Untersuchungen über Saponine und Sterine. (X. Mitteil.)

Synthesis of Estrone From Androstadienedione

“…A/V 0 Br Br IV ZV^Z \ZV /\zxz 0 Br VI 1 -^ 08 ß ß-3,17-dione, the starting material for the estrone preparation, was made by Inhoffen, Zuehlsdorff, and Huang-Minlon (5) by the Oppenauer oxidation of 1 i4-androstadiene-17-ol-3-one, and they reported a melting point of 139-140°. The substance with a melting point of 168°a ssigned the same structure by Fujii and Matsukawa (16) has been found by repetition of This unlikely monobrominntion reaction has not been described elsewhere in the chemical literature. [Compare, however, (10) page 77, paragraphs 4 and 5 which may be the source of the above mentioned report].…”

“…After drying at room temperature there was obtained 2.19 g. (92%) of 5-chloroandrostanedione. Apparently unnoticed by Fujii and Matsukawa (16), the compound melted wfith decomposition considerably below the melting point they reported. When immersed in a rapidly heated melting point bath (10°/min.)…”

“…2. In our hands the procedure of Fujii and Matsukawa for the preparation of Ali4-androstadiene-3,17-dione (16) gave a mixture of this and the corresponding 4•6 compound. Some of the intermediates in their synthesis differ in properties from those described in this paper.…”

“…[a]o +62.4°. Fujii and Matsukawa (16) report the melting point 160°with decomposition, while Ruzicka, Fischer, and Megu (20) report 156-157°:…”

“…It crystallized in clusters of flat needles which melted with gas evolution at 99-102°, solidified and then remelted at 160-167°. Fujii and Matsukawa (16) give the melting point 179°with decomposition.…”