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VOl. 74
A4n5). Anal. Calcd. for C21H3003: C, 76.33; H , 9.15. Found: C, 76.61; H, 9.36, Monoacetate, m.p. 134-135O; [o(Iz2D +107' (c, 0.33 in CHC13). Anal. Calcd. for acetyl: 11.6. Found: acetyl, 11.6. The position of the hydroxyl group in this substance followed froin its conversion into the known A16dehydroprogesterone4 (m.p. 190-191.505; [cY]'~D +134.3' (c, 0.90 in CHC13); 240 mp (E = 25,400) by means of aluminum butylate. The latter reaction has its analogy in the conversion of allopregnanetriol-3/3,16a,20/3(Marrian's triol) to A'6-allopregnenedione-3,20by means of aluminum isopropylate.6 The contributions to the molecular rotation made by the 16-hydroxyl group in the free ( [ M ] D O ~ . I - ~= -82') and in the acetylated form ([M]D~*'-" = -205') strongly suggest the crorientation for that group.' Preceding I in the chromatogram was pregnanol16cr-dione-3,20 (11) present in small amount only, 1n.p. 199-200'; [ c r I z 3 ~f90.5' (c, 0.82 in C H C ~ S ) ~ ; GEOFFREY \I.ILKIKSOX X$',k. 284 mp ( E = 65). Anal. Calcd. for C21H3203: I~)E:PARTMENT OF CHEXISTRT 11,ROSENBLUM €IARVARD UNIVERSITY I f . C. XHITINGC, 75.85; H, (3.72. Found: C, 76.12; H, 9.73. R . R.1VOODTT.4RD The latter on treatment with aluminum t-butylate CAXBRIDGE 39, MASSACECS yielded A16-pregnenedione-3,20, m.p. 196-198' ; RECEKEI)XIARCH 24, 1952 ~ 2 ; ~2 . : 111~ ~ = 0100).9 -1third substance present in small amount was MICROBIOLOGICAL HYDROXYLATION OF eluted with chloroform--acetone 3 : I, 1n.p. 215.5PROGESTERONE ](j;?". , [ Q ] * ~ D-39' (c, 0.78 in CHC13); 243 Sir : inp ( e = 14,400). It had the composition of a The hehydrogenation of steroid alcohols by bac- dihydroxyprogesterone. Anal. Calcd. for C21H3004 : teria and the reduction of steroid ketones by yeasts C, 72.80; H, 8.73. Found: C, 73.09; H, 8.68. has been studied in great detail by Mamoli, Vercel.B u t e n a n d t a n d J. Schmidt-Thome, Ber., 72, 182 (1939); cf. lone, Butenandt and their collaborators.1 Trufitt2 also(4)D..4K. Fukushima a n d T . Gallagher, THISJOURNAL, 73, 196 (1951). has effected oxidative ring cleavage and removal of ( 5 ) A mixture melting point of this material with a n authentic the steroidal side chain by the use of Proactino- sample of Ale-dehydroprogesterone kindly supplied by D r . Carl Djerassi myces species. We wish to report a novel type of (1n.p. 188-190° after three recrystallizations) showed n o depression. 16) K. E. Marker a n d D. L. Turner, THISJ O U R K A L 62, , 2541 (1940). microbiological oxidation, viz., the introduction of (7) T h e average values for [ M ] D ~ ~ a n~ d -for~ [ ~& -I ]~ D ~ ~ " - ~ ~ ~ - ~ one or more hydroxyl groups into the intact steroid are - 6 4 O a n d -284', respectively, while those for 16P-substituted nucleus by an unidentified actinomycete3 in sub- dfrivatives are +Boa n d +98', respectively. Cf.H. Hirschmann a n d F.IIirschmanri, J . Bid Chem., 184, 259 (19501, a n d D. K. Fukushinla nierged culture. F Gallagher, THISJOUKPAL, 73, 196 (19.51). In the example reported here progesterone (0.23 a n (d8T. ) T h e value for [ ~ I ] D ' - ' '(+%?lo) is in good agreement with t h a t g./l.) was used as the substrate in a simple medium for [?.I In l~.cliolestenone-coprostanone (f203"). containing glycine, glutamate, soybean oil and in
