The reactions of N-tosyl-O-2, 4, 6-trimethylbenzylhydroxylamine with primary alkyl halides yielded the protected hydroxylamines. The simultaneous cleavage of N-tosyl-and O-2, 4, 6- trimethylbenzyl groups with hydrogen bromide in acetic acid gave the corresponding N- monoalkylated hydroxylamines such as N-benzylhydroxylamine, 1-amino-3- hydroxyaminopropane and DL-3-hydroxyamino-2-aminopropionic acid.