Synthesis of cyclopropene derivatives and chemistry of fullerenes

[摘要] New synthetic routes leading to 1-vinylcyclopropene and methylenecyclopropene were established making use of the Vacuum Gas-Solid Reaction (VGSR) technique. Both syntheses were planned in a way that allowed the use of solid fluoride as the dehalosilylation inducing reagent in the last step. The decomposition of methylenecyclopropene at temperatures above $-$75$spcirc$C was investigated and a dimer of methylenecyclopropene was proposed as the initial decomposition product.Fullerenes have been synthesized and separated using chromatographic techniques. Helium containing isomers of higher fullerenes were analyzed by $sp3$He NMR spectroscopy and signals were assigned to isomers of C$sb{76}$, C$sb{78}$ and C$sb{84}$. A novel C$sb{60}$ derivative has been synthesized by the reaction of C$sb{60}$ with cyclopropa (b) naphthalene and the product of the reaction with $sp3$He@C$sb{60}$ revealed the signal of the new compound in the $sp3$He NMR. Fullerene hydrides $sp3$He@C$sb{60}$H$sb{36}$ and $sp3$He@C$sb{60}$H$sb{18}$ were synthesized by Birch reduction or reaction of $sp3$He@C$sb{60}$ with dihydroanthracene and the products were analyzed by $sp3$He NMR. The spectra revealed one isomer for C$sb{60}$H$sb{18}$ and two isomers for C$sb{60}$H$sb{36}$. The most intense signal for C$sb{60}$H$sb{36}$ was assigned to the isomer with D$sb{m 3dspprime}$ symmetry based on the $sp3$He NMR chemical shift value.

[发布机构] Rice University

[效力级别] chemistry