Reaction products of dichlorodiorganostannanes with sodium in liquid ammonia: In-situ investigations with 119Sn NMR spectroscopy and usage as intermediates for the synthesis of tetraorganostannanes
作者:Markus Trummer、Jérôme Zemp、Cédric Sax、Paul Smith、Walter Caseri
DOI:10.1016/j.jorganchem.2011.05.001
日期:2011.9
the reaction products with bromoethane and vice versa – a practice commonly described. Furthermore, we observed migration of the butyl groups both in-situ during the reaction of dichlorodibutylstannane with sodium in liquid ammonia, as well as in the final reaction product. By contrast in the case of the phenyl substituent, migration was detected not during the chemical event in liquid ammonia, but
二氯二丁基锡烷,二氯二辛基锡烷和二氯二苯基锡烷与不同量的钠在液氨中反应。在R 2 SnCl 2 / Na的摩尔比为1∶2的情况下,聚锡烷沉淀,在某些情况下伴随有环状低聚锡烷。由R 2 SnCl 2 / Na比为1:3至1:10的混合物得到的产物是可溶的,因此可以用119 Sn NMR光谱在液氨中原位研究。所获得的化合物中,R型的氢化锡2 SNH -和在组合物R的某些情况下distannides 4的Sn 2 2-基本上独立于R 2 SnCl 2 / Na之比而形成;这与文献中表达的观点相反。我们的实验表明,原位生成物质的化学结构无法得出与溴乙烷反应产物组成的结论,反之亦然-这是通常描述的一种做法。此外,我们观察到丁基均在原位迁移在二氯二丁基锡烷与钠在液氨中以及最终反应产物中的反应过程中。相反,在苯基取代基的情况下,在化学事件中在液氨中未检测到迁移,而仅在形成的化合物中检测到了迁移。这些观察结果暗示了丁基和苯基迁移的不同机制。