INVESTIGATIONS ON STEROIDS. XXIV. 19-HYDROXY-11-DESOXYCORTICOSTERONE AND 19-HYDROXYPROGESTERONE<sup>*1</sup>

Barber, Gerald; Ehrenstein, Maximilian

doi:10.1021/jo01376a007

Cited by 25 publications

(6 citation statements)

References 11 publications

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“…The aqueous layer was acidified and extracted with Et20. The organic layer was washed with water, dried, and concentrated to leave 958 mg of crude 17/3-carbomethoxy-l-oxo-l,2-seco-A-nor-5a-androstan-2-oic acid (39).…”

Section: Rasmusson Et Almentioning

confidence: 99%

Azasteroids as inhibitors of rat prostatic 5.alpha.-reductase

Rasmusson¹,

Reynolds²,

Utne³

et al. 1984

J. Med. Chem.

142

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A series of A-ring heterocyclic steroids has been prepared and tested for inhibition of rat prostatic steroid 5 alpha-reductase in vitro. Strikingly high inhibitory activity was found with a group of 17 beta-substituted 4-methyl-4-aza-5 alpha-androstan-3-ones. These compounds were prepared from 3-keto-delta 4-precursors by oxidative (O3 or NaIO4-KMnO4) A-ring cleavage followed, in turn, by ring closure with an amine and hydrogenation over platinum catalyst. Other A-ring azasteroids were made by Beckmann rearrangement of oximes of 2-oxo-A-nor, 3-oxo- and 4-oxo-5 alpha-androstanes. An A-nor-2-oxo-3-azasteroid was prepared by oxidative decarbonylation of a precursor 2,3-dioxo-4-azasteroid with m-chloroperbenzoic acid. A-ring modifications of the 4-azasteroids included delta 1-unsaturation, 2- and 4-substituents, and 3-carbonyl replacements. Side chains at the 17-position were varied with an emphasis on carboxylate derivatives (salts, esters, and amides).

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Section: Rasmusson Et Almentioning

confidence: 99%

Azasteroids as inhibitors of rat prostatic 5.alpha.-reductase

Rasmusson¹,

Reynolds²,

Utne³

et al. 1984

J. Med. Chem.

142

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“…This identity establishes the normal (a) configuration at position 14 in all compounds of this series. The normal (ß) configuration at position 17 follows from the previously (2) cited molecular rotation data. 19-oxoprogesterone (IV) produces 10 % of the progestational activity of progesterone.…”

mentioning

confidence: 99%

INVESTIGATIONS ON STEROIDS. XXV. 19-OXOPROGESTERONE AND 19-OXO-11-DESOXYCORTICOSTERONE^{*, 1}

Barber¹,

Ehrenstein²

1955

J. Org. Chem.

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The synthesis, starting from strophanthidin, of 19-hydroxyprogesterone (III) and 19-hydroxy-11-desoxycorticosterone (VII) has been described (1, 2) and the spatial similarity of VII to corticosterone has been pointed out (2). The present paper is concerned with the extension of that synthesis to the preparation of 19-oxoprogesterone (IV) and 19-oxo-l 1-desoxycorticosterone (VIII).In a brief investigation of methods for the oxidation of the 19-hydroxyl group, ethyl 19-hydroxy-3-oxo-A4-etienate (I) (3, 4) served as the model. Ethyl 3,19dioxo-A4-etienate (II) was prepared successfully by oxidation of I with sodium dichromate dihydrate in glacial acetic acid as well as with chromic anhydride in 95% acetic acid or in glacial acetic acid. The best yield of II was obtained with the last combination. Surprisingly, compound I was not oxidized by one equivalent of chromic anhydride in either pyridine2 *or tertiary butanol.Proceeding from this study, 19-hydroxyprogesterone (III) and 19-hydroxy-11-desoxycorticosterone 21-monoacetate (V) were oxidized with one equivalent of chromic anhydride in glacial acetic acid, yielding, respectively, 19oxoprogesterone (IV) and 19-oxo-l 1-desoxycorticosterone acetate (VI). Hydrolysis with potassium bicarbonate of VI gave the free 19-oxo-l 1-desoxycorticosterone (VIII), the structure of which was confirmed by reacetylation to give VI.The infrared studies pertaining to this paper were carried out on a Perkin-Elmer Model 21 double beam spectrometer in the Division of Steroid Metabolism of the Sloan-Kettering Institute for Cancer Research through the courtesy of Dr. Thomas F. Gallagher. The interpretation was done by Friederike Herling. The correlations are based upon those summarized in the publication of Jones and Herling (6). Only those bands are mentioned which appear to have a direct bearing upon the structure of the particular compound. Details of other correlations between spectrum and structure will be summarized at a later time by the group at the Sloan-Kettering Institute.

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“…It is of interest that 19-hydroxy-DOC was first obtained by degradation of strophanthidin itself. 12 The commercially available 21-hydroxypregnenolone diacetate I was converted to the chlorohydrin II in 70% yield by allowing it to react with freshly prepared and chlorine-free hypochlorite solution in acetone. The 6,19-oxide III was obtained in 70% yield from chlorohydrin II by the iodine-lead tetraacetate re-action13 and saponified to the diol IV with KHC03 in aqueous methanol in about 90% yield.…”

Section: Methodsmentioning

confidence: 99%

Reactions of Triphenylsilyl Azide with Tetraphenyldiphosphine and Diphenylphosphine

Paciorek¹,

Kratzer²

1966

J. Org. Chem.

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

Cited by 25 publications

References 11 publications

Azasteroids as inhibitors of rat prostatic 5.alpha.-reductase

Azasteroids as inhibitors of rat prostatic 5.alpha.-reductase

INVESTIGATIONS ON STEROIDS. XXV. 19-OXOPROGESTERONE AND 19-OXO-11-DESOXYCORTICOSTERONE^{*, 1}

Reactions of Triphenylsilyl Azide with Tetraphenyldiphosphine and Diphenylphosphine

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

Cited by 25 publications

References 11 publications

Azasteroids as inhibitors of rat prostatic 5.alpha.-reductase

Azasteroids as inhibitors of rat prostatic 5.alpha.-reductase

INVESTIGATIONS ON STEROIDS. XXV. 19-OXOPROGESTERONE AND 19-OXO-11-DESOXYCORTICOSTERONE*, 1

Reactions of Triphenylsilyl Azide with Tetraphenyldiphosphine and Diphenylphosphine

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

INVESTIGATIONS ON STEROIDS. XXV. 19-OXOPROGESTERONE AND 19-OXO-11-DESOXYCORTICOSTERONE^{*, 1}