Jun Iyoda

Reaction of organotin oxides, alkoxides and acyloxides with organosilicon hydrides. New preparative method of organotin hydrides☆

Abstract The reaction of organotin oxide, alkoxides and acyloxides with organosilicon hydrides was investigated by varying the mole ratio of the reactants. And it was found that SnO was easily cleaved by SiH giving SnH. Several organotin hydrides, such as tributyltin hydride, tripropyltin hydride and dibutyltin dihydride were obtained in good yields. For triphenyltin hydride and dimethyltin dihydride, it was necessary to use a radical inhibitor or iodine as a promoter and even then the yields were poor. New compounds of the type SiOSn, such as (tributylsiloxy)tributyltin, (triphenylsiloxy)tributyltin and (triphenylsiloxy)tripropyltin were also obtained.

Silicon—carbon unsaturated compounds: XVII. Photochemical behavior of 1-methyl-1-(trimethylsilyl)dibenzosilole and 1-phenyl-1-(trimethylsilyl)dibenzosilole

Abstract The photolysis of 1-methyl-1-(trimethylsilyl)dibenzosilole (I) and 1-phenyl-1-(trimethylsilyl)dibenzosilole (II) has been investigated. Irradiation of I in the presence of acetone afforded 1-isopropoxy-1-methyl-2-(trimethylsilyl)dibenzosilole(III), while in the presence of isobutene, I afforded 1-isobutyl-1-methyl-2-(trimethylsilyl)dibenzosilole (V). The photolysis of II in the presence of acetone or isobutene gave the rearranged addition products analogous to III and V. Irradiation of I in alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, produced 1-hydro-1-methyldibenzosilole (VII) in high yield. Similarly, irradiation of II in methyl alcohol or ethyl alcohol gave 1-hydro-1-phenyldibenzosilole in high yield.

The Preparation of Some Optically Active Alkoxysilanes and Siloxanes

ケイ素-水素結合をもつシラン化合物を一成分とするオレフィン重合触媒の研究試料として,ケイ素-水素結合をもつ光学活性アルコキシシランおよび低級シロキサンの合成を行なった。ピリジン存在下でのアルコールとクロルシランの反応でCH3(H)Si(OR)2,CH3(H)Si(OR)Cl,(R-l-メンチル, d-ボルニル, 以下同じ) を, また, アルコキシクロルシランから, ピリジンと炭酸水素ナトリウムによる縮合で,[CH3(H)(RO)Si]2O,[CH3(H)(RO)SiO]2Si(H)CH3を得た。メントールとメチルジクロルシランの直接反応では,複雑な縮合反応が起こり,塩化メンチル,メンテン,メンタンを副生する。また,メントキシシランと,クロルシランとの平衡化反応により,メントキシクロルシランが収率よく得られることを知った。