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A study of product ratios in the direct (313 nm) and Hg-sensitized (254 nm) photodecomposition of 2-methylcyclohexanone in the gas phase by G. O. Pritchard; C. C. Badcock; D. W. Follmer is a Chemistry article available to read on EtoBox.

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The photolysis of 2-methylcyclohexanone has been studied in the gas phase a t 313 nm, mainly at 100°C, over a range of pressures. The Hg(63P1) photosensitized decomposition has also been investigated at 100°C. Under conditions of high excitation and/or little collisional quenching the major products are carbon monoxide and the hydrocarbons: 1-hexene, trans-and cis-2-hexene and methylcyclopentane, with minor aldehyde formation. The various product ratios are presented in tabular form. At lower excitation energies, and with increased collisional deactivation, trans-and cis-5-heptenal become important products, and the translcis aldehyde ratio is seen to be slightly pressure dependent when all the systems are compared. Similarly, there is a small pressure dependence for the X hexenes/methylcyclopentane ratio. From experiments at 250°C the temperature dependence of this ratio was established, and for thermalized hexane-1,5diyl an activation energy difference (Ed -E,) = -1.3 kcal mo1-I has been determined for the disproportionation and combination of the biradical. The mechanism for the photolysis is discussed in terms of triplet state photochemistry and biradical intermediates as devel

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Author

G. O. Pritchard; C. C. Badcock; D. W. Follmer

Publisher

John Wiley and Sons; Wiley (John Wiley & Sons); John Wiley & Sons Inc.; Wiley (ISSN 0538-8066)

Published

1988

Language

EN

Field

Chemistry (Physical Sciences)