TY - JOUR
T1 - Photochemistry of Enolic Systems. IV. Irradiation of Enol Trichloroacetates and a Dienol Trichloroacetate
AU - Libman, Jacqueline
AU - Mazur, Yehuda
AU - Sprecher, Milon
PY - 1969/4
Y1 - 1969/4
N2 - The photolysis of enol trichloroacetates 1, 3, and 2 derived from 3-pentanone, 17β-acetoxy-5α-androstan-3-one (9) and cyclohexanone was investigated. The main products isolated in t-butyl alcohol were the α-trichloromethyl ketones 4 and 10 and an α-dichloromethylene ketone 7, respectively, the latter being formed from the α-trichloromethyl ketone 6 by loss of hydrogen chloride. In addition, the steroidal enol trichloroacetate 3 yielded the dimeric enol tetrachlorosuccinate 11. However, irradiation of 3 in cyclohexane or in isopropyl alcohol did not result in α-trichloromethyl ketone nor in its decomposition product. In cyclohexane three enol esters were isolated: 11, the enol dichloroacetate 13, and enol formate 14, and in isopropyl alcohol the two former esters and a solvent addition product 15a. Photolysis of steroidal dienol trichloroacetate 16 in both t-butyl alcohol and cyclohexane gave the trichloromethyl ketone 17 which was accompanied in the latter solvent by the α-dichloromethylene ketone 18. The properties of the novel compounds are described and the relevant photochemical pathways are discussed.
AB - The photolysis of enol trichloroacetates 1, 3, and 2 derived from 3-pentanone, 17β-acetoxy-5α-androstan-3-one (9) and cyclohexanone was investigated. The main products isolated in t-butyl alcohol were the α-trichloromethyl ketones 4 and 10 and an α-dichloromethylene ketone 7, respectively, the latter being formed from the α-trichloromethyl ketone 6 by loss of hydrogen chloride. In addition, the steroidal enol trichloroacetate 3 yielded the dimeric enol tetrachlorosuccinate 11. However, irradiation of 3 in cyclohexane or in isopropyl alcohol did not result in α-trichloromethyl ketone nor in its decomposition product. In cyclohexane three enol esters were isolated: 11, the enol dichloroacetate 13, and enol formate 14, and in isopropyl alcohol the two former esters and a solvent addition product 15a. Photolysis of steroidal dienol trichloroacetate 16 in both t-butyl alcohol and cyclohexane gave the trichloromethyl ketone 17 which was accompanied in the latter solvent by the α-dichloromethylene ketone 18. The properties of the novel compounds are described and the relevant photochemical pathways are discussed.
UR - http://www.scopus.com/inward/record.url?scp=33645774492&partnerID=8YFLogxK
U2 - 10.1021/ja01036a034
DO - 10.1021/ja01036a034
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AN - SCOPUS:33645774492
SN - 0002-7863
VL - 91
SP - 2062
EP - 2068
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 8
ER -