Chemistry ETDs

Publication Date

Spring 1-21-1970


The synthesis of six new azabenzo[a]pyrenes was undertaken in order that the carcinogenic and carcinostatic properties of these com­pounds might be tested. The compounds thus synthesized were 4-aza­ benzo[a]pyrene (1), 5-methyl-4-azabenzo[a]pyrene (2), 12-azabenzo[a]­pyrene (3), 11-methyl-12-azabenzo [a]pyrene (4),5 -azabenzo [a]pyrene (5), and 4-methy1-5-azabenzo[a]pyrene (6).

Compounds 1 and 2 were prepared from the intermediate 4-keto-1,2,3,4-tctrahydrochrysene. The azine from this ketone was dehydro­genated and the resulting aromatic amine was both formylated and acetylated. The amides were cyclized with polyphosphoric acid in a Bischler-Napieralski cyclodchydration giving fair yields of 1 and 2. The synthesis of compounds 3 and 4 was carried out in a similar sequence of reactions with the intermediate ketone being l-keto-1,2,3,4- tetrahydrobenz[a]anthracene in this case. The cyclization of the formyl and acetyl derivatives was also carried out with polyphosphoric acid in good yields.

Compounds 5 and 6 were synthesized from chrysene-5-carboxylic acid. A Schmidt reaction on this acid afforded 5-aminochrysene. The formyl and acetyl derivatives of this amine were both prepared and cyclized, again using polyphosphoric acid as the cyclizing agent, to give good yields of both 5 and 6.

The ultraviolet absorption and nuclear magnetic resonance spectra of each of the six compounds were measured. The ultraviolet absorption spectra of all six compounds were observed to be very similar to that of benzo[a]pyrene, while he nuclear magnetic resonance spectrum of each helped to confirm the structure of each compound.

Document Type


Degree Name


Level of Degree


Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Guido H. Daub

Second Committee Member

Raymond N. Castle

Third Committee Member

Milton Kahn

Fourth Committee Member

Roy Dudley Caton