DPE对正丁基锂及聚苯乙烯活性种缔合体的影响

以具有较大空间位阻的1,1-二苯基乙烯(DPE)作为盖帽剂,使用核磁锂谱研究了正丁基锂(n-BuLi)经其盖帽以后缔合态的变化。结果表明:DPE的加入使n-BuLi中的超大缔合体解缔合成六元缔合体,但是不会影响原有的六元缔合体。由1,1-二苯基己基锂引发的苯乙烯本体聚合实验中存在转化率突变点。在突变点前的聚合产物中存在超分子结构,并随着聚合反应的进行逐渐解缔合;突变点过后超分子结构解缔合完全,反应加速进行。     

Metallization of 1-substituted 1-benzyl-o-carboranes with n-butyllithium and some conversions of 1-R-2-benzyllithium-o-carboranes

It was shown that 1-R-2-benzyl-o-carboranes (R=Me, i-Pr, Ph, PhCH₂) and other derivatives of o-carborane containing an ArCH₂ group in positions 1 and 2 are readily metallized by n-butyllithium, forming the corresponding benzyllithium derivatives, which react with electrophilic reagents like the usual organolithium compounds, permitting the synthesis of various C-substituted 1-o-carboranes.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 431–435, February, 1992.