First synthesis of 1-aryl-4,4-dichlorobut-3-en-1-ones. The electrochemical reduction of 1-aryl-4,4,4-trichlorobut-2-en-1-ones as a key step |
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Authors: | Antonio Guirado Bruno Martiz Delia Bautista |
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Institution: | a Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30071 Murcia, Apartado 4021, Spain b Departamento de Química Física, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30071 Murcia, Apartado 4021, Spain |
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Abstract: | The first method for the synthesis of 1-aryl-4,4-dichlorobut-3-en-1-ones is reported. Treatment of acetophenones with anhydrous chloral leads to 1-aryl-4,4,4-trichloro-3-hydroxybutan-1-ones in near quantitative yields. These compounds were efficiently dehydrated with either sulfuric or p-toluenesulfonic acid to give 1-aryl-4,4,4-trichlorobut-2-en-1-ones, which were selectively converted to the title compounds in fair to quantitative yields by electrochemical reduction. The X-ray crystallographic structure of 4,4-dichloro-1-(4-methoxyphenyl)but-3-en-1-one has been determined. The preferential formation of β,γ-unsaturated ketones with total exclusion of the corresponding α,β-unsaturated isomers has been discussed with the aid of HF and B3LYP density functional theory methods. |
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Keywords: | Electrosynthesis Reduction Dechlorination Chloral β γ-Unsaturated ketones |
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