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Electrochemical Carboxylation of Vinyl Compounds

乙烯基化合物的电化学羧化

基本信息

批准号：
63550608
负责人：
KUNUGI Akira
金额：
$ 1.28万
依托单位：
The University of Tokushima
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

Carbon dioxide is well known to be a useful reagent for the trapping of anionic species in solution resulting in the formation of carboxylated products. For example, the electrolytic reduction of activated olefins such as 1-cyanostyrene in the presence of carbon dioxide gives the corresponding saturated compounds with the carboxyl group. With alpha, beta-unsaturated sulfoxides and sulfones, on the other hand, the substitution of sulfinyl or sulfonyl group by carbon dioxide will be expected to occur to yield the corresponding acrylic acid derivatives, in contrast to the above example.The present work deals with the electrochemical carboxylation of alpha, beta-unsaturated sulfoxides and sulfones with carbon dioxide in nonaqueous media. These results are shown below :(1) The electro-carboxylation of beta-methylsulfenyl-beta-methylsulfinylstyrene leads to alpha- (methylsulfenyl) cinnamic acid and beta-methylsulfenylstyrene.This electro-carboxylation is characterized as substitution of the methylsulfinyl group by carbon dioxide.(2) The electro-carboxylation of 1-methylthio-1-p-tolylsulfony1-2-arylethenes gives 3-arylpropenoic acids, indicating that the elimination of both methylthio and p-tolylsulphonyl groups happens.(3) In the electroreductive desulfurization and carboxylation of beta, beta-bis (methylsulfonyl) styrene, the selective cleavage of one carbon-sulfur bond takes place to afford beta-methylsulfonylstyrene in the presence of an efficient proton donor, but the corresponding carboxylated product is not obtained in the presence of carbon dioxide.(4) The electrochemical reduction of alpha, beta-bis (methylsulfonyl) styrene in nonaqueous media leads to beta-methylsulfonylstyrene. This is contrary to experience with above compounds, i. e., this electro-reduction brings about the elimination of the methylsulfonyl group at the alpha-position rather than the beta-position. The electro-carboxylation of this compound gives beta-methylsulfonyl-alpha-phenylacrylic acid.

众所周知，二氧化碳是一种有用的试剂，用于捕获溶液中的阴离子，从而形成羧基化产物。例如，在二氧化碳的存在下，电解还原活性烯烃（如1-氰苯乙烯）得到相应的具有羧基的饱和化合物。另一方面，与上述例子相反，对于α、β不饱和亚砜和砜，预期会发生亚砜基或磺酰基被二氧化碳取代的情况，从而产生相应的丙烯酸衍生物。本文研究了在非水介质中用二氧化碳催化α、β -不饱和亚砜和砜的电化学羧基化反应。结果如下：(1)-甲基磺酰基- -甲基磺酰基苯乙烯的电羧基化反应生成-（甲基磺酰基）肉桂酸和-甲基磺酰基苯乙烯。这种电羧基化的特点是甲基亚砜基被二氧化碳取代。(2) 1-甲基硫基-1-对甲基磺酰基-1- 2-芳基的电羧基化得到3-芳基丙烯酸，表明甲基硫基和对甲基磺酰基都发生了消除。(3)在-，- -双（甲基磺酰基）苯乙烯的电还原脱硫和羧化反应中，在有效质子供体存在的情况下，一个碳-硫键发生选择性裂解，得到- -甲基磺酰基苯乙烯，但在二氧化碳存在的情况下不能得到相应的羧化产物。(4) α， β -二（甲基磺酰基）苯乙烯在非水介质中电化学还原生成β -甲基磺酰基苯乙烯。这与上述化合物的经验相反，即这种电还原导致在α位置而不是在β位置消除甲基磺酰基。这种化合物的电羧基化得到-甲基磺酰基- -苯基丙烯酸。