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DE1195759B - Process for the preparation of 1-phenyl-2, 3-dimethyl-4- (salicoyl-oxyacetyl-amino) -pyrazolon- (5) - Google Patents

Process for the preparation of 1-phenyl-2, 3-dimethyl-4- (salicoyl-oxyacetyl-amino) -pyrazolon- (5)

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Publication number
DE1195759B
DE1195759B DESCH23132A DESC023132A DE1195759B DE 1195759 B DE1195759 B DE 1195759B DE SCH23132 A DESCH23132 A DE SCH23132A DE SC023132 A DESC023132 A DE SC023132A DE 1195759 B DE1195759 B DE 1195759B
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Germany
Prior art keywords
phenyl
dimethyl
amino
pyrazolone
pyrazolon
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
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DESCH23132A
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German (de)
Inventor
Rer Nat Felix H Schmidt Dr
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FELIX H SCHMIDT DR RER NAT
Original Assignee
FELIX H SCHMIDT DR RER NAT
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Publication date
Application filed by FELIX H SCHMIDT DR RER NAT filed Critical FELIX H SCHMIDT DR RER NAT
Priority to DESCH23132A priority Critical patent/DE1195759B/en
Publication of DE1195759B publication Critical patent/DE1195759B/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic 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
    • C07D231/14Heterocyclic 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
    • C07D231/44Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C07D231/50Acylated on said nitrogen atom

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

Verfahren zur Herstellung von l-Phenyl-2,3-dimethyl-4-(salicoyl-oxyacetyl-amino)-pyrazolon-(5) Die Erfindung betrifft ein Verfahren zur Herstellung von 1 -Phenyl-2,3-dimethyl-4-(salicoyloxyacetyl-amino)-pyrazolon-(5) der Formel das dadurch gekennzeichnet ist, daß man in an sich bekannter Weise entweder a) 1-Phenyl-2,3- dimethyl-4- amino- pyrazolon- (5) mit Salicoyloxyessigsäure oder deren funktionellen Derivaten, wie Säurehalogeniden oder -estern, kondensiert oder b) 1 - Phenyl - 2,3 - dimethyl - 4- (oxyacetylamino)-pyrazolon-(5) oder ein 1-Phenyl-2, 3-dimethyl-4-(halogenacetylamino)-pyrazolon-(5), wie das 1-Phenyl-2,3- dimethyl -4- (chloracetylamino)-pyrazolon-(5), mit Salicylsäure oder deren funktionellen Derivaten, z. B. den Salzen, umsetzt.Process for the preparation of l-phenyl-2,3-dimethyl-4- (salicoyl-oxyacetyl-amino) -pyrazolon- (5) The invention relates to a process for the preparation of 1-phenyl-2,3-dimethyl-4- ( salicoyloxyacetyl-amino) -pyrazolone- (5) of the formula which is characterized in that either a) 1-phenyl-2,3-dimethyl-4-aminopyrazolone (5) is condensed in a manner known per se with salicoyloxyacetic acid or its functional derivatives, such as acid halides or esters, or b ) 1 - Phenyl - 2,3 - dimethyl - 4- (oxyacetylamino) -pyrazolon- (5) or a 1-phenyl-2, 3-dimethyl-4- (haloacetylamino) -pyrazolon- (5), like the 1- Phenyl-2,3-dimethyl -4- (chloroacetylamino) pyrazolone- (5), with salicylic acid or its functional derivatives, e.g. B. the salts.

