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Abstract

Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water=acetonitrile were studied. Kinetic monitoring of the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO =NO 2 H 2 followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron donating substituents, and a good Hammett correlation was observed with À6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH % 3, decreasing strongly for higher pH values. The study in water=acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant.

Characterization of Nitrite-Related Reaction Products in Beer

“…In addition to the study of nitrite reaction products in the complex beer matrix, there was simultaneously paid attention to the substances formed by the nitrite reaction with few compounds previously described in beer. − These substances were 2-ethyl phenol, 2-methoxy phenol (guaiacol), vanillic acid, and amino acids (tyrosine, phenylalanine, and histidine). They were chosen with a criterion to contain a substituted aromatic ring, which is supposed to be favorable to form C -nitroso compounds. − …”