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saponification, gave on acidification the lactone- zation of the lip-epimer.'" Treatment of VIb (IC' dicarboxylic acid IIIa (R' = R 2 = C 0 2 H , R 3 = = H , R 2 = COCHzOBc) with potassium carbonate H ) which was transformed, through reaction of in aqueous methanol gave the C1; epimeric mixthe diacid chloride acetate IIIa (R'= R2= COCl, ture la from which dl-aldosterone readily was isoR 3 = Xc) with dimethylketene aceta1,j into the lated. The product was identified with authentic diketo-lactone IIIa (R' = R 2 = COCH,, R2 = materiallo by paper chromatographic behavior, in=IC) [isomer a! m.p. 1'72-173"; isomer b? m.p. frared spectroscopy and physiological activity. '?,' 145-146 "1. Rearrangement with trifluoroperace(12) Satisfactory analytical d a t a have been obtained for t h e n ? \ v tic acid6 afforded the triacetate IIIa (R' = R 2 = substances reported above. OAc, R3 = =IC) [isomer a, m.p. 1.10-141";isomer (13) W e are grateful t o the Sterling-Winthrop Research I n s t i t u t e . b, m.p. 142-143OI3 which, on mild saponification the Upjohn Company, t h e IVisconsin Alumni Research Foundation followed by Srbromoacetamide oxidation and re- and the National Science Foundation for assistance. acetylation, gave the 3-ketodiacetate [isomer a, L ~ I L L I A M S. JOHNSOS OF CHEMISTRY JOSEPH C. COLLISS 1n.p. 135-136'; isomer b, m.p. 14i-14S.5°].3 DEPARTMENT RAPHAEL PAPPO UXIVERSITV OF L~ISCONSIN Bromination and dehydrobromination' afforded MADISON,L~~ISCOKSIX MORDECAI B. RCBIS the unsaturated ketone IIIb (R' = R 2 = OAic) APRIL 18, 1938 RECEIVED [isomer a, m.p. 183-184"; isomer b, m.p. 15413.5°],3 which was converted? into the ketal IIIc (R1= R 2 = OXc) [isomer a, m.p. 155-156"; isoT H E COMPLEX FORMED FROM COBALT mer b, m.p. 175-1i1i"].3 Saponification gave the HYDROCARBONYL AND BUTADIENE diol IIIc (R'= R2 = OH), [isomer a, m.p. 1%Sir: 186"; isomer b, m.p. 203-207"3 which was transformed, by selective reaction with 2, .?-dimethylAlthough Prichard has reported the preparation benzenesulfonyl chloride in pyridine, into the mono- of a complex betm-een butadiene and dicobalt octaester IIIc (R'= OH, R2 = OS02C6H3hIe2).Oxi- carbonyl under Oxo conditions, l only an analysis dation u-ith Sarett's reagent converted the Czo hy- for cobalt and an analysis by the Orsat technique of droxyl to ketone; thus both epimers yielded the the sulfuric acid decomposition products were given. same product3 which, with potassium t-butoxide, \Ye have now been able to prepare and study underwent cyclizationgto the keto-lactone IVc, m.p. the stereochemical configuration of the complex 194-196". This substance mas partially isomerized formed between butadiene and cobalt hydrocarby base into the l i p epimer T'c, imp. 210-214' (re- bony1 in the absence of Oxo conditions. ported,'" 2013-208"). The latter substance and the Potassium cobaltcarbonylate was made to react corresponding ketone T%, n1.p. 215-219" (re- with glacial acetic acid and liquid butadiene in a ported,la 218-1320') were shown, by infrared and high pressure vessel. After twelve hours, a redmixed m.p. comparisons, to be identical with brown liquid, distilling at 33-35 o at less than 1 inm. authentic specimens. l o Vc has been converted pressure, was obtained. into aldosterone.la Analysis showed it to have the empirical coniAlthough our main objective was thus realized position CO(CO)~C~H:. I n benzene it gave a we hoped to obviate certain difficulties attending molecular weight of 195>compared to a calculated the last stages of the synthesis due t o the $-oriented molecular weight of 198. The compound is diaC1; side-chain'" by operating in the 170 series. magnetic and contains no acidic hydrogen. Tilth two mole-equivalent. of lithium aluminuni The infrared and ultraviolet absorption charachydride IVc was selectively reduced to the lactol teristics indicate the disappearance of the conjuT'Ic (R1 = H , R 2 = CHOHCH,). n1.p. 190-194", gated diolefin structure and the appearance of a which was hydrolyzed to IrIb (R1= H , R2 = structure producing absorption characteristics simCHOHCH3), m.p. 11'7-133 ', then treated with ilar t o those of cis monoolefins. The sharp peak methanol and acid to yield the lactol ether VIb a t 703 cm. which in the cobalt hydrocarbonyl has (R: = CHd, R2 = CHOHCH:j), m.p. 168-169.3". been a~signed'.~ to the hydrogen vibrations also has Oxidation with Sarett's reagent afforded the ke- disappeared. tone VIb (R' = CH3, R2 = COCH3), m.p. I(KHowever, carbon monoxide could react with l(jSo, which was converted'l into the 21-acetoxy butadiene to give cyclopentanone, which might compound YIb (R'= CH:I, R' = COCH~OAC), have some aromatic character and give a complex m.p. 138-140". Hydrolysis of the lactol ether similar to cyclopentadiene bis-carbonyl cobalt; with TO:;; acetic acid gave dl-lTa-aldosterone-21- however, the infrared data do not seem to be in line acetate, T-Ib (R'= H, R 2 = COCHZO-IC),m.p. with such a structure. 1 ~ X j - 1 T O o . The infrared spectrum was identical Experimental details and a reinterpretation of with that"' of material obtained by partial isomeri- the mechanism of the oxo rcactionJ,5fi will be rc( 5 ) S. RI. hlcElvain and G. I ) . ( i ) Cf. I
