CH320670A - Process for the preparation of 1,2-diphenyl-4-isobutyl-3,5-dioxo-pyrazolidine - Google Patents
Process for the preparation of 1,2-diphenyl-4-isobutyl-3,5-dioxo-pyrazolidineInfo
- Publication number
- CH320670A CH320670A CH320670DA CH320670A CH 320670 A CH320670 A CH 320670A CH 320670D A CH320670D A CH 320670DA CH 320670 A CH320670 A CH 320670A
- Authority
- CH
- Switzerland
- Prior art keywords
- dioxo
- diphenyl
- pyrazolidine
- parts
- isobutyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 9
- VWRRWRNOCUOOCP-UHFFFAOYSA-N 4-(2-methylpropyl)-1,2-diphenylpyrazolidine-3,5-dione Chemical compound O=C1C(CC(C)C)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VWRRWRNOCUOOCP-UHFFFAOYSA-N 0.000 title claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 230000000887 hydrating effect Effects 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 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
- 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
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002244 precipitate Substances 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
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07D231/34—Oxygen atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verfahren zur Herstellung von 1,2-Diphenyl-4-isobutyl-3,5-dioxo-pyrazolidik#s (f'esenstand vorliegenden Patentes ist ein Verfahren zur Herstellung des 1,2-Diphenyl- .l-isobutyl-3,5-dioxo-pyrazolidins. Das Verfah ren ist dadurch gekennzeichnet, dass man 1,2 -Diplienyl-4-niethallyl-3,5-dioxo-pyx#azolidin mit hydrierenden Mitteln behandelt.
Als hy drierendes Mittel eignet sich insbesondere durch Katalysatoren aktivierter Wasserstoff; -ils Katalysatoren können sowohl Edelmetall katalysatoren,wie Palladium-Kohle oder Pla- Tinoxyd, als auch Niekel-Katalysatoren, Ver wendung finden. Alkohol und Essigester zum Beispiel bilden f-eeignete Lösungsmittel. für die Hydrierung, welche bei Raumtemperatur unter Atniosphäreiidruck mit genügender Ge schwindigkeit vor sich geht.
Das als Ausgangsstoff benötigte 1,2-Diphe- nyl-4-methallyl-3,5-dioxo-pyrazolidin kann in an sieh bekannter Weise, z. B. durch Konden sation von Methallylmalonsäure-diätbylester mit. lIy(lrazobenzol, hergestellt werden.
Das nach dem erfindungsgemässen Verfah ren erhältliche 1,2-Diphenyl-4-isobutyl-3,5-di- oxo-py razolidin ist eine weisse kristalline Sub stanz, welche bei 132 schmilzt. Sie soll als solche oder in Form ihrer Salze als Arznei mittel Verwendung finden.
In den nachfolgenden Beispielen bedeuten die Teile Gewichtsteile; diese verhalten sieh zu Volumteilen wie g zu em #. - <I>Beispiel 1</I> 7u einer Lösung von .1,6 Teilen Natrium in 92 Volumteilen absolutem Alkohol lässt man 42,8 Teile Methallylmalonsäure-diäthylester (KP-12 112-114 ) einfliessen, gibt 37 Teile Hydrazolbenzol zu, destilliert etwa zwei Drit tel des Alkohols ab und versetzt.
mit 92 Vo- lumteilen absolutem Xylol. Ofine den abwärts gerichteten Kühler zu entfernen, wird die Mi schung 12 Stunden bei einer Badtemperatur von 140-145 gerührt. Man kühlt auf 0-5 , gibt 100 Teile Eis zu, trennt von Xylol ab, zieht noch zweimal mit Chloroform aus, stellt bei 0-5 mit 6n-Salzsäure kongosauer, nimmt den Niederschlag in Chloroform auf; wäscht die erhaltene Lösung zweimal mit Wasser, dann mit konz. Natriumehloridlösung, trock net über Natriumsulfat und dampft im Va kuum ein (Bad 20 ).
Der Rückstand, wird aus Alkohol umkristallisiert und liefert 1.,2-Diphe- nyl-4-methallyl-3,5-dioxopyrazolidin als weisse Nädelehen vom Schmelzpunkt 154-155 .
Man suspendiert 7,7 Teile 1,2-Diphenyl-4- methyllyl-3,5-dioxo-pyrazolidin in 154 Teilen Alkohol und lässt in Gegenwart von 8 Teilen Raney-Nickel bei Raumtemperatur und Atmo sphärendruck Wasserstoff einwirken.
Nach 13 Stunden ist die berechnete Menge Wasserstoff aufgenommen. Aus der filtrierten und eingeengten Lösung kristallisiert 1,2-Di- phenyl-4-isobutyl-3,5-dioxo-pyrazolidin in wei ssen Nadeln vom Schmelzpunkt 132 . Aus der Mutterlauge kann nochmals kristallisiertes Endprodukt gewonnen werden.
