ChemInform Abstract: SYNTHESIS OF ARYL AZIDES FROM 1‐AMINOBENZIMIDAZOLE

Кузьменко, В. В.; Komissarov, V. N.; Simonov, A. M.

doi:10.1002/chin.197936189

Cited by 1 publication

(2 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The corresponding reaction of the meta isomer should be much less facile because the 3-methoxy group can no longer interact with the nitrenium ion by resonance. The singlet nitrene can, in principle, also relax to lower-energy triplet nitrene 9 which will eventually form 3,3′-dimethoxyazobenzene (10).…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Lifetimes and Reactivities of Some 1,2-Didehydroazepines Commonly Used in Photoaffinity Labeling Experiments in Aqueous Solutions

2005

View full text Add to dashboard Cite

The reactive 1,2-didehydroazepine (cyclic ketenimine) intermediates produced upon photolysis of phenyl azide, 3-hydroxyphenyl azide, 3-methoxyphenyl azide, and 3-nitrophenyl azide in water and in HEPES buffer were studied by laser flash photolysis techniques with UV-vis detection of the transient intermediates. The lifetimes of the 1,2-didehydroazepines were obtained along with the absolute rate constants of their reactions with typical amino acids, nucleosides, and other simple reagents present in a biochemical milieu. The nitro substituent greatly accelerates the bimolecular reactions of the cyclic ketenimines, and the 3-methoxy group greatly decelerates the absolute reactivity of 1,2-didehydroazepines. The intermediate produced by photolysis of 3-hydroxyphenyl azide is much more reactive than the intermediate produced by photolysis of 3-methoxyphenyl azide. We propose that the hydroxyl-substituted 1,2-didehydoazepines rapidly (<10 micros) tautomerize in water to form azepinones and much more rapidly than the corresponding 3-methoxy-substituted cyclic ketenimines undergo hydrolysis. Azepinones react more rapidly with nucleophiles than do methoxy-substituted 1,2-didehydroazepines and are the active species present upon the photolysis of 3-hydroxyphenyl azide in aqueous solution.

show abstract

Section: Resultsmentioning

confidence: 99%

“…All chemicals were purchased from Aldrich and Acros Organics. Phenyl azide (7), 3-hydroxyphenyl azide (8), 3-methoxyphenyl azide (9), 3-nitrophenyl azide (10), and 3,3′-dinitroazobenzene (11) were prepared as described in the literature. An HP 6890 Series GC-MS spectrometer was used to analyze samples by gas chromatography.…”

Section: Methodsmentioning

confidence: 99%