CH622271A5 - Process for the preparation of polyhalosteroids - Google Patents

Process for the preparation of polyhalosteroids Download PDF

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Publication number
CH622271A5
CH622271A5 CH841679A CH841679A CH622271A5 CH 622271 A5 CH622271 A5 CH 622271A5 CH 841679 A CH841679 A CH 841679A CH 841679 A CH841679 A CH 841679A CH 622271 A5 CH622271 A5 CH 622271A5
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Switzerland
Prior art keywords
acid
chlorine
formula
alpha
dihydroxy
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Application number
CH841679A
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German (de)
Inventor
Jaroslav Dr Kalvoda
Georg Dr Anner
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Ciba Geigy Ag
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Publication of CH622271A5 publication Critical patent/CH622271A5/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J21/00—Normal steroids containing carbon, hydrogen, halogen or oxygen having an oxygen-containing hetero ring spiro-condensed with the cyclopenta(a)hydrophenanthrene skeleton
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J31/00—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring
    • C07J31/006—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring not covered by C07J31/003
    • 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
    • C07J5/0046—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 substituted in position 17 alfa
    • C07J5/0061—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 substituted in position 17 alfa substituted in position 16
    • C07J5/0069—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 substituted in position 17 alfa substituted in position 16 by a saturated or unsaturated hydrocarbon group
    • C07J5/0076—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 substituted in position 17 alfa substituted in position 16 by a saturated or unsaturated hydrocarbon group by an alkyl group
    • 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
    • C07J7/008—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms substituted in position 21
    • C07J7/0085—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms substituted in position 21 by an halogen atom

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Rheumatology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • Pain & Pain Management (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Steroid Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

9 alpha ,21-dihalo-11 beta ,17 alpha -dihydroxy-6 alpha -fluoro-16 alpha -methylpregna-1,4-diene -3,20-dione 17-esters of the formula <IMAGE> in which X is chlorine, X' is bromine or chlorine, and Ac is an acyl group derived from a carboxylic acid, are distinguished by high local antiinflammatory activity with a reduced systemic effect, for which reason they can be used in medicine to alleviate and control inflammatory states. They are obtained by conventional addition of hypochlorous acid onto a corresponding 9(11)-unsaturated starting material.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung neuer polyhalogenierten 11 ß,17 a-Dihydroxy-16 a-methyl-pregna-l,4-dien-3,20-dion-17-ester der Formel The invention relates to a process for the preparation of new polyhalogenated 11β, 17 a-dihydroxy-16 a-methyl-pregna-l, 4-diene-3,20-dione-17-esters of the formula

CH2x- CH2x-

HO /\p3 f° raX î Î ' *'*OAc ci .9*4 ì 1 HO / \ p3 f ° raX î Î '*' * OAc ci .9 * 4 ì 1

\ ^ \l/i\ ✓ \ \ \ ^ \ l / i \ ✓ \ \

• • JL • • 'nn • • JL • • 'nn

I I X I CHo I I X I CHo

• • • ^ • • • ^

/ \ ^ \ / / \ ^ \ /

(I) (I)

worin X Chlor, X' Brom oder insbesondere Chlor, und Ac eine von einer Carbonsäure abgeleitete Acylgruppe darstellt. wherein X represents chlorine, X 'bromine or especially chlorine, and Ac represents an acyl group derived from a carboxylic acid.

