CH651555A5 - METHOD FOR PRODUCING 4- (3-METHYL-2-BUTENYL) -1,2-DIPHENYL-3,5-DIOXOPYRAZOLIDINE. - Google Patents
METHOD FOR PRODUCING 4- (3-METHYL-2-BUTENYL) -1,2-DIPHENYL-3,5-DIOXOPYRAZOLIDINE. Download PDFInfo
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- CH651555A5 CH651555A5 CH6249/82A CH624982A CH651555A5 CH 651555 A5 CH651555 A5 CH 651555A5 CH 6249/82 A CH6249/82 A CH 6249/82A CH 624982 A CH624982 A CH 624982A CH 651555 A5 CH651555 A5 CH 651555A5
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- Prior art keywords
- methyl
- diphenyl
- dioxopyrazolidine
- butenyl
- bis
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pain & Pain Management (AREA)
- Pharmacology & Pharmacy (AREA)
- Rheumatology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von 4-(3-Methyl-2-butenyI)-l,2-diphenyl--3,5-dioxopyrazolidin. The present invention relates to a new process for the preparation of 4- (3-methyl-2-butenyl) -1, 2-diphenyl-3,5-dioxopyrazolidine.
Das britische Patent 1 301 857 beschreibt zwei Derivate von l,2-Diphenyl-3,5-dioxopyrazolidin und die Verfahren zu ihrer Herstellung. Eines der beiden Derivate ist 4-(3-Me-thyl-2-butenyl)-l,2-diphenyl-3,5-dioxopyrazolidin, Feprazon, ein wertvolles analgetisch-entzündungshemmendes Arzneimittel, das verbreitet bei der Behandlung von rheumatischen und arthritischen Zuständen und im allgemeinen bei der Behandlung von Entzündungskrankheiten angewandt wird. British Patent 1,301,857 describes two derivatives of 1,2-diphenyl-3,5-dioxopyrazolidine and the processes for their preparation. One of the two derivatives is 4- (3-methyl-2-butenyl) -1, 2-diphenyl-3,5-dioxopyrazolidine, feprazone, a valuable analgesic-anti-inflammatory drug that is widely used in the treatment of rheumatic and arthritic conditions and is generally used in the treatment of inflammatory diseases.
Unter dem Verfahren zur Herstellung dieser Verbindung ist die Reaktion von l,2-Diphenyl-3,5-dioxopyrazolidin oder eines seiner Alkalisalze mit einem Halogenid, z.B. 3-Methyl--2-butenylchlorid oder -bromid, beschrieben. Diese Reaktion besteht aus einer nukleophilen Substitution zwischen dem Anion von l,2-Diphenyl-3,5-dioxopyrazolidin, das eine aktivierte Methylengruppe besitzt und einem aktivierten Allylhalogenid, z.B. 3-MethyI-2-butenylchlorid. Among the processes for the preparation of this compound is the reaction of 1,2-diphenyl-3,5-dioxopyrazolidine or one of its alkali salts with a halide, e.g. 3-methyl-2-butenyl chloride or bromide. This reaction consists of a nucleophilic substitution between the anion of 1,2-diphenyl-3,5-dioxopyrazolidine which has an activated methylene group and an activated allyl halide, e.g. 3-methyl-2-butenyl chloride.
Einer der hauptsächlichen Vorteile der Erfindung ist, dass 3-Methyl-2-butenylacetat eine stabile und leicht handhabbare Substanz ist, im Gegensatz zu den 3-MethyI-2-bu-50 tenylhalogeniden. 3-Methyl-2-butenylacetat kann aus Isopren, Essigsäure und Essigsäureanhydrid in Anwesenheit eines geeigneten Katalysators erhalten werden (nach dem belgischen Patent 640 309). Weitere Vorteile, die durch das erfindungsgemässe Verfahren erreicht werden, sind die 55 Selektivität bezüglich der C- vs. O-Alkylierung und das Reduzieren der Eliminationsreaktion auf ein Minimum. One of the main advantages of the invention is that 3-methyl-2-butenyl acetate is a stable and easy to handle substance, in contrast to the 3-methyl-2-bu-50 tenyl halides. 3-Methyl-2-butenyl acetate can be obtained from isoprene, acetic acid and acetic anhydride in the presence of a suitable catalyst (according to Belgian patent 640 309). Further advantages which are achieved by the method according to the invention are the 55 selectivity with respect to the C- vs. O-alkylation and minimizing the elimination reaction.
