CH531487A - Antiinflammatory pregnene-diones - Google Patents
Antiinflammatory pregnene-dionesInfo
- Publication number
- CH531487A CH531487A CH860172A CH860172A CH531487A CH 531487 A CH531487 A CH 531487A CH 860172 A CH860172 A CH 860172A CH 860172 A CH860172 A CH 860172A CH 531487 A CH531487 A CH 531487A
- Authority
- CH
- Switzerland
- Prior art keywords
- beta
- pregnene
- acid
- sep
- methylene
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D9/00—Recording measured values
- G01D9/28—Producing one or more recordings, each recording being of the values of two or more different variables
- G01D9/30—Producing one or more recordings, each recording being of the values of two or more different variables there being a separate recording element for each variable, e.g. multiple-pen recorder
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J53/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by condensation with a carbocyclic rings or by formation of an additional ring by means of a direct link between two ring carbon atoms, including carboxyclic rings fused to the cyclopenta(a)hydrophenanthrene skeleton are included in this class
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
- G01D18/00—Testing or calibrating apparatus or arrangements provided for in groups G01D1/00 - G01D15/00
-
- G—PHYSICS
- G07—CHECKING-DEVICES
- G07C—TIME OR ATTENDANCE REGISTERS; REGISTERING OR INDICATING THE WORKING OF MACHINES; GENERATING RANDOM NUMBERS; VOTING OR LOTTERY APPARATUS; ARRANGEMENTS, SYSTEMS OR APPARATUS FOR CHECKING NOT PROVIDED FOR ELSEWHERE
- G07C3/00—Registering or indicating the condition or the working of machines or other apparatus, other than vehicles
- G07C3/08—Registering or indicating the production of the machine either with or without registering working or idle time
- G07C3/12—Registering or indicating the production of the machine either with or without registering working or idle time in graphical form
-
- G—PHYSICS
- G08—SIGNALLING
- G08G—TRAFFIC CONTROL SYSTEMS
- G08G1/00—Traffic control systems for road vehicles
- G08G1/01—Detecting movement of traffic to be counted or controlled
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- 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)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Trihydroxypregnene-3,20-diones (I) and especially 11 beta, 17 alpha, 21-trihydroxy-15, 16 beta-methylene-pregnene (4)-(and pregna-1,4-diene)-3,20-dione, for use as anti-inflammatories. R6 and R9 independently are H, halogen, R17, R21 independently are OH or O-acyl; Z is CO or beta-CH2OH. Preparation of (I) and 1,2-dehydro-deriv. by numerous methods e.g. (a) microbiological 11-hydroxylation of (I) (Z=CH2); (b) 1,2-dehydrogenation of a cmpd. (I); (c) adding HOCl or HOBr to the 9,11-double bond a cmpd. (I) or its, 1,2-dehydro-derivs. (Z = HC). In an example 11 beta, 17 alpha-21-trihydroxy-15,16 beta-methylene-pregnene (4)-3,20-dione, m.p. 219-221 degrees is obtained by microbiological hydroxylation of 17 alpha, 21-dihydroxy-15,16 beta-methylene-pregnene (4)-3,20-dione using Coniothyrium hellebori as organism.
Description
Verfahren zur Herstellung neuer Steroide der Pregnanreihe
Die Erfindung betrifft ein neuer Steroide der Formel
EMI1.1
<tb> Verfahren <SEP> zur <SEP> Herstellung <SEP> OH2 <SEP> R21
<tb> <SEP> 2 <SEP> 21
<tb> <SEP> H,C
<tb> <SEP> 0
<tb> <SEP> 1370
<tb> <SEP> ) <SEP> 1
<tb> <SEP> R
<tb> <SEP> R6
<tb> in der R6 und Rg unabhängig voneinander Wasserstoff, Fluor, Chlor oder Brom, R17 Hydroxy oder Acyloxy und R21 Acyloxy bedeuten bzw. deren 1,2-Dehydroderivaten.
