MOLECULAR ORBITAL THEORY IN ORGANIC CHEMISTRY.
Final rept. 1 Oct 61-30 Sep 65,
CALIFORNIA UNIV BERKELEY DEPT OF CHEMISTRY
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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, pKs 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-ads and of arene-d or ts 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
- Organic Chemistry