1035-69-4Relevant academic research and scientific papers
Synthesis of 11-substituted androstenediones and testosterones as human decidual cell growth inhibitors
Zhao, Qinjian,Li, Zhensu
, p. 190 - 195 (1994)
11α-Hydroxytestosterone (1a), 11β-hydroxytestosterone (1b), 11α- methoxytestosterone (1c), 11β-methoxytestosterone (1d), 11-ketotestosterone (1e), and Δ(9(11))-testosterone (1f) were synthesized from hydrocortisone (4b) or 11-epi-hydrocortisone (4a). The six target compounds, together with 11α-methoxyandrostenedione (2c), 11β-methoxyandrostenedione, (2d) and their lead compound, testosterone (1), were found to effectively inhibit the growth and differentiation of human decidual cells in culture. There is no observable binding of these compounds to estrogen receptor of rabbit uterus. The introduction of a polar group (e.g., hydroxyl and carbonyl) to C-11 of androstenes decreases both the relative binding affinities to progesterone receptor and the inhibitory effects on human decidual cell growth, while the methylation of 11-hydroxyl group minimizes these effects. The similar effects of a polar group at C-11 of testosterone (1) on the inhibitory effects on human decidual cell growth and the relative binding affinities to progesterone receptor of rabbit uterus may suggest that one of the mechanisms of human decidual cell growth inhibition by these compounds is the anti- progestational activity of these androgens.
Bismuth(III) triflate-catalyzed direct conversion of corticosteroids into highly functionalized 17-ketosteroids by cleavage of the C17-dihydroxyacetone side chain
Pinto, Rui M. A.,Salvador, Jorge A. R.,Le Roux, Christophe,Paixao, Jose A.
, p. 8488 - 8491 (2009)
(Chemical Equation Presented) The use of bismuth(III) triflate as catalyst for the direct conversion of corticosteroids into highly functionalized 17-ketosteroids by cleavage of the C17-dihydroxyacetone side chain is reported. This catalytic process is very chemoselective, since functionalities of the starting corticosteroids, such as Δ4-3-keto, Δ1,4-3-keto, 11β-hydroxyl, and 9β,11β-epoxide, remained intact.
A convenient syntheses of 9(11)-dehydrosteroids from 11β-hydroxysteroids
Zhao,Li
, p. 1473 - 1478 (1993)
11β-Hydroxy androstenedione was unexpectedly dehydrated during the ketalization of its 3,17-diones. This dehydration reaction can be exploited as a convenient method for the syntheses of 9(11)-dehydrosteroids.
A novel route for the preparation of betamethasone from 9α-hydroxyandrost-4-ene-3,17-dione (9αOH-AD) by chemical synthesis and fermentation
Tang, Jie,Liu, Xirong,Zeng, Chunlin,Meng, Hao,Tian, Mi,Guo, Cancheng
, p. 266 - 270 (2017)
A novel and efficient synthesis of betamethasone has been developed from the readily available 9α-hydroxyandrost-4-ene-3,17-dione (9αOH-AD). The 16α-methyl was introduced stereoselectively with CH3Br and converted to the 16β-methyl, the 17-side chain was installed with 2-chlorovinyl ethyl ether in the place of the toxic KCN/HOAc, and a mild fermentation was employed for the 1,2-dehydrogenation, replacing the DDQ oxidation. By adjustments and improvements of the steps, this route produced betamethasone in 11 steps with a 22.9% overall yield, showing its potential for industrial application with relatively low toxicity and cost.
An efficient procedure for the synthesis of 21-acetoxypregna-1,4,9(11),16-tetraene-3,20-dione
Huy, Luu D.,Diep, Nguyen T.,Vu, Tran K.,Savinova, Tatiana S.,Donova, Marina V.