Eine Acyloxygruppe enthält vorzugsweise den Rest einer gesättigten oder ungesättigten aliphatischen oder cycloaliphatischen, einer araliphatischen oder aromatischen Carbonsäure mit bis zu 20, vorzugsweise bis zu 12 C-Atomen. Beispiele solcher Säuren sind Ameisensäure, Essigsäure, Pivalinsäure, Propionsäure, Buttersäure, Capronsäure, Önanthsäure, Ölsäure, Palmitinsäure, Stearinsäure, Bernsteinsäure, Malonsäure, Fumarsäure, Zitronensäure, Cyclohexylpropionsäure, Phenylessigsäure und Benzoesäure.
Das erfindungsgemässe Verfahren ist dadurch gekennzeichnet, dass man eine Verbindung der Formel
EMI1.2
in der R6 und Rg die obige Bedeutung haben, oder ein entsprechendes 1,2-Dehydroderivat davon mindestens in der Stellung 21 acyliert.
Die erfindungsgemässe Acylierung kann in an sich bekannter Weise durch Behandlung mit einem Acylierungsmittel, wie einem Acylchlorid oder -anhydrid, z.B. Acetylchlorid, in Gegenwart eines säurebindenden Mittels, wie Pyridin, erfolgen.
Die Acylierung einer 17-Hydroxygruppe wird zweckmässig in Gegenwart eines sauren Katalysators, wie p-Toluolsulfonsäure, vorgenommen.
Zur Herstellung der Ausgangsstoffe kann auf die belgische Patentschrift Nr. 760392 verwiesen werden.
Die erfindungsgemäss erhältlichen Steroide sind endocrin, insbesondere antiinflammatorisch, wirksam. Sie können als Heilmittel in Form pharmazeutischer Präparate Verwendung finden, welche sie in Mischung mit einem für die enterale, perkutane oder parenterale Applikation geeigneten pharmazeutischen, organischen oder anorganischen inerten Trägermaterial enthalten. Die pharmazeutischen Präparate können in fester, in halbfester oder in flüssiger Form vorliegen. Gegebenenfalls enthalten sie Hilfsstoffe, wie Konservierungs-, Stabilisierungs-, Netz- oder Emulgiermittel, Salze zur Veränderung des osmotischen Druckes oder Puffer. Sie können auch noch andere therapeutisch wertvolle Stoffe enthalten.
Beispiel
0,5 g 17,21-Dihydroxy-15ss,16ss-methylen-pregn-4-en- 3,11,20-trion wurden mit 5 ml Pyridin und 5 ml Acetanhydrid 2 Stunden bei Raumtemperatur stehengelassen. Zur Aufarbeitung goss man auf Eiswasser und extrahierte mit Äther. Der Extrakt wurde mit Wasser neutral gewaschen, mit Na2SO4 getrocknet und im Vakuum eingedampft. Den Rückstand kristallisierte man aus Aceton-Hexan um und erhielt reines 21 -Acetoxy- 17-hydroxy- 15ss,1 6ss-methylen-pregn-4 en-3,11,20-trion vom Schmelzpunkt 259,5-262,5 .
[ai25 = +1900 (c = 0,1 in Dioxan)
Process for the production of new steroids of the Pregnan range
The invention relates to a new steroid of the formula
EMI1.1
<tb> Process <SEP> for <SEP> production <SEP> OH2 <SEP> R21
<tb> <SEP> 2 <SEP> 21
<tb> <SEP> H, C
<tb> <SEP> 0
<tb> <SEP> 1370
<tb> <SEP>) <SEP> 1
<tb> <SEP> R
<tb> <SEP> R6
<tb> in which R6 and Rg are each independently hydrogen, fluorine, chlorine or bromine, R17 is hydroxy or acyloxy and R21 is acyloxy or their 1,2-dehydro derivatives.
