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Nitrogen‐15 studies of the mechanisms of acetolyses of hexamethylenetetramine and 3,7‐diacetyl‐1,3,5,7‐tetraazabicyclo[3.3.1]nonane (DAPT)
Author(s) -
Cooney Aidan P.,
Crampton Michael R.,
Jones Michael,
Golding Peter
Publication year - 1987
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570240446
Subject(s) - hexamethylenetetramine , chemistry , nonane , diacetyl , medicinal chemistry , organic chemistry
[ 15 N 4 ]‐Hexamethylenetetramine (Hexamine), and [ 15 N 4 ]‐3,7‐diacetyl‐1,3,5,7‐tetraazabicyclo[3.3.1]nonane(DAPT) have been prepared starting from 15 NH 3 . Synthetic acetolysis reactions were performed using mixtures of pure [ 15 N 4 ]‐ and [ 14 N 4 ]‐compounds and the destination of the nitrogen isotopes in the products was determined mass spectrometrically. The results show that relatively little isotopic mixing occurs in the acetolysis of hexamine to DAPT though the formation of some products with isotopic composition [ 14 N 3 15 N 1 ] and [ 14 N 1 15 N 3 ] indicates limited ring cleavage. However the more severe conditions used in the formation of 1,3,5‐triacetyl‐1,3,5‐triazacyclohexane (TRAT) give rise to considerable isotopic scrambling. The acetolysis of DAPT to give 1,3,5,7‐tetraacetyl‐1,3,5,7‐tetraazacyclooctane occurs by selective cleavage of the methylene bridge.