MOLECULAR ORBITAL THEORY IN ORGANIC CHEMISTRY.
Abstract
In carbonium ion reactions, acetolysis of benzyl tosylates of 40C give the following relative rates: m-C1, 0.56; p-C1, 0.51; H, 1.00; p-F, 3.4; P-CH3, 60. The conductivity method developed is now being applied to polycyclic arylmethyltosylates for application of M.O. theory. In carbanion reactions, pK's were measured towards cesium cyclohexyamide in cyclohexylamine of 14 hydrocarbons. Representative values are 9-phenylfluorene (18.49); indene, 19.93; fluorene, 22.74; triphenylmethane, 31.48; diphenylmethane, 33.09. HMO theory gives a poor correlation of these data. Exchange rates were measured for other hydrocarbons of interest with lithium and cesium cyclohexylamide and the reactions were demonstrated to involve carbanionic intermediates and to provide valid measures of hydrocarbon acidities. The exchange rates of polycyclic methylarene-ad's and of arene-d (or t)'s are poorly correlated by HMO theory. In the arene case, a simple inductive field effect model was successful. An attempted synthesis of octalene was unsuccessful. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Sep 30, 1965
- Accession Number
- AD0628297
Entities
People
- Andrew Streitwieser Jr.
Organizations
- University of California, Berkeley