An acyloxy group preferably contains the residue of a saturated or unsaturated aliphatic or cycloaliphatic, an araliphatic or aromatic carboxylic acid having up to 20, preferably up to 12, carbon atoms. Examples of such acids are formic acid, acetic acid, pivalic acid, propionic acid, butyric acid, caproic acid, enanthic acid, oleic acid, palmitic acid, stearic acid, succinic acid, malonic acid, fumaric acid, citric acid, cyclohexylpropionic acid, phenylacetic acid and benzoic acid.
The inventive method is characterized in that a compound of the formula
EMI1.2
in which R6 and Rg have the above meaning, or a corresponding 1,2-dehydro derivative thereof is acylated at least in the 21-position.
The acylation according to the invention can be carried out in a manner known per se by treatment with an acylating agent such as an acyl chloride or anhydride, e.g. Acetyl chloride, in the presence of an acid binding agent such as pyridine.
The acylation of a 17-hydroxy group is expediently carried out in the presence of an acidic catalyst, such as p-toluenesulphonic acid.
For the preparation of the starting materials, reference can be made to Belgian patent specification No. 760392.
The steroids obtainable according to the invention are endocrine, in particular anti-inflammatory, effective. They can be used as remedies in the form of pharmaceutical preparations which they contain as a mixture with a pharmaceutical, organic or inorganic inert carrier material suitable for enteral, percutaneous or parenteral administration. The pharmaceutical preparations can be in solid, semi-solid or liquid form. They may contain auxiliaries, such as preservatives, stabilizers, wetting agents or emulsifiers, salts to change the osmotic pressure or buffers. They can also contain other therapeutically valuable substances.
example
0.5 g of 17,21-dihydroxy-15ss, 16ss-methylene-pregn-4-ene-3,11,20-trione were allowed to stand with 5 ml of pyridine and 5 ml of acetic anhydride for 2 hours at room temperature. For work-up, it was poured into ice water and extracted with ether. The extract was washed neutral with water, dried with Na2SO4 and evaporated in vacuo. The residue was recrystallized from acetone-hexane and pure 21-acetoxy-17-hydroxy-15ss, 16ss-methylene-pregn-4en-3,11,20-trione with a melting point of 259.5-262.5 was obtained.
[ai25 = +1900 (c = 0.1 in dioxane)
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH860172A CH531487A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH860172A CH531487A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH1883169A CH525872A (en) | 1969-12-17 | 1969-12-17 | Process for the production of new steroids of the Pregnan range |
Publications (1)
Publication Number | Publication Date |
---|---|
CH531487A true CH531487A (en) | 1972-12-15 |
Family
ID=4435537
Family Applications (11)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH859972A CH531490A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH859772A CH531485A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860172A CH531487A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH859872A CH529734A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860272A CH531492A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860672A CH531486A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860372A CH531493A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860472A CH531494A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860072A CH531491A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH1883169A CH525872A (en) | 1969-12-17 | 1969-12-17 | Process for the production of new steroids of the Pregnan range |
