Pj. Macleod et al., PHOTOCHEMICAL EQUILIBRATION ISOMERIZATION OF P-METHYLBENZONITRILE, M-METHYLBENZONITRILE, AND O-METHYLBENZONITRILE/, Journal of the American Chemical Society, 120(26), 1998, pp. 6443-6450
The phototransposition reactions in acetonitrile of p-, m-, and o-meth
ylbenzonitrile have been studied. Any one of the three is converted to
the other two by either a 1,2- or 1,3-isomerization in a primary phot
ochemical step. However, the reactivities are quite different with the
relative values for para:meta:ortho = 32:4:1. For both the para and m
eta isomers, extended irradiations approach a calculated steady-state
composition of para:meta:ortho = 3:20:77. Quenching of the excited tri
plet state of the para and meta isomers with 2,4-dimethyl-1,3-butadien
e indicates that these reactions are occurring from the excited Single
t state. Irradiation of selectively labeled 2,6-dideuterio-4-methylben
zonitrile demonstrates that only the cyano-substituted carbon undergoe
s migration.