Im besondern betrifft das neue Verfahren, gemäss der vorliegenden Erfindung, die Reaktion von 3-Methyl-2-bute-nylacetat mit einem Alkalisalz, vorzugsweise einem Na-60 trium-, Kalium- oder Lithiumsalz und besonders bevorzugt mit einem Lithiumsalz, von l,2-Diphenyl-3,5-dioxopyrazo-Iidin in Anwesenheit von Palladiumkomplexkatalysatoren. Bevorzugte Katalysatoren sind tetrakis-(Triphenylphosphin)-Palladium(O) [(Ph3P)4Pd<0)], bis-(Dibenzylidenaceton)Pal-65 ladium(O) [(dba)2Pd<o1] und bis-[l,2-(bis-Diphenylphosphin-ethan)]Palladium(0) [(DIPHOS2)Pd(0)], sehr geeignet ist tetrakis-(Triphenylphosphin)Palladium(0) in Anwesenheit von Liganden wie z.B. Triphenylphosphin (TPP), l,2-(bis- In particular, the new process, according to the present invention, relates to the reaction of 3-methyl-2-butenyl acetate with an alkali salt, preferably a sodium 60 trium, potassium or lithium salt and particularly preferably with a lithium salt, of 1, 2-Diphenyl-3,5-dioxopyrazo-iidin in the presence of palladium complex catalysts. Preferred catalysts are tetrakis (triphenylphosphine) palladium (O) [(Ph3P) 4Pd <0)], bis- (dibenzylidene acetone) Pal-65 ladium (O) [(dba) 2Pd <o1] and bis- [1,2 - (bis-diphenylphosphine-ethane)] palladium (0) [(DIPHOS2) Pd (0)], tetrakis (triphenylphosphine) palladium (0) is very suitable in the presence of ligands such as, for example Triphenylphosphine (TPP), l, 2- (bis-
3. 3rd
651555 651555
-Diphenylphosphinethan) (DIPHOS), Hexamethylphosphor-triamid (HMP), besonders bevorzugt ist Triphenylphosphin. Lösungsmittel die für diese Reaktion bevorzugt sind, sind ätherische Lösungsmittel, wie z.B. Tetrahydrofuran, 1,2-Di-methoxyethan und Dimethylsulfoxid, besonders bevorzugt Tetrahydrofuran unter wasserfreien Bedingungen. -Diphenylphosphinethan) (DIPHOS), Hexamethylphosphor-triamid (HMP), triphenylphosphine is particularly preferred. Solvents preferred for this reaction are ethereal solvents such as e.g. Tetrahydrofuran, 1,2-dimethoxyethane and dimethyl sulfoxide, particularly preferably tetrahydrofuran under anhydrous conditions.
Die Reaktion wird gewöhnlich durchgeführt durch Mischen von 3-Methyl-2-butenylacetat, gelöst in einem geeigneten Lösungsmittel, wie z.B. Tetrahydrofuran, mit dem Palladiumkomplex und dem geeigneten Liganden bei Raumtemperatur. Im allgemeinen genügen Mengen von 0,1 bis 10 Mol-% an Katalysatoren. Dazu wird die Lösung des Alkalisalzes von l,2-Diphenyl-3,5-dioxopyrazolidin (in der Regel 2 bis 4 Mol) rasch zugegeben und die Reaktionsmischung wird in der Regel bei Temperaturen zwischen Raumtemperatur und 70°C gerührt. The reaction is usually carried out by mixing 3-methyl-2-butenyl acetate dissolved in a suitable solvent, e.g. Tetrahydrofuran, with the palladium complex and the appropriate ligand at room temperature. In general, amounts of 0.1 to 10 mol% of catalyst are sufficient. For this purpose, the solution of the alkali salt of 1,2-diphenyl-3,5-dioxopyrazolidine (usually 2 to 4 mol) is added rapidly and the reaction mixture is generally stirred at temperatures between room temperature and 70 ° C.
Danach wird die Reaktionsmischung in der Regel in Waser, im allgemeinen angesäuert bis pH 4 bis 5, gegeben und mit einem geeigneten Lösungsmittel, wie z.B. Äthylace-tat, Äthyläther oder Dichlormethan, extrahiert. Das nach dem Verdampfen des Lösungsmittels erhaltene Produkt kann direkt durch Säulenchromatographie oder Rückextrak-tion mit einem basischen wässrigen Medium gereinigt werden. Im letzteren Fall wird das Produkt in der Regel mit einer Mineralsäure, vorzugsweise Salzsäure, angesäuert, mit einem geeigneten Lösungsmittel extrahiert und anschliessend isoliert. Thereafter, the reaction mixture is usually added to water, generally acidified to pH 4 to 5, and with a suitable solvent, e.g. Ethylacetate, ethyl ether or dichloromethane, extracted. The product obtained after evaporation of the solvent can be purified directly by column chromatography or back extraction with a basic aqueous medium. In the latter case, the product is generally acidified with a mineral acid, preferably hydrochloric acid, extracted with a suitable solvent and then isolated.
Eine zusätzliche Reinigung kann durch Säulenchromatographie erreicht werden. Additional purification can be achieved by column chromatography.
