Nitrosamine formation from ternary nitrogen compounds

When amides of pyrrolidine are heated with sodium nitrite, small amounts of NPYR are formed. Both the rate of reaction and the nitrosamine yield are increased when ethylene glycol and glycerine are used as solvents. Kinetic evidence suggests that these polyols react with the amide to form esters and the corresponding amine. The esters then react with sodium nitrite to give nitrite esters which rapidly nitrosate the amine. The heating of LDEA with sodium nitrite gives relatively high yields of NDELA in relatively short times and this nitrosation can be explained by this mechanistic hypothesis. 2-N,N-dimethylaminomethylpyrrole reacts very rapidly with nitrous acid at 25 degrees to give NDMA as the sole nitrosamine. This suggests a new mechanism of tertiary amine nitrosation.