DD252832A1 - PROCESS FOR THE PREPARATION OF ANDROSTA-4,16-DIEN-3,6-DION - Google Patents
PROCESS FOR THE PREPARATION OF ANDROSTA-4,16-DIEN-3,6-DION Download PDFInfo
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- DD252832A1 DD252832A1 DD29461286A DD29461286A DD252832A1 DD 252832 A1 DD252832 A1 DD 252832A1 DD 29461286 A DD29461286 A DD 29461286A DD 29461286 A DD29461286 A DD 29461286A DD 252832 A1 DD252832 A1 DD 252832A1
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- German Democratic Republic
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- androsta
- dione
- diene
- preparation
- dien
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- Steroid Compounds (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung von Androsta-4,16-dien-3,6-dion (Formel 1). Diese Verbindung ist ein neuer, bisher nicht beschriebener Vertreter aus der Reihe der 16-Androstene, der auf Grund verschiedener reaktiver Zentren im Molekuel als Zwischenprodukt zur Herstellung von Steroidpharmaka eingesetzt werden kann. Ziel der Erfindung ist ein Verfahren, das Androsta-4,16-dien-3,6-dion mit geringem synthetischem Aufwand und in guter Ausbeute zu synthetisieren gestattet. Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren anzugeben, um Androsta-4,16-dien-3,6-dion aus einem leicht zugaenglichen Ausgangsprodukt auf einfache Weise zu gewinnen. Erfindungsgemaess wird die Aufgabe dadurch geloest, dass Androsta-5,16-dien-3b-ol (2) mit Jones-Reagenz (Bowden, K., Heilbronn, I. M., Jones, E. R. H., Weedon, B. L. C.; J. Chem. Soc. 1946, 39), einem schonenden Oxydationsmittel zur Umsetzung von sekundaeren Alkoholen und Allylalkoholen zu Ketonen, oxydiert wird. Ueberraschenderweise bildet sich utner den Bedingungen des Jones-Reagenz (schwefelsaures CrO3, 0-5C, Aceton als Loesungsmittel), die sonst nur 3 Keto-D5-Steroide liefern, quantitativ das gewuenschte Androsta-4,16-dien-3,6-dion. Formel 1The invention relates to a process for the preparation of androsta-4,16-diene-3,6-dione (formula 1). This compound is a new, unprecedented member of the 16-androstene series, which can be used as an intermediate for the production of steroid drugs due to the presence of various reactive centers in the molecule. The aim of the invention is a process which allows to synthesize androsta-4,16-diene-3,6-dione with little synthetic effort and in good yield. The invention has for its object to provide a method to win androsta-4,16-diene-3,6-dione from a readily accessible starting product in a simple manner. According to the invention, the object is achieved by reacting androsta-5,16-diene-3b-ol (2) with Jones reagent (Bowden, K., Heilbronn, IM, Jones, ERH, Weedon, BLC, J. Chem. 1946, 39), a mild oxidizing agent for the reaction of secondary alcohols and allylic alcohols to ketones, is oxidized. Surprisingly, the conditions of the Jones reagent (sulfuric CrO3, 0-5C, acetone as a solvent), which otherwise yield only 3 keto-D5 steroids, are quantitatively formed by the desired androsta-4,16-diene-3,6-dione , formula 1
Description
Der Vorteil der Erfindung besteht darin, daß hierbei die zur Ausbildung der3,6-Diketo-A4-Struktur sonst notwendigen drastischen Bedingungen vermieden werden und Androsta-4,16-dien-3,6-dion in hoher Ausbeute anfällt. Gegenüber den Oxydationsverfahren in stark saurer Lösung spart das Verfahren außerdem erhebliche Zeit ein.The advantage of the invention is that in this case the drastic conditions otherwise necessary for the formation of the 3,6-diketo-A 4 structure are avoided and androsta-4,16-diene-3,6-dione is obtained in high yield. Compared to the oxidation process in strongly acidic solution, the process also saves considerable time.
