DE2264001C2 - 11β-Hydroxy-2',2'-dimethyl-1,4-pregnadieno[17,16α-d]-1',3'-oxathiolan-3,20-dion - Google Patents
11β-Hydroxy-2',2'-dimethyl-1,4-pregnadieno[17,16α-d]-1',3'-oxathiolan-3,20-dionInfo
- Publication number
- DE2264001C2 DE2264001C2 DE2264001A DE2264001A DE2264001C2 DE 2264001 C2 DE2264001 C2 DE 2264001C2 DE 2264001 A DE2264001 A DE 2264001A DE 2264001 A DE2264001 A DE 2264001A DE 2264001 C2 DE2264001 C2 DE 2264001C2
- Authority
- DE
- Germany
- Prior art keywords
- dione
- hydroxy
- dimethyl
- pregnadieno
- oxathiolane
- 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.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims 3
- 201000004624 Dermatitis Diseases 0.000 claims 1
- 206010012442 Dermatitis contact Diseases 0.000 claims 1
- 206010012455 Dermatitis exfoliative Diseases 0.000 claims 1
- 201000009053 Neurodermatitis Diseases 0.000 claims 1
- 208000008350 Pruritus Vulvae Diseases 0.000 claims 1
- 201000004681 Psoriasis Diseases 0.000 claims 1
- 206010056530 Vulvovaginal pruritus Diseases 0.000 claims 1
- 208000010668 atopic eczema Diseases 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 208000010247 contact dermatitis Diseases 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 230000000144 pharmacologic effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000005457 ice water Substances 0.000 description 6
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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
- C07J7/0005—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21
- C07J7/001—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group
- C07J7/004—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group substituted in position 17 alfa
- C07J7/005—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group substituted in position 17 alfa substituted in position 16
- C07J7/006—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group substituted in position 17 alfa substituted in position 16 by a hydroxy group free esterified or etherified
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J13/00—Normal steroids containing carbon, hydrogen, halogen or oxygen having a carbon-to-carbon double bond from or to position 17
- C07J13/005—Normal steroids containing carbon, hydrogen, halogen or oxygen having a carbon-to-carbon double bond from or to position 17 with double bond in position 16 (17)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J31/00—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring
- C07J31/003—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring the S atom directly linked to a ring carbon atom of the cyclopenta(a)hydrophenanthrene skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J41/00—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring
- C07J41/0033—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005
- C07J41/005—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005 the 17-beta position being substituted by an uninterrupted chain of only two carbon atoms, e.g. pregnane derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
- C07J71/0005—Oxygen-containing hetero ring
- C07J71/001—Oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
- C07J71/0073—Sulfur-containing hetero ring
- C07J71/0089—Sulfur-containing hetero ring containing sulfur and oxygen
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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
1 g /p
werden mit 600 mg Zinkstaub in 40 ml Eisessig bei Raumtemperatur 3 Stunden gerührt Nach Abfiltrieren
des Zinkstaubs wird die Lösung in Eiswasser eingerührt. Der Niederschlag wird abgesaugt, getrocknet und aus
Aceton/Hexan umkristallisiert Es werden 383 mg 1 l/?-Acetoxy-l,4,16-pregnatrien-3,20-dion vom
Schmelzpunkt 239—2410C erhalten.
Eine Lösung von 1 g lip-Acetoxy-lAlo-pregnatrien-3,20-dion
in einem Gemisch aus 75 ml tert.-Butanol und 15 ml Wasser wird mit 0,2 ml 70%iger Perchlorsäure
versetzt und auf 0° abgekühlt. Dann wird 1 g N-Bromsuccinimid zugesetzt und 5 Stunden bei Raumtemperatur
gerührt. Die Reaktionslösung wird in Eiswasser eingerührt, der Niederschlag wird abgesaugt
und in Methylenchlorid aufgenommen. Die Lösung wird nacheinander mit Natriumthiosulfatlösung und Wasser
gewaschen. Nach Umkristallisation aus Aceton/Hexan
werden 490 mg y
pregnacien-3,20-dion vom Schmelzpunkt 156° C (Zers.)
erhalten.
