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COMMUNICATIONS TO THE EDITOR
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to the Editor, there is described the transforma(regenerated from its semicarbazome) gave a 6OQ; to 11-ketosteroids by way yield of retene, m.p. 99.5-100.5" (picrate m.p. tion of such A7~9(11)-diene~ 123.5-126.5'1, undepressed with an authentic sam- of Aknsaturated and thence saturated 7,11diones. We should like to record herewith an ple prepared from dehydroabietic acid.5 The structural identity of the synthetic dl-1 alternate procedure for the synthesis of ll-oxygenated steroids from ring C unsubstituted steroids keto-7-isopropyl-12-methyl-1,2,3,4,9,10,11,12-octa hydrophenanthrene (IC) with the Cl8 d-ketonc. rc' via ')-dienes, which does not involve the cently obtained from dehydroabietic acid" is coti- above mentioned5s6intermediates. In addition to firmed by comparison of their infrdrctl ipcctra its versatility, the presently described method exhibits the attractive feature of representing a novel (Fig. 1). The extension of this work to the stereospecific and convenient synthesis for the hitherto unknown synthesis of the resin acids is being actively pursued. 11a-hydroxyallopregnanes and sapogenins.6a Performic acid oxidation of A7x9(11)-allopregnaCHEMICAL LABORATORIE? 1IARVARD UNIVERSITY GILBERTSTORK diene-3P,20/3-diol diacetate (I) readily led to CAMBRIDGE 38, MASSACHUSETTS ALBERTRURGSTAHLER' 9 q 11cu-oxidoallopregnane-3~,20/3-diol-7-one diaceRECEIVED J U U E 15, 1951 tate (11) (m.p. 260-262' (all m.p.s are uncorrected), - -___ 5 ) L Ruzicka and H M aldmann Hclv Chzm Acta, 16, 842 (1933) [LY]~OD -55' (CHClSj, no ultraviolet maximum, (6) A Brossi, H Gutmann and 0 Jeger z b i d , 99, 1730 (1950) hnujol max 1736 c m - I (acetate) and 1718 mi.-' (7(7) National Institute> of Health Predoctoral rellow HarvArd ketone), no free hydroxyl band; found: C, 68.96; L niveraty, 195O-lqil H, 8.39). Alkaline hydrolysis was accompanied by isomerization and afforded in high yield AE-alloSTEROIDS. XX1V.l INTRODUCTION OF THE 11- pregnene-3P,l la,20/3-triol-7-one (111) (m.p. 250KETO AND Ila-HYDROXY GROUPS INTO RING C 252', [ c ~ ] ~ ' D -23' (EtOH), XzH:; 264 mk, UN SUBSTITUTED STEROIDS log E 4. 11, 1662 cni.-l, found: C, 72.52; Sir : found: C, The conversion of A5-3P-hydroxy steroids to a H, 8.97; triacetate, n1.p. 203-205'; number of A7p9(11)-dienes of the pregnane and 68.21 ; H, 8.06). Catalytic hydrogenation (palsapogenin series with both the allo and normal con- ladized charcoal in ethanol solution) of 111 profiguration a t C-5 has recently been reported from duced 78% of allopregnane-313,ll a,20P-triol-7-one this L a b ~ r a t o r y . l - ~In two C o m m u n i ~ a t i o n s ~(IV) ~ ~ (m.p. 246-248', [~]*OD -112' (EtOH), no ultraviolet maximum, CHa CH CHa Amax, nujol 1718 em.-'; found: C, I I I AcOCH llcOCH HOCH 71.58; H, 10.01). WolffKishner reduction gave alloA A, A'/\ pregnane - 3P, 11a,20/3-triol(Vaj O\l (m.p. 253-255', [&]'OD -28' (EtOH), no carbonyl band in A!&A P '-infrared; found: C, 74.63; H, + 10.83), which formed a triacetate (Vb) (m.p. 162-164', [a]'?'D -16' (CHCl,), 1736 cm.-l (acetate), no free hydroxyl band; found: C, 70.4i; H, 9.26). Chromiuni trioxide oxidation of the triol Va led to the known7 allopregnane-3,11,20-trione (VIa) (m.p. 211-213', [&I2'D +129' (EtOH); found: C, 76.19; H, 9.39), which on Raney nickel reduction smoothly yielded allopregnane - 11,20dione-3P-ol (VIb) (m.p. 1921%'. fal?OD 4-99' (CHC1,): found: &c: 75.44; H, 6.56) ai'i upon acetylation the acetate ( V I C ) (m.p. ~ 143-144', 1736 and 1710 cm.-l, no ' I ) Paper XXIII,J. Roino. C, Rosenkrariz a n d C !.ljeriissi, 'I"Is Icu]"D 4-89' (CHCla), I
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JOURNAL, in press. (2) R . Yashin, G. Rosenkranzand C. Djerassi. i b i d . , 1 S , (1951) inpress. (3) G. Rosenkranz, J , Romo, E. Ratres and C. Djerassi, J Ovg. Chem., 16, 298 (1951). (4) C. Djerassi, J. Romo and G. Rosenkranz, ibid., 16, 754 (1951). 79, 2397 (6) L. F. Fieser, J . E. Herz and W.Huang THISJOURNAL, l
