DE1242611B - Process for the preparation of therapeutically active steroid compounds - Google Patents

Process for the preparation of therapeutically active steroid compounds

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Publication number
DE1242611B
DE1242611B DEU10469A DEU0010469A DE1242611B DE 1242611 B DE1242611 B DE 1242611B DE U10469 A DEU10469 A DE U10469A DE U0010469 A DEU0010469 A DE U0010469A DE 1242611 B DE1242611 B DE 1242611B
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DE
Germany
Prior art keywords
preparation
hydroxy
therapeutically active
steroid compounds
water
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
DEU10469A
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German (de)
Inventor
William Julius Wechter
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
Priority claimed from US256106A external-priority patent/US3132160A/en
Application filed by Upjohn Co filed Critical Upjohn Co
Publication of DE1242611B publication Critical patent/DE1242611B/en
Pending legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/56—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids
    • A61K31/57—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane or progesterone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/56—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids
    • A61K31/565—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol
    • A61K31/568—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol substituted in positions 10 and 13 by a chain having at least one carbon atom, e.g. androstanes, e.g. testosterone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J3/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by one carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J33/00—Normal steroids having a sulfur-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J5/00—Normal 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J75/00—Processes for the preparation of steroids in general
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Steroid Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

(UNDESREPUBLIK DEUTSCHLAND DEUTSCHES AHa^ PATENTAMT(UNDESREPUBLIK DEUTSCHLAND DEUTSCHES AHa ^ PATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. Cl.: Int. Cl .:

,C O 7 j, C O 7 j

Deutsche Kl.: 12 ο - 25/04German class: 12 ο - 25/04

Nummer: Aktenzeichen: Anmeldetag: Auslegetag:Number: File number: Filing date: Display date:

U 10469IV b/12 ο
4. Februar 1964
22. Juni 1967U 10469IV b / 12 ο
4th February 1964
June 22, 1967

Gegenstand der Erfindung ist ein Verfahren zur Herstellung therapeutisch wirksamer Stcroidvcrbindungen der allgemeinen FormelThe invention relates to a process for the production of therapeutically effective steroid compounds the general formula

HOHO

RORO

in der R Wasserstoff oder der Acetylrest ist.in which R is hydrogen or the acetyl radical.

Das erfindungsgemäße Verfahren besteht darin, daß man in an sich bekannter Weise eine VerbindungThe method according to the invention consists in that you establish a connection in a manner known per se

der Formelthe formula

C2H5 C 2 H 5

HaCHaC

HO-HO-

mit Methyllithium umsetzt und gegebenenfalls anschließend die 3-ständige Hydroxylgruppe acetyliert.Reacts with methyllithium and optionally then acetylated the 3-position hydroxyl group.

Die Verfahrensprodukte wirken beruhigend auf das Zentralnervensystem. Diese Wirkung ist überraschend, da das vergleichbare 11/J-Hydroxy-lla-mcthyl-5/i-pregnan-3,20-dion ein Stimulans für das Zentralnervensystem darstellt.The products of the process have a calming effect on the central nervous system. This effect is surprising because the comparable 11 / J-hydroxy-lla-methyl-5 / i-pregnane-3,20-dione represents a stimulant for the central nervous system.

Auf Grund ihrer beruhigenden, analgetischen, sedativen und muskelentspannenden Wirkung eignen sich die Verfahrensprodukte zur Behandlung von nervösen Zuständen, überhöhtem Blutdruck und verwandten Krankheiten bei Mensch und Tier. Sie können an Menschen, Säugetieren und Vögel in verschiedenen oralen und parenteralen Dosierungsformen allein oder im Gemisch mit ihre Wirkung ergänzenden Verbindungen verabreicht werden. Hierzu werden sie zweckmäßig in einem festen oder flüssigen Träger gelöst, dispergiert oder suspendiert. Als feste Präparate eignen sich z. B. Tabletten. Pulver, Kapsein und Pillen, vorzugsweise in Einheitsdosierungsform. Flüssige Präparate können als Verfahren zur Herstellung therapeutisch
wirksamer SteroidverbindungenDue to their calming, analgesic, sedative and muscle-relaxing effects, the process products are suitable for the treatment of nervous conditions, excessive blood pressure and related diseases in humans and animals. They can be administered to humans, mammals and birds in various oral and parenteral dosage forms, alone or in admixture with compounds complementary to their effects. For this purpose, they are expediently dissolved, dispersed or suspended in a solid or liquid carrier. As solid preparations are such. B. Tablets. Powders, capsules and pills, preferably in unit dosage form. Liquid preparations can be used as a method of manufacture therapeutic
effective steroid compounds

