Mkaline saponification &ded 17dihydroequilenin178 with m. p. 240-248' (capillary), undepressed on admixture 'i&h a specimen prepared according to method A, [ u ] % 66' (dioxane). The ultraviolet absorption spectrum was practically identical with that depicted in Fig. 2 for niaterial prepared by procedure A. I
S
Summary A recapitllfatioii of the earlier work of Inhoffen and Rutenandt on the bromination of A*-3-ketosteroids (I), which had led to the conclusion that these ketones could not be employed for the partial synthesis of the estrogens, has demonstrated several inconsistencies. The reinvestigation of the tlibromination in ether -acetic acid solution of A*-:+-ketosteroids(I), in particular of the androstane series, has shown that the resulting dibromo derivatives on collidine dehydrobromination produce A'~4~ti-trien-3-ones \ (XII) in satisfactory over\ all yield. On the basis of these results, several alternate structures are proposed for the intermedi.ite dibromo compounds, taking into consideration their marked tendency toward rearrangement and their ultraviolet absorption spectra. I;ig 2 Citrdvrolct absorptroti spectr.i - - 1; A ' , ' fl--Xndrostadiene-3, 17-dione (XIIb), thus tlihydroequileniti-l;B X - 17 dihydroequilt.iiiii cibtaiiied, has already' been converted into A6178 3,17-dincet&c. isoequilin, estrone and equileiiin, and its correAcetylation produced 173ihydroequilenk.1-178 3,17spoiiling t 7-acetoxy derivative u n siniilar treatdiacekte with m. p. 194-126' (Kofler), [ a l Z o -~l Z c , tririit Itas tiow led to P6-dehydroestradiol, estrau. v. spectrum Fig. 2; reported," m. p. 124". (tic11 aiitt 1 ;-dihydroeyuilenin-l78. The stereoAnal. Calcd. for C::HJ.h: C, 74.98; H, 6.86, Vouriri c,heiiiistry of the C -1T isomeric dihydroeyuilenins C, 75.19; H,7.04. B. By Selenium Diaxide Dehydrogenation of A6-De- is discussed. hydroestradiol 3,17-Diacetate.-Dehydrogenation of 1 g '1'h~ present experiments thus constitute a of didcetate TTith 156 mg. hly sublimed selenium iiovel, partial synthesis of all of the major, natuacid for eight minute. dioxide in 15 cc. of boiling produced 0.81 g. of 17-Ph oequilenin-17p 3,l'i-diace - rally occurring female sex hormones from the potate with in. p. 11.5-118 . Recrystallization from ether- tent iiiale hormones testosterone and i"-androheraneraisedthem. p. t o 126-127' (Kofler), [ L Y ] ~ -15". D itetiP-;j,17-dione. \'
No depression of the in. p. was observed on mixing with the sample prepared by method A and the ultraviolet absorption spectra proved to be identical.
I,.ic.~haUAYHAA 413 .\IEXrC