Die analgetische, antipyretische und antiphlogistische Wirksamkeit des 1-Phenyl-2, 3-dimethylpyrazolons-(5) und verschiedener seiner Derivate ist bekannt. Man hat auch bereits einige bAcylamino-Derivate des 1-Phenyl-2, 3-dimethyl-pyrazolons-(5) hergestellt. z. B. die Formyl-, Acetyl-, Isovaleroyl-und Nicotinoylverbindung; diese Verbindungen weisen jedoch hinsichtlich ihrer Wirkung keine wesentlichen Unterschiede gegenüber dem 1-Phenyl-2,3-dimethyl-pyrazolon-(5) auf. Insbesondere ist es bislang noch nicht gelungen, Derivate des l-Phenyl-2,3-dimethyl-pyrazolons-(5) mit guter antirheumatischer Wirkung herzustellen. Auch die in der Patentschrift 8453 des Amtes für Erfindungs- und Patentwesen in der sowjetischen Besatzungszone Deutschlands beschriebenen 4-Glykoloyl-amino-Derivate des l-Phenyl-2,3-dimethyl-pyrazolons-(5) weisen nur eine relativ geringe antiphlogistische Wirksamkeit auf, so daß sie als Rheumamittel nicht brauchbar sind. The analgesic, antipyretic and anti-inflammatory effectiveness 1-Phenyl-2, 3-dimethylpyrazolons- (5) and various of its derivatives are known. There are already some bAcylamino derivatives of 1-phenyl-2, 3-dimethyl-pyrazolone- (5) manufactured. z. B. the formyl, acetyl, isovaleroyl and nicotinoyl compounds; these However, compounds show no significant differences in terms of their effect compared to 1-phenyl-2,3-dimethyl-pyrazolone- (5). In particular, it is so far not yet succeeded in making derivatives of l-phenyl-2,3-dimethyl-pyrazolons- (5) with good to produce anti-rheumatic effects. Also that in the Office's patent specification 8453 for inventions and patents in the Soviet zone of occupation in Germany 4-Glykoloyl-amino-Derivate des l-Phenyl-2,3-dimethyl-pyrazolons- (5) have only a relatively low anti-inflammatory effectiveness, so that they as Rheumatoid drugs are not useful.

Das Verfahrensprodukt besitzt nun eine hervorragende antirheumatische und antiphlogistische Wirksamkeit. Da die neue Verbindung, wie sich aus den nachfolgenden Versuchen ergibt, daneben auch gute antipyretische und analgetische Eigenschaften aufweist und ihre Toxizität gering ist, stellt sie ein aus- gezeichnetes Arzneimittel zur Schmerz- und Entzündungsbekämpfung dar. The process product now has an excellent antirheumatic and anti-inflammatory effectiveness. As the new connection, as can be seen from the subsequent Experiments also show good antipyretic and analgesic properties and its toxicity is low, it exhibits an drawn medicine to fight pain and inflammation.

Als Vergleichssubstanzen dienten bei den Versuchen Cortison, 3,5-dioxo-1,2-diphenyl-4-n-butyl-pyrazolidin, 1-Phenyl-2,3-dimethyl-pyrazolon-(5), Salicylaid und 1-Phenyl-2,3-dimethyl-4-dimethylaminopyrazolon-(5). In the tests, cortisone, 3,5-dioxo-1,2-diphenyl-4-n-butyl-pyrazolidine, 1-phenyl-2,3-dimethyl-pyrazolone- (5), salicylaid and 1-phenyl-2,3-dimethyl-4-dimethylaminopyrazolone- (5).

Aus den Versuchsergebnissen sind überlegene Eigenschaften des Verfahrensproduktes gegenüber den bekannten Verbindungen ersichtlich. The test results show superior properties of the process product visible compared to the known connections.

Antiphlogistische Wirksamkeit 1. Formaldehydarthritis (nach H. S e 1 y e, J. Canad. Anti-inflammatory effectiveness 1. Formaldehyde arthritis (according to H. S e 1 y e, J. Canad.

Med. Ass., 61, S. 353, 1949) Bei einer täglichen Gabe von 30 mg je Kilogramm Rattengewicht an zwölf Ratten ergibt sich nach sechsmaliger Gabe eine Abnahme des Gelenkdurchmessers der Rattenpfote um 600/0 gegenüber einem unbehandelten Tierkollektiv. Insgesamt wurden 180 mg/kg als Suspension in Tylose verabfolgt. Die Einwirkung von 3.5-Dioxo-l ,2-diphenyl-4-n-buty1-pyrazolidin als Na-Salz bewirkt eine Abnahme von 550/0. Med. Ass., 61, p. 353, 1949) With a daily dose of 30 mg each One kilogram of rat weight on twelve rats results after six doses Decrease in the joint diameter of the rat paw by 600/0 compared to an untreated one Animal collective. A total of 180 mg / kg was administered as a suspension in Tylose. the Effect of 3.5-dioxo-1,2-diphenyl-4-n-buty1-pyrazolidine as Na salt causes a decrease of 550/0.