Anmelder:Applicant:

The Upjohn Company,The Upjohn Company,

Kalamazoo, Mich. (V. St. A.)Kalamazoo, me. (V. St. A.)

Vertreter:Representative:

Dr. W. Beil, A. HoeppenerDr. W. Beil, A. Hoeppener

und Dr. H. J. Wolff, Rechtsanwälte,and Dr. H. J. Wolff, lawyers,

Frankfurt/M.-Hoechst, Adelonstr. 58Frankfurt / M.-Hoechst, Adelonstr. 58

Als Erfinder benannt:
William Julius Wechter,
Kalamazoo, Mich. (V. St. A.)Named as inventor:
William Julius Wechter,
Kalamazoo, me. (V. St. A.)

Beanspruchte Priorität:
V. St. v. Amerika vom 4. Februar 1963
(256 106)Claimed priority:
V. St. v. America February 4, 1963
(256 106)

Lösungen, Emulsionen, Suspensionen, Sirupe und Elixiere verabreicht werden. Die Verfahrensprodukte fördern auch die Emulgierwirkung von Fetten.Solutions, emulsions, suspensions, syrups and elixirs can be administered. The process products also promote the emulsifying effect of fats.

Zur Herstellung des Ausgangsstoffes für das erfindungsgemäße Verfahren, 3a - Hydroxy - 17/9 - äthyl-5/J-androstan-ll-on, wird 3a-Hydroxy-5ß-pregnan-11,20-dion durch Umsetzung mit einem Alkandithiol, wie Äthandithiol, in Gegenwart einer organischen Säure und eines starken Lewis-Katalysators, wie Bortrifluoridätherat, in ein 3«-Hydroxy-5/i-pregnan-ll,20-dion-20-thioketal übergeführt, dessen Desulfurierung nach Mozingo, z. B. durch Hydrierung in Gegenwart eines Hydrierungskatalysators, wie Raney-Nickel, 3a-Hydroxy-17/S-äthyl-5/>'-androstan-ll-on ergibt.For the preparation of the starting material for the present process, 3a - hydroxy - 17/9 - ethyl-5 / J-androstan-ll-one, 3a-hydroxy-5ß-pregnane-11,20-dione by reaction with an alkanedithiol, such as Ethanedithiol, in the presence of an organic acid and a strong Lewis catalyst, such as boron trifluoride etherate, converted into a 3 ″ -hydroxy-5 / i-pregnane-ll, 20-dione-20-thioketal, whose desulfurization according to Mozingo, z. B. by hydrogenation in the presence of a hydrogenation catalyst such as Raney nickel, 3a-hydroxy-17 / S-ethyl-5 />'- androstan-ll-one results.

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

Beispielexample

A. Zur Herstellung des Ausgangsstoffes, 3u-Hydroxy-17/S-äthyl-5ß-androstan-ll-on, wurden 4 g 3«-Hydroxy-5/?-pregnan-ll,20-dion (J. Amer. Chem. Soc, 74, S. 483 [1952]) in 40 ml Eisessig gelöst und mit 15 ml Äthandithiol und 15 ml Bortrifluoridätherat in 40 ml Eisessig etwa 16 Stunden bei Raum-A. For the preparation of the starting material, 3u-hydroxy-17 / S-ethyl-5ß-androstan-ll-one, 4 g of 3 "-hydroxy-5 /? - pregnan-ll, 20-dione (J. Amer. Chem. Soc, 74, p. 483 [1952]) dissolved in 40 ml of glacial acetic acid and mixed with 15 ml of ethanedithiol and 15 ml of boron trifluoride etherate in 40 ml glacial acetic acid for about 16 hours at room

