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DE1159946B - Process for the preparation of therapeutically active steroid compounds - Google Patents

Process for the preparation of therapeutically active steroid compounds

Info

Publication number
DE1159946B
DE1159946B DEU8307A DEU0008307A DE1159946B DE 1159946 B DE1159946 B DE 1159946B DE U8307 A DEU8307 A DE U8307A DE U0008307 A DEU0008307 A DE U0008307A DE 1159946 B DE1159946 B DE 1159946B
Authority
DE
Germany
Prior art keywords
preparation
steroid compounds
therapeutically active
active steroid
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
DEU8307A
Other languages
German (de)
Inventor
Alan Hart Nathan
John Alexander Hogg
William Paul Schneider
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pharmacia and Upjohn Co
Original Assignee
Upjohn Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Upjohn Co filed Critical Upjohn Co
Publication of DE1159946B publication Critical patent/DE1159946B/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J5/00Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07JSTEROIDS
    • C07J75/00Processes for the preparation of steroids in general

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Steroid Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

U 8307 IVb/12 »U 8307 IVb / 12 »

ANMELDETAG: 8. SEPTEMBER 1959REGISTRATION DATE: SEPTEMBER 8, 1959

BEKANNTMACHUNG
DER ANMELDUNG
UND AUSGABE DER
AUSLEGESCHRIFT: 27. DEZEMBER 1963
NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: DECEMBER 27, 1963

Gegenstand der Erfindung ist ein Verfahren zur Herstellung von therapeutisch wirksamen Steroidverbindungen der allgemeinen FormelThe invention relates to a process for the production of therapeutically active steroid compounds the general formula

Verfahren zur HerstellungMethod of manufacture

von therapeutisch wirksamenof therapeutically effective

SteroidverbindungenSteroid compounds

in der R Wasserstoff oder der Acylrest einer niederen Kohlenwasserstoffcarbonsäure ist.in which R is hydrogen or the acyl radical of a lower hydrocarbon carboxylic acid.

Diese Verbindungen werden erfindungsgemäß da- 2a durch erhalten, daß man eine Ve; bindung der allgemeinen FormelAccording to the invention, these compounds are da- 2a by getting that one a Ve; binding the general formula

CH2-O-AcCH 2 -O-Ac

r- OHr- OH

CH3 CH 3

in der Ac der Acylrest einer niederen Kohlenwasserstoffcarbonsäure ist, in an sich bekannter Weise mit Fluorwasserstoff oder einem Fluorwasserstoff abgebenden Mittel behandelt und gegebenenfalls anschließend die 21 ständige Acyloxygruppe hydrolysiert. in Ac the acyl radical of a lower hydrocarbon carboxylic acid is, in a manner known per se, donating with hydrogen fluoride or a hydrogen fluoride Treated agent and then optionally hydrolyzed the 21 acyloxy group.

Die erfindungsgemäß herstellbaren 2-Fluorverbindungen besitzen ausgeprägte therapeutische Wirksamkeit und sind bezüglich ihrer Wirkung auf den Mineral- und Wasserstoffwechsel den natürlichen Nebennierenrindenhormonen, wie Hydrocortison und Cortison, sowie anderen bekannten Steroidverbindungen ohne Fluorsubstituenten in 2-Stellung überAnmelder: The 2-fluorine compounds which can be prepared according to the invention have pronounced therapeutic effectiveness and are with regard to their effect on the Mineral and hydrogen change the natural adrenal cortex hormones, such as hydrocortisone and Cortisone, as well as other known steroid compounds without fluorine substituents in the 2-position via applicant:

The Upjohn Company, Kalamazoo, Mich. (V. St. A.)The Upjohn Company, Kalamazoo, Mich. (V. St. A.)

Vertreter: Dr. W. Beil,
A. Hoeppener und Dr. H. J. Wolff,
Representative: Dr. W. Beil,
A. Hoeppener and Dr. HJ Wolff,

Rechtsanwälte,
Frankfurt/M.-Höchst, Antoniterstr. 36
Lawyers,
Frankfurt / M.-Höchst, Antoniterstr. 36

Beanspruchte Priorität:
V. St. v. Amerika vom 8. September \·ά8 (Nr. 759 432)
Claimed priority:
V. St. v. America of September 8th \ ά8 (No. 759 432)

Alan Hart Nathan, John Alexander Hogg
und William Paul Schneider, Kalamazoo, Mich.
Alan Hart Nathan, John Alexander Hogg
and William Paul Schneider, Kalamazoo, Mich.

