Triazene

About: Triazene is a research topic. Over the lifetime, 759 publications have been published within this topic receiving 8714 citations. The topic is also known as: Triazene cleavage & 1-triazene.

Specificity of DNA Alkylation by 1-(2-Chloroethyl)-3-alkyl-3-acyltriazenes Depends on the Structure of the Acyl Group: Kinetic and Product Studies

Abstract: The reactions of calf thymus DNA with ten 1-(2-chloroethyl)-3-alkyl-3-acyltriazenes of varying acyl side chain structure were studied alone, or in the presence of porcine liver esterase in pH 7.0 phosphate buffer. In several of the key triazenes, the acyl substituent contained a free carboxylic acid group. With esterase present in the reaction mixture, the resultant levels of DNA alkylation could be correlated with the kinetic rates of decomposition of the triazenes. Under these conditions, the predominant pathway of decomposition involved deacylation of the parent triazene and eventual production of an alkanediazonium ion. This intermediate subsequently alkylated DNA--guanine to give 7-alkylguanine as the principal reaction product. In the absence of esterase, the order of DNA alkylation for all of the acyltriazenes did not correlate with their respective rates of decomposition, leading to the conclusion that the triazenes did not decompose by the expected mode of uncatalyzed N(2)-N(3) heterolyic cleavage. The major DNA alkylation product from the N(3)-methyltriazenes was 7-methylguanine, instead of the expected 7-(chloroethyl)- and 7-(hydroxyethyl)guanine products, which suggested that the acyl group was being hydrolyzed. However, acyltriazenes with an N(3)-benzyl group rather than a methyl in this position produced very little 7-benzylguanine product, contrary to prediction. An alternative mechanism involving internally assisted hydrolysis of the side chain ester is proposed to explain these results. NMR product analysis and computational studies were carried out to lend support to the postulated mechanism.

Chemistry of ruthenium. Part 10. Triazene 1-oxide complexes of bis(2,2′-bipyridine)ruthenium-(II) and -(III). Synthesis, spectra, and electrochemistry

Abstract: Mixed ruthenium complexes of type [Ru(bipy)2L]ClO4·H2O derived from 2,2′-bipyridine (bipy) and triazene 1-oxides, RN(O)N–NH–C6H4X-p(HL: R = Et or Ph; X = Me, H, Cl, CO2Et, or NO2) are described. In solution they display two quasi-reversible reductions due to electron transfer to co-ordinated bipy units. The RuIII–RuII couple occurs in the range 0.16–0.44 V versus s.c.e. The formal potential of this couple is linearly related to the Hammett constant of substituent X. The low-spin ruthenium(III) analogue, [Ru(bipy)2L]2+, is furnished by both coulometric and chemical oxidations. The energy of the ligand-to-metal charge-transfer band of [Ru(bipy)2L]2+ correlates linearly with the RuIII–RuII formal potential.

The Base-Induced Fragmentation of N,N-Dibenzyl-N′-aryltriazenes

Abstract: Deprotonation of N,N-dibenzyl-N'-aryltriazenes, either in liquid phase or on solid support, by a strong base (n-BuLi or LDA) leads to fragmentation of the N-N single bond to give an imine and a diazenyl anion, which decomposes by loss of nitrogen to the parent aryl anion. The imine is deprotonated to give a 2-aza allyl anion, which is subsequently trapped by electrophiles. As an overall result, this fragmentation of the Ti triazene anchoring group represents a new traceless cleavage mode of this linker. The same mode of fragmentation was observed for the T2 linker leading to 2-aza allyl anions in liquid phase. The dibenzylamino moiety is apparently crucial since pyrrolidinodiazenylarenes can be metallated at the heterocycle without cleavage.