709 607/543709 607/543

temperatur behandelt. Die Lösung wurde mit 15 ml Wasser verdünnt, die leichtflüchtigen Bestandteile wurden unter verringertem Druck entfernt, und der Rückstand wurde mit Wasser auf etwa 500 ml gebracht. Darauf wurde das Produkt mit Äther extrahicrt. Die Ätherextrakte wurden nacheinander mit verdünnter Natriumhydroxydlösung und gesättigter Natriumchloridlösung gewaschen, über Natriumsulfat getrocknet und zur Trockne eingedampft. Beim Kristallisieren des Rückstands aus Aceton erhielt man 2,14 g eines Produkts vom Schmelzpunkt 171,5 bis 174,5°C. Die Umkristallisation ergab analysen-temperature treated. The solution was diluted with 15 ml of water, the volatile components were removed under reduced pressure and the residue was brought to about 500 ml with water. The product was then extracted with ether. The ether extracts were successively with dilute sodium hydroxide solution and saturated sodium chloride solution, washed over sodium sulfate dried and evaporated to dryness. Was obtained on crystallization of the residue from acetone 2.14 g of a product with a melting point of 171.5 to 174.5 ° C. are obtained. The recrystallization gave analytical

ketal-3-acctat vom Schmelzpunkt 174,0 bis 177,00C; IR-Absorptionsmaxima bei 1725 und 1696 cm "1. t5 Analyse für C25H38O3S2:ketal-3-acctat a melting point of 174.0 to 177.0 0 C; IR absorption maxima at 1725 and 1696 cm " 1. t5 analysis for C25H38O3S2:

Berechnet ... C 66,62, H 8,50, S 14,23;
gefunden ... C 66,58, H 8,63, S 14,18.Calculated ... C 66.62, H 8.50, S 14.23;
Found ... C 66.58, H 8.63, S 14.18.

1 g 3a-Hydroxy-5/9-pregnan-ll,20-dion-20-thioketal-3-acetat wurde in 50 ml Alkohol gelöst, darauf mit 15 ml Wasser versetzt, die 1 g Kaliumcarbonat enthielten, und die Lösung auf einem Dampfbad etwa 16 Stunden erhitzt. Beim Verdünnen mit 125 ml heißem Wasser erhielt man 950 mg eines kristallinen Feststoffes vom Schmelzpunkt 175,0 bis 177°C. Nach zweimaligem Umkristallisieren wurde analysenreines 3a-Hydroxy-5|?-pregnan-ll,20-dion-20-thioketal vom Schmelzpunkt 175,0 bis 177,00C erhalten; IR-Absorptionsmaxima bei 3430. 3340 (Schulter) und 1688 cm-'.1 g of 3a-hydroxy-5/9-pregnan-ll, 20-dione-20-thioketal-3-acetate was dissolved in 50 ml of alcohol, then mixed with 15 ml of water containing 1 g of potassium carbonate, and the solution on a Steam bath heated for about 16 hours. On dilution with 125 ml of hot water, 950 mg of a crystalline solid with a melting point of 175.0 to 177 ° C. were obtained. After two recrystallizations was analytically pure 3-hydroxy-5 | pregnan-ll, 20-dione-20-thioketal a melting point of 175.0 to 177.0 0 C obtained?; IR absorption maxima at 3430, 3340 (shoulder) and 1688 cm- '.

Analyse für C23H36O2S2:Analysis for C23H36O2S2:

Berechnet ... C 67,59, H 8,88, S 15,69;
gefunden ... C 67,53, H 9,06, S 15,55.Calculated ... C 67.59, H 8.88, S 15.69;
Found ... C 67.53, H 9.06, S 15.55.

