Pulsed-laser photolysis, nitrile ylides

It was found that the azirine-nitrile ylide isomerization was a completely reversible process. The unlabeled nitrile ylide showed a prominent band at 1926 cm that underwent a 66-cm shift with N substitution. This shift was interpreted as being consistent with an allene-like skeleton (8) rather than the alternative pwpargyl-like stmcture (9). This conclusion was supported by the spectra from the C- and H-labeled variants. Warming the nitrile ylide in a xenon matrix from 12 to 82 K provided no new absorptions suggesting that the allene-like structure may also be adopted in solution. Some absorption spectra for benzonitriho benzylide (DPNY) and some substituted benzonitrilio methylides obtained via pulsed-laser photolysis of azirines are given in Table 7.1 (5). 

Much work has been done since the early 1980s on the detailed investigation of the azirine-nitrile ylide interconversion using pulsed-laser photolysis. Thus the azirines 103 (R =R =Ph, R =H R =Me, R = R =Ph R = p-napthyl, R = Me, R = H), on irradiation in isooctane, gave intense long-hved absorptions (250-400 nm) attributed to the nitrile ylides 104 (44). Quenching studies with electon-deficient alkenes led to the determination of absolute rate constants that were similar to those reported earlier for steady-state trapping experiments. The nitrile ylide-olefin reactions are discussed in more detail in Section 7.3.1. 

---