CH860572A CH531495A (en) | 1969-12-17 | 1970-10-30 | Antiinflammatory pregnene-diones |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH859972A CH531490A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH859772A CH531485A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
Family Applications After (8)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH859872A CH529734A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860272A CH531492A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860672A CH531486A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860372A CH531493A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860472A CH531494A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH860072A CH531491A (en) | 1969-12-17 | 1969-12-17 | Antiinflammatory pregnene-diones |
CH1883169A CH525872A (en) | 1969-12-17 | 1969-12-17 | Process for the production of new steroids of the Pregnan range |
CH860572A CH531495A (en) | 1969-12-17 | 1970-10-30 | Antiinflammatory pregnene-diones |
Country Status (17)
Country | Link |
---|---|
JP (1) | JPS4920774B1 (en) |
AT (8) | AT315396B (en) |
BE (1) | BE760392A (en) |
CA (1) | CA955931A (en) |
CH (11) | CH531490A (en) |
DE (1) | DE2061183C3 (en) |
ES (2) | ES386503A1 (en) |
FI (1) | FI47484C (en) |
FR (1) | FR2081369B1 (en) |
GB (1) | GB1276419A (en) |
HU (1) | HU162802B (en) |
IE (1) | IE34816B1 (en) |
IL (1) | IL35790A (en) |
NL (1) | NL7016761A (en) |
NO (1) | NO135528C (en) |
YU (1) | YU34700B (en) |
ZA (1) | ZA708096B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2740344A (en) * | 1951-12-05 | 1956-04-03 | Messrs Lumoprint Zindler K G | Device for treating directly exposed photopapers |
DE2453823C2 (en) * | 1974-11-11 | 1984-08-09 | Schering AG, 1000 Berlin und 4709 Bergkamen | 11β, 17α-dihydroxy-15α, 16α-methylene-1,4-pregnadiene-3,20-dione |
JPS56109115A (en) * | 1980-12-05 | 1981-08-29 | Fukui Kikai Kk | Controlling method for feeder for strip material |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3438975A (en) * | 1966-07-01 | 1969-04-15 | Syntex Corp | 15alpha,16alpha-methylene pregnanes and 19-nor-pregnanes |
CH503714A (en) * | 1968-04-22 | 1971-02-28 | Hoffmann La Roche | Hormone active steroids |
-
1969
- 1969-12-17 CH CH859972A patent/CH531490A/en not_active IP Right Cessation
- 1969-12-17 CH CH859772A patent/CH531485A/en not_active IP Right Cessation
- 1969-12-17 CH CH860172A patent/CH531487A/en not_active IP Right Cessation
- 1969-12-17 CH CH859872A patent/CH529734A/en not_active IP Right Cessation
- 1969-12-17 CH CH860272A patent/CH531492A/en not_active IP Right Cessation
- 1969-12-17 CH CH860672A patent/CH531486A/en not_active IP Right Cessation
- 1969-12-17 CH CH860372A patent/CH531493A/en not_active IP Right Cessation
- 1969-12-17 CH CH860472A patent/CH531494A/en not_active IP Right Cessation
- 1969-12-17 CH CH860072A patent/CH531491A/en not_active IP Right Cessation
- 1969-12-17 CH CH1883169A patent/CH525872A/en not_active IP Right Cessation
-
1970
- 1970-10-30 CH CH860572A patent/CH531495A/en not_active IP Right Cessation
- 1970-11-14 IE IE1600/70A patent/IE34816B1/en unknown
- 1970-11-16 NL NL7016761A patent/NL7016761A/xx unknown
- 1970-11-26 FI FI703190A patent/FI47484C/en active
- 1970-11-30 ZA ZA708096*A patent/ZA708096B/en unknown
- 1970-12-02 HU HUHO1335A patent/HU162802B/hu unknown
- 1970-12-04 IL IL35790A patent/IL35790A/en unknown
- 1970-12-07 YU YU2980/70A patent/YU34700B/en unknown
- 1970-12-10 CA CA100,261A patent/CA955931A/en not_active Expired
