4127-66-6Relevant academic research and scientific papers
REACTION OF AROMATIC COMPOUNDS WITH NUCLEOPHILIC REAGENTS IN LIQUID AMMONIA. V. THE MECHANISM AND DIRECTION OF HYDROXYLATION OF p-SUBSTITUTED NITROBENZENES WITH POTASSIUM HYDROXIDE
Malykhin, E. V.,Kolesnichenko, G. A.,Shteingarts, V. D.
, p. 1048 - 1056 (2007/10/02)
In the reaction of p-substituted nitrobenzenes 4-XC6H4NO2 (X = Cl, Br, I) with potassium hydroxide and oxygen in liquid ammonia (-33 deg C) the corresponding 5-substituted 2-nitrophenols are formed with high yields.Under analogous conditions 4-fluoronitrobenzene and 1,4-dinitrobenzene are converted into 4-nitrophenol.When K18OH was used, the hydroxyl group of the reaction products contained the 18O isotope preferentially in both cases.The action of KO2 and K2O2 in the presence of oxygen on 4-chloronitrobenzene or of oxygen on the product from the reduction of 4-chloronitrobenzene with potassium leads to the formation of 4-nitrophenol.This set of experimental data agrees with the scheme for the hydroxylation of p-substituted nitrobenzenes with alkali and oxygen in liquid ammonia involving the formation of anionic ? complexes for both directions of the process and their oxidation by molecular oxygen in the case of substitution of a hydrogen atom.
