Author:
Schaefer Ted,Peeling James,Sebastian Rudy
Abstract
The 1H and 19F nmr spectra of benzyl fluoride, although very tightly coupled at 300 MHz, are analyzed for dilute CS2 and acetone solutions. 13C, 19F spin–spin coupling constants for benzyl fluoride in a series of solvents are also measured. Geometry-optimized STO 3G MO computations on benzyl fluoride indicate a small twofold barrier to rotation about the exocyclic C—C bond in the gas phase. All the long-range couplings between 19F and ring protons or carbon-13 nuclei and between methylene and ring protons are consistent with the conclusion that the barrier to internal rotation in benzyl fluoride is small and that the conformation in which the C—F bond lies in a plane perpendicular to the benzene plane is stabilized by 2 kJ/mol in going from CS2 to DMSO or acetone solutions. The solvent dependence of the internal barrier may account for the diversity of conformational conclusions in the literature. Furthermore, it is clear that the internal barrier will depend on the presence of substituents at any site in the ring.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
37 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献