Die genannte Acylgruppe Ac leitet sich von den in der Steroidchemie gebräuchlichen Carbonsäuren mit 1-18 C-s Atomen, insbesondere von niederaliphatischen Mono- oder Dicarbonsäuren mit 1-7 C-Atomen, wie z.B. von der Essigsäure, Buttersäure, Isobuttersäure, Valeriansäure, Isovalerian-säure, Trimethylessigsäure, Hexansäure, Heptansäure und vor allem der Propionsäure, ab. Man kann aber auch Säuren io verwenden, welche ungesättigt, verzweigt, und/oder in üblicher Weise substituiert sind, wie z.B.: Diäthylessigsäure, 2,2- oder 3,3-Dimethylbuttersäure, Phenyl und Cyclohexylessigsäure, Phenoxyessigsäure, Cyclopentylpropionsäure, Halogenessigsäuren, Aminoessigsäure, Oxypropionsäure, Benzoesäure oder ls Undecylensäure. The acyl group Ac mentioned is derived from the carboxylic acids with 1-18 C-s atoms customary in steroid chemistry, in particular from lower aliphatic mono- or dicarboxylic acids with 1-7 C-atoms, such as e.g. on acetic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, trimethylacetic acid, hexanoic acid, heptanoic acid and especially propionic acid. However, it is also possible to use acids which are unsaturated, branched and / or substituted in the customary manner, for example: diethyl acetic acid, 2,2- or 3,3-dimethylbutyric acid, phenyl and cyclohexylacetic acid, phenoxyacetic acid, cyclopentylpropionic acid, haloacetic acids, amino acetic acid, Oxypropionic acid, benzoic acid or ls undecylenic acid.

Die Verbindungen der Formel I besitzen wertvolle pharmakologische Eigenschaften, wodurch sie zur Anwendung als Therapeutika geeignet sind. So zeichnen sie sich durch eine hervorragende antiinflammatorische Wirksamkeit bei lokaler 20 Applikation aus, wobei im Verhältnis dazu ihre systemische (zentrale) Wirkung bemerkenswert niedrig ist, wie sich im Tierversuch nachweisen lässt. Wegen dieser günstigen Verteilung der biologischen Eigenschaften sind diese Verbindungen in der Medizin in allen Indikationen verwendbar, die für Glu-2S cocorticoid-Analoga mit entzündungshemmenden Eigenschaften vorgesehen sind, insbesondere aber als lokal anzuwendende antünflammatorische Glucocorticoide. Besonders hervorzuheben sind 17-Niederalkylcarbonsäureester sowohl des 2 l-Brom-2,9 a-dichlor-6 a-fluor-11 ß, 17 a-dihydroxy- 16 a-30 methyl-pregna-l,4-dien-3,20-dions als auch insbesondere des 2,9a,21-Trichlor-6a-fluor-llß,17a-dihydroxy-16a-methyl-pregna-l,4-dien-3,20-dions, welche z.B. in Rohwattegranulom-test an der Ratte im Dosisbereich von 0.003 bis 0.3 mg/Pellet bei lokaler Applikation antiinflammatorisch wirksam sind. Bei gleicher Versuchsanordnung sind die ersten Zeichen einer systemischen Wirkung, wie sie durch die Abnahme des Körper* und insbesondere des Nebennieren- und Thymus-Gewichts feststellbar ist, erst oberhalb der Dosis von 0.3 mg/ Pellet merklich. The compounds of formula I have valuable pharmacological properties, which makes them suitable for use as therapeutic agents. They are characterized by excellent anti-inflammatory activity when applied locally, although their systemic (central) effect is remarkably low in comparison, as can be demonstrated in animal experiments. Because of this favorable distribution of the biological properties, these compounds can be used in medicine in all indications which are intended for Glu-2S cocorticoid analogs with anti-inflammatory properties, but in particular as locally applicable anti-inflammatory glucocorticoids. Particularly noteworthy are 17-lower alkyl carboxylic acid esters of both 2 l-bromo-2,9 a-dichloro-6 a-fluoro-11β, 17 a-dihydroxy-16 a-30 methyl-pregna-l, 4-diene-3.20 -dions and in particular of 2,9a, 21-trichloro-6a-fluoro-11ß, 17a-dihydroxy-16a-methyl-pregna-l, 4-diene-3,20-dione, which, for example in a raw cotton granuloma test on the rat in the dose range from 0.003 to 0.3 mg / pellet with local application are anti-inflammatory. With the same experimental setup, the first signs of a systemic effect, as can be seen from the decrease in body * and in particular the adrenal and thymus weight, are noticeable only above the dose of 0.3 mg / pellet.

Die Verbindungen der Formel I können zudem als wertvolle Zwischenprodukte für Herstellung anderer nützlicher Stoffe, insbesondere anderer pharmakologisch wirksamer Steroide, Anwendung finden. The compounds of formula I can also be used as valuable intermediates for the production of other useful substances, in particular other pharmacologically active steroids.

