Partial Synthesis of Compounds Related to Adrenal Cortical Hormones. XVI. Preparation of Cortisone and Related Compounds¹

CHEMICAL STUDIES WITH 11-OXYGENATED STEROIDS. IV1,2 THE REACTION OF HYPOHALOUS ACIDS WITH STEROID ENOL ACETATES

“…The dienol acetate VI (6) reacted with hypobromous acid only at the 17 position, forming the bromide VII. Similar selectivity is reported for the reaction of peracids with VI (7). The preparation of the bromide VII from the mono enol acetate VIII was previously described in a publication from these laboratories (8).…”

“…Found: C, 64.47, 64.23; H, 6.37, 6.52; Cl, 7.15. 17-Bromo-8a-acetoxypregnane-ll ,90-dione (VII). The addition of hypobromous acid to 3 , 11,20-triacetoxy-9(11), 17-pregnadiene (VI) (7) in the manner previously described gave 61% yield of VII, m.p. 134-151°.…”

“…172-175°( 54%) of XII was obtained. Kalamazoo, Michigan 7 Westvaco brand of magnesium silicate. 8 It was necessary to heat this mixture in order to obtain a solution which was quickly cooled before adding immediately to the solution of enol acetate.…”

The Equilibrium between Symmetrical and Unsymmetrical Monoglycerides and Determination of Total Monoglycerides

“…*MP = Monopalmitin. 5 By periodate determination, ref. 3. 'Fats have compositions as follows: A, 33.3% palmitic acid, 33.3% 1,3-dipalmitin and 33.3% 1,2-dipalmitin; B, 50% 1,3-dipalmitin and 50% 1,2-dipalmitin; C, 31% palmitic acid, 14% 1,3-dipalmitin and 55% tripalmitin; D, 32% palmitic acid, 12% 1,3-dipalmitin and 56% cottonseed oil.…”

“…Chloroform.-Technical or C.p. chloroform must be purified by the following steps in sequence or incomplete isomerization may result: (1) the chloroform is washed with */< its volume of concentrated sulfuric acid; (2) it is waterwashed until clear; (3) it is subjected to distillation, discarding the first and last 10% portions; (4) the distillate is dried by shaking with approximately V20 its weight of anhydrous sodium sulfate; (5) after drying, it is filtered into an amber glass bottle and 0.5% by volume of ethanol is added. The satisfactory performance of the chloroform solvent is established by isomerization of a known 2-MG sample.…”