1.7 g n-Brom-löjS-hydroxy-ll/i-acetoxy-M-pregnadien-3,20"dion
werden in 15 ml Dimethylformamid mit 1,5 g Kaliumacetat 4 Stunden bei 60° gerührt Das
Reaktionsgemisch wird in Eiswasser eingerührt, der Niederschlag wird abgesaugt, getrocknet und aus
Aceton/Hexan umkristallisiert. Es werden 1,0 g
ίο 1 l^
dion vom Schmelzpunkt 175 — 176° C erhalten.
660 mg j
dien-3,20-dion werden in 50 ml Eisessig mit 500 mg p-Toluolsulfonsäure versetzt Die Lösung wird mit
Schwefelwasserstoff gesättigt und 12 Stunden bei Raumtemperatur stehengelassen. Das Reaktionsgemisch
wird in Eiswasser eingerührt, der Niederschlag wird abgesaugt und getrocknet. Nach Chromatographieren
an Kieselgel mit 6,4—7,2% Aceton/Methylenchlorid und Umkristallisation aus Aceton/Hexan
werden 153 mg 16/9- Hydroxy-11 ß-acetoxy-17-mercapto-l,4-pregnadien-3,20-dion
vom Schmelzpunkt 171-173-C erhalten.
3,7 g löjS-Hydroxy-lljS-acetoxy-Uix-mercapto-l^-
pregnadien-3,20-dion werden in 50 ml Aceton mit 1 ml 70%iger Perchlorsäure 1 Stunde bei Raumtemperatur
stehengelassen. Das Reaktionsprodukt wird in Eiswasser gegeben, der Niederschlag wird abgesaugt und
getrocknet Nach Chromatographieren an Kieselgel mit 8—10% Aceton/Methylenchlorid werden 1,7 g
llj?-Acetoxy-2',2'-dimethyl-l,4-pregnadieno[17,16oc-d]-l',3'-oxathiolan-3,20-dion
als öl erhalten.
1,6 g 1 ljS-Acetoxy^'^'-dimethyl-M-pregnadie-
no[17,16«-d]-l',3'-oxathiolan-3,20-dion werden in 50 ml 0,2-n-methanolischer Kaliumhydroxidlösung 12 Stunden
bei Raumtemperatur unter Stickstoff stehengelassen. Die Reaktionslösung wird in chlorwasserstoffhaltiges
Eiswasser eingerührt. Das Reaktionsprodukt wird mit Methylenchlorid extrahiert, die Lösung wird neutral
gewaschen. Nach Chromatographieren an Kieselgel mit 5—8% Aceton/Methylenchlorid und Umkristallisation
aus Aceton/Hexan werden 700 mg ll^-Hydroxy-2',2'-
dimethyl-1,4-pregnadieno[l 7,16«-d]-1 ',3'-oxathiolan-3,20-dion
vom Schmelzpunkt 297° C (Zers.) erhalten.
Claims (1)
- Patentanspruch:1 l/?-Hydroxy-2\2'-dimethyl-l ,4-pregnadieno-[17,16a-d]l ',3'-oxathioIan-^,20-dion,Die Erfindung betrifft die in dem Patentanspruch gekennzeichnete Verbindung, welche sich im Vergleich zu strukturanalogen Verbindungen durch eine überlegene pharmakologische Wirksamkeit auszeichnet (Siehe die entsprechende US-Patentschrift 38 94 004.)Die neue Verbindung ist — in Kombination mit den in der galenischen Pharmazie üblichen Trägerstoffen — gut geeignet zur Behandlung von z. B. Kontaktdermatitis, Ekzemen der verschiedensten Art, Neurodermatitis, Erythrodermie, Verbrennungen, Pruritus vulvae et ani, Psoriasis etc.Das nachfolgende Ausführungsbeispiel dient zur Erläuterung der Synthese der erfindungsgemäßen Verbindung.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2264001A DE2264001C2 (de) | 1972-12-22 | 1972-12-22 | 11β-Hydroxy-2',2'-dimethyl-1,4-pregnadieno[17,16α-d]-1',3'-oxathiolan-3,20-dion |
| CH1729773A CH609066A5 (de) | 1972-12-22 | 1973-12-10 | |
| DK688673A DK132123C (da) | 1972-12-22 | 1973-12-18 | Analogifremgangsmade til fremstilling af 11-oxygenerede pregnen-(17,16alfa-d)-1',3'-oxathiolaner |
| GB5877373A GB1457439A (en) | 1972-12-22 | 1973-12-19 | 11-oxygenated pregneno-17,16a-d-1,3,-oxathiolans |