(V. St. A.),
sind als Erfinder genannt worden
(V. St. A.),
have been named as inventors

legen. Auf Grund ihrer guten entzündungswidrigen Wirkung und ihrer geringen Salz- und Wasserretention sind sie besonders wertvoll bei der Behandlung von Entzündungserscheinungen, die in Verbindung mit chronischer, kongestiver Herzschwäche, Lebercirrhose, Nierensyndromen, sowie Eklampsie und Präeklampsie auftreten.
Die neuen 2-Fluorverbindungen gemäß der Erfindung können, gegebenenfalls unter Verwendung der hierfür üblichen Träger und Verdünnungsmittel, oral, parenteral oder örtlich angewendet werden. Dabei kann die Zumischung anderer, die Wirkung der Steroidverbindungen ergänzender oder verstärkender Arzneimittel, z. B. von Antibiotika und Sulfonamiden, von Vorteil sein. Sie können ferner durch Einführung eines 21-Fluorsubstituenten oder durch Umwandlung in Verbindungen, die in 21-Stellung keinen Substituenten tragen, in weitere therapeutisch
place. Due to their good anti-inflammatory effect and their low salt and water retention, they are particularly valuable in the treatment of inflammatory symptoms that occur in connection with chronic, congestive heart failure, liver cirrhosis, kidney syndromes, as well as eclampsia and preeclampsia.
The new 2-fluoro compounds according to the invention can be administered orally, parenterally or topically, if appropriate using the carriers and diluents customary for this purpose. The admixture of other drugs that complement or enhance the effect of the steroid compounds, e.g. B. antibiotics and sulfonamides, be beneficial. They can also be used therapeutically by introducing a 21-fluorine substituent or by converting them into compounds which do not have any substituents in the 21-position

-,0 wertvolle Substanzen übergeführt werden.-, 0 valuable substances are transferred.

Das folgende Beispiel erläutert das erfindungsgemäße Verfahren.The following example explains the method according to the invention.

' ' · 309 770/484'' · 309 770/484

Beispielexample

a)a)

y&
4-pregnen-3,20-dion-21 -acetat
y &
4-pregnen-3,20-dione-21 acetate

Einer Lösung von 230 mg 2-Fluor-6a-methyl-9^,11/3-oxido-17a,21 -dioxy^-pregnen-S^O-dion-21-acetat in 5 ml Methylenchlorid wurden 1,2 ml einer 48°/oigen Fluorwasserstofflösung zugesetzt. Das entstandene 2-Phasensystem wurde 20 Stunden gerührt, dann mit 15 ml Methylenchlorid verdünnt und vorsichtig in 40 ml Wasser, das 4 g Natriumbicarbonat enthielt, gegossen. Das Gemisch wurde geschüttelt, um den überschüssigen Fluorwasserstoff zu neutralisieren, das Methylenchlorid abgetrennt und die wäßrige Phase nochmals mit Methylenchlorid extrahiert. Die vereinigten Methylenchloridauszüge wurden über wasserfreiem Natriumsulfat getrocknet, mit 25 ml Äther verdünnt und über 20 g Magnesiumsilikat, bekannt unter dem Handelsnamen »Florisil«, chromatographiert. Die Säule wurde mit Hexankohlenwasserstoffen, bekannt unter dem Handelsnamen »Skellysolve B«, die steigende Mengen Aceton enthielten, eluiert. Man erhielt praktisch reines 2,9a-Difluor-6a-methyl-ll/J,17a-21-trioxy-4-pregnen-3,20-dion-21-acetat vom Schmelzpunkt 206 bis 2080C.A solution of 230 mg of 2-fluoro-6a-methyl-9 ^, 11/3-oxido-17a, 21 -dioxy ^ -pregnen-S ^ O-dione-21-acetate in 5 ml of methylene chloride was 1.2 ml of a 48% hydrogen fluoride solution added. The resulting 2-phase system was stirred for 20 hours, then diluted with 15 ml of methylene chloride and carefully poured into 40 ml of water containing 4 g of sodium bicarbonate. The mixture was shaken in order to neutralize the excess hydrogen fluoride, the methylene chloride was separated off and the aqueous phase was extracted again with methylene chloride. The combined methylene chloride extracts were dried over anhydrous sodium sulfate, diluted with 25 ml of ether and chromatographed over 20 g of magnesium silicate, known under the trade name "Florisil". The column was eluted with hexane hydrocarbons, known under the trade name "Skellysolve B", which contained increasing amounts of acetone. One practically give pure 2.9A-difluoro-6a-methyl-ll / J, 17a-21 trioxy-4-pregnene-3,20-dione 21-acetate of melting point 206 to 208 0 C.

