I. The mechanism of aminations of halobenzenes. II. Quantum mechanical calculations of electrical effects of substituents in para-substituted anilines

• Main Author: Semenow, Dorothy Ann
• Format: Others
• Published: 1955
• Online Access: https://thesis.library.caltech.edu/260/1/Semenow_da_1955.pdf; Semenow, Dorothy Ann (1955) I. The mechanism of aminations of halobenzenes. II. Quantum mechanical calculations of electrical effects of substituents in para-substituted anilines. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/C8SK-WN09. https://resolver.caltech.edu/CaltechETD:etd-01212004-110215 <https://resolver.caltech.edu/CaltechETD:etd-01212004-110215>

PART I. The Mechanism of Aminations of Halobenzenes. An elimination-addition mechanism, probably involving a "benzyne" intermediate, was established for the rearrangements which often occur in the conversion of non-activated aryl halides to arylamines with metallic amides. The evidence for the "benzyne" intermediate was obtained through 14C-tracer studies of rearrangements with iodobenzene, experiments designed to determine the role of the hydrogen atom located ortho to the displaced halogen atom and studies of orientations in the reactions of substituted halobenzenes. PART II. Quantum Mechanical Calculations of Electrical Effects of Substituents in Para-substituted Anilines. Calculations made by the simple molecular orbital method indicated that the relative basicities of aromatic amino groups para to electron-attracting substituents provide a reasonable measure of the charge on C4.