CH215560A - Process for the preparation of a ketol of the cyclopentanopolyhydrophenanthrene series. - Google Patents
Process for the preparation of a ketol of the cyclopentanopolyhydrophenanthrene series.Info
- Publication number
- CH215560A CH215560A CH215560DA CH215560A CH 215560 A CH215560 A CH 215560A CH 215560D A CH215560D A CH 215560DA CH 215560 A CH215560 A CH 215560A
- Authority
- CH
- Switzerland
- Prior art keywords
- preparation
- ester
- ketol
- malonic
- sodium
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002690 malonic acid derivatives Chemical class 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- -1 dinitriles Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 1
- HIAJCGFYHIANNA-QIZZZRFXSA-N 3b-Hydroxy-5-cholenoic acid Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@@H](CCC(O)=O)C)[C@@]1(C)CC2 HIAJCGFYHIANNA-QIZZZRFXSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 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 getols der Cyclopentanopolyhydrophenanthren-Reihe. Es wurde gefunden, dass man zu einem Ketol ider Cyclopentanopolyhydrophenan- threnreihe gelangen kann, wenn man ein Halogenid einer d s,6_3-A,cylogy-ätiocholen- säure mit einer Metallverbindung eines Malon- säurederivates,
das an der reaktionsfähigen Methylengruppe einen zur Hydroxylgruppe hydrolysierbaren Substituenten trägt, um setzt, das Kondensationsprodukt mit hydro- lys:ierenden Mitteln behandelt und die ent standene Dicarbonsäure durch Erhitzen de- carbogyliert.
Das so erhaltene d 5,6-Pregnen-3,2,1-:diol- 20-on der Formel
EMI0001.0027
bildet farblose Kristalle.
Zur verfahrensgemässen Umsetzung mit den Carbons@äuraha@logeniden eignen sich zum Beispiel die folgenden Verbindungen: Metall- derivate, wie zum Beispiel Alkali- oder Na- ,gnesiumderivatevonMaIonsäure-Diestern, -Di- nitrilen, -Diamiden, -Esternitrilen, -Esterami- den oder -Ndtrilamiden,
welche an der reak- tionsfähigen Methylengruppe ausser dem Me- tallatom noch einen zur Hydroxylgruppe hy- Uro'lysierbaren Substituenten tragen.
Ein sol cher Subs.tituent ist zum Beispiel eine durch organische oder anorganische Säuren ver- esterte oder eine veräthertg Hydrogylgruppe. In. zweiter Stufe werden die so erhaltenen Kondensationsprodukte mit hydrolysieren- -den Mitteln behandelt,
wobei insbesondere vorhandene Ester-, Nitril-, Amid,- oder Acyl- gruppen verseift werden und der zu einer Hydrogylgruppe umwandelbare Substituent in eine freie Hydroxylgruppe übergeführt wird. Man erhitzt @dann die in Freiheit ge- <RTI
ID="0001.0090"> setzten Säuren zwecks Decarbogylierung in Substanz, in neutraler oder saurer Läsung bezw. Buspension. Die auf die neue und einfache Weise er haltene Verbindung mit einer a-Keto-alkohol- gruppierung in der Seitenkette ist therapeu tisch wirksaan oder lässt sich in Verbindungen mit therapeutischer Wirkung überführen.
<I>Beispiel:</I> Eine Suspension von \?- Teilen Natrium- chlormalonsäurediäthyles.ter (dargestellt zum Beispiel durch Umsetzung von Chlorma.lon- ,säurediäthylester mit Natriumalkohol;at und Ausfällen mit Ligroin) in 50 Teilen Benzol setzt man mit einer benzolischen Lösung von 4 Teilen 45>6-3-Acetoxy-ätio cholensäure ehl;orid bis, zur beendeten Reaktion um.
Hier auf giesst man in Wasser, trennt die Schichten, wäscht die benzolische Lösung mit Wasser, trocknet sie und dampft sie ein. Der Rück stand wird alkalisch verseift, dann angesäuert und zur Abspaltung der Kohlensäure erhitzt. Das Reaktionsprodukt nimmt man in Äther auf, wäscht die ätherische Lösung mit ver dünnter Sodalösung und Wasser, trocknet und dampft sie ein.
Aus dem Rückstand ge winnt man durch Umkristallisation, chromato- graphische Adsorbtion oder über Konden sationsprodukte mit Carbonyl- oder Carbinol- reagentien das 45,6-Pregnen-3,21-diol-20-on in farblosen Kristallen.
An Stelle eines Metall-halogenmalonsäure- derivates kann zum Beispiel auch ein 31etall- alkoxy-malonsäurederivat Verwendung fin den.
Process for the preparation of a getol of the cyclopentanopolyhydrophenanthrene series. It has been found that a ketole in the cyclopentanopolyhydrophenanthene series can be obtained if a halide of a d s, 6_3-A, cylogy-etiocholenic acid is used with a metal compound of a malonic acid derivative,
which carries a substituent hydrolyzable to the hydroxyl group on the reactive methylene group and converts it, treats the condensation product with hydrolysing agents and decarbogylates the dicarboxylic acid formed by heating.
The thus obtained d 5,6-pregnen-3,2,1-: diol-20-one of the formula
EMI0001.0027
forms colorless crystals.
For example, the following compounds are suitable for the reaction with the carbons @ auraha @ logenides: metal derivatives, such as alkali or sodium, magnesium derivatives of malonic acid diesters, dinitriles, diamides, ester nitriles, ester amides or -ndtrilamides,
which on the reactive methylene group carry, in addition to the metal atom, a substituent which can be hydrolyzed to the hydroxyl group.
Such a substituent is, for example, an esterified by organic or inorganic acids or an etherified hydroyl group. In. second stage, the condensation products thus obtained are treated with hydrolyzing agents,
in particular, the ester, nitrile, amide or acyl groups present are saponified and the substituent which can be converted into a hydroyl group is converted into a free hydroxyl group. One then heats the RTI that has been given free
ID = "0001.0090"> put acids for the purpose of decarbogylation in substance, in neutral or acidic solution, respectively. Bus boarding. The connection with an α-keto alcohol grouping in the side chain obtained in the new and simple way is therapeutically effective or can be converted into compounds with a therapeutic effect.
<I> Example: </I> A suspension of \? - parts of sodium chlormalonsäurediäthyles.ter (prepared for example by reacting Chlorma.lon, acid diethyl ester with sodium alcohol; ate and precipitation with ligroin) in 50 parts of benzene is added a benzene solution of 4 parts of 45> 6-3-acetoxy-ätio cholenic acid ehl; orid until the reaction is complete.
Here you pour water, separate the layers, wash the benzene solution with water, dry it and evaporate it. The residue is saponified under alkaline conditions, then acidified and heated to split off the carbonic acid. The reaction product is taken up in ether, the ethereal solution is washed with dilute soda solution and water, dried and evaporated.
The 45,6-pregnene-3,21-diol-20-one is obtained in colorless crystals from the residue by recrystallization, chromatographic adsorption or via condensation products with carbonyl or carbinol reagents.
Instead of a metal halomalonic acid derivative, it is also possible, for example, to use a metal alkoxy malonic acid derivative.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH211651T | 1937-07-14 | ||
| CH215560T | 1938-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH215560A true CH215560A (en) | 1941-06-30 |
Family
ID=25725054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH215560D CH215560A (en) | 1937-07-14 | 1938-11-19 | Process for the preparation of a ketol of the cyclopentanopolyhydrophenanthrene series. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH215560A (en) |
-
1938
- 1938-11-19 CH CH215560D patent/CH215560A/en unknown
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