Synthesis and Chemistry of Strained and Conjugated Fluorocarbons
Abstract
The objective of this project was to synthesize and study the chemistry of an array fluorocarbons and fluorocarbon derivatives in order to further understanding of fluorine as substituent in organic chemistry. Target molecules, all of which incorporated conjugation and/or strain, were chosen on the basis of unusual and/or interesting structural features. This investigation has accomplished the synthesis of many new fluorocarbons and derived molecules, and has included exploration of new synthetic methodology in fluorocarbon chemistry, determination of thermodynamic and kinetic parameters for fluorocarbon valence isomerizations, study of negative hyperconjugation, and examination of mechanisms of fluorocarbon reactions. Much has been learned about how to synthesize perfluorinated annulenes and their relatives, and much information has been acquired about potential energy surfaces for fluorocarbon valence isomerizations. A study of rotational barriers in alpha-fluoramines has revealed that negative hyperconjugation can have powerful energetic consequences even in neutral molecules. Insights into fluorocarbon reaction mechanisms, both thermal and photochemical, have emerged from synthetic explorations as well as from explicitly mechanistic studies. Keywords: Fluorocarbons; Organic synthesis; Annulenes; Ring strain; Dynamic NMR; Valence isomers; Negative hyperconjugation; Thermodynamic parameters; Kinetic parameters; Reaction mechanisms.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jul 01, 1989
- Accession Number
- ADA211633
Entities
People
- D. M. Lemal
Organizations
- Dartmouth College