Nitrous acid reactions

These reactions involve a diazonium ion (see 12-47) and are much faster than ordinary hydrolysis for benzamide the nitrous acid reaction took place 2.5 x lo times faster than ordinary hydrolysis. Another procedure for difficult cases involves treatment with aqueous sodium peroxide. In still another method, the amide is treated with water and f-BuOK at room temperature. " The strong base removes the proton from 107, thus preventing the reaction marked k j. A kinetic study has been done on the alkaline hydrolyses of A-trifluoroacetyl aniline derivatives. Amide hydrolysis can also be catalyzed by nucleophiles (see p. 427). 

Bonner, F. T., Kada, J., and Phelan, K. G. (1983). Symmetry of the intermediate in the hydroxylamine-nitrous acid reaction. Inorg, Chem. 22, 1389-1391. 

The OH (X2n) can be generated from the photolysis of water, hydrogen peroxide, and nitric and nitrous acid. Reactions of OH(A2n) with various hydrocarbons arc important in understanding photochemical smog formation (see Section VIII—2). 

Reaction of azide ion with nitrous acid (13) has been studied in connection with diazotisation and other nitrous acid reactions including those involved in oxygen exchange, viz. 

Proceeding via diazohydroxide (126), the nitrous acid deamination is subject, in principle, to the ramifications discussed in Section 4.3.3. In aqueous nitrous acid reactions the role of the counterion is poorly defined. Secondary alkylamines give alcohols with predominant inversion of configuration155). An 180 study on the deamination of cyclohexylamine has shown that most of the oxygen atoms of the alcohol are derived from the solvent156. ... 

The amino group in 8-aminopyrido[2,3-b]pyrazine is hydrolyzed to give the 8-0x0 compound by treatment with sodium hydroxide. Similarly the 6-amino groups in compounds 103 and 104 have been replaced by treatment with nitrous acid." Reaction of 5-alkyl quaternary salts of pyrido[2,3-b]pyrazine with a variety of nucleophiles has been recently described " (see Section IIIl). 

Reduction of Cerium(IV) by Nitrous Acid Reaction Kinetics. Since the effect of nitrate ion on G(Cem) was previously attributed (23) to intermediate formation of nitrite ion, the thermal reduction of cerium (IV) by nitrous acid was investigated with reactant concentrations comparable with those encountered in the post-irradiation reaction. We discovered that the reduction of cerium (IV) by nitrous acid was slow, with reaction rates comparable with those rates observed in post-irradiation reactions. Typical experimental data are shown in Figure 3. About 5 seconds were required to prepare the mixture before the optical density could be recorded as a function of time after mixing. 

Reeve, R. M. (1968). Histochemical differentiation between tyrosine and chlorogenic acid in plant tissues Nitrous acid reactions and metal chelation of nitrosotyrosine. J. Histochem. Cytochem. 16, 191-198. 

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