GB543265A - Manufacture of carbonyl compounds having a cyclopentanopoly-hydrophenanthrene ring structure and enol esters thereof - Google Patents

Abstract

543,265. Cyclopentanophenanthrene ketones. SOC. OF CHEMICAL INDUSTRY IN BASLE. Aug. 16, 1940. Nos. 13096 and 13097. Convention dates, July 28, 1939, and June 11, 1940. [Class 2 (iii)] Carbonyl compounds having a polynuclear ring structure are prepared from the corresponding glycols or esters thereof by treatment with finely divided zinc, cadmium or copper in the presence of an inert organic diluent. The final products may if desired be treated with a hydrolysing agent. Suitable diluents mentioned include hydrocarbons such as toluene, xylene, decahydronaphthalene 'and methylcyclohexane, alcohols such as butyl and amyl alcohols, and pyridine. Parent materials mentioned include allo-pregnane-3 : 17 : 20 : 21- tetrols, allo-pregnane-3: 11 17 : 20 : :21-pentols, allo-pregnane-3 : 17 : 20-triols, #<SP>4</SP>- pregnene-3-one-11 : 17 : 20 : 21-tetrols, # <SP>5-</SP> pregnene-3 : 17 : 20-triols, #<SP>5</SP>-pregnene-3 : 17 : 20:21-tetrols, # <SP>4</SP>-pregnene-3-one-17:20:21-triols, #<SP>4</SP>-pregnene-3-one-17 :20-diols, #<SP>4</SP>-oxymethylandrostene-3-one-17-ols, #<SP>4</SP>-21-dialkoxy-pregnene-3-one-17 : 20-diols. 3:9:11- or 3 : 11 : 12- trioxycholanic-acids, oestriol, cafesterol and their sterioisomers. In examples (1) a mixture of the #<SP>4</SP>-pregnene-3-one-17α : 20 : 21-triol- 20 : 21 diacetates which are isomeric about the 20-position are heated with zinc dust in toluene solution to give desoxy-corticosterone acetate. If as parent material there is used the corresponding 17 #-compound the product obtained is 17-iso-desoxy-corticosterone acetate. Hydrolysis with aqueous alcoholic bicarbonate gives the corresponding 17-isodesoxy-corticosterone. (2) #<SP>4</SP>-pregnene-3-one- 17x : 20α : 21-triol-20 : 21 diacetate obtained by fractional crystallization of the mixture used in example (1) is heated with zinc dust in toluene solution to give desoxy-corticosterone acetate. The isomeric 17α-20#-compound when used as parent material also yields the same desoxy-corticosterone acetate. (3) A mixture of #<SP>5</SP>-pregnene-3 : 17# : 20-triol-3 : 20 diacetates isomeric with respect to the 20-position is treated with zinc dust in pyridine solution to give #<SP>5</SP>-17 -iso-pregnene-3-ol-20-one-acetate, which may be saponified to the corresponding # <SP>5</SP>-17-iso-pregnene-3-ol-20-one. In analogous manner allo-pregnane-3 : 11 : 17 : 20 : 21-pentol- 3 20 : 21-triacetate yields 17-iso-allo-pregnane- 3 11 : 21-triol-20-one-3 : 21-diacetate, and allopregnane-3 17 : 20 : 21-tetrol-11-one-3 : 20 : 21- triacetate yields 17-iso-3 : 21-diacetoxy-allopregnane-11 : 20-dione. (4) Cafesterol is treated with zinc dust in toluene solution to give anhydro-cafesterol. (5) 3 : 11-diacetoxy-9- oxy-cholanic acid is treated with zinc dust in pyridine solution to give 3-acetoxy-11-ketocholanic acid. Since the parent material for this example can be prepared from #<SP>9:</SP><SP>11</SP>-3- oxycholenic acid by hydroxylation of the double linkage with osmium tetroxide and acylation, and from other 9:11-unsaturated steroids 11-keto compounds may be similarly prepared and since the 9 : 11-unsaturated compounds can be obtained from 12-keto compounds, the invention provides a way of converting 11-keto-steroids into 12-keto-steroids. The parent materials of the invention may be readily prepared by the attachment of hydroxyl groups to unsaturated linkages. Thus the mixture of #<SP>4</SP>-pregnene-3-one-17α: 20 : 21- triol-20 : 21-diacetates used in example (1) was prepared by hydroxylation of 17-vinyl-testosterone with osmium tetroxide followed bv acylation, and the mixture of # <SP>5</SP>-pregnene- 3 À: 17# : 20-triol-3 : 20-diacetates used in example (3) was prepared by the hydroxylation of #<SP>5</SP>:<SP>17</SP> -3-acetoxy-pregnadiene by osmium tetroxide, followed by acylation. The Specification as open to inspection under Sect. 91 describes the use of any finely divided metal as the catalyst. This subjectmatter does not appear in the Specification as accepted.