Journal of the Chemical Society - Faraday Transactions p. 409 - 415 (1992)
Update date:2022-09-26
Topics:
Johnstone, Duncan E.
Sodeau, John R.
The UV photolysis of the α,β-unsaturated aldehydes acrolein, methacrolein and crotonaldehyde in argon matrices at λ > 300 nm has shown a major photochemical deactivation pathway to be conformational isomerism to the thermodynamically less stable s-cis form.This type of isomerization may account for the rapid internal conversion observed in the gas phase.Matrix-isolated crotonaldehyde undergoes further isomerization to ethylketene and enol-crotonaldehyde, as observed in the analogous gas-phase photolysis.In addition, another H-abstraction product was detected (νOH = 3674 cm-1) which is probably derived from the photolysis of s-cis-crotonaldehyde.At shorter excitation wavelenths (λ > 230 nm) acrolein and methacrolein isomerize to methylketene and dimethylketene, respectively.
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