5 g Sa-Hydroxy-S/J-pregnan-ll^O-dion^O-thioketal wurden in 200 ml Alkohol, der 50 ml Wasser enthielt, gelöst und mit etwa 15 g Raney-Nickel etwa 4 Stunden unter Rückfluß behandelt. Der Katalysator wurde abfiltriert und mit Alkohol gewaschen und das Filtrat auf etwa 50 ml eingeengt, worauf 3 g kristalline Tafeln vom Schmelzpunkt 149 bis 1521C ausfielen. Nach zweimaligem Umkristallisieren aus einem Gemisch von Aceton, Äthanol und Wasser erhielt man analysenreines 3a-Hydroxy-17/3-äthyl-5/5-androstan-ll-on vom Schmelzpunkt 153,0 bis 154,00C; IR-Absorptionsmaxima bei 3270, 3190 (Schulter) und 1700 cm"1.5 g of Sa-hydroxy-S / J-pregnan-II ^ O-dione ^ O-thioketal were dissolved in 200 ml of alcohol containing 50 ml of water and refluxed with about 15 g of Raney nickel for about 4 hours. The catalyst was filtered off and washed with alcohol and the filtrate was concentrated ml to about 50, whereupon 3 g crystalline panels failed melting point of 149 to 152 1 C. After two recrystallizations from a mixture of acetone, ethanol and water gave analytically pure 3-hydroxy-17/3-ethyl-5/5 androstan-ll-one of melting point 153.0 to 154.0 0 C; IR absorption maxima at 3270, 3190 (shoulder) and 1700 cm " 1 .

Analyse für C21H34O2:Analysis for C21H34O2:

Berechnet ... C 79,19, H 10,76; gefunden ... C 78,98, H 10,87.Calculated ... C 79.19, H 10.76; Found ... C 78.98, H 10.87.

B. 3a, 11/J-Dihydroxy-lla-methyl-17/?-äthyl-5/?-androstan B. 3a, 11 / J-dihydroxy-lla-methyl-17 /? - ethyl-5 /? - androstane

35 trum keine CO-(Carbonyl)-Banden aufwies. Eine Lösung des Produkts in Äthylenchlorid wurde an 125 g synthetisches Magnesiumsilikat adsorbiert und unter Gewinnung von 15 Fraktionen mit von 2 bis 10% ansteigenden Mengen Aceton in Hexankohlenwasserstoffen eluiert. Die Fraktionen 3 bis 7 enthielten 3,7 g 3a,ll/:MDihydroxy-lla-metbyl-17/?--äthyl-5/?-androstan; die IR-Absorption stimmte mit der angenommenen Struktur überein. 35 had no CO (carbonyl) bands. A solution of the product in ethylene chloride was adsorbed on 125 g of synthetic magnesium silicate and eluted with acetone in hexane hydrocarbons increasing from 2 to 10% to obtain 15 fractions. Fractions 3 to 7 contained 3.7 g of 3a, ll /: MDihydroxy-lla-metbyl-17 /? - ethyl-5 /? - androstane; the IR absorption was consistent with the assumed structure.

C. 3a, 11 ^-Dihydroxy-11 a-methyl-17/J-äthyl-5/V-androstan-3-acetat C. 3a, 11 ^ -dihydroxy-11a-methyl-17 / J-ethyl-5 / V-androstane-3-acetate

Eine Lösung von 3,7 g 3a,1 l/f-Dihydroxy-lla-methyl-17/J-äthyl-5/5-androstan in 8 ml Pyridin und 4 ml Acetanhydrid wurde etwa 20 Minuten auf einem Dampfbad erwärmt und dann etwa 16 Stunden bei Raumtemperatur stehengelassen. Darauf wurde die Lösung mit Wasser auf etwa 50 ml verdünnt und der erhaltene Niederschlag mit Wasser gewaschen. Der Feststoff wurde darauf in Äthanol gelöst und aus einem Gemisch von Äthanol und Wasser kristallisiert. Man erhielt 2,63 g eines Produktes vom Schmelzpunkt 96,5 bis 98° C. Durch Umkristallisation wurde analysenreines 3ß,Hß - Dihydroxylla-methyl-n^-äthyl-S/J-androstan-S-acetat vom Schmelzpunkt 98,0 bis 99°C erhalten; IR-Absorptionsmaxima bei 3480, 1740 (Schulter) 1720 und 1265 cm-i.A solution of 3.7 g of 3a, 1 l / f-dihydroxy-lla-methyl-17 / J-ethyl-5/5-androstane in 8 ml of pyridine and 4 ml of acetic anhydride was heated on a steam bath for about 20 minutes and then for about Left to stand at room temperature for 16 hours. The solution was then diluted to about 50 ml with water and the resulting precipitate was washed with water. The solid was then dissolved in ethanol and crystallized from a mixture of ethanol and water. 2.63 g of a product with a melting point of 96.5 ° to 98 ° C. were obtained. By recrystallization, analytically pure 3β, Hβ -dihydroxylla-methyl-n ^ -ethyl-S / I-androstane-S-acetate with a melting point of 98.0 ° C. was obtained 99 ° C obtained; IR absorption maxima at 3480, 1740 (shoulder) 1720 and 1265 cm-i.

