87450-06-4Relevant articles and documents
OPEN-CHAIN NITROGEN COMPOUNDS. PART VI. THE FORMATION OF BIS(1-ARYL-3-METHYLTRIAZEN-3-YLMETHYL) METHYLAMINES IN THE REACTION OF DIAZONIUM IONS WITH MIXTURES OF FORMALDEHYDE AND METHYLAMINE
Manning, Hartford W.,Hemens, Chantal M.,LaFrance, Ronald J.,Tang, York,Vaughan, Keith
, p. 749 - 754 (2007/10/02)
The synthesis of a series of N,N-bis(1-aryl-3-methyltriazen-3-ylmethyl) methylamines from coupling diazonium salts with mixtures of methylamine and formaldehyde is described.These novel bis-triazenes, or heptazanonadienes, have significant anti-tumour activity against the TLX5 lymphoma in mouse.The mechanism of formation of these triazenes is discussed with reference to the implication to the presumed equilibria taking place in the methylamine/formaldehyde solution.The formation of the bis-triazene is usually accompanied by the formation of a 3-hydroxymethyltriazene, and it has been shown that the hydroxymethyltriazene can be transformed into the bis-triazene.The proportions of the two products are strongly influenced by the relative amounts of methylamine and formaldehyde.Coupling the p-bromobenzenediazonium salt to a 1:1 methylamine/formaldehyde mixture affords mainly the bis-triazene, whereas a 1:50 mixture gives almost totally the hydroxymethyl triazene.These results suggest that the two triazenes arise from diazonium coupling to different species in the amine/formaldehyde mixture; this hypothesis is supported by the formation of identical product mixtures from coupling the diazonium ion with (a) a 1:1 MeNH2/CH2O mixture, and (b) the cyclic trimer of the carbinolamine MeNHCH2OH, and by the identification of a minor product from the reaction of p-chlorobenzenediazonium fluoroborate with MeNH2/CH2O as bis(1-p-chlorophenyl-3-methyltriazen-3-yl) methane.