Die Verbindungen der Formel (I) werden erfindungsgemäss 45 hergestellt, indem man eine Verbindung der allgemeinen Formel According to the invention, the compounds of the formula (I) are prepared by using a compound of the general formula

35 35

40 40

• CH. CO • CH. CO

/ M / M

ci . fsü- r~! ci. fsü- r ~!

Y Y Y v --ch Y Y Y v --ch

• •• • OAc • •• • OAc

3 3rd

(II) (II)

55 55

60 60

✓ W ✓ W

worin Ac und X' die für die Formel I angegebenen Bedeutungen haben, mit unterchloriger Säure oder einem unterchlorige Säure abgebenden Mittel behandelt. wherein Ac and X 'have the meanings given for the formula I, treated with hypochlorous acid or a hypochlorous acid releasing agent.

Dabei addiert man an die 9,11-Doppelbindung der Verbin-65 düngen der Formel (II) in an sich bekannter Weise die Elemente der unterchlorigen Säure. Man arbeitet z.B. mit wässri-ger unterchloriger Säure oder mit einem unterchlorige Säure abgebenden Mittel, wie einem N-Chlorcarbonsäureamid oder The elements of hypochlorous acid are added to the 9,11 double bond of the compound 65 of the formula (II) in a manner known per se. One works e.g. with aqueous hypochlorous acid or with a hypochlorous acid releasing agent such as an N-chlorocarboxamide or

3 3rd

622271 622271

-imid, (vgl. US-Patentschrift 3 057 886). Die Reaktion führt man in einem inerten Lösungsmittel, wie einem tertiären Alkohol, z.B. Butanol, einem Äther, z.B. Diäthyläther, Methylisopropyläther, Dioxan oder Tetrahydrofuran, oder einem Keton, z.B. Aceton, gegebenenfalls in Gegenwart von Wasser und/oder einer starken Säure, durch. Eine vorteilhafte Ausführungsart dieses Verfahrens stellt der Umsatz mit t-Butyl-hypochlorit in einem inerten, mit Wasser nichtmischbaren Lösungsmittel, wie z.B. einem NitrokohlenWasserstoff, in Gegenwart von Perchlorsäure dar. (Vgl. Deutsche Patentschrift 2 011 559). -imide, (see U.S. Patent 3,057,886). The reaction is carried out in an inert solvent, such as a tertiary alcohol, e.g. Butanol, an ether e.g. Diethyl ether, methyl isopropyl ether, dioxane or tetrahydrofuran, or a ketone, e.g. Acetone, optionally in the presence of water and / or a strong acid. An advantageous embodiment of this process is the conversion with t-butyl hypochlorite in an inert, water-immiscible solvent, e.g. a nitrocarbon, in the presence of perchloric acid. (Cf. German Patent 2,011,559).

Die für die Ausführung der oben genannten Verfahrensmethode nötigen Ausgangsstoffe können in an sich bekannter Weise hergestellt werden. The starting materials required for carrying out the above-mentioned method can be prepared in a manner known per se.

Die gemäss der vorliegenden Erfindung erhaltenen Endstoffe können mit Vorteil der Herstellung von pharmazeutischen Präparaten zur Anwendung in der Human- oder Veterinärmedizin dienen, welche die neuen, oben beschriebenen pharmakologisch wirksamen Stoffe der Formel I als aktive Substanzen zusammen mit einem pharmazeutischen Trägermaterial enthalten. The end products obtained according to the present invention can advantageously be used for the production of pharmaceutical preparations for use in human or veterinary medicine which contain the new pharmacologically active substances of the formula I described above as active substances together with a pharmaceutical carrier material.

In den folgenden Beispielen wird die Temperatur in Celsiusgraden angegeben. In the following examples the temperature is given in degrees Celsius.

