o-Phenylene Silicon Derivatives. Dihydrosilanthrene and Related Compounds1
o-Phenylene Silicon Derivatives. Dihydrosilanthrene and Related Compounds1
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邻亚苯基硅衍生物。
DOI：
10.1021/ja01499a032
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发表时间：
1960
影响因子：
15
通讯作者：
E. A. Zuech
中科院分区：
文献类型：
--
作者：
H. Gilman;E. A. Zuech
由邻亚苯基锂(I)与二苯基二氯硅烷和二苄基二氯硅烷反应，得到5,5,10,10-四苯基-5,10-二氢硅烷(II)和5,5,10,10-四苄基-5,10-二氢硅烷。 I与二苯基硅烷的反应得到邻亚苯基双-(二苯基硅烷)(III)以及其他化合物。功能衍生物III已用多种有机锂试剂处理。由于无法获得合适的格氏试剂和有机锂试剂，含有邻亚苯基单元的有机金属和有机金属衍生物的合成在某些情况下极其困难。格氏试剂，例如邻溴苯基溴化镁2·3和邻溴苯基碘化镁4，已经制备出来，但没有为邻亚苯基衍生物的合成提供可行的路线。类似地，通过邻二溴苯和正丁基锂的相互作用，可以以低收率制备邻溴苯基锂5，但与其他邻卤苯基锂化合物一样，其用途有限。 Wittig 和 Bickelhaupt6 最近制备了邻亚苯基锂 (I)，为邻亚苯基衍生物的合成提供了一条新路线。二锂化合物I是通过锂金属裂解邻亚苯基汞而获得的，其身份通过碳酸化提供邻苯二甲酸而得到证实，收率69%。
From the reaction of o-phenylenedilithium (I) with diphenyldichlorosilane and with dibenzyldichlorosilane, 5, 5, 10, 10-tetraphenyl-5, 10-dihydrosilanthrene (II) and 5, 5, 10, 10-tetrabenzyl-5, 10-dihydrosilanthrene wrere obtained. The reaction of I with diphenylsilane afforded o-phenylenebis-(diphenylsilane)(III), along with other compounds. The functional de-rivative III has been treated with a variety of organolithium reagents.The synthesis of organometallic and organometal-loidal derivatives containing the o-phenylene unit has been extremely arduous in some instances due to the inaccessibility of suitable Grignard and or-ganolithium reagents. Grignard reagents, such as o-bromophenylmagnesium bromide2· 3 and o-bromophenylmagnesium iodide, 4 havebeen prepared but do not afford a practicable route for the synthesis of o-phenylene derivatives. Similarly, o-bromophen-yllithium5 has been prepared in low yields by the interaction of o-dibromobenzene and w-butyllith-ium, but is of limited utility as are the other o-halophenyllithium compounds. Wittig and Bickelhaupt6 recently have prepared o-phenylenedilithium (I) providing a new synthetic route to o-phenylene derivatives. The dilithium compound I was obtained by the lithium metal cleavage of o-phenylene-mercury, with the identity being confirmed by carbonation furnishing phthalic acid in 69% yield.