Document Type
Thesis
Date of Award
1-31-1986
Degree Name
Master of Science in Chemical Engineering - (M.S.)
Department
Chemical Engineering, Chemistry and Environmental Science
First Advisor
Howard David Perlmutter
Second Advisor
David S. Kristol
Third Advisor
R. P. T. Tomkins
Abstract
The electrochemical reduction of two highly hindered quaternary ammonium salts was attempted. The reductions were performed in hexamethylphosphoramide at a controlled potential using platinum electrodes. It was anticipated that these reductions would provide a route to the formation of anti-Bredt bridgehead olefins. This work is an extension of the work of Dubois, Monvernay and Lacaze who electrochemically reduced quaternary ammonium salts such as trimethyl-t-butylammonium iodide (XX).
Trimethy1-2,4,4-trimethy1-2-pentylammonium iodide (XXIII) was reduced to form 2,4,4-trimethyl-l-pentene (XXVI) and 2,2,4-trimethylpentane (XXV). The yields of the two runs of this reduction were 10% and 20% and in the first run of the reduction 75% of the product was 2,4,4-trimethyl-l-pentene (XXVI) and in the second run 90% of the product was 2,4,4-trimethyl-l-pentene (XXVI). 2,4,4-trimethyl-2-pentene (XXIV) was not formed in either run.
The other quaternary salt, 1-azoniatricyclo-(3,3,3,0)-undecane bromide (XVIII) was not readily reduced. The first run of the reduction produced a small amount of product which could not be definitely confirmed as being either the desired 1-azabicyclo-(3,3,3)-undec-4-ene (I) or 4-allyl-l-azabicyclo-(3,3,0)-octane (XIX). Following the second run of the reduction four separation schemes were tried in order to find the best way of recovering any product. However, none were successful and only the first showed that it might contain a trace of a product.
Recommended Citation
Kapichak, Rudolph K., "Electrochemical reduction of quaternary ammonium salts" (1986). Theses. 3414.
https://digitalcommons.njit.edu/theses/3414
