Improvements in or relating to the Preparation of Aldehydes and Ketones

摘要

1,190,257. Oxidation of alcohols to aldehydes and ketones. UPJOHN CO. 23 Oct., 1967 [16 Nov., 1966], No. 48108/67. Headings C2C and C2U. Primary and secondary alcohols are oxidized to the corresponding aldehydes and ketones by reaction with liquid hydrocarbon sulphoxides and sulphur trioxide, or complexes containing it, in the presence of tertiary amines. Substantially anhydrous conditions are preferably used. A preferred sulphur trioxide complex is that with pyridine, a preferred sulphoxide is dimethyl sulphoxide and preferred tertiary amines are alkylamines such as triethylamine. The process is particularly applicable to steroidal alcohols, and also more generally to allylic alcohols, steroidal or otherwise. It may particularly be employed to oxidize selectively a 20-hydroxy group in an 11#,20-dihydroxy steroid, the 11#-hydroxy group remaining unoxidized due to steric hindrance. The preparation of hydrocortisone acetate, progesterone, 11# - hydroxy - 4,17 - pregnadien - 3 - on-21-al, 16-dehydroprogesterone, ergosta- 4,7,22-trien-3-one, 17α,20-epoxy-11#-hydroxy 4-pregnen - 3 - on-21-al, 11#,17α-dihydroxy - 4 - pregnene-3,20-dion-21-al, 4-sitosten-3-on-19- al, 16α,17α-epoxyprogesterone, perillyaldehyde, 4 - androstene - 3,17 - dione, 11 - ketoprogesterone, 5α-chloestanone, l-menthone, p-nitrobenzaldehyde, propionaldehyde, methyl ethyl ketone diethyl ketone, actonol-1, cyclohexanone, cycloheptanone, cyclo - dodecanone, cyclododecane-1,6-dione, 4,41- dioxo bi-cyclohexyl, 31-O-acetylthymidine- S1-aldehyde, bicyclo[3.2.1]octan-6-one, cyclobutanecarboxaldehyde, predrisolone acetate and 5α,11#,17α,21 - tetrahydroxy - 6# - methyl pregnane-3,20-dione 21-acetate is described.