Heterocyclic N-acetoxyarylamines, models for the putative ultimate carcinogens of aromatic amines: 2-acetoxyamino-5-phenylpyridine and 2-acetoxyaminopyridine.
The structures of O-acetyl-N-(5-phenyl-2-pyridyl)-hydroxylamine, C13H12N2O2, (I), and O-acetyl-N-(2-pyridyl)hydroxylamine, C7H8N2O2. (II), have been determined in order to confirm earlier structure assignments based on spectroscopic information. Compound (I) is the probable mutagenic metabolite of the phenylalanine pyrolysis product 2-amino-5-phenyl-pyridine. The crystal structures of (I) and (II) are the first reported for heterocyclic N-acetoxyarylamines, the corresponding homocyclic arylamine derivatives being extremely unstable. In the solid state, both (I) and (II) exist as hydrogen-bonded dimers, with the arylamine N atom acting as donor and the pyridine N atom of a neighboring inversion-related molecule as acceptor; the distance between donor and acceptor N atoms is 3.007(2) in (I) and 2.956(2) A in (II). This orientation of the N-H bond results in the rotation of the acetoxy group out of the plane of the pyridine ring by 22.5(2) in (I) and 27.4(2) degrees in (II).
Ojala
W H
WH
Department of Chemistry, University of St. Thomas, St. Paul, MN 55105, USA.
Iyer
R A
RA
Hanna
P E
PE
Gleason
W B
WB
D000588:Amines / Q000737:chemistry*; D000631:Aminopyridines / Q000737:chemistry*; D002273:Carcinogens / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation
C106721:2-acetoxyamino-5-phenylpyridine; C106722:2-acetoxyaminopyridine; D000588:Amines; D000631:Aminopyridines; D002273:Carcinogens; D006571:Heterocyclic Compounds