acetate and water and between n-hexane and 3c/;: THE STRUCTURES OF DELTALINE AND DELPHELINE ethanol. The corticosteroid fraction was sub- Sir: jected to reversed phase partition chromatography U'e wish to suggest Structure I (I, It' = -OXc, on purified acetylated filter paper (Schleicher R 2 = -OH) for deltaline and I1 (11, R' = -OH, and Schuell) in the system recently developed,? R 2 = -H) for delpheline.' 1 and I1 embody a n-butyl acetatel'23% aqueous ethanol, a t 22-25 " perhydrophenanthrene skeleton differing slightly for 18.5 hours, collecting the overflow for the iso- but importantly from the ring system proposed lation of aldosterone. for lycoctonine derivatives.2 We believe t h a t a Ultraviolet contact photography of the paper rearrangement of the iVagner-Meerwein type ocstrips showed a spot parallel t o corticosterone, but curs during acidic hydrolysis of the cyclic acetal no spots were detected corresponding to cortisone groups and converts the perhydrophenanthreiic or cortisol; the methanol eluate of the spot gave skeleton into the lycoctonine A,,. a t 2-10 mp (EtOH), with an optical density The tertiary hydroxyl group of I reacts sluggishly equivalent to 15.1 p g . of corticosterone An with acetyl chloride to yield acetyldcltaline (111, aliquot of the sample reduced blue tetra~olium,g.~"R' = -OAic, R 2 = -OXc), CzeH&09, n1.p. with a typical color development within 10 minutes. lL-lsti0,3a[ -31.0' (CHCl;J?b Pyrolysis of LVhen treated with concd. sulfuric acid a t 24" for 111 a t 210-220" and dehydrohalogenation of 2 hours," another aliquot of the sample showed chloroacetyldelpheline (II', R1 = --O;\c, R 2 = A,,,. a t 287, 375 and 4.75 mp and a shoulder a t -C1) in refluxing collidinc both gave clc~hytlro330 m p , and optical density ratios of 1.0, 0.30, cEeso.~ydeifali~zc(Xj, R 1 = ---O.lc, IC13 = C 5 < ) , Ca;H39NOi,3" 1ii.p. 14S..5-1X.O0, fluorometer there was a maximum in the activation [ a ] p Z 3-136.0" (XeOH), vmax. S32 c m - l Cataspectrum a t 463 mp. Xctivation a t this wave lytic hydrogenation of V over platinum in ethanol length gave a fluorescent ~ p e c t r u m ' ~ with , ~ ~A,, , . gave acetyldelpheline (VI, R 1 = -OXc, It2 = a t 510 mp. -H).4 The two new routes from deltaline to The overflow collected from the chromatograin delpheline strengthen our assumption t h a t no gave a A,,. at 233 mp(EtOH), equivalent to skeletal rearrangement occurred during the previous 34.5pg. of aldosterone. After the fraction had interconversion. Saponification of I in refluxing alcoholic potasbeen rerun for 5 hours in the same system, ultraviolet contact photography showed a single intense sium hydroxide gave deltamine (VII, R' = -OH, spot parallel to standard aldosterone with X fvalues R 2 = --OH),j C2jH&07, m.p. 239-240", CY]^)^^ different from cortisone, cortisol, epicortisol, and - 10.25O (MeOH) . 3 b Hydrolysis of the acetal 2Oa- and 20P-hydroxycortisol, run on parallel function of \TI with hot loyo sulfuric acid yields strips. The eluate of the spot from the paper formaldehyde and dcmefhylenedcltaminc (VIII, I t 1 chromatogram gave a A,,. a t 230 nip (EtOH), = -OH, RZ= -OH, R 3= -OH, R 4 = -OH) as n1.p. !)5-07 with an optical density equivalent to 31.6pg. of the dihydrate, Cz4H3~NO~.2H20,6 +2T.0° 3 (SleOH). Demethylenealdosterone. An aliquot (12 p g . ) treated with (dec.), [ a ] 1 3 2 1 ml. of concd. sulfuric acidL4a t 24" for 2 hours deltamine (17111) consumed two moles of periodic a t 288 mp. After an additional incu- acid" to give a diseco-acid, not isolated, which gave A,,. bation in a water-bath a t 90" for one hour the spontaneously formed a y-lactone (1x1, C24H35+ (SIeOH), spectruni was characteristically changed, and was SOi,3" m.p. %13.0-21ti.2", [ a ] l , 2 -64.3" identical with t h a t of standard aldosterone eluted vmax. 1'780 and 1712 an.-'. y-Lactonization established the relationship of from the paper chromatogram, with A,,,. a t 245, 28.5 and 3S0 mp and optical density ratios of 1.0 ' the tertiary hydroxyl group of I with respect to "0.3. \Vhen a 2 - p g . aliquot was treated with the carbon atom which eventually becomes a tetrazolium for 40 minutes,li it gave a char- carboxyl during the periodate oxidation of YIII. a t 520 m p . Biological If no rearrangement had occurred during the acidic acteristic color, with A,,. assay of the product indicated that it had a sodium- genesis of VIII, I would then be expected to possess retention activity'j comparable to t h a t possessed Structure X (R1 = -Odc, R 2 = -OH, K3-R4 = -O-CH2-O-)R on the basis of the interconversion by an authentic sample of dl-aldosterone. to desoxylycoctonine. Placement of the OH group H O R M O S E l
