Birch Reduction Of Benzamide, N-Substituted Benzamides And Biphenylene

Author

Luther Dickson, University of the Pacific

Date of Award

1972

Document Type

Dissertation

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Chemistry

First Advisor

Charles A. Matuszak

First Committee Member

Donald K. Wedegaertner

Second Committee Member

Paul H. Gross

Third Committee Member

Dale McNeal Jr.

Fourth Committee Member

Herschel Frye

Abstract

The Birch reduction of benzamide with sodium and absolute ethanol. 95% ethanol, or tert-butanol in liquid ammonia gave 1,4-dihydrobenzamide in varying amounts. The amide group was not reduced. The two most important variables encountered were the alcohol used and whether or not ammonium chloride was added after the reduction was completed. Without this addition of ammonium chloride, little or no 1,4-dihydrobenzamide was present after workup, while with its addition some 1,4-dihydrobenzamide formed whether the proton source was absolute ethanol, 95% ethanol, or tert-butanol. The highest yield was obtained with tert-butanol with ammonium chloride being added. Addition of ammonium chloride apparently prevents the disproportionation of 1,4-dihydrobenzamide to benzaminde and a tetrahydrobenzamide by neutralizing the strongly basic alkoxide which would otherwise be present. Ammonium chloride addition may also prevent air oxidation of the 1,4-dihydrobenzamide to benzamide. A blank experiment starting with 1,4-dihydrobenzamide confirmed this disproportionation.

Pages

133

Recommended Citation

Dickson, Luther. (1972). Birch Reduction Of Benzamide, N-Substituted Benzamides And Biphenylene. University of the Pacific, Dissertation. https://scholarlycommons.pacific.edu/uop_etds/3317