Die folgenden Beispiele dienen zur Illustration der vorliegenden Erfindung. The following examples serve to illustrate the present invention.
Beispiel 1 example 1
3-Methyl-2-butenylacetat (5 g, 0,039 Mol), Triphenylphosphin (0,93 g) und tetrakis-(Triphenylphosphin)Palla-dium(O) (1,42 g, 0,00123 Mol) wurden in 75 ml trockenem 3-Methyl-2-butenyl acetate (5 g, 0.039 mol), triphenylphosphine (0.93 g) and tetrakis (triphenylphosphine) palladium (O) (1.42 g, 0.00123 mol) were dried in 75 ml
Tetrahydrofuran während 15 Minuten bei Raumtemperatur gerührt. Dazu wurde in einem Mal eine Lösung des Lithiumsalzes von l,2-Diphenyl-3,5-dioxopyrazolidin (20,13 g, 0,078 Mol) in 200 ml wasserfreiem Tetrahydro-5 furan gegeben und die resultierende Mischung wurde während 15 Stunden unter Stickstoffatmosphäre rückflussiert. Die Reaktionslösung wurde konzentriert und dann auf einen Überschuss von Wasser gegossen. Nach dem Ansäuern bis zum pH 4 bis 5 wurde die wässrige Lösung mit Methylen-io chlorid extrahiert. Die organische Phase wurde abgetrennt, mit Magnesiumsulfat getrocknet und eingedampft, um das Rohprodukt der Titelverbindung zu erhalten. Eine Reinigung durch Säulenchromatographie (Silicagel) (CH2Cl/ CH3CN 98:2 V/V) ergab das gewünschte Produkt in reiner 15 Form. Tetrahydrofuran stirred for 15 minutes at room temperature. A solution of the lithium salt of 1,2-diphenyl-3,5-dioxopyrazolidine (20.13 g, 0.078 mol) in 200 ml of anhydrous tetrahydro-5 furan was added all at once and the resulting mixture was refluxed under a nitrogen atmosphere for 15 hours . The reaction solution was concentrated and then poured onto an excess of water. After acidification to pH 4 to 5, the aqueous solution was extracted with methylene chloride. The organic phase was separated, dried with magnesium sulfate and evaporated to give the crude product of the title compound. Purification by column chromatography (silica gel) (CH2Cl / CH3CN 98: 2 V / V) gave the desired product in pure form.
Schmelzpunkt 156°C. Melting point 156 ° C.
Analyse für C20H20N2O2: Analysis for C20H20N2O2:
ber.: (in %) C 74,97 H 6,29 N 8,74 gef.: (in %) C 75,14 H 6,37 N 8,68 calc .: (in%) C 74.97 H 6.29 N 8.74 found: (in%) C 75.14 H 6.37 N 8.68
20 20th
Beispiel 2 Example 2
3-Methyl-2-butenylacetat (5 g, 0,039 Mol), l,2-(bis-Di-phenylphosphinethan) (0,155 g, 0,39 mMol), und bis-(Di-benzylidenaceton) Pailadium(O) (0,3 g, 0,522 mMol) wurden 25 in 75 ml wasserfreiem Tetrahydrofuran während 10 Minuten bei Raumtemperatur gerührt. Dazu wurde in einem Mal die Lösung des Lithiumsalzes von l,2-Diphenyl-3,5--dioxopyrazolidin (20,13 g, 0,078 Mol) in 150 ml wasserfreiem Tetrahydrofuran zugegeben und die resultierende 3o Mischung 48 Stunden bei Raumtemperatur gerührt. Dann wurde, wie in Beispiel 1 angegeben, fortgefahren. Die gewünschte Verbindung wurde erhalten. 3-methyl-2-butenyl acetate (5 g, 0.039 mol), l, 2- (bis-diphenylphosphineethane) (0.155 g, 0.39 mmol), and bis- (di-benzylidene acetone) pailadium (O) (0 , 3 g, 0.522 mmol) were stirred in 75 ml of anhydrous tetrahydrofuran for 10 minutes at room temperature. For this, the solution of the lithium salt of 1,2-diphenyl-3,5-dioxopyrazolidine (20.13 g, 0.078 mol) in 150 ml of anhydrous tetrahydrofuran was added all at once and the resulting mixture was stirred at room temperature for 48 hours. Then, as indicated in Example 1, the procedure was continued. The desired connection was obtained.
Schmelzpunkt 156°C. Melting point 156 ° C.
