HYDROGEN ROLE IN SELECTIVITY OF SUBSTITUTED NITRO-AZOBENENES HYDROGENI-ZATION ON SKELETAL NICKEL IN 2-PROPANOL AQUEOUS SOLUTIONS

Abstract

Elucidation of the substituted nitrobenzenes transformations sequence, in particular, containing several reactive groups and the development of approaches to the control of the selectivity of processes involving them is of interest from both theoretical and practical points of view. The article is devoted to the analysis of the hydrogenation kinetics of 2-nitro-2'-hydroxy-5'-methylazobenzene, 4-nitro-2'-hydroxy-5'-methyl-isobenzene, 4-nitroaniline, 4-amino-2'-hydroxy-5'-methylazobenzene on skeletal nickel in 2-propanol aqueous solutions of different composition, including with the addition of acetic acid or sodium hydroxide with various initial amounts of organic compound. The rise in the 4-nitro-2'-hydroxy-5'-methylazobenzene initial amount leads to increase in the nitro group transformation rate in the starting compound and to decrease in the azo-group transformation rate. The effect of sodium hydroxide additives in the 2-propanol aqueous solution on the nitro- and azo-groups conversion rate into 4-nitro-2'-hydroxy-5'-methyl-isobenzene is analogous to the change in the individual compounds hydrogenation rates (4-nitroaniline and 4-amino-2'-hydroxy-5'-methylazobenzene). Obtained results do not contradict the parallel-sequential scheme concept for the 4-nitro-2'-hydroxy-5'-methylazobenzene transformations. One of the directions is associated with the azo-group transformation into 4-nitro-2'-hydroxy-5'-methylazobenzene and 4-nitroaniline and 2-amino-4-methylphenol formation, and the second with the 4-nitro-2'-hydroxy-5'-methyl-isobenzene conversion through 4-amino-2'-hydroxy-5'-methyl-isobenzene by the nitro-group reducing. At the reaction end, all intermediate compounds are reduced to 2-amino-4-methylphenol and 1,4-phenylenediamine. When 2-nitro-2'-hydroxy-5'-methylazobenzene is hydrogenated, one of the directions leads to the 2-nitro-2'-hydroxy-5'-methylhydrazobenzene formation, and the second to the product containing the triazole cycle - N-oxide 2-2'-hydroxy-5'-methylphenylbenzotriazole. At the reaction end, these compounds are reduced to 2-2'-hydroxy-5'-methylphenylbenzotriazole and 2-amino-4-methylphenol and 1,2-phenylenediamine, respectively. In the solution at the sodium hydroxide presence, 2-nitro-2'-hydroxy-5'-methylhydrazobenzene transforms into the N-oxide 2-2'-hydroxy-5'-methylphenylbenzotriazole as a result of intramolecular rearrangement.