Part I. The Structure of 1,2-Dimethylnorbornyl Cation. Part II. The Relative Stabilities of Some Tertiary Aliphatic Cations

Citation

McFarland, James Thomas (1969) Part I. The Structure of 1,2-Dimethylnorbornyl Cation. Part II. The Relative Stabilities of Some Tertiary Aliphatic Cations. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/NJST-QK11. https://resolver.caltech.edu/CaltechTHESIS:03292017-092122515

Abstract

Part I.

The pmr spectrum of 1,2-dimethylnorbornyl cation indicates that the Wagner-Meerwein rearrangement is rapid on the nmr time scale at -100° C. Furthermore the protons at C-6 are deshielded by 1.3 ppm with respect to the protons at C-5. This is consistent with the nonclassical structure for this cation.

Part II.

Mixtures of organic chlorides have been forced to compete for less than one equivalent of antimony penta-fluoride in order to judge relative cation stabilities. The results indicate no stabilization of 2,3,3-trimethyl- 2-butyl cation by methyl bridging. However methylene bridging seems to stabilize 1,2-dimethylnorbornyl cation. The qualitative order of cation stabilities measured by this method is not always the same as that measured by solvolysis experiments.

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