iaju - 19" (1:; ill pyridiiie); iriixture 1 i i . p . lvitli t e t r a d prepared from trans-tetraol diacetate VII, 280282.5'. 58,6P-Oxidopregnane-3P,2Op-diol (111).-A solution of 150 mg. (0.288 millimole) of pregnane-3P,5a,68,20P-tetraol tetraacetate X and 300 mg. of potassium hydroxide in 7 ml. of methanol and 2 ml. of water was boiled undcr reflux for 5.75 hours, and allowed to stand at room temperature for 3.75 hours. A few drops of water was added, the solution was concentrated until i t became turbid, methanol was added to clear the solution, and it was cooled overnight. The yield of 5P,6p-oxidopregnane-3P,20P-diol (111), was 70 tng. (73%,), m.p. 213-217". One recrystallization from chloroform-acetone gave 60 mg., m.p. 216-2175", [ a ] -8.5'; ~ 3420, 3520 cm.-l. A sample for analysis was recrystallized from chloroform-petroleum ether, dried at 100" ( 1 mm.) for 6.5 hours, and then had m.p. 211-213'. Anal. Calcd. for C ~ ~ H 3 1 0C,~ i:5 . 4 0 ; H, 10.24. Found: C,i 5 . 6 3 ; H, 10.38. 58,6B-Oxidopregnane-3p,2O~-diol Diacetate II.-.1 solution o f 40.0 nig. (0.12 millimole) of the oxidodiol 111 in 1 nil. of pyridine and 1 nil. of acetic auhydride was allowed to stand for 5.5 hours a t room temperature, and then heated on a steam-bath for 1.75 hours. The solution was then cooled, diluted with water and extracted three times with ether. The ether extract was washed successively with dilute hydrochloric acid (twice), 1056 sodium bicarbonate solution (twice), and with saturated brine, and then dried with anhydrous magnesium sulfate and the ether was removed. The residue was crystallized from ether-petroleum ether to give 1 ( J rng. ( 8 0 % ) of 5p,AP-oxidopregnaiie-3p,~OP-diol diacetate 11, 11i.p. 171-173". Oiie recrystallization gave 30 2X(i.5",
[ C o s r ~ i n u r r o FWX s
THE
nig.,
1ri.p.
170-171",
iiiixturc 111.1,. 170.5-l72" with
ail
authentic saniple,
Cholestane-3p,5~~,6p-triol Triacetate XI.--Cholestane-3@, 5a,6p-triol3 (IX) (1.0 g.) was treated as described above for the trans-tetraol diacetate VI1 and 943 mg. (73%) of cholestane-3p,5a,6P-triol t r i a y t a t e XI was obtained, m.p. 151.2-1\1.8", [ a ]-32 ~ ; reported m.p. 148-149'2; m.p. 149-150 , [ a ] D -35°.3 5p,6P-Oxidocholestan-3~-ol(IV).-To a solution of 1.7 g. (0.074 g. atom) of sodium in 90 ml. of absolute ethanol was added 2.20 g. (4.03 millimoles) of cholestane-3P,5~~,6Striol triacetate X I . The solution was boiled under reflux for 3.5 hours, and then, after the addition of a few ml. of water, concentrated nearly t o dryness under reduced pressure. The residue was extracted with three portions of ether, thc ether extract was waslied with saturated brine, dried with anhydrous sodium sulfate, and the ether was evaporated. The residue was crystallized from acetone-methanol to give 1.18 g. (7370) of ~~,6~-oxidocholestat13B-ol ( I V ) , m.p. 130.5--133°,[O]D +g , i g ' 3 3360 ern.-'. One recrystallization gave 1.02 g., m.p. 130-133.5"; reported'ob m.p. 131132', [a]Df11.5', 10.7'. 5P,6~-0xidocholestan-3~-ol Acetate V.--A solution o f 200 mg. (0.498 millimole) of the P-oxide I V in 4 ml. of pyridine and 4 ml. of acetic anhydride was heated on a steam-bath for 4 hours and worked up as above for the 8-oxide diacetatr 11. Recrystallization of the product from aqueous methanol gave 153 xng. (69%) of 5~,6P-oxidocholestan-3~-ol acetate ( V ) , m.p. 100-102.5", ["ID -1.7", ?:A: 1736 cm.-l. Two additional recrystallizations gave m.p. 107-109'; 1Il.r). 112-113", [.ID -1'. P R ~ V I D E S12, CE I