- 1970-12-11 DE DE2061183A patent/DE2061183C3/en not_active Expired
- 1970-12-15 GB GB59497/70A patent/GB1276419A/en not_active Expired
- 1970-12-16 JP JP45111944A patent/JPS4920774B1/ja active Pending
- 1970-12-16 AT AT675472A patent/AT315396B/en not_active IP Right Cessation
- 1970-12-16 FR FR7045351A patent/FR2081369B1/fr not_active Expired
- 1970-12-16 NO NO4845/70A patent/NO135528C/no unknown
- 1970-12-16 AT AT675672A patent/AT315397B/en not_active IP Right Cessation
- 1970-12-16 AT AT675272A patent/AT316771B/en active
- 1970-12-16 AT AT675572A patent/AT316773B/en not_active IP Right Cessation
- 1970-12-16 ES ES386503A patent/ES386503A1/en not_active Expired
- 1970-12-16 AT AT675372A patent/AT316772B/en not_active IP Right Cessation
- 1970-12-16 AT AT675772A patent/AT316774B/en active
- 1970-12-16 AT AT675172A patent/AT315395B/en not_active IP Right Cessation
- 1970-12-16 AT AT1130470A patent/AT308292B/en not_active IP Right Cessation
- 1970-12-16 BE BE760392A patent/BE760392A/en unknown
-
1972
- 1972-06-10 ES ES403723A patent/ES403723A2/en not_active Expired
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE3243482A1 (en) | NEW 6 (ALPHA) METHYL CORTICOIDS, THEIR PRODUCTION AND USE | |
CH531487A (en) | Antiinflammatory pregnene-diones | |
CH625809A5 (en) | Process for the preparation of polyhalogenated steroids | |
CH505080A (en) | Hormone active steroids | |
DE1793600A1 (en) | Process for making steroid compounds | |
DE2144405A1 (en) | Saponification of pregnane series esters - using silica gel | |
DE1568175A1 (en) | Process for the manufacture of new steroids | |
DE2448662C2 (en) | 6α-Fluoro-16α-methyl-1,4,8-pregnatriene-3,20-dione derivatives, processes for their preparation and pharmaceuticals containing them | |
CH527808A (en) | 9beta 10alpha-steroids progestatives | |
AT361644B (en) | METHOD FOR PRODUCING NEW D-HOMOSTEROIDS | |
AT231618B (en) | Process for the preparation of 1, 4, 9 (11) -unsaturated compounds of the pregnane series | |
AT333993B (en) | PROCESS FOR MANUFACTURING NEW D-HOMO STEROIDS OF THE PREGNAN SERIES | |
DE1418684C (en) | Process for the production of delta 4 or delta 1.4 3.20 Dioxo 17 alpha acyloxy 16 alpha methyl 6 alpha fluor or 6 alpha chlorpregnenen | |
AT336205B (en) | PROCESS FOR MANUFACTURING NEW D-HOMO STEROIDS OF THE PREGNAN SERIES | |
AT336204B (en) | PROCESS FOR MANUFACTURING NEW D-HOMO STEROIDS OF THE PREGNAN SERIES | |
CH553759A (en) | PROCESS FOR THE PREPARATION OF NEW 4-CHLORO-1,2 (ALPHA) -METHYLENE (DELTA) 4,6-PREGNADIEN-17 (ALPHA) -OL-3,20-Dione, OR ITS 17ESTER. | |
DE1113453B (en) | Process for the production of substitution products of Reichsteins-Substance-S or their 21-acylates | |
CH606114A5 (en) | 9-Alpha-11-beta-dihalo-D-homo-pregn-4-en-3,20-diones | |
CH499505A (en) | Steroids of the partial formula (I):- where R1 is halogen (at wt.100) or alkyl Q is oxo or 1,2-alkylenedioxy (2-4C) M is the remainder of the | |
CH606115A5 (en) | 9-Alpha-11-beta-dihalo-D-homo-pregn-4-en-3,20-diones | |
DE1168902B (en) | Process for the preparation of therapeutically active steroid compounds | |
DE1193041B (en) | Process for making delta 7, delta 7.9, (11), delta 7.9, (11), 16, delta 7, delta 8 or delta 8.16 steroids | |
DE1937195A1 (en) | Acetals or ketals of 16alpha, 17alpha-dihydroxysteroids and processes for their preparation | |
DE1048915B (en) | Process for the preparation of 6-methyl-9ª ‡, 21-difluoro-11ª ‰, 17ª ‡ -dioxy-1,4-pregnadiene-3,20-dione and its 11-keto analogues | |
CH507925A (en) | 19-alkyl steroids |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PL | Patent ceased |