Beispiel 1 example 1

Eine gerührte Suspension von 7,45 g 2,21-Dichlor-6a-fluor- A stirred suspension of 7.45 g of 2,21-dichloro-6a-fluoro

17a-hydroxy-16a-methyl-pregna-l,4,9(ll)-trien-3,20-dion-17-propionat in 150 ml t-Butylalkohol wird unter Stickstoff nacheinander mit 7,55 ml einer 10%igen Perchlorsäurelösung und 2,15 ml t-Butylhypochlorit versetzt. Nach 2 Stunden s weiterem Rühren hat sich das Steroid vollständig gelöst, nach 5 Stunden scheidet sich jedoch wieder ein kristallines Material aus. Nun werden 80 ml Wasser zugegeben, noch etwas weitergerührt und dann abgenutscht. Das Nutschgut wird zunächst mit 45 ml Methanol/Wasser (1:1), dann gründlich mit Wasser io gewaschen und im Vakuum getrocknet. Das getrocknete Produkt wird anschliessend in Aceton gelöst und in der Wärme mit Tierkohle behandelt. Man versetzt sodann die filtrierte Lösung mit Toluol und dampft das Aceton im Vakuum ab, nutscht die ausgeschiedenen Kristalle ab, wäscht sie mit Toluol 15 nach und trocknet sie im Vakuumexsiccator, wodurch 2,9a,21-Trichlor-6 a-fluor-11 ß, 17 a-dihydroxy-16 a-methyl-pregna-l,4-dien-3,20-dion-17-propionat resultiert, welches bei 260-261° schmilzt. 17a-hydroxy-16a-methyl-pregna-l, 4,9 (ll) -triene-3,20-dione-17-propionate in 150 ml of t-butyl alcohol is treated in succession with nitrogen with 7.55 ml of a 10% perchloric acid solution and 2.15 ml of t-butyl hypochlorite were added. After 2 hours of stirring, the steroid has completely dissolved, but after 5 hours a crystalline material is again excreted. Now 80 ml of water are added, the mixture is stirred a little further and then suction filtered. The filter cake is first washed with 45 ml of methanol / water (1: 1), then thoroughly with water and dried in vacuo. The dried product is then dissolved in acetone and treated with animal charcoal in the heat. Then the filtered solution is mixed with toluene and the acetone is evaporated off in vacuo, the separated crystals are filtered off, washed with toluene 15 and dried in a vacuum desiccator, whereby 2,9a, 21-trichloro-6 a-fluoro-11β , 17 a-dihydroxy-16 a-methyl-pregna-l, 4-diene-3,20-dione-17-propionate results, which melts at 260-261 °.

20 20th

Beispiel 2 Example 2

In der im Beispiel 1 beschriebenen Weise wird 2,21-Dichlor-6a-fluor-17 a-hydroxy-16 a-methyl-pregna-1,4,9(11)-trien-3,20-dion-17-valerianat in amorphes 2,9a,21-Trichlor-25 6 a-fluor-11 ß, 17 a-dihydroxy-16a-methyl-pregna-1,4-dien-3,20-dion-17-valerianat umgewandelt. In the manner described in Example 1, 2,21-dichloro-6a-fluoro-17 a-hydroxy-16 a-methyl-pregna-1,4,9 (11) -triene-3,20-dione-17-valerianate converted into amorphous 2,9a, 21-trichloro-25 6 a-fluoro-11β, 17 a-dihydroxy-16a-methyl-pregna-1,4-diene-3,20-dione-17-valerianate.

B B

Claims (5)

