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Electrosynthesis of Sulfur-containing Organic Compounds using a Reactive Sulfur-Graphite Electrode

使用活性硫石墨电极电合成含硫有机化合物

基本信息

批准号：
10650810
负责人：
KUNUGI Akira
金额：
$ 2.24万
依托单位：
The University of Tokushima
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

项目摘要

Sulfur-containing organic compounds could be transformed to an aimed compound by applying the fruitful sulfur chemistry. Therefore, it is interesting to study incorporation of sulfur functionality into the organic compounds using a reactive sulfur-graphite electrode (S-C electrode). In the present work, we carried out introducing of sulfur functionality into the following compounds : cumulenes havingtrifluoromethyl groups, phenylsulfonylpropennitriles, and phenylsulfonylpropennitriles having a trifluoromethyl group. The present work leads to the following conclusions.(1) Electroreduction of cumulenes with trifiuoromethyl groups using the S-C electrode afforded dimeric compounds with a 1,2,5,6-tetrathiocin skeleton as the major products. There was a large difference in the main product between the cumulenes with and without trifluoromethyl groups, cumulenes without trifluoromethyl groups yielding 7-membered ring compounds with five sulfur atoms such as pentathiepins.(2) 3-Aryl-2-phenylsulfonylpropenenitriles having geminal cyano and sulfonyl groups gave dimeric 5-arylisothiazoles bridged with two or three sulfur atoms at the 3-position in moderate yields. 2-Phenyl-3-phenylsulfonylpropenenitrile havingvicinal cyano and sulfonyl groups yielded dimeric 4-phenylisothiazole bridged with two sulfur atoms together with 3-[(Z)-2-cyano-2-phenylethenylthio]-5-phenylisothiazole. This electrosynthesis of sulfur-containing compounds is characterized as elimination of a phenylsulfonyl group accompanying the addition of polysulfide anion(s) produced by electroreduction of elemental sulfur.(3) 2-(4-Biphenylyl)-3-phenylsulfonyl-3-trifluoromethylpropenenitrile afforded a coupling compound bridged with a nitrogen atom of isothiazole and 1,2-dithiolane skeleton.

应用丰富的硫磺化学可以将含硫有机化合物转化为目标化合物。因此，使用反应性硫-石墨电极(S-C电极)研究硫官能团与有机化合物的结合是很有意义的。在本工作中，我们将硫官能团引入到以下化合物中：含三氟甲基的异丁烯、苯磺酰基丙烯腈和含三氟甲基的苯磺酰基丙腈。本工作得到以下结论：(1)在S-C电极上，三氟甲基异丁烯的电还原反应生成了以1，2，5，6-四硫杂环为主要骨架的二聚化合物。含三氟甲基和不含三氟甲基的异丁烯的主要产物有较大差异，无三氟甲基的异丁烯生成五硫杂环化合物。(2)含双氰基和磺基的3-芳基-2-苯基磺酰基丙烯腈以中等的产率得到3-位与两个或三个硫原子桥联的二聚体5-芳基异噻唑。含邻位氰基和磺酰基的2-苯基-3-苯基磺酰基丙烯腈与3-[(Z)-2-cyano-2-phenylethenylthio]-5-phenylisothiazole.反应生成双硫桥联的二聚体4-苯基异噻唑这种含硫化合物的电合成的特征是消除了苯磺酰基，同时加成了元素硫的电还原生成的多硫阴离子(S)。(3)2-(4-Biphenylyl)-3-phenylsulfonyl-3-trifluoromethylpropenenitrile提供了一个以异噻唑氮原子和1，2-二硫杂环戊烷骨架为桥联的偶联化合物。