Novel preparation method and synthetic applications of cyclopropyl trimethylsilyl ketones

环丙基三甲基硅酮的制备新方法及合成应用

基本信息

批准号：
62550627
负责人：
NAKAJIMA Tadashi
金额：
$ 1.15万
依托单位：
Kanazawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

A series of new cyclopropyl trimethylsilyl ketones has been prepared in moderate yield from the novel reaction of 1-trimethylsilylcyclopropyllithium derivartives with dichloromethyl methyl ether. This reaction involves the intramolecular 1,2-silicon shift from carbon to carbon. The spectroscopic properties of these silyl ketones have been measured.The ketones obtained here react with various halogen acids under milder conditions compared to that of their carbon analogs to give the ring opening products, 3-chloropropyl silyl ketones, or the ring enlargement products, 2-silyl-4,5-dihydrofuran derivatives in some cases. The reaction with sulfuric acid or trifluoromethane sulfonic acid affords only the corrensponding silyldihydrofurans in good yield. Especially, it is noteworty that the reaction of 2-phenylcyclopropyl silyl ketone with sulfuric acid yields 2-phenylcyclobutanone. The formation of these comounds is interpreted on the basis of the effect that silicon stabilizes a cation to it … More .Wittig reactions of cyclopropyl silyl ketones with alkylidene-triphenylphosphoranes proceed stereoselectively to give the corresponding Z-1-silyl-1-cyclopropyl alkenes. The protiodesilylation of silyl cyclopropyl alkenes with tetrabutylammonium fluoride proceeds with retention of configuration to give E-cyclopropyl alkenes, although the reaction with hydrogen halides was unsuccessful due to the cleavage of the three membered ring.The reaction of sulfur ylides in THF with cyclopropyl silyl ketones resulted in the formation of the corresponding siloxyalkenes or -ketosilanes. The relative ratio of these compounds varies with the reaction temperature, the porality of solvents used, and the preparation method of ylide. It is noteworthy that the reaction with salt free ylide affords siloxyalkenes and that of the ylide containing inorganic salt -ketosilanes, selectively. These two type of products would be formed by the anionotropic and cationotropic rearrangement of silyl group in the betaine intermediate. Less

一系列新的环丙基三甲基酮基因酮已经从hium衍生物与二氯甲基甲基以太元的反应中以中等的收益制备，已测量了slyl酮的OPIC特性。在某些情况下，给出打开环的产物，3-氯丙基slyl酮或环增大产物，在某些情况下为2-S-S-S-S-4,5-二氢呋喃衍生物的衍生物。值得注意的是，2-苯基环丙丙烯酮与硫酸的R相互作用是基于硅的形成。给出相应的Z-Cycycloproproploplopyl烷烯，其在氟化物中的Si Lyl cylyproplopyl烷烯酸酯的propiesillation liveration的二甲基铵含量为halchochu，并没有氢化硫酸盐。 THF环酮中的Ylides导致形成相关的Siloxyalkenes或-Ketosilanes。在小甜菜中，在小菜一指的中间组中，将形成cationotropititic cattrangent