NO823596L - PROCEDURE FOR PREPARING 4- (3-METHYL-2-BUTENYL) -1,2-DIPHENYL-3,5-DIOXOPYRAZOLIDINE - Google Patents

PROCEDURE FOR PREPARING 4- (3-METHYL-2-BUTENYL) -1,2-DIPHENYL-3,5-DIOXOPYRAZOLIDINE

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Publication number
NO823596L
NO823596L NO823596A NO823596A NO823596L NO 823596 L NO823596 L NO 823596L NO 823596 A NO823596 A NO 823596A NO 823596 A NO823596 A NO 823596A NO 823596 L NO823596 L NO 823596L
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Norway
Prior art keywords
methyl
diphenyl
butenyl
dioxopyrazolidine
palladium
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NO823596A
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Norwegian (no)
Inventor
Arturo Donetti
Myrna Gil Quintero
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Angeli Inst Spa
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Publication of NO823596L publication Critical patent/NO823596L/en

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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

Denne oppfinnelse angår en ny fremgangsmåte for fremstilling av 4-(3-metyl-2-butenyl)-1,2-difenyl-3,5-diokso-pyrazolidin. This invention relates to a new process for the production of 4-(3-methyl-2-butenyl)-1,2-diphenyl-3,5-dioxo-pyrazolidine.

Britisk patent 1.301.857 - beskriver to derivater av 1,2-difenyl-3,5-dioksopyrazolidin og fremgangsmåter for fremstilling derav. ■Et av disse to derivater er 4-(3-metyl-2-butenyl)-1,2-difeny1-3,5-dioksopyrazolidin, feprazon, et verdifullt smertestillende og antiinflammatorisk middel som for tiden anvendes ved behandling av reumatiske og artrittiske British patent 1,301,857 - describes two derivatives of 1,2-diphenyl-3,5-dioxopyrazolidine and processes for their preparation. ■One of these two derivatives is 4-(3-methyl-2-butenyl)-1,2-diphenyl1-3,5-dioxopyrazolidine, feprazone, a valuable analgesic and anti-inflammatory agent currently used in the treatment of rheumatic and arthritic

■lidelser og generelt véd behandling av inflammatoriske lidelser. ■disorders and generally véd treatment of inflammatory disorders.

Blant'.de • metoder som finnes for fremstilling av denne forbindelse, er beskrevet omsetningen av 1,2-difenyl-3,5-diokso-pyrazolidin eller et av dens alkalisalter med et halogenid, Among the • methods that exist for the preparation of this compound, the reaction of 1,2-diphenyl-3,5-dioxo-pyrazolidine or one of its alkali salts with a halide is described,

dvs. 3-metyl-2-butenyl-klorid eller -bromid.ie 3-methyl-2-butenyl chloride or bromide.

Denne omsetning omfatter en nukleofil fortrengning mellom anionet av 1,2-difenyl-3,5-dioksopyrazolidin, som har en aktiv metylengruppe,• og det aktive'allylhalogenid, f.eks. 3-metyl-2-buteriylklorid, This reaction involves a nucleophilic displacement between the anion of 1,2-diphenyl-3,5-dioxopyrazolidine, which has an active methylene group, and the active allyl halide, e.g. 3-methyl-2-buteriyl chloride,

Formålet med foreliggende oppfinnelse er å tilveiebringe en ny fremgangsmåte for fremstilling av 4—(3-metyl-2-butenyl)-1,2-difenyl-3,5-dioksopyrazolidin, og fremgangsmåten karakteriseres ved at 3-metyl-2-butenyl-acetat omsettes med et alkalimetallsalt av 1,2-difenyl-3,5-dioksopyrazolidin i nærvær av palladiumkomplekser som katalysatorer,.! henhold The purpose of the present invention is to provide a new process for the production of 4-(3-methyl-2-butenyl)-1,2-diphenyl-3,5-dioxopyrazolidine, and the process is characterized by the fact that 3-methyl-2-butenyl- acetate is reacted with an alkali metal salt of 1,2-diphenyl-3,5-dioxopyrazolidine in the presence of palladium complexes as catalysts,.! according to

. til følgende skjema:. to the following form:

En av.hovedfbrdelene ved oppfinnelsen som beskrevet oven-for, er at 3-metyl-2-butenyl-acetat, i motsetning til 3-metyl-2-butenyl-halogénidene, er et stabilt og håndterbart stoff: Det kan fremstilles fra isopren, eddiksyre og eddiksyreånhydrid i nærvær av en passende katalysator, i henhold til belgisk .patent 640.309. André fordeler som oppnås i henhold til opp-" finnelsen, er selektiviteten av C- i forhold til 0-alkyler.ing, og minimalisering av eliminasjonsreaksjonen. One of the main advantages of the invention as described above is that 3-methyl-2-butenyl acetate, in contrast to the 3-methyl-2-butenyl halides, is a stable and manageable substance: It can be produced from isoprene, acetic acid and acetic anhydride in the presence of a suitable catalyst, according to Belgian patent 640,309. Other advantages obtained according to the invention are the selectivity of C- to O-alkylation and minimization of the elimination reaction.