2. Kaolin-Udemtest Die Verbindung hat bei Ratten von allen untersuchten Derivaten die beste antiphlogistische Wirkung. Bei dieser subacut verlaufenden Entzündung hat nur das Cortison eine annähernd gleich starke Wirkung gezeigt. 2. Kaolin-Udemtest The compound has been examined in rats by all Derivatives have the best anti-inflammatory effects. With this subacute inflammation only the cortisone showed an almost equally strong effect.

Testanordnung nach J. H i 11 e b r e c h t (Arzneimittelforschung. 4. S. 607, 1954), Einzeldosis 30 mg/ kg p. o. sechs Versuchstiere. Test arrangement according to J. H i 11 e b r e c h t (drug research. 4. S. 607, 1954), single dose 30 mg / kg p. o. six experimental animals.

3. Eiereiweiß-Ödem Das sehr akut ablaufende Eiereiweiß-Ödem wurde von der verfahrensgemäß erhaltenen Verbindung signifikant gehemmt. Hier hat sie die gleiche Wirkung wie das 3,5-Dioxo-1,2-diphenyl-4-n-butyl-pyrazolidin und 1 - Phenyl - 2,3-dimethyl-4-dimethylaminopyrazolon45), übertrifft aber Cortison und l-Phenyl-2,3-dimethyl-pyrazolon-(5). 3. Egg-protein edema The very acutely running egg-protein edema was is significantly inhibited by the compound obtained according to the method. Here she has the same effect as the 3,5-dioxo-1,2-diphenyl-4-n-butyl-pyrazolidine and 1 - Phenyl - 2,3-dimethyl-4-dimethylaminopyrazolone45), but surpasses cortisone and 1-phenyl-2,3-dimethyl-pyrazolone- (5).

Testanordnung nach G. W i 1 h e 1 m i und R.Domenjoz (Arch. exp. Path., 212, S. 125. Test arrangement according to G. W i 1 h e 1 m i and R Domenjoz (Arch. Exp. Path., 212, p. 125.

1950), EiereiweiSUdem am Mäuseohr, gemessen an der Verzögerung der Trypanblauausscheidung.1950), egg protein on the mouse ear, measured by the delay in the Trypan blue excretion.

4. Kaolin-Pleuritis Die Messung der Exsudatmenge bei Albinoratten ergibt bei Kontrollratten nach 18 Stunden 1,8 ml. 4. Kaolin Pleurisy The measurement of the amount of exudate in albino rats results in 1.8 ml in control rats after 18 hours.

Unter einer einmaligen oralen Gabe von 30 mg/kg ergibt sich eine Hemmung um 34,60/0. Nach dreimaliger Gabe von lOmg/kg beträgt die Hemmung 35,8%. Weder l-Phenyl-2, 1 3-dimethyl-pyrazolon-(5), I-Phenyl-2, 3-dimethyl-3-dimethylamino-pyrazolon-(5) noch Cortison ergaben gleich starke Hemmungen der Exsudatmenge.A single oral dose of 30 mg / kg results in inhibition at 34.60 / 0. After three doses of 10 mg / kg, the inhibition is 35.8%. Neither l-phenyl-2, 1 3-dimethyl-pyrazolone- (5), I-phenyl-2, 3-dimethyl-3-dimethylamino-pyrazolone- (5) even cortisone produced equally strong inhibitions in the amount of exudate.

Analgetische Messungen an Mäusen Nach Gabe von 10 mg/kg s. c. ergab sich eine Erhöhung der Reaktionszeit um mehr als 100% (2 Stunden nach Gabe). Die vergleichsweise geprüften Verbindungen Salicylamid und 1-Phenyl-2,3-dimethyl-Pdimethylamino-pyrazolon-( 5) hatten wesentlich geringere analgetische Effekte. Analgesic measurements on mice After administration of 10 mg / kg s.c. revealed an increase in the reaction time by more than 100% (2 hours after administration). the comparatively tested compounds salicylamide and 1-phenyl-2,3-dimethyl-Pdimethylamino-pyrazolone- ( 5) had much less analgesic effects.

Für die Analgesiemessung wurde die Brennstrahlmethode nach 5 m i t h - d' Am o u r (J. Pharm. exp. For the analgesia measurement, the focal beam method was used after 5 m i t h - d 'Am o u r (J. Pharm. exp.