<I>Beispiel 2</I> Man suspendiert 15,4 Teile 1,2-Diphenyl- 4-methallyl-3,5-dioxo-pyrazolidin in 150 Tei len Essigester, welche 1,5 Teile Eisessig ent halten, und lässt in Gegenwart von 2,5 Tei- len 4%iger Palladium-Kohle bei Raumtem- peratur und Atmosphärendruck Wasserstoff einwirken. Nach 6 Stunden ist die berechnete Menge aufgenommen.
Aus der filtrierten Lö sung kristallisiert 1,2-Diphenyl-4-isobutyl-3,5- dioxo-pyrazolidin in weissen Nadeln vom Schmelzpunkt 132 . Aus der eingeengten Mut terlauge kristallisiert noch eine weitere Menge des Endproduktes.
<I>Beispiel 3</I> Man hydriert analog wie in Beispiel 1 an gegeben, unter Verwendung von 0,38 Teilen Platinoxyd an Stelle von 8 Teilen Raney-Nik- kel. Die berechnete Menge Wasserstoff wird in einer Stunde aufgenommen. Die Aufarbei tung erfolgt analog Beispiel 1.
Process for the production of 1,2-diphenyl-4-isobutyl-3,5-dioxo-pyrazolidik # s (according to the present patent is a process for the production of 1,2-diphenyl- .l-isobutyl-3,5- Dioxo-pyrazolidine: The process is characterized in that 1,2 -diplienyl-4-niethallyl-3,5-dioxo-pyrazolidine is treated with hydrogenating agents.
Hydrogen activated by catalysts is particularly suitable as a hy drierendes agent; -ils catalysts can both noble metal catalysts, such as palladium-carbon or platinum oxide, as well as Niekel catalysts, are used. Alcohol and ethyl acetate, for example, are suitable solvents. for the hydrogenation, which takes place at room temperature under atmospheric pressure with sufficient speed.
The 1,2-diphenyl-4-methallyl-3,5-dioxo-pyrazolidine required as a starting material can be used in a manner known per se, e.g. B. by condensation of methallylmalonic acid dietbyl ester with. lIy (lrazobenzene).
The 1,2-diphenyl-4-isobutyl-3,5-dioxo-pyrazolidine obtainable by the process according to the invention is a white crystalline substance which melts at 132. It should be used as a medicament as such or in the form of its salts.
In the following examples, the parts are parts by weight; These behave like g to em # for volume parts. - <I> Example 1 </I> 7u of a solution of .1.6 parts of sodium in 92 parts by volume of absolute alcohol, 42.8 parts of methallylmalonic acid diethyl ester (KP-12 112-114) are poured in, 37 parts of hydrazolebenzene are added, distilled about two thirds of the alcohol and added.
with 92 parts by volume of absolute xylene. Ofine to remove the downward facing condenser, the mixture is stirred for 12 hours at a bath temperature of 140-145. The mixture is cooled to 0-5, 100 parts of ice are added, the xylene is separated off, extracted twice more with chloroform, acidified to Congo at 0-5 with 6N hydrochloric acid, the precipitate is taken up in chloroform; the solution obtained washes twice with water, then with conc. Sodium chloride solution, dry over sodium sulfate and evaporated in a vacuum (bath 20).
The residue is recrystallized from alcohol and gives 1,2-diphenyl-4-methallyl-3,5-dioxopyrazolidine as white needle looms with a melting point of 154-155.
7.7 parts of 1,2-diphenyl-4-methyllyl-3,5-dioxo-pyrazolidine are suspended in 154 parts of alcohol and hydrogen is allowed to act in the presence of 8 parts of Raney nickel at room temperature and atmospheric pressure.
After 13 hours the calculated amount of hydrogen has been absorbed. 1,2-Diphenyl-4-isobutyl-3,5-dioxo-pyrazolidine crystallizes in white needles with a melting point of 132 from the filtered and concentrated solution. The end product which has crystallized again can be obtained from the mother liquor.
<I> Example 2 </I> 15.4 parts of 1,2-diphenyl-4-methallyl-3,5-dioxo-pyrazolidine are suspended in 150 parts of ethyl acetate, which contain 1.5 parts of glacial acetic acid, and let in In the presence of 2.5 parts of 4% palladium-carbon, hydrogen act at room temperature and atmospheric pressure. The calculated amount is absorbed after 6 hours.
1,2-Diphenyl-4-isobutyl-3,5-dioxo-pyrazolidine crystallizes from the filtered solution in white needles with a melting point of 132. A further amount of the end product crystallizes from the concentrated mother liquor.
<I> Example 3 </I> The hydrogenation is carried out analogously to that given in Example 1, using 0.38 part of platinum oxide instead of 8 parts of Raney nickel. The calculated amount of hydrogen is absorbed in one hour. The processing is carried out as in Example 1.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH320670T | 1953-07-31 | ||
| CH317695T | 1953-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH320670A true CH320670A (en) | 1957-03-31 |
Family
ID=25736156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH320670D CH320670A (en) | 1953-07-31 | 1953-07-31 | Process for the preparation of 1,2-diphenyl-4-isobutyl-3,5-dioxo-pyrazolidine |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH320670A (en) |
-
1953
- 1953-07-31 CH CH320670D patent/CH320670A/en unknown
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