Mer spesielt omfatter fremgangsmåten ifølge oppfinnelsen omsetning av 3-mety'l-2-buteny 1-acetat med et alkalisalt, More particularly, the method according to the invention comprises reaction of 3-methyl-2-buteny 1-acetate with an alkali salt,

,så som natrium-, kalium- eller litiumsalter, hensiktsmessig litiumsaltet, av 1,2-difenyl-3,5-dioksopyrazolidin i nærvær av palladiumkomplekser som katalysatorer. Foretrukne katalysatorer er tetrakis (trifenylfosfin)palladium (0) [(Ph-^P)^Pd] , bis-(dibenzyliden-aceton)palladium (0) [ (dba)2Pd^1 og ,such as sodium, potassium or lithium salts, suitably the lithium salt, of 1,2-diphenyl-3,5-dioxopyrazolidine in the presence of palladium complexes as catalysts. Preferred catalysts are tetrakis(triphenylphosphine)palladium (0) [(Ph-^P)^Pd] , bis-(dibenzylidene-acetone)palladium (0) [ (dba)2Pd^1 and

bis-[bis- (1,2-difenylfosfinoetan) Ipalladium (0)' [ (DIPH0S2)Pd (o}] , hensiktsmessig tetrakis-(trifenylfosfin)-palladium (0) i nærvær av slike ligander som trif enylfosf in (TPP) 1, 2-(bis-dif eny 1-fosfinoetan) (DIPHOS), heksametylfosfortriamid (HMP), fortrinns-, vis trifenylfosfin. Oppløsningsmidler som fortrinnsvis anvendes ved omsetningen, er eter-oppløsningsmidler så som tetrahydrofuran, .1, 2-dimetoks.yetan og dimetylsulf oksyd , særlig tetrahydrofuran under vannfrie betingelser. bis-[bis-(1,2-diphenylphosphinoethane) Ipalladium (0)' [ (DIPH0S2)Pd (o}] , conveniently tetrakis-(triphenylphosphine)-palladium (0) in the presence of such ligands as triphenylphosphine (TPP) 1, 2-(bis-diphenyl 1-phosphinoethane) (DIPHOS), hexamethylphosphoric triamide (HMP), preferably triphenylphosphine. Solvents which are preferably used in the reaction are ether solvents such as tetrahydrofuran, .1, 2-dimethoxy. butane and dimethylsulfoxide, especially tetrahydrofuran under anhydrous conditions.

Omsetningen foretas vanligvis, ved at 3-metyl-2-butenyl-acetat oppløst i det passende oppløsningsmiddel, f. eks. tetrahydrofuran,. blandes ved romtemperatur med palladiumkomplekset og den passende ligand. Tilfredsstillende mengder av The reaction is usually carried out by dissolving 3-methyl-2-butenyl acetate in the appropriate solvent, e.g. tetrahydrofuran,. mixed at room temperature with the palladium complex and the appropriate ligand. Satisfactory amounts of

katalysator varierer fra 0,1 til 10 mol?.. ■ Oppløsningen av alkalimetallsaltet av 1,2-difenyl-3,5-dioksopyrazolidin catalyst varies from 0.1 to 10 mol?.. ■ The solution of the alkali metal salt of 1,2-diphenyl-3,5-dioxopyrazolidine

(2 til 4 mol) • tilsettes derefter raskt, og blandingen omrøres ved en temperatur fra romtemperatur til ?0°C. Derefter helles (2 to 4 moles) • is then rapidly added, and the mixture is stirred at a temperature from room temperature to ?0°C. Then pour

reaksjonsblandingen.i surt vann (pH 4 til 5), ekstraheres med et egnet oppløsningsmiddel, f.eks. etylacetat, etyleter eller diklor-metan. Produktet oppnådd eftef avdampning av opp-løsningsmidlet renses direkte ved kolonnekromatografi eller ved reekstraksjon med et basisk, vandig medium. I sistnevnte tilfelle isoleres produktet efter surgjøring med en mineralsyre, fortrinnsvis saltsyre, og ekstraksjon med et passende oppløsnings-middel. Ytterligere rensning oppnås' ved kolonnekromatografi. the reaction mixture in acidic water (pH 4 to 5), is extracted with a suitable solvent, e.g. ethyl acetate, ethyl ether or dichloromethane. The product obtained after evaporation of the solvent is purified directly by column chromatography or by re-extraction with a basic, aqueous medium. In the latter case, the product is isolated after acidification with a mineral acid, preferably hydrochloric acid, and extraction with a suitable solvent. Further purification is achieved by column chromatography.