Therapy, 72, S. 74, 1941) verwendet. Die Werte wurden pro Substanz an zwölf Mäusen gleicher Reaktionszeit ermittelt.Therapy, 72, p. 74, 1941) was used. The values were per substance determined on twelve mice with the same reaction time.

Antipyretischer Versuch Im Antipyrese-Versuch am Meerschweinchen (Fiebererzeugung durch die unter dem Handelsnamen bekannten Eiweißstoffe Pyrifer) ergaben sich nach Gabe von 300 mg/kg p. o. nach 41/2 Stunden Temperatursenkungen zur Norm. Die vergleichsweise untersuchten Verbindungen Salicylamid und l-Phenyl-2,3-dimethyl-pyrazolon-(5) hatten wesentlich schwächere Effekte zur Folge. Antipyretic experiment In the antipyretic experiment on guinea pigs (Fever generated by the protein substances known under the trade name Pyrifer) after administration of 300 mg / kg p. o. temperature drops after 41/2 hours to the norm. The comparatively investigated compounds salicylamide and l-phenyl-2,3-dimethyl-pyrazolone- (5) resulted in much weaker effects.

Toxizität Die Dbo an der weißen Maus nach i. v. Gabe (20 Stunden) beträgt 435 mg/kg (als Lösungsvermittler wurde eine kleine Menge Dimethylformamid verwendet). Toxicity The Dbo in the white mouse after i. v. Gift (20 hours) is 435 mg / kg (a small amount of dimethylformamide was used as a solubilizer used).

Das Verfahrensprodukt ist gegenüber 3,5-Dioxo-1,2-diphenyl-4-n-butyl-pyrazolidin viermal weniger und gegenüber 1-Phenyl-2,3 -dimethyl -4-dimethylamino-pyrazolon-(5) halb so toxisch. The process product is opposite to 3,5-dioxo-1,2-diphenyl-4-n-butyl-pyrazolidine four times less and compared to 1-phenyl-2,3-dimethyl -4-dimethylamino-pyrazolone- (5) half as toxic.

Beispiel 1-Phenyl-2,3-dimethyl-4-(salicoyloxyacetyl-amino)-pyrazolon-(5) 20 g 1 -Phenyl-2,3-dimethyl-4-amino-pyrazolon-(5) werden in benzolischer Lösung mit 6 g Chloracetylchlorid versetzt und 3 Stunden unter Rückfluß zum Sieden erhitzt. Nach dem Erkalten saugt man den entstandenen Niederschlag ab und wäscht ihn mit Äther. Durch Behandeln des Niederschlags mit Wasser wird das als Nebenprodukt gebildete l-Phenyl-2,3-dimethyl-4-amino-pyrazolon-(5)-hydrochlorid in Lösung gebracht. Der Rückstand wird aus Äthanol umkristallisiert. Man erhält auf diese Weise in etwa 700/oiger Ausbeute das als Ausgangssubstanz dienende 1-Phenyl-2, 3-dimethyl-4-chloracetyl aminopyrazolon-(5) vom Schmelzpunkt 187°C. Example 1-Phenyl-2,3-dimethyl-4- (salicoyloxyacetyl-amino) -pyrazolone- (5) 20 g of 1-phenyl-2,3-dimethyl-4-aminopyrazolone- (5) are in a benzene solution 6 g of chloroacetyl chloride are added and the mixture is refluxed for 3 hours. After cooling, the precipitate formed is suctioned off and washed with it Ether. By treating the precipitate with water, that is formed as a by-product Brought l-phenyl-2,3-dimethyl-4-aminopyrazolone (5) hydrochloride in solution. Of the The residue is recrystallized from ethanol. You get something like this in this way 700% yield of the 1-phenyl-2,3-dimethyl-4-chloroacetyl used as the starting substance aminopyrazolone- (5) of melting point 187 ° C.

