111409-74-6Relevant academic research and scientific papers
1,2-Didehydroazepines from the Photolysis of Substituted Aryl Azides: Analysis of Their Chemical and Physical Properties by Time-Resolved Spectroscopic Methods
Li, Yu-Zhuo,Kirby, John P.,George, Michael W.,Poliakoff, Martyn,Schuster, Gary B.
, p. 8092 - 8098 (2007/10/02)
A series of substituted 1,2-didehydroazepines was prepared by photolysis of their precursor aryl azides.The chemical and physical properties of the didehydroazepines were probed by means of conventional chemical trapping experiments and by time-resolved spectroscopy with IR and UV detection.The didehydroazepines are formed from the azides with efficiencies that depend systematically on the nature of the substituent.In some cases, didehydroazepines are not formed at all.The didehydroazepines react relatively rapidly with starting aryl azide and with added amines.The rate of their reaction is largely controlled by the electronic properties of the substituent on the didehydroazepine.These results permit prediction of the reactivity of didehydroazepines from their structure.
Photochemistry of 3- and 4-Nitrophenyl Azides: Detection and Characterization of Reactive Intermediates
Liang, Tsuei-Yun,Schuster, Gary B.
, p. 7803 - 7810 (2007/10/02)
Irradiation of nitro-substituted aromatic azides initiates a complex series of chemical reactions that lead to different products depending on the details of the experiment.There is evidence that four reactive intermediates participate in product-determining reactions.These are the singlet nitrene, the triplet nitrene, the triplet azide, and the ring-expanded dehydroazepine.The chemical and physical properties of each of these species is modified by the nitro substituent.The reactivity of the singlet nitrene with nucleophilic amines is increased, the lifetime of the dehydroazepine is shortened, and the triplet nitrene becomes a powerful single-electron acceptor.Nitro-substituted aromatic azides are widely used in photolabeling experiments.The findings of this study suggest that they may be inappropriate choices as photolabeling agents in many circumstances.
PHOTOLYSIS OF 3-NITROPHENYL AZIDE: TRAPPING THE REACTIVE INTERMEDIATES
Liang, Tsuei-Yun,Schuster, Gary B.
, p. 3325 - 3328 (2007/10/02)
Irradiation of 3-nitrophenyl azide gives four trappable intermediates; the singlet nitrene, two isomeric dehydroazepines, and the triplet nitrene.
