Comparison of the Photochemistry of 3‑Methyl-2-phenyl‑2H‑azirine and 2‑Methyl-3-phenyl‑2H‑azirine

• Published in: Journal of organic chemistry Vol. 79; no. 2; pp. 653 - 663
• Main Authors: Zhang, Xiaoming, Sarkar, Sujan K, Weragoda, Geethika K, Rajam, Sridhar, Ault, Bruce S, Gudmundsdottir, Anna D
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 17.01.2014
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo402443w

Photolysis of 3-methyl-2-phenyl-2H-azirine (1a) in argon-saturated acetonitrile does not yield any new products, whereas photolysis in oxygen-saturated acetonitrile yields benzaldehyde (2) by interception of vinylnitrene 5 with oxygen. Similarly, photolysis of 1a in the presence of bromoform allows the trapping of vinylnitrene 5, leading to the formation of 1-bromo-1-phenylpropan-2-one (4). Laser flash photolysis of 1a in argon-saturated acetonitrile (λ = 308 nm) results in a transient absorption with λmax at ∼440 nm due to the formation of triplet vinylnitrene 5. Likewise, irradiation of 1a in cryogenic argon matrixes through a Pyrex filter results in the formation of ketene imine 11, presumably through vinylnitrene 5. In contrast, photolysis of 2-methyl-3-phenyl-2H-azirine (1b) in acetonitrile yields heterocycles 6 and 7. Laser flash photolysis of 1b in acetonitrile shows a transient absorption with a maximum at 320 nm due to the formation of ylide 8, which has a lifetime on the order of several milliseconds. Similarly, photolysis of 1b in cryogenic argon matrixes results in ylide 8. Density functional theory calculations were performed to support the proposed mechanism for the photoreactivity of 1a and 1b and to aid in the characterization of the intermediates formed upon irradiation.