622271 622271 PATENTANSPRÜCHE 1. Verfahren zur Herstellung von polyhalogenierten 11 ß, 17 a-Dihydroxy-16a-methyl-pregna-1,4-dien-3,20-dion-17-estern der allgemeinen Formel PATENT CLAIMS 1. Process for the preparation of polyhalogenated 11β, 17 a-dihydroxy-16a-methyl-pregna-1,4-diene-3,20-dione-17-esters of the general formula CH2X' H0„ ÇH3 j 0 CH2X 'H0 „ÇH3 j 0 \/ \l ci . 9^1 i . \ ^ \|/:\ / \ / •. • • A • \ / \ l ci. 9 ^ 1 i. \ ^ \ | /: \ / \ / •. • • A • •* "-OAc • * "-OAc (I) (I) ì i x i " *ch3 « /. • J ì i x i "* ch3« /. • J S \ S\ / S \ S \ / worin X Chlor, X Brom oder Chlor, und Ac eine von einer Carbonsäure abgeleitete Acylgruppe darstellt, dadurch gekennzeichnet, dass man eine Verbindung der allgemeinen Formel pi2x' wherein X represents chlorine, X bromine or chlorine, and Ac represents an acyl group derived from a carboxylic acid, characterized in that a compound of the general formula pi2x ' . CH_ CO . CH_ CO / \l / \ l I I. OAc OAc (II) (II) ci .n ci .n \ ? \i/ \ ✓ \ / % \? \ i / \ ✓ \ /% • • • • rw- • • • • rw- III 3 III 3 </V'V </ V'V worin Ac und X' die oben angegebene Bedeutung haben, mit unterchloriger Säure oder einem unterchlorige Säure abgebenden Mittel behandelt. wherein Ac and X 'have the meaning given above, treated with hypochlorous acid or a hypochlorous acid releasing agent. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man mit t-Butylhypochlorit in Anwesenheit von Perchlorsäure behandelt. 2. The method according to claim 1, characterized in that treatment with t-butyl hypochlorite in the presence of perchloric acid. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man eine Verbindung der Formel I herstellt, worin X und X' je für Chlor und Ac für den Acylrest einer niederaliphatischen Monocarbonsäure mit 2 bis 7 Kohlenstoffatomen steht. 3. The method according to claim 1 or 2, characterized in that one produces a compound of formula I, wherein X and X 'each represent chlorine and Ac for the acyl radical of a lower aliphatic monocarboxylic acid having 2 to 7 carbon atoms. 4. Verfahren gemäss einem der Ansprüche 1-3, dadurch gekennzeichnet, dass man eine Verbindung der Formel I herstellt, worin Ac für Propionyl steht. 4. The method according to any one of claims 1-3, characterized in that one produces a compound of formula I, wherein Ac is propionyl. 5. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man 2,9a,21-Trichlor-6a-fluor-llß,17a-dihy-droxy-16a-methyl-pregna-l,4-dien-3,20-dion-17-propionat herstellt. 5. The method according to claim 1 or 2, characterized in that 2.9a, 21-trichloro-6a-fluoro-11ß, 17a-dihydroxy-16a-methyl-pregna-l, 4-diene-3.20- produces dion-17-propionate.
CH841679A 1975-12-12 1979-09-18 Process for the preparation of polyhalosteroids CH622271A5 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1615175A CH621801A5 (en) 1975-12-12 1975-12-12 Process for the preparation of polyhalosteroids

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CH622271A5 true CH622271A5 (en) 1981-03-31

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ID=4414846

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Application Number Title Priority Date Filing Date
CH1615175A CH621801A5 (en) 1975-12-12 1975-12-12 Process for the preparation of polyhalosteroids
CH841579A CH622270A5 (en) 1975-12-12 1979-09-18 Process for the preparation of polyhalosteroids
CH841479A CH621802A5 (en) 1975-12-12 1979-09-18 Process for the preparation of polyhalosteroids
CH841679A CH622271A5 (en) 1975-12-12 1979-09-18 Process for the preparation of polyhalosteroids

Family Applications Before (3)

Application Number Title Priority Date Filing Date
CH1615175A CH621801A5 (en) 1975-12-12 1975-12-12 Process for the preparation of polyhalosteroids
CH841579A CH622270A5 (en) 1975-12-12 1979-09-18 Process for the preparation of polyhalosteroids
CH841479A CH621802A5 (en) 1975-12-12 1979-09-18 Process for the preparation of polyhalosteroids

Country Status (4)

Country Link
BE (1) BE849268A (en)
CH (4) CH621801A5 (en)
SE (1) SE423903B (en)
ZA (1) ZA767382B (en)

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ZA767382B (en) 1977-11-30
SE7613920L (en) 1977-06-13
CH621801A5 (en) 1981-02-27
CH622270A5 (en) 1981-03-31
BE849268A (en) 1977-06-10
SE423903B (en) 1982-06-14
CH621802A5 (en) 1981-02-27

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