obtain reaction liquid after the reaction is completed; and filtering, concentrating and column chromatography separating the reaction liquid according to a conventional method to obtain the alpha-alkylated ketone. The method provided by the invention is efficient, rapid and environmental-friendly.

Description

technical field [0001] The invention relates to α-alkyl ketones in the field of organic synthetic chemistry, in particular to a method for preparing α-alkylated ketones by coupling alcohols with α-methyl / methylene ketones. Background technique [0002] The coupling reaction of α-methyl ketones with alcohols is an important pathway for C-C bond formation. It has been widely concerned for a long time, and transition metal-catalyzed alcohols as alkylating reagents are the focus of attention of chemists from all over the world in the research of organic synthesis! This kind of reaction not only has a high atom utilization rate, but also the by-product is water, which has no pollution to the environment and is green and environmentally friendly. At present, many achievements have been made in the coupling reaction of α-methyl ketone and alcohol. Studies on such reactions have been reported for a long time, but there are certain limitations. In 2002, the Cho group used RuCl 2 ...

Claims

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Application Information

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IPC IPC(8): C07C45/71C07C49/784C07C49/813C07C49/76C07C49/657C07C49/84C07C49/753
CPCC07C45/71C07C2601/08C07C2601/14C07C49/784C07C49/813C07C49/76C07C49/657C07C49/84C07C49/753
Inventor 杜正银黄莉娜刘伟
Owner 盐城盐西幸福产业发展有限公司
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