11,2 g der erhaltenen Verbindung werden mit 6,4 g wasserfreiem Natriumsalicylat in 60 ccm absolutem Äthanol unter Rückfluß erhitzt. Das entstandene Natriumchlorid wird abfiltriert und das Filtrat im Vakuum eingeengt. Das 1 -Phenyl-2,3-dimethyl-(salicoyloxyacetyl-amino)-pyrazolon-(5) wird mit Wasser ausgefällt. Nach Umkristallisation aus verdünntem Alkohol schmilzt die Verbindung bei 189°C. 11.2 g of the compound obtained are mixed with 6.4 g of anhydrous sodium salicylate heated under reflux in 60 cc of absolute ethanol. The resulting sodium chloride is filtered off and the filtrate is concentrated in vacuo. The 1-phenyl-2,3-dimethyl- (salicoyloxyacetyl-amino) -pyrazolon- (5) is precipitated with water. Melts after recrystallization from dilute alcohol the compound at 189 ° C.

Das Verfahren zur Herstellung des Ausgangsmaterials wird hier nicht beansprucht. The method of making the starting material is not mentioned here claimed.

Claims (1)

Patentanspruch: Verfahren zur Herstellung von 1-Phenyl-2,3-dimethyl-4-(salicoyloxyacetyl-amino)-pyrazolon-(5) der Formel dadurch gekennzeichnet, daß man in an sich bekannter Weise entweder a) 1-Phenyl-2,3-dimethyl-4-amino-pyrazolon-(5) mit Salicoyloxyessigsäure oder deren funktionellen Derivaten kondensiert oder b) 1-Phenyl-2,3-dimethyl-4-oxyacetylamino-oder ein 1-Phenyl-2,3- dimethyl -4-halogenacetylamino-pyrazolon-(5) mit Salicylsäure oder deren funktionellen Derivaten umsetzt.Claim: Process for the preparation of 1-phenyl-2,3-dimethyl-4- (salicoyloxyacetyl-amino) -pyrazolon- (5) of the formula characterized in that either a) 1-phenyl-2,3-dimethyl-4-amino-pyrazolone- (5) is condensed with salicoyloxyacetic acid or its functional derivatives, or b) 1-phenyl-2,3- Reacts dimethyl-4-oxyacetylamino- or a 1-phenyl-2,3-dimethyl -4-haloacetylamino-pyrazolone- (5) with salicylic acid or its functional derivatives. In Betracht gezogene Druckschriften: Schweizerische Patentschrift Nr. 233 731; Patentschriften Nr. 7425, 8453 des Amtes für Erfindungs- und Patentwesen in der sowjetischen Besatzungszone Deutschlands; Journal für praktische Chemie, Bd. 130 (1931), S. 293 bis 303. Publications considered: Swiss patent specification No. 233,731; Patent documents No. 7425, 8453 of the Office for Invention and Patents in the Soviet occupation zone of Germany; Journal of Practical Chemistry, Vol. 130 (1931), pp. 293-303.
DESCH23132A 1957-11-20 1957-11-20 Process for the preparation of 1-phenyl-2, 3-dimethyl-4- (salicoyl-oxyacetyl-amino) -pyrazolon- (5) Pending DE1195759B (en)

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DESCH23132A DE1195759B (en) 1957-11-20 1957-11-20 Process for the preparation of 1-phenyl-2, 3-dimethyl-4- (salicoyl-oxyacetyl-amino) -pyrazolon- (5)

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DESCH23132A DE1195759B (en) 1957-11-20 1957-11-20 Process for the preparation of 1-phenyl-2, 3-dimethyl-4- (salicoyl-oxyacetyl-amino) -pyrazolon- (5)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE8453C (en) * H. KÖHLER in Braunschweig, Kastanien-Allee 33 Side coupling for railway wagons
DE7425C (en) * C. HAUPT, Gewerbeschullehrer, in Brieg Zinc muffle furnace with gas firing, the hearth is also heated from below and the calcining and tempering furnace is heated by the evacuating fire gases
CH233731A (en) * 1942-04-17 1944-08-15 Ag Sandoz Process for the preparation of an aromatic carboxamide.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE8453C (en) * H. KÖHLER in Braunschweig, Kastanien-Allee 33 Side coupling for railway wagons
DE7425C (en) * C. HAUPT, Gewerbeschullehrer, in Brieg Zinc muffle furnace with gas firing, the hearth is also heated from below and the calcining and tempering furnace is heated by the evacuating fire gases
CH233731A (en) * 1942-04-17 1944-08-15 Ag Sandoz Process for the preparation of an aromatic carboxamide.

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