Analyse für C24O40O.?:Analysis for C24O40O.?:

Berechnet ... C 76,55, H 7,71;
gefunden ... C 76,25, H 10,28.Calculated ... C 76.55, H 7.71;
Found ... C 76.25, H 10.28.

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung therapeutisch wirksamer Steroidverbindungen der allgemeinen Formel Process for the preparation of therapeutically active steroid compounds of the general formula CH3 C2H5 CH 3 C 2 H 5 H3CH 3 C 5555 4 g 3<ii-Hydroxy-17/?-äthyl-5,a(-androstan-ll-on, gelöst in 100 ml trocknen! Benzol und 100 ml Äther, wurden bei 0°C mit einer Lösung von Methyllithium (hergestellt aus 9,5 g Metbylbromid und 1,33 g Lithium in 200 ml Äther) behandelt, worauf man das Gemisch im Verlauf von etwa 16 Stunden auf Raumtemperatur erwärmen ließ, überschüssiges Methyllithium wurde durch Zugabe von Wasser zerstört. Die organische Schicht wurde abgetrennt, mit Wasser und gesättigter Natriumchloridlösung gewaschen, mit Natriumsulfat getrocknet und unter verringertem Druck eingeengt. Man erhielt ein gummiartiges Produkt, dessen IR-Absorptionsspek-RO 4 g 3 <ii-hydroxy-17 /? - ethyl-5, a (-androstan-ll-one, dissolved in 100 ml dry! Benzene and 100 ml ether, were at 0 ° C with a solution of methyllithium (prepared from 9.5 g methyl bromide and 1.33 g lithium in 200 ml ether), whereupon the mixture was allowed to warm to room temperature over about 16 hours, excess methyl lithium was destroyed by adding water, and the organic layer was separated with water and saturated sodium chloride solution, concentrated, dried with sodium sulfate and concentrated under reduced pressure. It is a rubber-like product, the IR received RO Absorptionsspek- in der R Wasserstoff oder der Acetylrest ist, dadurch gekennzeichnet, daß man in an sich bekannter Weise eine Verbindung der Formelin which R is hydrogen or the acetyl radical, characterized in that one a compound of the formula in a manner known per se C2H5 C 2 H 5 HOHO mit Methyllithium umsetzt und gegebenenfalls anschließend die 3-ständige Hydroxylgruppe acetyliert. Reacts with methyllithium and optionally then acetylated the 3-position hydroxyl group.
DEU10469A 1963-02-04 1964-02-04 Process for the preparation of therapeutically active steroid compounds Pending DE1242611B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US256106A US3132160A (en) 1963-02-04 1963-02-04 3, 11-dioxygenated-17-desoxy-5beta-androstanes and processes therefor

Publications (1)

Publication Number Publication Date
DE1242611B true DE1242611B (en) 1967-06-22

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ID=22971116

Family Applications (1)

Application Number Title Priority Date Filing Date
DEU10469A Pending DE1242611B (en) 1963-02-04 1964-02-04 Process for the preparation of therapeutically active steroid compounds

Country Status (5)

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CH (1) CH458337A (en)
DE (1) DE1242611B (en)
ES (1) ES296044A1 (en)
FR (1) FR3847M (en)
GB (1) GB998369A (en)

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ES296044A1 (en) 1964-04-01
FR3847M (en) 1966-01-17
GB998369A (en) 1965-07-14
CH458337A (en) 1968-06-30

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