J. Hartsuiker, S. Vries, J. Cornelisse
Jan 1, 1971
Citations
0
Influential Citations
3
Citations
Journal
Recueil des Travaux Chimiques des Pays-Bas
Abstract
The behaviour of photo‐excited 4‐nitroanisole toward nucleophilic reagents in aqueous solution is intriguing and only partially understood2,3,4. With hydroxide it yields 4‐nitrophenoxide and 4‐methoxy‐phenoxide5,6. On irradiation with alkylamines it gives N‐alkyl‐4‐nitro‐anilines7. A considerable amount of nitrite ion has been detected in the reaction with amines8, but it has as yet not been possible to isolate the corresponding substitution product.Letsinger and his coworkers5 demonstrated that 4‐nitroanisole on photoreaction with pyridine affords N‐(4‐methoxyphenyl)pyridinium nitrite. Interestingly, 4‐nitroanisole in its excited state undergoes substitution by cyanide ion exclusively at the position meta with respect to the nitro group, yielding 2‐cyano‐4‐nitroanisole9. This reaction is sensitive to oxygen: in solutions well purged with nitrogen, yields of 2‐cyano‐4‐nitroanisole are much lower than in air‐saturated solutions3.