De følgende eksempler skal tjene til å illustrere oppfinnelsen ytterligere: E ksempel 1 The following examples shall serve to further illustrate the invention: Example 1

3-metyl-2-buteny1-acetat (5 g, 0,039 mol),. trifenylfosfin (0,93 g) og tetrakis-(trifenylfosfin)-palladium (0) (1,42 g, 0,00123.mol) i 75 ml tørr tetrahydrofuran ble omrørt i 3-Methyl-2-butenyl-acetate (5 g, 0.039 mol). triphenylphosphine (0.93 g) and tetrakis-(triphenylphosphine)-palladium (0) (1.42 g, 0.00123.mol) in 75 ml of dry tetrahydrofuran were stirred in

15 minutter ved romtemperatur. En oppløsning av litiumsaltet15 minutes at room temperature. A solution of the lithium salt

av 1,2-difenyl-3,5-dioksopyrazolidin (20,13 g, 0,078 mol) opp-løst i 200 ml vannfri tetrahydrofuran ble derefter tilsatt.alt på en gang, og den resulterende blanding ble tilbakeløps-behandlet i 15 timer under nitrogen. Reaksjonsoppløsningen ble konsentrert og derefter hellet i overskudd av vann. Efter sur-' gjøring til pH 4-5 ble den vandige oppløsning ekstrahert med metylenklorid. Det organiske lag ble fraskilt, tørret (MgSO^) og inndampet til tørrhet for å gi tittelforbindelsen som råprodukt. Rensning ved kolonnekromatografi (silikagel) of 1,2-diphenyl-3,5-dioxopyrazolidine (20.13 g, 0.078 mol) dissolved in 200 mL of anhydrous tetrahydrofuran was then added all at once, and the resulting mixture was refluxed for 15 h under nitrogen. The reaction solution was concentrated and then poured into excess water. After acidification to pH 4-5, the aqueous solution was extracted with methylene chloride. The organic layer was separated, dried (MgSO 4 ) and evaporated to dryness to give the title compound as crude product. Purification by column chromatography (silica gel)

(CH^jC^/CH^CN 98:2 volum/volum) ga den ønskede forbindelse i ren form, sm.p. 15 6°C. (CH^jC^/CH^CN 98:2 v/v) gave the desired compound in pure form, m.p. 15 6°C.

Analyse for C2oH20N2C2:Analysis for C2oH20N2C2:

Beregnet: % C 74,79, H 6,29, N 8,74Calculated: % C 74.79, H 6.29, N 8.74

Funnet: % C 75,14, H 6,37, N 8,68. Found: % C 75.14, H 6.37, N 8.68.

Eksempel 2 Example 2

3-metyl-2-butény1-acetat (5'g, 0,039 mol), 1-2-(bis-difenylfosfinoetan) (0,155 g, 0,39 mmol) og bis-(dibenzylidenaceton)-palladium (0) (0,3 g, 0,522 mmol) i 75 ml vannfri tetrahydrofuran ble omrørt i 10 minutter ved romtemperatur. En oppløsning 3-Methyl-2-butenyl-acetate (5 g, 0.039 mol), 1-2-(bis-diphenylphosphinoethane) (0.155 g, 0.39 mmol) and bis-(dibenzylideneacetone)-palladium (0) (0, 3 g, 0.522 mmol) in 75 ml anhydrous tetrahydrofuran was stirred for 10 minutes at room temperature. A solution

av .litiumsaltet av 1,2-difenyl-3,5-dioksopyrazolldin (20,13 g, 0,078 mol') i 150 ml vannfri .tetrahydrofuran ble derefter-tilsatt alt på en gang, og den resulterende blanding ble omrørt i 48 timer ved romtemperatur. Ved derefter å gå frem som beskrevet i eksempel 1, fikk man den ønskede forbindelse, sm.p. 156°C. Analyse for C2o<H>20<*S,>2°2<:>of the lithium salt of 1,2-diphenyl-3,5-dioxopyrazolidine (20.13 g, 0.078 mol') in 150 mL of anhydrous tetrahydrofuran was then added all at once, and the resulting mixture was stirred for 48 h at room temperature. By then proceeding as described in example 1, the desired compound was obtained, m.p. 156°C. Analysis for C2o<H>20<*S,>2°2<:>

Beregnet: I c 74, 97, I! 6,29, N 8,74Calculated: I c 74, 97, I! 6.29, N 8.74

Funnet: % C 74,85, H 6,11, N- 8,81 Found: % C 74.85, H 6.11, N- 8.81

Claims (9)