Analyse für C24H32F2O6:
Berechnet ... C 63,42, H 7,10, F 8,36%;
gefunden ... C 64,19, H 7,60, F 8,48%.
Analysis for C24H32F2O6:
Calculated ... C 63.42, H 7.10, F 8.36%;
Found ... C 64.19, H 7.60, F 8.48%.

b) 2,9a-Difluor-6a-methyl-l 10,l7a,21-trioxy-4-pregnen-3,20-dion b) 2,9a-Difluoro-6a-methyl-l 10,17a, 21-trioxy-4-pregnen-3,20-dione

100 mg 2,9a-Difluor-6a-methyl-ll/S,17a,21-trioxy-4 - pregnen - 3,20 - dion - 21 - acetat wurden in einer Mischung aus 2 ml Methanol und 0,1ml Wasser, die zuvor mit Stickstoff vom Luftsauerstoff befreit worden war, gelöst. Die Lösung wurde darauf mit 50 mg Kaliumcarbonat versetzt, 6 Stunden bei Zimmertemperatur unter Stickstoff stehengelassen, darauf mit 5%iger wäßriger Salzsäure neutralisiert, mit 5 ml Wasser verdünnt und gekühlt. Dann wurde abfiltriert und der feste Stoff aus Aceton-wSkellysolve B« umkristallisiert; F. = 213 bis 216°C.100 mg of 2,9a-difluoro-6a-methyl-II / S, 17a, 21-trioxy-4 - pregnen - 3.20 - dione - 21 - acetate were in a mixture of 2 ml of methanol and 0.1 ml of water, which had previously been freed from atmospheric oxygen with nitrogen, dissolved. The solution was based on it 50 mg potassium carbonate added, left to stand for 6 hours at room temperature under nitrogen, then neutralized with 5% aqueous hydrochloric acid, diluted with 5 ml of water and cooled. Then became filtered off and the solid substance from acetone-wSkellysolve B «recrystallized; M.p. = 213 to 216 ° C.

Claims (1)

PATENTANSPRUCH:PATENT CLAIM: Verfahren zur Herstellung von therapeutisch wirksamen Steroidverbindungen der allgemeinen FormelProcess for the preparation of therapeutically active steroid compounds of the general formula CH2-O —RCH 2 -O -R CO
-OH
CO
-OH
CH3 CH 3 in der R Wasserstoff oder der Acylrest einer niederen Kohlenwasserstoffcarbonsäure ist, da durch gekennzeichnet, daß man eine Verbindung der allgemeinen Formelin which R is hydrogen or the acyl radical of a lower hydrocarbon carboxylic acid, characterized in that one is a compound of the general formula CH3 CH 3 in der Ac der Acylrest einer niederen Kohlenwasserstoffcarbonsäure ist, in an sich bekannter Weise mit Fluorwasserstoff oder einem Fluorwasserstoff abgebenden Mittel umsetzt und gegebenenfalls anschließend die 21 ständige Acyloxygruppe hydrolysiert.in which Ac is the acyl radical of a lower hydrocarbon carboxylic acid, more known per se Way with hydrogen fluoride or a hydrogen fluoride releasing agent and optionally then the acyloxy group in position 21 is hydrolyzed. Ο 3» TlOIiH 12.63Ο 3 » TlOIiH 12.63
DEU8307A 1958-09-08 1959-09-08 Process for the preparation of therapeutically active steroid compounds Pending DE1159946B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US894604XA 1958-09-08 1958-09-08

Publications (1)

Publication Number Publication Date
DE1159946B true DE1159946B (en) 1963-12-27

Family

ID=22217769

Family Applications (2)

Application Number Title Priority Date Filing Date
DEU6441A Pending DE1115246B (en) 1958-09-08 1959-08-21 Process for the preparation of therapeutically active steroid compounds
DEU8307A Pending DE1159946B (en) 1958-09-08 1959-09-08 Process for the preparation of therapeutically active steroid compounds

Family Applications Before (1)

Application Number Title Priority Date Filing Date
DEU6441A Pending DE1115246B (en) 1958-09-08 1959-08-21 Process for the preparation of therapeutically active steroid compounds

Country Status (3)

Country Link
DE (2) DE1115246B (en)
FR (1) FR1453202A (en)
GB (1) GB894604A (en)

Also Published As

Publication number Publication date
FR1453202A (en) 1966-06-03
GB894604A (en) 1962-04-26
DE1115246B (en) 1961-10-19

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