ARYLAMINE-NUCLEOSIDE ADDUCT FORMATION - EVIDENCE FOR ARYLNITRENE INVOLVEMENT IN THE REACTIONS OF AN N-ACETOXYARYLAMINE

N-Acetoxyarylamines are reactive metabolites that are produced from N- arylhydroxamic acids by N-arylhydroxamic acid N,O-acyltransferase and by the acetyl coenzyme A-dependent O-acetylation of N-arylhydroxylamin es. Solvolytic decomposition of 7-acetyl-2-(N-acetoxyamino)fluorene (3 ) afforded 7-acetyl-2-aminofluorene (4) and 7,7'-diacetyl-2,2'-azofluo rene (5). Solvolysis of 3 in the presence of 2'-deoxyguanosine resulte d in formation of N-(deoxyguanosin-8-yl)-7-acetyl-2-aminofluorene (2), along with smaller yields of 4 and 5 than were obtained in the absenc e of 2'-deoxyguanosine. The inclusion of nitrene trapping agents, such as piperylene, triethyl phosphite, 1-chloro-4-nitrosobenzene, and oxy gen, in the reaction medium with 3 and 2'-deoxyguanosine caused a redu ction in the yields of 2, 4, and 5. Additionally, products that would be expected to be formed through reaction with an arylnitrene intermed iate were obtained when triethyl phosphite, 1-chloro-4-nitrosobenzene, and oxygen were included in the incubations with 3 and 2'-deoxyguanos ine. The results support the proposal that a nitrene intermediate is i nvolved in the formation of 2, 4, and 5 from 3.