1. Fremgangsmåte for fremstilling- av 4-(3-metyl-2-butenyi)-1,2-difenyl-3,5-dioksopyrazolidin med formelen 1. Process for the preparation of 4-(3-methyl-2-butenyl)-1,2-diphenyl-3,5-dioxopyrazolidine with the formula karakterisert ved at 3-metyl-2-buteny1-acetat omsettes med et alkalimetallsalt av 1;2-difenyl-3,5-dickso-pyrazolidin i nærvær av en egnet katalysator og av en ligand. 2 i Fremgangsmåte ifølge krav 1, karakterisert ■ved at natrium-, kalium- eller litiumsaltet av 1,2-difenyl-3 ,5-dioksopyrazolidin anvendes-.characterized in that 3-methyl-2-buteny1-acetate is reacted with an alkali metal salt of 1,2-diphenyl-3,5-dixo-pyrazolidine in the presence of a suitable catalyst and of a ligand. 2 in Method according to claim 1, characterized ■ in that the sodium, potassium or lithium salt of 1,2-diphenyl-3,5-dioxopyrazolidine is used. 3. Fremgangsmåte ifølge krav 1 og 2, karakterisert ved at det. som katalysator anvendes; et palladiumkompleks...3. Method according to claims 1 and 2, characterized in that as a catalyst is used; a palladium complex... 4. Fremgangsmåte ifølge krav 3, karakterisert ved at det som palladiumkompleks anvendes tetrakis-(trifenylfosfiri)palladium (0), bis-(dibenzylidenaceton)- palladium - (0) eller, bis-[bis-(1,2-difenylfosfinoetan]-palladium (0).4. Method according to claim 3, characterized in that tetrakis-(triphenylphosphiri)palladium (0), bis-(dibenzylideneacetone)- palladium - (0) or, bis-[bis-(1,2-diphenylphosphinoethane]-palladium (0). 5. Fremgangsmåte ifølge krav 1 til'4, . karakterisert ved at det som ligand anvendes trifenylfosfin, 1,2 - (bis-difenylfosfinoetan) eller heksametylfosfortriamid..5. Method according to claims 1 to 4, . characterized in that it is used as a ligand triphenylphosphine, 1,2 - (bis-diphenylphosphinoethane) or hexamethylphosphoric triamide.. 6. Fremgangsmåte ifølge krav 1 til- 5, karakterisert ved at omsetningen utføres i nærvær av et inert, organisk oppløsningsmiddel.6. Method according to claim 1 to 5, characterized in that the reaction is carried out in the presence of an inert, organic solvent. 7. Fremgangsmåte ifølge krav 6, karakteriser, t ved at det som inert organisk oppløsningsmiddel anvendes tetrahydrofuran, 1,2-dimetoksyetan eller dimetylsulfoksyd.7. Method according to claim 6, characterized in that tetrahydrofuran, 1,2-dimethoxyethane or dimethylsulfoxide is used as inert organic solvent. 8..-Fremgangsmåte ifølge krav 1 til 7', karakterisert ved at omsetningen utføres ved en temperatur fra 20 til 70°C.8..-Procedure according to claims 1 to 7', characterized in that the reaction is carried out at a temperature from 20 to 70°C. 9. " Anvendelse, av 3-metyl-2-butenyl-acetat ved fremstilling av feprazon.9. "Use of 3-methyl-2-butenyl acetate in the manufacture of feprazone.
NO823596A 1981-10-29 1982-10-28 PROCEDURE FOR PREPARING 4- (3-METHYL-2-BUTENYL) -1,2-DIPHENYL-3,5-DIOXOPYRAZOLIDINE NO823596L (en)

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

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NO823596L true NO823596L (en) 1983-05-02

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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) ES8308855A1 (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)

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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

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GB2108125A (en) 1983-05-11
CA1179354A (en) 1984-12-11
PH19644A (en) 1986-06-04
FI823545A7 (en) 1983-04-30
GR77724B (en) 1984-09-25
FR2515646B1 (en) 1986-02-14
GB2108125B (en) 1985-03-20
AR231832A1 (en) 1985-03-29
ES516902A0 (en) 1983-10-01
PT75755A (en) 1982-11-01
NL8204170A (en) 1983-05-16
ATA370382A (en) 1985-04-15
IT1168184B (en) 1987-05-20
IT8124772A1 (en) 1983-04-29
PT75755B (en) 1985-11-20
FI823545L (en) 1983-04-30
FR2515646A1 (en) 1983-05-06
CH651555A5 (en) 1985-09-30
SE8206143D0 (en) 1982-10-28
JPS5888365A (en) 1983-05-26
DK477882A (en) 1983-04-30
FI823545A0 (en) 1982-10-18
YU240282A (en) 1985-03-20
AT379151B (en) 1985-11-25
SE8206143L (en) 1983-04-30
ES8308855A1 (en) 1983-10-01
KR840001955A (en) 1984-06-07
IT8124772A0 (en) 1981-10-29

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