Open chain nitrogen compounds. Part XIII. 1-Aryl-3-arylthiomethyl-3-methyltriazenes and 3-(arylazo)-1,3-thiazolidines

Abstract

Reaction of 3-acetoxymethyl-1-aryl-3-methyltriazenes with sodium thiophenolate or thiocresolate in anhydrous dimethylformamide affords a new series of 3-arylthiomethyltriazenes (2), Ar-S-CH2-NMe-N=N-Ar'. These triazenes are remarkably labile in aqueous buffer and may be good pro-drugs for the active metabolite of the antitumour dimethyltriazenes. The reaction of arenediazonium fluoroborates with 1,3-thiazolidine in aqueous acetone affords a new series of N-arylazo-1,3-thiazolidines (4); the arylazothiazolidines represent a new class of triazene in which the N3 nitrogen is incorporated into a heterocyclic unit, in this case a 1,3-thiazolidine. Nuclear magnetic resonance spectra of the arylazothiazolidines show evidence for rotational isomerism of the exocyclic N2-N3 bond in the triazene moiety. La reaction des acCtoxymCthy1-3 aryl-1 methyl-3 triaztnes avec le thiophknolate ou le thiocrCsolate de sodium, dans le dimCthylformamide anhydre, fournit une nouvelle sene d'arylthiomkthyl-3 triaztnes (2), Ar-S-CHI-NMe-N=N-Ar '. Dans des tampons aqueux, ces triaztnes sont remarquablement labiles et, pour cette raison, ils peuvent Ctre de bons prCcurseurs de drogues pour le mCtabolite actif des dimCthyltriazknes antitumoraux. La rkaction des fluoroborates d'artnediazonium avec la thiazolidine-1,3, dans de I'acCtone aqueuse, fournit une nouvelle sdrie de N-arylazothiazolidines-1,3 (4); les arylazothiazolidines correspondent 1 une nouvelle classe de triazkne dans laquelle l'azote N3 est incorporC dans un hCtCrocycle; dans ce cas, il s'agit d'une thiazolidine-1,3. Les spectres en resonance magnCtique nucltaire des arylazothiazolidines suggtrent l'existence d'une isomCrie de rotation autour de la liaison exocyclique N2-N3 de la portion triaztne.[Traduit par la revue]

Useful yields of organic molecules under dynamic SIMS cluster bombardment

“…Die Arbeitsgruppen von Vaughan40, 41 und Rosa42, 43 haben eine Vielzahl von Hydroxymethyltriazen‐Derivaten hergestellt und hinsichtlich der Entwicklung von Wirkstoffvorstufen untersucht. Rosa und Mitarbeiter entwickelten eine allgemeine Synthesemethode für diese Stoffklasse.…”

Triazenes: A Versatile Tool in Organic Synthesis

“…The groups of Vaughan40, 41 and Rosa42, 43 have synthesized hydroxymethyl derivatives of triazenes for studies relating to the development of prodrugs. Rosa and co‐workers have developed a general synthetic method for these systems, which involves loss of water in acidic solution followed by nucleophilic attack of the iminium ion by an alcohol 44.…”

Sustained antiproliferative mechanisms by RB24, a targeted precursor of multiple inhibitors of epidermal growth factor receptor and a DNA alkylating agent in the A431 epidermal carcinoma of the vulva cell line

“…Despite the significant body of results that confirm its formation during the process of hydrolysis of acetoxymethyltriazenes (Hemens et al, 1984;Hemens and Vaughan, 1986;Iley, 1987;Vaughan and Manning, 1988;Merrin and Hooper, 1992), its implication in the DNA-damaging properties of the latter class of compounds is yet to be demonstrated. In contrast, it is now common knowledge that the methyldiazonium is capable of inducing significantly high levels of DNA alkylation particularly at N7 and O6 positions of guanine, thereby inducing DNA damage and lethal mutations in tumour cells (Bodell et al, 1985;Tisdale, 1987;Baer et al, 1993).…”