532,262. Hydration of acetylenic steroids. SOC. OF CHEMICAL INDUSTRY IN BASLE. July 20, 1939, Nos. 21083, 21084 and 21085. Convention dates, July 23, 1938, Nov. 19, 1938 and April 27, 1939. [Class 2 (iii)] Acetylene derivatives of steroids are hydrated by treatment with a mineral or an organic acid, an acid halide, a phenol or an alcohol in the presence of a metalloid catalyst. The products obtained may comprise an end derivation, an acetal or an ester. Parent materials mentioned include #<SP>3</SP>-17-ethinyl-androstene-3-ol, #<SP>4</SP>-17- ethinyl-androstene-3-one, #<SP>5</SP>-17-ethinyl-androstene - 3:17 - diol, 17-ethinyl - androstane - 3:17- diol, 17-ethinyl-testosterone, 17-ethinyldihydrotestosterone, 17-ethinyl oestradiol, 17-ethinyl-dihydroequiline, 17-ethinyl-dihydroequilenine, # <SP>4</SP>.<SP>16</SP>-17-ethinyl-androstadiene- 3-one, # <SP>5</SP>.<SP>16</SP>-17-ethinyl androstadiene-3-ol. Non- metallic halide catalysts mentioned include the halides of metalloids of the third and fourth group of the periodic system such boronfluoride, and silicon-chloride. Then catalysts may be used in the form of their complex ether compounds. Additional catalysts such as a heavy metal salt or a heavy metal oxide may also be present. If the parent material does not contain a further substituent at the carbon atom containing the ethinyl group, the products obtained possess the same carbon skeleton as the parent material, but this is not the case where there is attached a hydroxyl group on the carbon atom to which the ethinyl group is attached. The reaction may if desired take place in the presence of a diluent. In examples (1) # <SP>5</SP>-17-ethinyl-androstene-3:17-diol is added to a glacial acetic acid solution of mercuric oxide, acetic anhydride and a boron fluoride ether catalyst. The mixture is shaken for one week at room temperature. On working up and partially saponifying the product there is obtained a dioxyketone-monoacetate which on complete hydrolysis gives the pure dioxyketone. (2) # <SP>5</SP>-17-ethinyl-androstene-3:17-diol-3-monoacetate, glacial acetic acid, acetic anhydride, mercuric oxide and boronfluoride-ether-catalyst are reacted together and worked up as in example (1) to give the same dioxyketone as was obtained before. (3) #<SP>5</SP>-17-ethinyl-androstene- 3:17-diol-diacetate, mercuric oxide, glacial acetic acid, acetic anhydride and boronfluorideether catalyst are reacted together in a sealed tube and worked up as before to yield the same dioxyketone. (4) # <SP>5</SP>-17-ethinyl-androstene- 3:17-diol-3-acetate-17-benzoate, mercuric oxide, glacial acetic acid, acetic anhydride and boronfluoride ether catalyst are reacted at room temperature for 15 minutes and worked up to give the same dioxyketone as before. (5) Ethinyl testosterone, mercuric oxide, glacial acetic acid, acetic anhydride and boronfluoride ether catalyst are reacted for 15 hours at 20‹C. and worked up using the chromatographic separation method to give an acetate of an oxydiketone. This on saponification gives the oxydiketone itself. (6) 17-Ethinyl-androstane-3:17-diol-3-monoacetate, mercuric oxide, glacial acetic acid, acetic anhydride, and boronfluoride-ether catalyst are reacted for 16 hours at room temperature and then evaporated to dryness in a vacuum at 40‹C. On working up and purifying by the chromatographic method, there is obtained the diacetate of a dioxyketone. From the mother liquors of the chromatographic separation an isomeric diacetate of a dioxyketone may be isolated. In each case saponification yields the corresponding dioxyketone. (7) 17-Ethinyl-3:17-diacetoxy-androstane, mercuric oxide, glacial acetic acid, acetic anhydride and boronfluoride ether catalyst are reacted at room temperature for two days and then worked up as described in example (6) to give the first dioxyketone isolated in example (6). (8) #<SP>5</SP>-17-Ethinyl-androstene-3:17-dioldiacetate and mercuric oxide are dissolved in acetic acid containing acetic anhydride, and then silicon tetrachloride run in. The reaction mixture is allowed to stand for 15 hours and worked up as before and purified with activated aluminium oxide. The Specification as open to inspection under Sect. 91 describes also the treatment of compounds in which the ethinyl group is attached to other points of the cyclopentanopolyhydrophenanthrene nucleus than the 17- position. This subject-matter does not appear in the Specification as accepted.