, p. 225 - 231 (2020/04/27)
Background: Halogenated corticosteroids are widely used in medicine, and the global need of these steroidal APIs is estimated to be 40 - 70 tons, annually. Vietnam currently imports the pharmaceutical compounds up to 90%, in particular 100% of steroidal drugs. Currently, industrial production is based on the chemical syntheses of corticosteroids from either 16-dehydropregnenolone acetate (obtained from diosgenin) or androstenedione (obtained from phytosterol). The development of shorter synthetic schemes and more economically feasible technologies is of great significance. Introduction of 1(2)-double bond at the final stages of the corticosteroids synthesis results inpoor yield. 21-Acetoxypregna-1,4,9(11),16-tetraene-3,20-dione (tetraene acetate) is a key intermediate in the synthesis of highly active halogenated corticosteroids such as dexamethasone and other halogenated corticosteroids. 21-acetoxypregna-1,4,9(11),16-tetraene-3,20-dione is a key intermediate in the synthesis of dexamethasone from the readily available and cheap 9α-hydroxyandrost-4-ene-3,17-dione. Objective: The purpose of this study was the development of an efficient and shorter procedure for the synthesis of 21-acetoxypregna-1,4,9(11),16-tetraene-3,20-dione from 9α-hydroxyan-drostenedione, which is a product of a bio-oxidative degradation of the side chain of phytosterols. Methods: Pregnane side chain was constructed using cyanohydrin method. For 1(2)-dehydrogenation, selene dioxide was applied for the introduction of Δ1(2)-double bond. Other stages of the synthesis were epimerization, Stork’s iodination procedure and dehydration. Result: 21-Acetoxypregna-1,4,9(11),16-tetraene-3,20-dione was prepared from 9α-hydroxyandrostenedione in yield more than 46%. Conclusion: An efficient and practically feasible procedure for the synthesis of 21-acetoxypregna-1,4,9(11),16-tetraene-3,20-dione from 9α-hydroxyandrostenedione, a key intermediate for the synthesis of 9-haloidated corticoids, has been developed. The procedure can be applied for the production of value-added 9-haloidated corticoids.
Efficient preparation method of delta-canrenone
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Paragraph 0034; 0035, (2020/12/31)
The invention discloses an efficient preparation method of delta-canrenone, and belongs to the technical field of preparation of intermediates of medicines. The method comprises the following steps of: by taking 9 alpha-hydroxyl-4-androstenedione as a raw material, firstly removing 9-site hydroxyl through dehydration reaction to generate delta double bonds, then protecting 3-site carbonyl, then performing epoxidation on 17-site carbonyl, condensing with malonic acid diester to form a lactone ring, and performing oxidative decarboxylation or decarboxylation oxidation reaction to obtain delta-canrenone. According to the method, the raw materials are cheap and easy to obtain, the cost is low, reaction products in all steps are easy to purify, the total mass yield of the final product is higher than 80%, and the method is high in operability, extremely high in commercial competitiveness, suitable for industrial large-scale production and good in economic benefit.
METHODS FOR PREPARING DEOXYCHOLIC ACID
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Paragraph 0020-0022, (2018/05/03)
The present invention discloses method for preparing deoxycholic acid (DCA) or an ester thereof or a pharmaceutically acceptable salt thereof. Said compounds may be applied to remove a fat deposition.
A pregna - 1, 4, 9 (11), 16 (17) - tetraene - 3, 20 - dione synthetic method and intermediate
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Paragraph 0026; 0027; 0028; 0029, (2017/08/25)
The invention relates to a synthesis method and main intermediates of pregnene-1,4,9 (11),16 (17)-tetraenol-3, 20-diketone. The synthesis method sequentially comprises the following steps of reacting a second intermediate and tosylmethyl isocyanide in an organic solvent at the temperature of lower than 35 DEG C below zero to generate a third intermediate; reacting the third intermediate and a methylated reagent in an organic solvent at the temperature of 70-90 DEG C, and then, removing methyl ether protecting groups and tosylmethyl isocyanide under the action of an acid to obtain a fourth intermediate; and reacting the fourth intermreidate under the action of 3-ketosteroid-1-dehydrogenase to generate pregnene-1,4,9 (11),16 (17)-tetraenol-3, 20-diketone. Raw materials of pregnene-1,4,9 (11),16 (17)-tetraenol-3, 20-diketone are cheap and available; the yield of pregnene-1,4,9 (11),16 (17)-tetraenol-3, 20-diketone is relatively high; a C17-position side chain is introduced by using tosylmethyl isocyanide, so that acetone cyanohydrin serving as a highly-toxic reagent is prevented from being used; and the synthesis method is safe, environment-friendly and suitable for industrial production.
Preparation method of steroidal compound with multiple olefins
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Paragraph 0060-0077, (2017/10/31)
The invention relates to a preparation method of a steroidal medicine intermediate, in particular to a method for preparing a steroid carrying medicine intermediate, namely steroid carrying-1,4,9 (11), 16 (17)-tetraterpene-3,20-diketone and steroid carrying-4,9 (11)-diene-3,20-diketone-17 alpha-hydroxyl, with androstane-4-alkene-3,17-diketone-9 alpha-hydroxyl as a substrate.
METHODs for THE Preparation of Deoxycholic Acid
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Paragraph 0020; 0021; 0022, (2017/04/28)
The present invention is directed to methods for the preparation of deoxycholic acid, or ester or pharmaceutically acceptable salts thereof.? The compounds are effective for reduction of fatty deposits.
