SYNTHESES WITH TRIARYLVINYLMAGNESIUM BROMIDES - ALPHA,GAMMA-BISDIPHENYLENE-BETA-PHENYLALLYL, A STABLE FREE RADICAL
SYNTHESES WITH TRIARYLVINYLMAGNESIUM BROMIDES - ALPHA,GAMMA-BISDIPHENYLENE-BETA-PHENYLALLYL, A STABLE FREE RADICAL
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DOI：
10.1021/ja01573a053
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发表时间：
1957-01-01
影响因子：
15
通讯作者：
KOELSCH, CF
中科院分区：
文献类型：
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作者：
KOELSCH, CF
与α，α，3，7，γ-五苯基烯丙醇不同，α，7-双二亚苯基-5-苯基烯丙醇可以转化为氯化物，因为其几何形状阻碍其环化为茚。氯化物已转化为相应的自由基，这是一种高度离解且对氧非常稳定的物质。齐格勒四苯基烯丙基自由基，(CeH5) 2C= CH—C (C6H5) 2 及其取代衍生物特别引人注目，因为尽管它们在甲烷碳原子上仅含有两个芳基，但分子量测定显示它们大部分是单分子。它们在溶液或固态中的深颜色以及它们对氧的敏感性也证明了它们的高度离解。这种离解程度远远超过三苯甲基，齐格勒对此进行了解释，因为 1, 1-二苯基乙烯比苯更不饱和，二苯基乙烯基比苯基具有更大的“化合价要求”。完全苯基化的烯丙基，五苯基烯丙基，至今仍未知，由于构成三苯基乙烯基位于四苯乙烯之间的中间位置，其双键不添加，因此引起人们的兴趣。溴和 1, 1-二苯基乙烯，其容易加成溴。
Unlike a, a,/3, 7, y-pentaphenylallyl alcohol, a, 7-bisdiphenylene-5-phenylallyl alcohol can be converted into a chloride be-cause its geometry hinders it from cyclization to an indene. The chloride has been converted into the corresponding free radical, a substance which is highly dissociated and remarkably stable to oxygen.Ziegler’s2 tetraphenylallyl radical,(CeH5) 2C= CH—C (C6H5) 2, and its substituted derivatives are particularly remarkable in that although they con-tain only two aryl groups on the methane carbon atom, molecular weight determinations show them to be largely monomolecular. Their deep colors in solution or in the solid state, and their sensitivity toward oxygenalso attest their high degree of dis-sociation. This degree of dissociation, so much ex-ceeding that of triphenylmethyl, was explained by Ziegler on the ground that as 1, 1-diphenylethylene is more unsaturated than benzene, diphenylvinyl has a larger “valence requirement’’than phenyl. The completely phenylated allyl radical, penta-phenylallyl, as yet unknown, is of interest because of the intermediate position of the constituent tri-phenylvinyl group between tetraphenylethylene, whose double bond does not add bromine, and 1, 1-diphenylethylene, which adds bromine readily.