CH211649A - Process for the preparation of a new enol derivative containing the sterol core. - Google Patents
Process for the preparation of a new enol derivative containing the sterol core.Info
- Publication number
- CH211649A CH211649A CH211649DA CH211649A CH 211649 A CH211649 A CH 211649A CH 211649D A CH211649D A CH 211649DA CH 211649 A CH211649 A CH 211649A
- Authority
- CH
- Switzerland
- Prior art keywords
- preparation
- new
- derivative containing
- acid
- cholestenone
- Prior art date
Links
- 150000002085 enols Chemical class 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 4
- 125000002328 sterol group Chemical group 0.000 title claims description 3
- -1 enol benzoate Chemical class 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- GGCLNOIGPMGLDB-GYKMGIIDSA-N cholest-5-en-3-one Chemical compound C1C=C2CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 GGCLNOIGPMGLDB-GYKMGIIDSA-N 0.000 claims description 3
- NYOXRYYXRWJDKP-UHFFFAOYSA-N cholestenone Natural products C1CC2=CC(=O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 NYOXRYYXRWJDKP-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001225 therapeutic effect Effects 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 4
- 229930182558 Sterol Natural products 0.000 description 3
- 150000003432 sterols Chemical class 0.000 description 3
- 235000003702 sterols Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NYTOUQBROMCLBJ-UHFFFAOYSA-N Tetranitromethane Chemical compound [O-][N+](=O)C([N+]([O-])=O)([N+]([O-])=O)[N+]([O-])=O NYTOUQBROMCLBJ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung eines neuen den Sterinkern enthaltenden Enold-erivates. Es wurde gefunden, dass man überraschen derweise zu neuen den Sterinkern enthalten den Enolderivaten gelangen kann, wenn man auf den Sterinkern enthaltende 3-Ketoverbin- dungen Acylierungsmittel in An- oder Ab wesenheit säurebindenderMitteleinwirken lässt.
Als Acylierungsmittel kommen z. B. orga nische oder anorganische Säurehalogenide oder -anhydride in Betracht. Bei Anwendung orga nischer Säurehalogenide können organische Ester der Enole und/oder deren Halogenide entstehen. Erstere entstehen vorzugsweise beim Arbeiten im offenen Gefäss, wobei der gebildete Halogenwasserstoff entweichen kann, letztere vorwiegend in geschlossenem Gefäss.
So gewinnt man zum Beispiel durch Ein wirkung von Benzoylchlorid auf d°,5-Chole- stenon-(3) entweder den Benzoesäureester des Enols der Formel I oder dessen Chlorid der Formel II.
EMI0001.0026
Gegenstand des vorliegenden Patentes bildet ein Verfahren zur Darstellung eines neuen den Sterinkern enthaltenden Enolderi- vates, welches dadurch gekennzeichnet ist, dass man auf 44,5-Cholestenon-(3) ein benzo- ylierendes Mittel einwirken lässt.
Das so gewonnene Enolbenzoat des Chole- stenons bildet Kristalle vom F. 116-1170. Mit Tetranitromethan färbt es sich intensiv rot.
Das neue Enolderivat soll therapeutische Verwendung finden oder als Zwischenprodukt zur Gewinnung therapeutisch wirksamer Ver bindungen dienen.
<I>Beispiel:</I> 10 Teile dr@'-Cholestenorr-(3) werden mit 8 Teilen Benzoylchlorid in 50 Teilen reinem Benzin (Siedepunkt<B>1000)</B> während 40 Stun den gekocht. Nach möglichst weitgehendem Abdestillieren des Benzins und Benzoyl- chlorides im Vakuum wird das Reaktions- produktmit'/2 n-Natronlauge auf dem \Vasser- bad erwärmt, hierauf mit Wasser verdünnt und in Äther aufgenommen.
Die Ätherlösung wird mit Natronlauge und Wasser gewaschen und über Natriumsulfat getrocknet. Das Enol- benzoat des Cholestenons kristallisiert zum Teil beim Verdampfen des Lösungsmittels aus; es wird mit wenig Aceton zu einem Brei angerührt, abgenutscht und auf der Nutsche mit kaltem Aceton nachgewaschen, bis dieses farblos abläuft. So können 9,1 Teile farbloser Ester vom F. 116-117 erhalten werden. Aus der Mutterlauge lässt sich noch eine weitere Menge gewinnen. Mit Tetranitromethan färbt sich der Enolester intensiv rot.
Die Reaktion kann auch in Abwesenheit eines Lösungsmittels, zum Beispiel durch Er hitzen von Cholesterron mit Benzoylchlorid auf<B>160-1701</B> vorgenommen werden. Ferner kann man zur Bindung der entstehenden Salz säure zum Beispiel eitre tertiäre Base, wie Pyridin und dergleichen, zugeben.
Process for the preparation of a new enold derivative containing the sterol core. It has been found that, surprisingly, new enol derivatives containing the sterol nucleus can be obtained if acylating agents are allowed to act on the sterol nucleus containing 3-keto compounds in the presence or absence of acid-binding agents.
As acylating agents such. B. organic or inorganic acid halides or anhydrides into consideration. When using organic acid halides, organic esters of the enols and / or their halides can be formed. The former arise primarily when working in an open vessel, whereby the hydrogen halide formed can escape, the latter predominantly in a closed vessel.
For example, the action of benzoyl chloride on d °, 5-cholestenone- (3) gives either the benzoic acid ester of the enol of the formula I or its chloride of the formula II.
EMI0001.0026
The subject of the present patent is a process for the preparation of a new enol derivative containing the sterol nucleus, which is characterized in that a benzoylating agent is allowed to act on 44,5-cholestenone- (3).
The enol benzoate of cholestenone obtained in this way forms crystals of F. 116-1170. With tetranitromethane it turns an intense red color.
The new enol derivative is intended to be used therapeutically or to serve as an intermediate product for obtaining therapeutically effective compounds.
<I> Example: </I> 10 parts of dr @ '- Cholestenorr- (3) are boiled with 8 parts of benzoyl chloride in 50 parts of pure gasoline (boiling point <B> 1000) </B> for 40 hours. After the gasoline and benzoyl chloride have been distilled off as much as possible in vacuo, the reaction product is heated with 1/2 N sodium hydroxide solution in the water bath, then diluted with water and taken up in ether.
The ether solution is washed with sodium hydroxide solution and water and dried over sodium sulfate. The enol benzoate of cholestenone partially crystallizes out on evaporation of the solvent; it is mixed with a little acetone to a paste, suction filtered and washed on the suction funnel with cold acetone until it runs colorless. 9.1 parts of colorless ester of F. 116-117 can be obtained in this way. A further amount can be obtained from the mother liquor. With tetranitromethane, the enol ester turns an intense red color.
The reaction can also be carried out in the absence of a solvent, for example by heating cholesterron with benzoyl chloride to <B> 160-1701 </B>. Furthermore, to bind the hydrochloric acid formed, for example, a tertiary base such as pyridine and the like can be added.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH211649T | 1936-05-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH211649A true CH211649A (en) | 1940-10-15 |
Family
ID=4447432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH211649D CH211649A (en) | 1936-05-18 | 1936-05-18 | Process for the preparation of a new enol derivative containing the sterol core. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH211649A (en) |
-
1936
- 1936-05-18 CH CH211649D patent/CH211649A/en unknown
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