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
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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DOI：
10.1016/j.tet.2006.11.054
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发表时间：
2007-01-29
期刊：
影响因子：
2.1
通讯作者：
Galvez, Jesus
中科院分区：
文献类型：
--
作者：
Guirado, Antonio;Martiz, Bruno;Galvez, Jesus
报道了1-芳基-4，4-二氯丁-3-烯-1-酮的第一种合成方法。用无水三氯乙醛处理苯乙酮以接近定量的产率得到1-芳基-4，4，4-三氯-3-羟基丁-1-酮。这些化合物用硫酸或对甲苯磺酸有效脱水得到1-芳基-4，4，4-三氯丁-2-烯-1-酮，其通过电化学还原以相当定量的产率选择性地转化为标题化合物。本文测定了4，4-二氯-1-（4-甲氧基苯基）丁-3-烯-1-酮的X射线晶体结构。借助于HF和B3 LYP密度泛函理论方法，讨论了β，γ-不饱和酮的优先生成和相应的α，β-不饱和异构体的完全排斥. (c)2006爱思唯尔有限公司保留所有权利。
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 beta,gamma-unsaturated ketones with total exclusion of the corresponding alpha,beta-unsaturated isomers has been discussed with the aid of HF and B3LYP density functional theory methods. (c) 2006 Elsevier Ltd. All rights reserved.