95239-71-7Relevant articles and documents
Triazenes as Transport Form of Sulfur Mustard: Synthesis of 3-aryltriazenes and Study of Their Reactions in Aqueous and Nonaqueous Solutions
Singh, Ranjit
, p. 1088 - 1097 (2007/10/02)
A group of biologically active 1-aryl-3-triazenes has been synthesized.The rates of decomposition of a selected triazene, determined polarographically, increase with decrease in pH from 7.1 to 5.1.The products of aqueous decomposition have been analyzed by GC and GC-MS.A selectively deuterated triazene is found helpful in discriminating between alternative decomposition pathways.The data are consistend with initial protonation of the triazene and generation therefrom of a S-(2-chloroethyl)thioethyl cation (or its kinetic equivalent) which undergoes rearrangements as detected by deuterium scrambling.A second competing pathway may involve cyclization of the triazene to a 1-aryl-1,2,3-triazathiaoctene intermediate which then undergoes nucleophilic opening with attendant loss of nitrogen.These triazenes readily esterify 3,5-dinitrobenzoic acid and diethyl phosphate in etheral solutions.The use of deuterium labelled triazene indicates that these triazenes esterify predominantly via ion-pair mechanism and SN2 displacement is the minor pathway.A selected triazene is observed to alkylate the N3-position of triacetyluridine, also via a combination of ion-pair and SN2 displacement mechanisms as studied by the application of deuterium labelling.These studies are expected to assist in the interpretation of the cytotoxic effects of these triazenes.
