Open-chain nitrogen compounds. Part V. Hydroxymethyltriazenes: synthesis of some new alkyl homologues of the anti-tumour 3-methyl-3-hydroxymethyltriazenes and preparation of the derived acetoxymethyl-, benzoyloxymethyl-, and methoxymethyltriazenes

The synthesis of some new 1-aryl-3-alkyl-3-hydroxymethyltriazenes is described. The method of coupling a diazonium salt with an alkylamine/formaldehyde mixture has been extended to (a) some diazonium ions with para substituents other than—M groups, (b) those with substituents in the ortho position, and (c) to homologous alkylamines (e.g. ethylamine, propylamine, etc.). Hydroxymethyltriazenes can also be prepared by the reaction of a 1-aryl-3-methyltriazene with formaldehyde. Several new derivatives of the hydroxymethyl function have been prepared. Reaction with acetic anhydride or benzoyl chloride in pyridine affords respectively the acetoxymethyl- and benzoyloxymethyl-triazenes; the acetates and benzoates react readily with methanol to give the novel methoxymethyltriazenes. This is the first report of a series of dialkyltriazenes with an ether linkage in the α position. An ether of this type has also been obtained directly from the diazonium fluoroborate salt by coupling with a mixture of benzylamine and formaldehyde in ethanolic solution.