Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene

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...

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Bibliographic Details
Published in:Journal of organic chemistry 2014-10, Vol.79 (19), p.9325-9334
Main Authors: Rajam, Sridhar, Jadhav, Abhijit V, Li, Qian, Sarkar, Sujan K, Singh, Pradeep N. D, Rohr, Ahleah, Pace, Tamara C. S, Li, Rui, Krause, Jeanette A, Bohne, Cornelia, Ault, Bruce S, Gudmundsdottir, Anna D
Format: Article
Language:English
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Summary: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 λmax at ∼300 nm and a lifetime of ∼1 ms. Vinylnitrene 1c is formed with a rate constant of 4.25 × 105 s–1 from triplet 1,2-biradical 1b. Laser flash photolysis of 1 in oxygen-saturated acetonitrile results in 1c-O (λmax = 430 nm, τ ≈ 420 μs 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.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo501898p