Synthesis of Polysilanes by Electrochemical Reactions.

通过电化学反应合成聚硅烷。

• 批准号: 03453104
• 负责人: ISHIKAWA Mitsuo
• 金额: $ 4.22万
• 依托单位: HIROSHIMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453104/
• 关键词: Electrolytic Reduction of Chlorosilanes; Copper Electrodes; Synthesis of Polysilanes; Disilanylene Polymer; Chlorination of Hydrosilanes; CuCl_2-CuI Reagent; 電解還元; クロロシラン; ジシラニレンポリマ-

Synthesis of polysilanes by electrochemical method has been investigated. Cathodic reduction of chlorosilanes with the use of copper electrode system in dimethoxyethane in an undivided cell afforded some lower homologues of polysilanes such as disilanes, trisilanes, tetrasilanes, and pentasilanes selectively in high yields. Similar electrolyses of 1,2-bis(chloromethylphenylsilyl)ethane and 1,2-bis[chloromethyl(rho-tolyl)silyl]ethane afforded poly(disilanylene)ethylenes with high molecular weights, in which no siliconoxygen bonds in the polymer backbone are included. Moreover, reduction of 1,2-bis- (chloromethylphenylsilyl)benzene afforded poly(disilanylene)phenylene.A highly selective synthesis of chlorosilanes from hydrosilanes has also been investigated. The reaction of dimethylphenylsilane, methyldiphenylsilane, and di(n-butyl)- methylsilane with 2 equiv of copper(II) chloride and a catalytic amount of copper(I) iodide afforded the respective triorganochlorosilanes. Similar reactions of polyhydrosilanes such as diethylsilane, methylphenylsilane, phenylsilane, 1,1,2,2-tetraethyldisilane, and 1,2- dimethyl-1,2-diphenyldisilane with 2 equiv of the CuCl_2(CuI) reagent gave the corresponding monochlorinated hydrosilanes selectively, while treatment with 4 equiv of the reagent afforded dichlorosilanes as the sole product.

研究了电化学法合成聚硅烷。在无隔膜电解槽中，用铜电极系统在二甲氧基乙烷中阴极还原氯硅烷，以高产率选择性地得到了一些聚硅烷的低级同系物，如乙硅烷、丙硅烷、四硅烷和五硅烷。1，2-双（氯甲基苯基甲硅烷基）乙烷和1，2-双[氯甲基（对甲苯基）甲硅烷基]乙烷的类似电解得到具有高分子量的聚（亚二硅烷基）乙烯，其中在聚合物主链中不包括硅氧键。此外，还研究了1，2-双（氯甲基苯基硅基）苯还原得到聚亚二硅基苯。二甲基苯基硅烷、甲基二苯基硅烷和二（正丁基）-甲基硅烷与2当量的氯化铜（II）和催化量的碘化铜（I）的反应提供相应的三有机氯硅烷。多氢硅烷如二乙基硅烷、甲基苯基硅烷、苯基硅烷、1，1，2，2-四乙基二硅烷和1，2-二甲基-1，2-二苯基二硅烷与2当量的CuCl_2（CuI）反应，选择性地得到相应的一氯代氢硅烷，而与4当量的CuCl_2（CuI）反应，则只得到二氯代硅烷。

项目成果

Atsutaka KUNAI: "Electrochemistry of Organosilicon Compounds.1.Synthesis of Diーand Trisilanes by Mercury and Silver Electrode Systems." Organometallics. 10. 893-895 (1991)

Atsutaka KUNAI：“有机硅化合物的电化学。1.通过汞和银电极系统合成二硅烷和丙硅烷。” 10. 893-895 (1991)

Atsutaka KUNAI: "Electrochemistry of Organosilicon Compounds.1.Synthesis of Di- and Trisilanes with Use of Mercury and Silver Electrode Systems" Organometallics. 10. 893-895 (1991)

Atsutaka KUNAI：“有机硅化合物的电化学。1.使用汞和银电极系统合成二硅烷和三硅烷”有机金属化合物。

Atsutaka KUNAI: "Highly Selective Synthesis of Chlorosilanes from Hydrosilanes." Organometallics. 11. (1992)

Atsutaka KUNAI：“从氢硅烷中高度选择性合成氯硅烷。”

石川 満夫: "新しい有機ケイ素ポリマー" 共立出版, 80 (1991)

Mitsuo Ishikawa：“新型有机硅聚合物”Kyoritsu Shuppan，80 (1991)

Atsutaka Kunai: "Electrochemistry of Organosilicon Compounds. 2. Synthesis of Polysilane Oligomers by a Copper Electrode System" Organometallics. 10. 2001-2003 (1991)

Atsutaka Kunai：“有机硅化合物的电化学。2.通过铜电极系统合成聚硅烷低聚物”有机金属。