1- Phenyl-1 -hydroxy-3-cyclohexanone

Cathodic reduction of 1,3-diphenyl-propenone leads to l-hydroxy-2-benzoyl-3,4-diphenyl cyclopentanes with exclusive cis configuration of the two phenyl groups. With l-phenyl-l-pentene-3-one the cyclodimer 2-methyl-3,5-diphenyl-4-(l-propionyl)-cyclohexanone is formed with a 100% yield in an intramolecular Michael addition via an electrogenerated base. The substituents are all in the most stable equatorial position [277]. 

The procedure reported here provides a convenient method for the a-hydroxylation of ketones which form enolates under the reaction conditions. The reaction has been applied successfully to a series of para-substituted acetophenones, 1-phenyl-1-propanone, 3-pentanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclododecanone, 2-methyl cyclohexanone, 2-norbornanone and benzalacetone. In the case of a steroidal example it was shown that a carbon-carbon double bond and a secondary hydroxyl group are not oxidized. A primary amino function, as in the case of p-aminoacetophenone, is not affected.5 Similarly, a tertiary amino ketone such as tropinone undergoes the a-hydroxy at ion reaction.5... 

HYDROXY-1-CYCLOHEXENE-1-CARBOXALDEHYDE 1-CYCLOHEXENE-1 -CARBOXALDEHYDE, 3-HYDROXY- (67252-14-6), 67, 205 (S)-(+)-3-HYDROXY-2,2-DIMETHYLCYCLOHEXANONE Cyclohexanone, 3-hydroxy-2,2-dimethyl-, (S)- (87655-21-8), 68, 56 Hydroxylamine, N-phenyl-, 67, 187 a-Hydroxylation of ketones, 66, 138... 

Analog wird (l-Hydroxy-cyclohexyl)-phenyl-pkosphinsaure-chlorid (85%) aus Cyclohexanon erlialten. 

Phosphinsaure (1-Hydroxy-cyclohex-yl)-phenyl- -chlorid E2, 155 (R -PC12 + R-COOH Cyclohexanon)... 

Treatment of the epoxy sulfones obtained thus with MgBr2 produces a-bromo ketones or a-bromo al-dehyde. This conversion can be applied to stereoselective preparations of a-bromo methyl ketones from cyclohexanone derivatives. Thus, treatment of 17-P-hydroxy-5-a-androstan-3-one (134) with 1-chloroethyl phenyl sulfone provides an epoxy sulfone (135), which is cleaved by MgBr2 to give a 99 1 mixture of 3-acetyl-3-bromoandrostanes (136 and 137 equation 33), whereas similar treatment of 17-p-hydroxy-5-B-androstan-3-one (138) gives a 4 96 mixture of 3-acetyl-3-bromoandrostanes (139 and 140 equation 34). These facts may reflect the steric course of the initial attack of the a-sulfonyl carbanion on the carbonyl face. 

A soln. of cyclohexanone anil and malonic acid in acetic anhydride allowed to stand 20 hrs. at 20°, POCI3 added to the mixture containing the intermediate 2-spirocyclohexane-3-phenyl-4,6-dioxotetrahydro-l,3-oxazine, and the product isolated after 24 hrs. l-phenyl-4-hydroxy-5,6,7,8-tetrahydrocarbostyril. Y 94%. F. e., also isolation of the intermediates, s. E. Ziegler, K. Belegratis, and G. Brus, M. 98, 555 (1967). 

---