Nitrite ion as a nitrosating reagent. Nitrosation of morpholine and diethylamine in the presence of formaldehyde

Abstract

The kinetics of the nitrosation of morpholine and diethylamine in the presence of formaldehyde has been studied at pH values between 6.5–8.2 and 6.9–8.7, respectively. The results are interpreted through a mechanism that implies the reaction between both the nitrite NO₂^– and iminium R₂[graphic omitted]CH₂ ions. The latter ion results from the dehydration of the conjugated acid of the carbinolamine, R₂[graphic omitted]HCH₂OH, the initial product of the amine–formaldehyde reaction. The results allow the calculation of the equilibrium constants of formation of carbinolamine, R₂NCH₂OH, and methanediamine, R₂NCH₂NR₂(only for the morpholine–formaldehyde system), and their conjugate acids.