| US426600A US3894004A (en) | 1972-12-22 | 1973-12-20 | Novel 11-oxygenated pregneno (17,16{60 -D)-1,3-oxathiolanes and process for the preparation thereof |
| DD175540A DD108530A5 (de) | 1972-12-22 | 1973-12-20 | |
| JP49004709A JPS4994659A (de) | 1972-12-22 | 1973-12-21 | |
| BE139170A BE808984A (fr) | 1972-12-22 | 1973-12-21 | Pregneno(17,16alpha-d)-1', 3'-oxathiolanes 11-oxygenes et leur procede de preparation |
| NL7317655A NL7317655A (de) | 1972-12-22 | 1973-12-22 | |
| FR7346232A FR2211258B1 (de) | 1972-12-22 | 1973-12-26 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2264001A DE2264001C2 (de) | 1972-12-22 | 1972-12-22 | 11β-Hydroxy-2',2'-dimethyl-1,4-pregnadieno[17,16α-d]-1',3'-oxathiolan-3,20-dion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2264001A1 DE2264001A1 (de) | 1974-07-04 |
| DE2264001C2 true DE2264001C2 (de) | 1982-08-26 |
Family
ID=5865746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2264001A Expired DE2264001C2 (de) | 1972-12-22 | 1972-12-22 | 11β-Hydroxy-2',2'-dimethyl-1,4-pregnadieno[17,16α-d]-1',3'-oxathiolan-3,20-dion |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US3894004A (de) |
| JP (1) | JPS4994659A (de) |
| BE (1) | BE808984A (de) |
| CH (1) | CH609066A5 (de) |
| DD (1) | DD108530A5 (de) |
| DE (1) | DE2264001C2 (de) |
| DK (1) | DK132123C (de) |
| FR (1) | FR2211258B1 (de) |
| GB (1) | GB1457439A (de) |
| NL (1) | NL7317655A (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5792758A (en) * | 1995-12-08 | 1998-08-11 | G. D. Searle & Co. | Steroid nitrite ester derivatives useful as anti-inflammatory drugs |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3170920A (en) * | 1962-08-10 | 1965-02-23 | Shionogi & Co | 3-oxo-16beta-mercapto-17beta-hydroxy-5alpha-androstane-16-17 acetonides and the process for the production thereof |
| US3770726A (en) * | 1972-03-16 | 1973-11-06 | Schering Ag | Pregnano717,16alpha-d)-1',3'-oxathiolanes |
-
1972
- 1972-12-22 DE DE2264001A patent/DE2264001C2/de not_active Expired
-
1973
- 1973-12-10 CH CH1729773A patent/CH609066A5/xx not_active IP Right Cessation
- 1973-12-18 DK DK688673A patent/DK132123C/da active
- 1973-12-19 GB GB5877373A patent/GB1457439A/en not_active Expired
- 1973-12-20 DD DD175540A patent/DD108530A5/xx unknown
- 1973-12-20 US US426600A patent/US3894004A/en not_active Expired - Lifetime
- 1973-12-21 BE BE139170A patent/BE808984A/xx unknown
- 1973-12-21 JP JP49004709A patent/JPS4994659A/ja active Pending
- 1973-12-22 NL NL7317655A patent/NL7317655A/xx not_active Application Discontinuation
- 1973-12-26 FR FR7346232A patent/FR2211258B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2211258B1 (de) | 1976-09-03 |
| FR2211258A1 (de) | 1974-07-19 |
| DK132123C (da) | 1976-03-29 |
| CH609066A5 (de) | 1979-02-15 |
| DE2264001A1 (de) | 1974-07-04 |
| JPS4994659A (de) | 1974-09-09 |
| NL7317655A (de) | 1974-06-25 |
| DK132123B (da) | 1975-10-27 |
| DD108530A5 (de) | 1974-09-20 |
| GB1457439A (en) | 1976-12-01 |
| BE808984A (fr) | 1974-06-21 |
| US3894004A (en) | 1975-07-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OD | Request for examination | ||
| D2 | Grant after examination | ||
| 8339 | Ceased/non-payment of the annual fee |