The exploratory far-UV photochemistry of 1-methyl-1-silabicyclo[2.2.1]hept-2-ene and 2-trimethylsilylbicyclo[2.2.1]hept-2-ene
作者:Mark G. Steinmetz、Qing Chen、Yan Zheng
DOI:10.1016/0022-328x(95)06087-d
日期:1996.6
1-Methyl-1-silabicyclo[2.2.1]hept-2-ene was synthesized in 27% yield by chloramine-T oxidation of mixture of C-2/C-3 phenylselenide derivatives of 1-methyl-1-silabicyclo[2.2.1]heptane. The phenylselenides in turn were produced in 8% yield by GifIII oxidation of 1-methyl-1-silabicyclo[2.2.1]heptane. The 214 nm photolysis of the rigid 1-silanorbornene in MeOH or (CH3)3COH resulted in [1,3-C] migration
通过氯胺-T氧化1-甲基-1-甲硅烷基[2.2]的C-2 / C-3苯基硒化物衍生物的混合物,以27%的收率合成了1-甲基-1-甲硅烷基环[2.2.1]庚-2-烯。 .1]庚烷。苯硒化物通过1-甲基-1-硅双环[2.2.1]庚烷的Gif III氧化依次以8%的产率生产。刚性1-silanorbornebornene在MeOH或(CH 3)3 COH中的214 nm光解导致[1,3-C]迁移,从而提供带有量子点的3-烷氧基-3-甲基-3-硅双环[4.1.0]庚烷产率为0.053(甲氧基衍生物)和0.062(叔丁氧基衍生物)。对于甲醇,光子化的效率估计为f <0.01,对于叔酸则可以忽略不计丁醇。在戊烷和(CH 3)3 COH中2-三甲基甲硅烷基双环[2.2.1]庚-2-烯的214 nm辐照下,也观察到[1,3-C]光重排,但是主要的光过程似乎是可逆的[1, 2-Si]迁移得到卡宾中间体,将其