作者:Christopher J. Moore、William Kitching
DOI:10.1016/s0022-328x(00)95038-1
日期:1973.10
series of meta- and para-substituted benzyltrimethylstannanes have been prepared and their reactions with sulfur dioxide in methanol solvent at 30° have been studied kinetically by an 1H NMR method. Insertion occurs exclusively into the benzyl—tin bond, irrespective of substituent (m- and p-CH3, m- and p-CF3, m- and p-Cl, m- and p-OCH3), and the reaction exhibits good second-order kinetics for at least
制备了一系列间位和对位取代的苄基三甲基锡烷,并通过1 H NMR法动力学研究了它们与二氧化硫在甲醇溶剂中于30°的反应。不论取代基是什么(m-和p -CH 3,m-和p -CF 3,m-和p -Cl,m-和p -OCH 3),并且该反应在至少70%的反应中显示出良好的二级动力学。该反应的显着特征是速率对取代基的相对不敏感性,最大的影响是p -CF 3速率提高了2.2 。虽然这表明过渡态的苄基碳有一定的碳负离子特征发展,但电子不给力基团m-和p -CH 3引起速率略有增加(分别为1.2和1.07)这一事实也表明,反应机理随着温度的变化而变化。取代基,并带有电荷以使其最好地被取代基分散。