Androsta-3,16-dien-3/3-ol (960 mg = 3,5 mmol) wurde in Aceton (125 ml) gelöst und in ein Kühlbad (0-50C) gestellt. Unter Rühren wurde Jones-Reagenz (2,5 ml) zugetropft. Es bildete sich klebriger, grüner Bodensatz. Dünnschichtchromatographische Kontrolle nach 10min zeigte die quantitative Umsetzung an.Androsta-3,16-diene-3/3-ol (960 mg = 3.5 mmol) was dissolved in acetone (125 ml) and placed in a cooling bath (0-5 0 C). While stirring, Jones reagent (2.5 ml) was added dropwise. It formed sticky, green dregs. Thin-layer chromatography after 10 minutes indicated quantitative conversion.
Überschüssiges Cr(VI) wurde mit Isopropanol reduziert und der Ansatz in Wasser (250ml) eingerührt. Extraktion mit Benzen. (2 χ 50ml), Waschen und Trocknen des Extraktes und Entfernen des Benzens am Rotationsverdampfer lieferte öliges · Rohprodukt, das säulenchromatographisch gereinigt wurde. Ausbeutean(1): 854mg = 3mmol = 86% Analyse:Excess Cr (VI) was reduced with isopropanol and the reaction stirred into water (250 ml). Extraction with benzene. (2 × 50 ml), washing and drying the extract and removing the benzene on a rotary evaporator yielded oily crude product, which was purified by column chromatography. Yield (1): 854mg = 3mmol = 86% Analysis:
MS:Molpeakm/e284,1786(berechnet284,1776fürCl9H24O2)undFragmenteM+ - CH3(269),M+- C2H4(256),M+ -C3H6(242), M+- C7H10 (190) und M+- C11H14 (138).MS: Molpeakm / e284,1786 (berechnet284,1776fürC l9 H 24 O 2) undFragmenteM + - CH 3 (269), M + - C 2 H 4 (256), M + -C 3 H 6 (242), M + - C 7 H 10 (190) and M + - C 11 H 14 (138).
UV:Xmax247nrn(lge = 4,0). :UV: X max 247nrn (lge = 4.0). :
IR: 730,758,872,954,1034,1104,1118,1222,1250,1332,1380,1420, 1460,1700,3050,3065cm"1.IR: 730,758,872,954,1034,1104,111,18,1222,1250,1332,1380,1420, 1460,1700,3050,3065cm " 1 .
13C-NMR: Zwei Ketokohlenstoffsignale (C[3] 198,8, C[6] 201,4ppm), vier olefinische Signale (C[4] 125,4ppm und OR-Dublett, C[5] 160,6ppm und OR-Singulett, C[16] 143,0ppm, OR-Dublett, C[17] 129,0ppm und OR-Dublett).13C-NMR: two ketocarbon signals (C [3] 198.8, C [6] 201.4 ppm), four olefinic signals (C [4] 125.4 ppm and OR doublet, C [5] 160.6 ppm and OR Singlet, C [16] 143ppm, OR doublet, C [17] 129.0ppm and OR doublet).
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DD29461286A DD252832B1 (en) | 1986-09-23 | 1986-09-23 | PROCESS FOR THE PREPARATION OF ANDROSTA-4,16-DIEN-3,6-DION |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DD29461286A DD252832B1 (en) | 1986-09-23 | 1986-09-23 | PROCESS FOR THE PREPARATION OF ANDROSTA-4,16-DIEN-3,6-DION |
Publications (2)
Publication Number | Publication Date |
---|---|
DD252832A1 true DD252832A1 (en) | 1987-12-30 |
DD252832B1 DD252832B1 (en) | 1989-07-19 |
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ID=5582587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DD29461286A DD252832B1 (en) | 1986-09-23 | 1986-09-23 | PROCESS FOR THE PREPARATION OF ANDROSTA-4,16-DIEN-3,6-DION |
Country Status (1)
Country | Link |
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DD (1) | DD252832B1 (en) |
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1986
- 1986-09-23 DD DD29461286A patent/DD252832B1/en not_active IP Right Cessation
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DD252832B1 (en) | 1989-07-19 |
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