INVESTIGATIONS ON STEROIDS. XVII. DEHYDRATION STUDIES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID *1

1954

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1. 19-Acetoxy-3-oxo-A4-etienic acid (I), obtainable by degradation of strophanthidin (6), has been converted by way of the diazoketone (II) into 19hydroxy-11 -desoxycorticosterone (IX) and 19-hydroxyprogesterone (X) respectively. The 19-monoacetate (VI), the 21-monoacetate (VIII), and the 19,21-diacetate (V) of IX have been described. X was characterized by the acetate (XI).2. The bioassays of 19-hydroxy-11 -desoxycorticosterone (IX) and of 19hydroxyprogesterone (X) are reported.3. The preparations of 19-hydroxy-3-oxo-A4-etienamide (IV) and of 3-oxo-A4-etienamide are discussed.Philadelphia 4, Pennsylvania

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confidence: 99%

“…Purchased from the Aldrich Chemical Company, Inc., Milwaukee 3, Wis 6. Remarks of microanalyst: The molecular weight values are questionable.…”

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confidence: 99%

INVESTIGATIONS ON STEROIDS. XXIV. 19-HYDROXY-11-DESOXYCORTICOSTERONE AND 19-HYDROXYPROGESTERONE^*1

Barber¹,

1954

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“…The sodium salt (IIa) of 3p , 19-diacetoxy-5-hydroxyetiocholanic acid (11) (13) was treated with oxalyl chloride (2) and, without purifying the acid chloride (IV), the product was reacted with diazomethane, followed by treatment of the crude diazoketone with ethereal hydrogen chloride. On account of the rather poor over-all yield of the resulting 21-chloropregnane-3j3 , 5,19-trio1-20-one 3 , 19diacetate (V) the preparation by this route of the corresponding 21-acetoxy compound was not attempted.…”

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confidence: 99%

“…In an experiment originally designed to transform 3/3,19-diacetoxy-5-hydroxyetiocholanic acid (II) into 21 -chloro-A4-pregnene-19-ol-3,20-dione, II was first treated with thionyl chloride in the absence of pyridine. In analogy to experi- ments described in the preceding paper (13) this must have furnished a mixture of the unsaturated acid chlorides XII and XIII. In order to produce the chloromethyl ketone, the crude reaction product was successively treated with diazomethane and with hydrogen chloride.…”

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confidence: 99%

INVESTIGATIONS ON STEROIDS. XVIII. CHLORIDES AND CYCLIC SULFITES IN THE SERIES OF 3β, 5, 19-TRIHYDROXYETIOCHOLANIC ACID. A CASE OF ASYMMETRIC SULFUR^*1

Herzig¹,

1952

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“…(9, p. 1979; 10, p. 1520). 5 The acid material probably results from the oxidation in the alkaline medium of the ketol side chain by the oxygen of the air (c/. 11, 12).…”

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confidence: 99%

Investigations on steroids. XIX. Further Degradation Products of Strophanthidol

Balant¹,

1952

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In attempts to prepare analogs of steroid hormones having the angular carbon atom 19 present in an oxygenated form, strophanthidol (I) was selected as a suitable and easily accessible starting material. In an earlier publication (1) the oxidation in acetone solution of strophanthidol diacetate (la) with potassium permanganate was described. This yielded mainly an acid, non-crystalline, reaction product which upon deacetylating gave the crystalline 3/3,5,14,19-tetrahydroxy-14-isoetiocholanic acid (II). This acid has served as an intermediate for subsequent transformations (2-6).As has been shown in numerous instances by Reichstein and his associates (Lit. cf. 7, p. 90), cardiac aglycones may be degraded with ozone to glyoxylates which in turn can be hydrolyzed to ketols of the type of the adrenal cortical steroids. It was decided to apply this degradation to strophanthidol diacetate (la) in order to examine the products as possible useful intermediates in the synthesis of analogs of steroid hormones.Ozonization of la and reductive cleavage of the resulting ozonide yielded 3^,19-diacetoxy-21-glyoxyloxy-14-isopregnane 5,14-diol-20-one (III). This substance resisted crystallization, even after chromatography. Treatment of compounds of this type with aqueous methanolic potassium bicarbonate is reported (Lit. cf. 7, p. 90) to produce invariably a partial saponification to a free ketol in the side chain while the acetoxy group at carbon atom 3 is retained. In the present case (III) no uniform major reaction product was isolated. The evidence presented in the experimental section suggests that the reaction product was a mixture of 14-isopregnane-3/3,5,14,19,21-pentol-20-one (IV) and 3j3-acetoxy-14isopregnane-5,14,19,21-tetrol-20-one (V). This view is supported by observations made in this laboratory [2, p. 284 (c)] that, under these experimental conditions, compounds having acetoxy groups at Gig and at C3 are rather easily deacetylated in the 19-and in the 3-position. All attempts to obtain the com-1 This investigation was supported by research grants from: (a) the American Cancer Society on the recommendation of the Committee on Growth of the National Research Council; (b) the National Cancer Institute of the National Institutes of Health, Public Health Service; (c) the Rockefeller Foundation.* The findings of this paper were incorporated in the Robert Gnehm Lecture delivered on July 7,1952, at the Eidgenóssische Technische Hochschule in Zurich [cf. M. Ehrenstein, Chimia, 6, 287-289 (1952).] 8 Predoctoral Fellow (1949Fellow ( -1951 of the American Cancer Society, Inc., upon recommendation of the Committee on Growth of the National Research Council. This paper is based on a section of a thesis submitted by Charles P. Balant to the Graduate School of Arts and Sciences of the University of Pennsylvania in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Physiological Chemistry (June 1952).