Open chain nitrogen compounds. Part XI. 3,7-Bis(arylazo)-1,3,5,7-tetraazabicyclo[3,3,1]nonanes: the reaction of diazonium ions with ammonia–formaldehyde mixtures

Abstract

Reaction of a series of diazonium salts with either hexamine or an aqueous mixture of ammonia–formaldehyde affords 3,7-bis(arylazo)-1,3,5,7-tetraazabicyclo[3,3,1]nonanes; several new examples of this novel class of bicycloheterocycle have been prepared and characterized. Analysis of the low-temperature nmr spectra of one compound in this series shows that the bicyclic system prefers the chair–chair conformation. The bis(arylazo)tetraazabicyclononanes, which are surprisingly stable in aqueous buffer compared to analogous triazenes of open-chain structure, do undergo slow decomposition at slightly acidic pH in an acetone–buffer mixture. The apparent product of this decomposition is the arylamine, which is observed as the Mannich condensation product, ArNH•CH2CH2COCH3.

Synthesis and Characterization of Novel Bis-Triazenes: 3,8-Di[2-aryl-1-azenyl]-1,3,6,8-tetraazabicyclo[4.4.1]undecanes and 1,3-Di-2-[(4-methoxyphenyl)-1-diazenyl]imidazolidine. The Reaction of Diazonium Ions with Ethylenediamine/Formaldehyde Mixtures

“…1,3,6,8-Tetraazatricyclo[4.4.1.1 3,8 ]dodecane ( 7 ) has been shown via X-ray crystal structure to be the condensation product of ethylenediamine with formaldehyde in the solid state. Therefore, the reaction mechanism for the formation of 3,8-di[2-aryl-1-azenyl]-1,3,6,8-tetraazabicyclo[4.4.1]undecanes is believed to be the route shown in Scheme , which is analogous to the mechanism for bis(arylazo)tetraazabicyclononane ( 3 ) formation previously reported . Supporting evidence for the mechanism in Scheme is the fact that direct diazonium coupling with the dodecane ( 7 ) results in a higher yield of 6 .…”

“…For example, reaction of the diazide N 3 CH 2 CH 2 N 3 with an alkyllithium reagent affords 1,2-bis(alkyltriazeno)ethanes (1), which are potently cytotoxic due possibly to their ability to cross-link DNA . Under appropriate conditions, the reaction of a diazonium salt with a mixture of methylamine and formaldehyde affords the bis(triazenyl)methylamine ( 2 ), whereas similar diazonium coupling with a mixture of formaldehyde and ammonia produces the bis (triazenyl)tetraazabicyclononane ( 3 ) …”

Open-chain nitrogen compounds. Part XII. Methanolysis of 3-alkyl-3,4-dihydro-1,2,3-benzotriazin-4-ols: evidence for ring-chain tautomerism with the cytotoxic monoalkyltriazenes

“…Recrystallization of some of the triazinols from solvent mixtures containing methanol frequently resulted in failure to recover the Chydroxytriazine and it became apparent that the carbinolamines were undergoing methanolysis to give new products, the 4-methoxytriazines (14)(15)(16)(17)(18)(19)(20). When this methanolysis was studied in pure methanol, it was found that the reaction can give virtually quantitative yields of the methyl ethers and also that the rate of reaction is strongly dependent on the nature of the substituents R' and R~.…”

“…Nuclear magnetic resonance spectra of these novel cyclic carbinolamines suggest that they exist in equili-'For part XI, see ref. 15. '~uthor to whom all correspondence should be addressed.…”

The first controlled reduction of the high explosive RDXElectronic supplementary information (ESI) available: full experimental details on the synthesis and analysis of the reported compounds. See http://www.rsc.org/suppdata/cc/b2/b207885f/

“…Hexamethylenetetramine is known to react with diazonium salts to form a diazononane derivative. [22][23][24] Use of diazotised groups commonly used for surface adsorption such as benzotriazole 25 and hydroxyquinoline 20 appeared to give small amounts of the desired product but were difficult to isolate and † Electronic supplementary information (ESI) available: full experimental details on the synthesis and analysis of the reported compounds. See http:// www.rsc.org/suppdata/cc/b2/b207885f/ characterize.…”