Analyse für C20H20N2O2: Analysis for C20H20N2O2:
35 ber.: (in %) C 74,97 H 6,29 N 8,74 gef.: (in %) C 74,85 H 6,11 N 8,81 35 calc .: (in%) C 74.97 H 6.29 N 8.74 found: (in%) C 74.85 H 6.11 N 8.81
v v
Claims (9)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT24772/81A IT1168184B (en) | 1981-10-29 | 1981-10-29 | PROCESS FOR THE PREPARATION OF 4- (3-METHYL-2-BUTANYL) -1,2-DIPHENYL-3,5 DICHETOPYRAZOLIDINE |
Publications (1)
Publication Number | Publication Date |
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CH651555A5 true CH651555A5 (en) | 1985-09-30 |
Family
ID=11214682
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH6249/82A CH651555A5 (en) | 1981-10-29 | 1982-10-26 | METHOD FOR PRODUCING 4- (3-METHYL-2-BUTENYL) -1,2-DIPHENYL-3,5-DIOXOPYRAZOLIDINE. |
Country Status (19)
Country | Link |
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JP (1) | JPS5888365A (en) |
KR (1) | KR840001955A (en) |
AR (1) | AR231832A1 (en) |
AT (1) | AT379151B (en) |
CA (1) | CA1179354A (en) |
CH (1) | CH651555A5 (en) |
DK (1) | DK477882A (en) |
ES (1) | ES516902A0 (en) |
FI (1) | FI823545L (en) |
FR (1) | FR2515646B1 (en) |
GB (1) | GB2108125B (en) |
GR (1) | GR77724B (en) |
IT (1) | IT1168184B (en) |
NL (1) | NL8204170A (en) |
NO (1) | NO823596L (en) |
PH (1) | PH19644A (en) |
PT (1) | PT75755B (en) |
SE (1) | SE8206143L (en) |
YU (1) | YU240282A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107778247A (en) * | 2016-08-30 | 2018-03-09 | 天津太平洋制药有限公司 | A kind of preparation method of feprazone and its intermediate |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1301857A (en) * | 1969-06-27 | 1973-01-04 |
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1981
- 1981-10-29 IT IT24772/81A patent/IT1168184B/en active
-
1982
- 1982-10-07 AT AT0370382A patent/AT379151B/en not_active IP Right Cessation
- 1982-10-14 PH PH27984A patent/PH19644A/en unknown
- 1982-10-18 FI FI823545A patent/FI823545L/en not_active Application Discontinuation
- 1982-10-26 GR GR69645A patent/GR77724B/el unknown
- 1982-10-26 YU YU02402/82A patent/YU240282A/en unknown
- 1982-10-26 CH CH6249/82A patent/CH651555A5/en not_active IP Right Cessation
- 1982-10-27 PT PT75755A patent/PT75755B/en unknown
- 1982-10-28 KR KR1019820004867A patent/KR840001955A/en unknown
- 1982-10-28 DK DK477882A patent/DK477882A/en not_active Application Discontinuation
- 1982-10-28 ES ES516902A patent/ES516902A0/en active Granted
- 1982-10-28 JP JP57189954A patent/JPS5888365A/en active Pending
- 1982-10-28 NO NO823596A patent/NO823596L/en unknown
- 1982-10-28 CA CA000414428A patent/CA1179354A/en not_active Expired
- 1982-10-28 SE SE8206143A patent/SE8206143L/en not_active Application Discontinuation
- 1982-10-28 GB GB08230767A patent/GB2108125B/en not_active Expired
- 1982-10-28 NL NL8204170A patent/NL8204170A/en not_active Application Discontinuation
- 1982-10-29 FR FR8218200A patent/FR2515646B1/en not_active Expired
- 1982-10-29 AR AR291152A patent/AR231832A1/en active
Also Published As
Publication number | Publication date |
---|---|
NL8204170A (en) | 1983-05-16 |
GB2108125B (en) | 1985-03-20 |
DK477882A (en) | 1983-04-30 |
FR2515646B1 (en) | 1986-02-14 |
JPS5888365A (en) | 1983-05-26 |
SE8206143D0 (en) | 1982-10-28 |
ES8308855A1 (en) | 1983-10-01 |
AR231832A1 (en) | 1985-03-29 |
CA1179354A (en) | 1984-12-11 |
GB2108125A (en) | 1983-05-11 |
PT75755A (en) | 1982-11-01 |
FR2515646A1 (en) | 1983-05-06 |
NO823596L (en) | 1983-05-02 |
FI823545A0 (en) | 1982-10-18 |
IT8124772A0 (en) | 1981-10-29 |
PH19644A (en) | 1986-06-04 |
KR840001955A (en) | 1984-06-07 |
FI823545L (en) | 1983-04-30 |
AT379151B (en) | 1985-11-25 |
SE8206143L (en) | 1983-04-30 |
PT75755B (en) | 1985-11-20 |
YU240282A (en) | 1985-03-20 |
GR77724B (en) | 1984-09-25 |
IT1168184B (en) | 1987-05-20 |
ES516902A0 (en) | 1983-10-01 |
ATA370382A (en) | 1985-04-15 |
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