GB536210A - Manufacture of pure compounds of the cyclopentanopolyhydrophenanthrene series - Google Patents

Abstract

536,210. Cyclopentanophenanthrene compounds. FAIRBROTHER, H. (Naamlooze Vennootschap Organon). July 28, 1939, Nos. 22011 and 25986. [Class 2 (iii)] Cyclopentanopolyhydrophenanthrene compounds which contain a -COÀR group in the 17- position (R being alkyl) are oxidized by lead tetracetate to produce oxidation products in which either or both the R group and the hydrogen atom in the 17-position is or are substituted by acetyl groups, and these compounds are separated from the other products of the reaction by a process of chromatographic selection. The preferred method of procedure is to treat the starting material with lead tetracetate in glacial acetic acid solution, the optimum conditions of reaction for the particular starting material being determined by trial using varying concentrations of reagents under varying temperature conditions. The resulting products may be saponified if desired. In examples (1) Progesterone is treated with lead tetracetate in glacial acetic acid solution for 7 hours at 80‹C. and the resulting syrup chromatographed to yield a principal product of desoxycorticosterone acetate ; (2) Allopregnane-3-acetoxy-21-one is treated with lead tetracetate in a mixture of anhydrous acetic acid and acetic anhydrides and the product chromatographed. Product isolated and identified included allopregnane- 3:21-diacetoxy-20-one, and allopregnane-3:17: 21-triacetoxy-20-one. The latter product on treatment with potassium bicarbonate in methanol yielded a product in which the 21- acetyl group was saponified. Oxidation of this saponification product with periodic acid and further saponification yielded 3 (B) : 17 (B)- dioxy-etioallocholanic acid; (3) #<SP>3</SP>-pregnene- 3-acetoxy-20-one is treated with lead tetracetate in a mixture of anhydrous acetic acid and acetic anhydride under the same conditions as in example (1), and the resulting product chromatographed to give #<SP>5</SP>-pregnene-3:21- acetoxy-20-one and #<SP>5</SP>-pregnene-3:17:21-triacetoxy-20-one. Specifications 500,767, 502,474 and 524,006, are referred to.