期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 79, 期 19, 页码 9325-9334出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo501898p
关键词
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资金
- National Science Foundation
- Ohio Supercomputer Center
- U.C. Chemistry Department
- Zimmer program
- Natural Sciences and Engineering Council of Canada (NSERC)
- CGS-D fellowship
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1057481] Funding Source: National Science Foundation
Photolysis of vinylazide 1, which has a built-in acetophenone triplet sensitizer, in argon-saturated toluene results in azirine 2, whereas irradiation in oxygen-saturated toluene yields cyanide derivatives 3 and 4. Laser flash photolysis of azide 1 in argon-saturated acetonitrile shows formation of vinylnitrene 1c, which has a lambda(max) at similar to 300 nm and a lifetime of similar to 1 ms. Vinylnitrene 1c is formed with a rate constant of 4.25 X 10(5) s(1) from triplet 1,2-biradical 1b. Laser flash photolysis of 1 in oxygen-saturated acetonitrile results in 1c-O (lambda(max) = 430 nm, tau approximate to 420 mu s acetonitrile). Density functional theory (DFT) calculations were used to aid in the characterization of the intermediates formed upon irradiation of azide 1 and to validate the proposed mechanism for its photoreactivity.
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