the corresponding disiloxane, disilazanes and disilthiane. The molecular structure of Si,Si′-(Naphthalene-1,8-diyl)-N-phenyldisilazane (8) was determined by X-ray diffraction. Treatment of 2 with substoichiometric amounts of triflic acid and subsequent reaction of the resulting monosilyl triflate with tert-butylamine gives a related chiral N-tert-butyl-Si-(4-methoxyphenyl)disilazane 10. Its molecular
Synthesis and structural characterization of exemplary silyl triptycenes
作者:Adam Mames、Agnieszka Osior、Piotr Grzegorz Szkudlarek、Mariusz Pietrzak、Sławomir Szymański、Tomasz Ratajczyk
DOI:10.1039/c9nj00934e
日期:——
derivatives, 9-(p-methoxyphenyl)-silyltriptycene (TRP) and sterically congested 1,4-dichloro-9-(p-methoxyphenyl)-silyltriptycene (TRPCl), are reported. TRP was prepared via both cycloaddition and a more efficient carbanion route. TRPCl, due to sterical congestion, was synthesized via the cycloaddition route. An optimal strategy for the synthesis of sterically congested silyl triptycene derivatives is discussed
报道了两种新的三萜衍生物,即9-(对甲氧基苯基)-甲硅烷基三萜(TRP)和空间上拥挤的1,4-二氯-9-(对甲氧基苯基)-甲硅烷基三萜(TRPC1)。TRP是通过环加成和更有效的碳负离子路线制备的。由于空间拥塞,通过环加成路线合成了TRPC1。讨论了一种用于合成空间拥挤的甲硅烷基三茂衍生物的最佳策略。通过NMR,X射线和PXRD方法对化合物进行表征。NMR显示,TRPC1以两种旋转异构体的形式存在于溶液中:TRPC1-R1和TRPC1-R2。在TRPC1-R2中,–SiH 2 –组中的质子不等价,并且两个相应的耦合常数1 J(H–Si)相差25 Hz(约12%,高水平)。从可变温度NMR谱,为的互阿列纽斯活化能TRPCl -R2成TRPCl -R1,和自由焓和这些旋转异构体之间的差异熵评价为19.6±0.3千卡摩尔-1,0.54±0.03千卡摩尔-1和分别为1.23±0.11 cal mol