Deamination of Primary Aminoalkanols. Formation of Substituted N-Nitroso-1,3-oxazolidines and N-Nitroso-1,3-tetrahydrooxazines

Article abstract of DOI:10.1021/jo00326a002

The deamination of 2-amino- and 3-aminoalkanols in the presence of nitrous acid is reported.The 2-aminoalkanols generated aldehydes upon loss of nitrogen, followed by oxazolidine formation by reaction with starting material and finally nitrosation to substituted N-nitroso-1,3-oxazolidines.Ethanolamine gave N-nitroso-2-methyl-1,3-oxazolidine; 2-amino-2-methyl-1-propanol was converted to N-nitroso-2-isopropyl-4,4-dimethyl-1,3-oxazolidine.Deamination of 1-amino-2-propanol gave propionaldehyde, which upon further reaction produced cis- and trans-N-nitroso-2-ethyl-5-methyl-1,3-oxazolidines. (E)- and (Z)-N-nitroso-2-ethyl-4-methyl-1,3-oxazolidines were obtained from the deamination of 2-amino-1-propanol.Propionaldehyde and formaldehyde were produced by diazotiazation of 1-amino-3-propanol.Further reaction of the aldehydes with unreacted amine formed N-nitroso-1,3-tetrahydrooxazine and N-nitroso-2-ethyl-1,3-tetrahydrooxazine.Nuclear magnetic resonance and deuterium-exchange studies of these compounds are discussed.