THE PHOTOCHEMISTRY OF α-OXIMINO KETONES. 2-OXIMINOCYCLODODECANONE

Article abstract of DOI:10.1016/S0040-4020(01)92384-1

Irradiation of (E)-2-oximinocyclododecanone (12) in methanol with a medium pressure mercury lamp gives (Z)-2-oximinocyclododecanone (13), 12-hydroxybicyclo<8.2.0>dodecan-11-one oxime (14), (2-oxocyclodecane)acetonitrile (17), and methyl 10-undecenoate (18).The nitrile 17 has been shown to be formed from the oxime 14 on irradiation of the latter in methanol or on treatment with acetic anhydride in pyridine.It is proposed that the ester 18 arises, like oxime 14, via γ-H-abstraction by the O atom of the CO group of the α-oximino ketone 12, and that the primary photochemical processes under the conditions used are limited to geometrical isomerization about the C=N bond and such γ-H-abstraction.