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Preparation of Multi-substituted Dienyltin Compounds Using Zirconacycles and It's Application

锆环化合物多取代二烯基锡化合物的制备及其应用

基本信息

批准号：
12650841
负责人：
TAKAHASI Tamotsu
金额：
$ 2.3万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

项目摘要

Zirconium-carbon bonds of zirconacycles are cleaved by the reaction with halogenation reagents such as NCS, NBS or iodine. After the halogenation of one of zirconium-carbon bond, we expected the reaction with trialkyltin chloride can afford dienyltin compounds. Unfortunately, this reactions did not proceed, but we found that in the presence of CuCl, the desired compounds were obtained. First, tetraethylzirconacyclopentadiene was chlorinated with NCS and then tributyltin chloride was added to the mixture. To this mixture was added CuCl. The desired dienyltin compound was obtained in 77% yield. In a similar way, 4-bromo-1-dienyltin compounds were obtained in 70% and 75% yield.Unsymmetrical zirconacyclopentadienes with alkyl or aryl substitutents can be selectively monohalogenated. Usually, the first chlorination or bromination proceeded at the sp2 carbon. However, the sp2 carbon having aryl substituents does not react with NCS or NBS. Reaction with iodine afforded diiodinated compounds. In contrast, zirconium-benzyne complex gave the halodienyltin derivative in 67% yield.When tetraphenylzirconaycclopentadiene was used, under different conditions, dienylmonotin compounds and 1,4-dienylditin compounds were selectively prepared in 55% and 46% yields, respectively. In a same way, tetraethyldienylditin compound was obtained in 46% yield. In the presence of a stoichiometric or catalytic amount of copper chloride, various kinds of stanacyclopentadienes were obtained.

锆环的锆-碳键通过与卤化试剂如NCS、NBS或碘反应而断裂。锆碳键之一卤化后，我们预计与三烷基氯化锡反应可以得到二烯基锡化合物。不幸的是，这个反应没有进行，但我们发现在 CuCl 存在下，得到了所需的化合物。首先，用NCS氯化四乙基环戊二烯锆，然后将三丁基氯化锡添加到混合物中。向该混合物中添加CuCl。以77％的产率获得所需的二烯基锡化合物。以类似的方式，获得了4-溴-1-二烯基锡化合物，收率分别为70%和75%。带有烷基或芳基取代基的不对称环戊二烯锆可以选择性地单卤化。通常，第一次氯化或溴化在 sp2 碳上进行。然而，具有芳基取代基的sp2碳不与NCS或NBS反应。与碘反应得到二碘化化合物。相比之下，锆-苯炔络合物以67%的收率得到卤二烯基锡衍生物。当使用四苯基锆环戊二烯时，在不同条件下，选择性地制备了二烯基单锡化合物和1,4-二烯基二锡化合物，收率分别为55%和46%。以同样的方式得到四乙基二烯基二锡化合物，收率46％。在化学计量或催化量的氯化铜存在下，获得各种类型的环戊二烯。