CH303946A - Process for the preparation of a derivative of 3,5-dioxo-pyrazolidine. - Google Patents
Process for the preparation of a derivative of 3,5-dioxo-pyrazolidine.Info
- Publication number
- CH303946A CH303946A CH303946DA CH303946A CH 303946 A CH303946 A CH 303946A CH 303946D A CH303946D A CH 303946DA CH 303946 A CH303946 A CH 303946A
- Authority
- CH
- Switzerland
- Prior art keywords
- pyrazolidine
- dioxo
- ethyl
- derivative
- parts
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 4
- DNTVKOMHCDKATN-UHFFFAOYSA-N pyrazolidine-3,5-dione Chemical class O=C1CC(=O)NN1 DNTVKOMHCDKATN-UHFFFAOYSA-N 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 5
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 4
- -1 p-methoxy-phenylmercapto Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- 150000003218 pyrazolidines Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/28—Two oxygen or sulfur atoms
- C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
- C07D231/32—Oxygen atoms
- C07D231/36—Oxygen atoms with hydrocarbon radicals, substituted by hetero atoms, attached in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung eines Derivates des 3,5-Dioxo-pyrazolidins. Gegenstand vorliegenden Patentes ist ein Verfahren zur Herstellung eines Derivates des 3.5-Dioxo-pyrazolidins, Das Verfahren ist, da durch gekennzeichnet, dass man eine den Rest
EMI0001.0003
abgebende Verbindung, wie z.
B. einen Diester, ein Dilialogenid oder ein rsterhalogenid der (p-3lethoxy-pheM7 lmereapto )-äthyl] -malon- säure, mit einer Verbindung der Formel
EMI0001.0012
wobei K einen sieh bei der Reaktion abspal tenden Rest bedeutet, wie z. B. mit Hydrazo- benzol oder einem N-Acylderiv at desselben, umsetzt. Die Umsetzung erfolgt zweckmässig in Gegenwart eines Kondensationsmittels bzw.
eines säurebindenden Mittels.
Die erhaltene neue Verbindung, das 1,2- D iplienyl-3, 5 - dioxo-4- [ ss - (p - met.hoxy - phenyl- in.erea.pto) - äthyl] - pyrazolidin, zeigt einen Schmelzpunkt von 106-l08 .
Sie soll als solche oder in Form ihrer Salze therapeutische Verwendung finden.
Beispiel <I>1:</I> Zn einer warmen Natriumäthylatlösung aus ?3 Teilen Natrium und 460 Volumteilen Alkohol werden zunächst 326 Teile [ss-(p- tIethoxy-phenylmercapto) -äthyl] - malonsäure- diäthylester und hierauf 203 Teile Hydrazo- benzol unter Rühren zugefügt.
Hierauf wird ungefähr die Hälfte des Alkohols abdestilliert und allmählich durch 230 Volumteile Xylol ersetzt. Ohne den abwärts gerichteten Kühler zu entfernen, wird die Temperatur des Öl bades während 12 Stunden unter ständigem Rühren auf etwa 140 gehalten, so dass der noch vorhandene und der durch die Konden sation freibesetzte Alkohol abdestilliert, aber das Xy lol als Lösungsmittel zurückbleibt.
Nach dem Abkühlen werden 460 Teile Wasser eingerührt, die wässerige Schicht vom Xylol abgetrennt, zweimal mit je 46 Volum- teilen Chloroform ausgeschüttelt und hierauf mit konzentrierter Salzsäure kongosauer ge stellt. Das ausgeschiedene Öl wird in Äthyl- acetat aufgenommen und die erhaltene Lö sung mit Wasser gewaschen.
Nach Trocknen äber Natriumsulfat wird das Lösungsmittel unter vermindertem Druck abdestilliert und der Rückstand aus Alkohol umkristallisiert. Das 1.,2-Diphenyl-3,5-dioxo-4-[ss-(p-methoxy- phenjmercapto)-äthyl]-pyrazolidin schmilzt bei 1.06-108 .
<I>Beispiel 2:</I> Ziu einer Mischung von 50 Teilen absolu tem Pyridin imd 200 Volumteilen absolutem Äther tropft man bei etwa 0 30,6 Teile [ss-(p- Methoxy-pheny lmercapto)-äthyl] -malonsäure- dichlorid, gibt dann 18 Teile Hydrazobenzol, gelöst in 100 Volumteilen Äther, hinzu und rührt zwei Stunden bei Zimmertemperatur.
Die lJösung wird zunächst zur 1Jntfernting des Pyridins mit 2n-Salzsäure ausgeschüttelt, hierauf mit 2n-Natriumcarbonatlösung. Die Natriumcarbonatlösung, welche das Natrium- salz des 1,2-Diphenirl-3,5-dioxo-4-[ss-(p-metli- oxy-phenyimereapto) -äthyll -pyrazolidins ge- löst enthält,
wird mit 10%iger Salzsäure an- gesäuert, wobei sich das freie Pyrazolidinderi- vat ausscheidet. Dieses wird in Essigester auf genommen, die Essigesterlösung mit Wasser gewaschen und eingedampft und der Rück stand aus Alkohol umkristallisiert.
Process for the preparation of a derivative of 3,5-dioxo-pyrazolidine. The subject of the present patent is a process for the preparation of a derivative of 3,5-dioxo-pyrazolidine
EMI0001.0003
issuing connection, such as
B. a diester, a dilialogenide or a rsterhalogenid of (p-3lethoxy-pheM7 lmereapto) -ethyl] -malonic acid, with a compound of the formula
EMI0001.0012
where K a see in the reaction abspal border radical means such. B. with hydrazzo benzene or an N-acyl derivative of the same, reacted. The reaction is conveniently carried out in the presence of a condensing agent or
an acid binding agent.
The new compound obtained, 1,2-dipienyl-3, 5-dioxo-4- [ss - (p - met.hoxy - phenyl - in.erea.pto) - ethyl] - pyrazolidine, has a melting point of 106 -l08.
It should find therapeutic use as such or in the form of its salts.
Example <I> 1: </I> In a warm sodium ethylate solution of 3 parts of sodium and 460 parts by volume of alcohol, 326 parts of [ss- (p-ethoxy-phenylmercapto) -ethyl] malonic acid diethyl ester and then 203 parts of hydrazine benzene was added with stirring.
About half of the alcohol is then distilled off and gradually replaced by 230 parts by volume of xylene. Without removing the downward-facing cooler, the temperature of the oil bath is kept at about 140 for 12 hours with constant stirring, so that the alcohol still present and the alcohol released by the condensation is distilled off, but the xylene remains as a solvent.
After cooling, 460 parts of water are stirred in, the aqueous layer is separated from the xylene, extracted twice with 46 parts by volume of chloroform and then acidified to Congo with concentrated hydrochloric acid. The separated oil is taken up in ethyl acetate and the solution obtained is washed with water.
After drying over sodium sulfate, the solvent is distilled off under reduced pressure and the residue is recrystallized from alcohol. The 1st, 2-diphenyl-3,5-dioxo-4- [ss- (p-methoxyphenymercapto) ethyl] pyrazolidine melts at 1.06-108.
<I> Example 2: </I> A mixture of 50 parts of absolute pyridine and 200 parts by volume of absolute ether is added dropwise to about 0.30.6 parts of [ss- (p-methoxyphenylmercapto) -ethyl] -malonic acid- dichloride, then add 18 parts of hydrazobenzene, dissolved in 100 parts by volume of ether, and stir for two hours at room temperature.
The solution is first shaken out with 2N hydrochloric acid to remove the pyridine, then with 2N sodium carbonate solution. The sodium carbonate solution, which contains the sodium salt of 1,2-diphenirl-3,5-dioxo-4- [ss- (p-metli-oxy-phenyimereapto) -ethyl-pyrazolidine in dissolved form,
is acidified with 10% hydrochloric acid, whereby the free pyrazolidine derivative is precipitated. This is taken up in ethyl acetate, the ethyl acetate solution washed with water and evaporated and the residue was recrystallized from alcohol.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH727405X | 1950-11-06 | ||
| CH303946T | 1950-11-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH303946A true CH303946A (en) | 1954-12-15 |
Family
ID=25734702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH303946D CH303946A (en) | 1950-11-06 | 1950-11-06 | Process for the preparation of a derivative of 3,5-dioxo-pyrazolidine. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH303946A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1088500B (en) * | 1956-08-03 | 1960-09-08 | Geigy Ag J R | Process for the preparation of therapeutically active 1,2-diaryl-3,5-dioxo-pyrazolidine-4-acetic acids and their salts |
-
1950
- 1950-11-06 CH CH303946D patent/CH303946A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1088500B (en) * | 1956-08-03 | 1960-09-08 | Geigy Ag J R | Process for the preparation of therapeutically active 1,2-diaryl-3,5-dioxo-pyrazolidine-4-acetic acids and their salts |
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