DE968560C - Process for the preparation of 1, 2-dimethyl-3-phenylpyrazolone- (5) - Google Patents

Process for the preparation of 1, 2-dimethyl-3-phenylpyrazolone- (5)

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Publication number
DE968560C
DE968560C DEF10233A DEF0010233A DE968560C DE 968560 C DE968560 C DE 968560C DE F10233 A DEF10233 A DE F10233A DE F0010233 A DEF0010233 A DE F0010233A DE 968560 C DE968560 C DE 968560C
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Germany
Prior art keywords
phenylpyrazolone
dimethyl
parts
methyl
preparation
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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.)
Expired
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DEF10233A
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German (de)
Inventor
Dr Kurt Windisch
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Hoechst AG
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Hoechst AG
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Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to DEF10233A priority Critical patent/DE968560C/en
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Publication of DE968560C publication Critical patent/DE968560C/en
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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
    • C07D231/18One oxygen or sulfur atom
    • C07D231/20One oxygen atom attached in position 3 or 5
    • C07D231/22One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Description

Verfahren zur Herstellung von 1, 2-Dimethyl-3-phenylpyrazolon-(5) Das i, 2-Dimethyl-3-phenylpyrazolon-(5) erhält man nach Michaelis und Dorn, Liebigs Annalen der Chemie, Bd. 352, Seite 176, am besten, indem man i-Methyl-3-phenylpyrazolon-(5) mit jodmethyl und einigen Tropfen Methanol im Einschmelzrohr im Wasserbad erhitzt.Process for the preparation of 1, 2-dimethyl-3-phenylpyrazolone- (5) The i, 2-dimethyl-3-phenylpyrazolone- (5) is obtained according to Michaelis and Dorn, Liebigs Annalen der Chemie, vol. 352, page 176, best by using i-methyl-3-phenylpyrazolon- (5) heated with iodomethyl and a few drops of methanol in a melting tube in a water bath.

Nach der gleichen Literaturstelle erhält man es auch durch Erhitzen von 3-Phenylpyrazolon-(5), Jodmethyl und etwas Methanol im Einschmelzrohr. Doch entstehen nach dieser Methöde neben etwa 5 Teilen i, 2-Dimethyl-3-phenylpyrazolon-(5) 3 Teile i-Methyl-3-phenylpyrazolon-(5), z. B. aus 6o g 3-Phenylpyrazolon, 36 g i, 2-Dimethyl-3-phenylpyrazolon-(5) und 2i g i-Methyl-3-phenylpyrazolon-(5). Zur Darstellung von i-Methyl-3-phenylpyrazolon-(5) verwendeten Michaelis und Dorn, gemäß der angeführten Literaturstelle, Dimethylsulfat bei Wasserbadtemperatur, und zwar nahmen sie hierbei Zoo °/o der zur Einführung von zwei Methylgruppen in das 3-Phenylpyrazolon, d. h. der zur Bildung von i, 2-Dimethyl-3-phenylpyrazolon-(5) notwendigen Menge, ohne etwas anderes zu erhalten- als i-Methyl-3-phenylpyrazolon-(5). Es war offenbar nicht erkannt worden, daß zur Entstehung der i, 2-Dimethylverbindung wesentlich höhere Temperaturen als Wasserbadtemperatur notwendig sind.According to the same reference, it can also be obtained by heating of 3-phenylpyrazolone- (5), iodomethyl and some methanol in the melting tube. Indeed According to this method, in addition to about 5 parts of i, 2-dimethyl-3-phenylpyrazolone- (5) 3 parts of i-methyl-3-phenylpyrazolone- (5), e.g. B. from 6o g 3-phenylpyrazolone, 36 g i, 2-dimethyl-3-phenylpyrazolone- (5) and 2i g i-methyl-3-phenylpyrazolone- (5). For representation of i-methyl-3-phenylpyrazolon- (5) used Michaelis and Dorn, according to the cited Reference, dimethyl sulfate at water bath temperature, and they took it here Zoo ° / o that of introducing two methyl groups into the 3-phenylpyrazolone, i.e. H. the amount necessary for the formation of i, 2-dimethyl-3-phenylpyrazolon- (5), without to get something other than i-methyl-3-phenylpyrazolone- (5). Apparently it wasn't it has been recognized that the formation of the i, 2-dimethyl compound is much higher Temperatures as the water bath temperature are necessary.

Es wurde nun ein Verfahren zur Herstellung von i, 2-Dimethyl-3-phenylpyiazolon-(5) durch Behandeln von 3-Phenylpyrazolon-(5) mit methylierenden Mitteln ' oei erhöhter Temperatur gefunden, bei dem man -bezogen auf das 3-Phenylpyrazolon-(5) - mit der etwa theoretischen Menge Dimethylsulfat auf etwa i5o bis 2oti°, beziehungsweise mit Brommethyl und Methanol auf. etwa i2o bis i5o° erhitzt und die so erhaltenen Schmelzen in an' sich bekannter Weise aufarbeitet.There has now been a process for the preparation of i, 2-dimethyl-3-phenylpyiazolon- (5) by treating of 3-phenylpyrazolone- (5) with methylating agents 'found at an elevated temperature at which - based on the 3-phenylpyrazolone- (5) - with the approximately theoretical amount of dimethyl sulfate to about 15o to 2oti °, respectively with bromomethyl and methanol. heated to about i2o to i5o ° and the resulting Melting worked up in a manner known per se.

Bei dieser Arbeitsweise gelangt man zu einer fast quantitativen Ausbeute an =, 2-Diriiethyl-3;phenylpyrazolon-(5) ohne Beimengungen von. i-Methyl-3-phenylpyrazolon-(5). Letzteres braucht auch vorher nicht isoliert zu werden, wie bei der einen Variante des jodmethylverfahrens nach Michaelis und Dorn (Liebigs Annalen der Chemie, Bd. 352, S. 176, Zeilen 4 bis 8), denn ihnen gelingt nur mit isoliertem i-Methyl-3-phenylpyrazolon-(5) vollständige Methylierung zu i, 2-Dimethyl-3-phenylpyrazolon-(5), während sie unter den gleichen Versuchsbedingungen (a. a. O., Absatz 3, Zeilen i bis 7) des Erhitzens mit jodmethyl und Methanol im Einschmelzrohr auf dem Dampfbad direkt aus 3-Phenylpyrazolon-(5) lediglich ein umständlich zu trennendes Gemisch von i-Methyl-3-phenylpyrazolon-(5) und i, 2-Dimethyl-3-phenylpyrazolon-(5) gewännen.This procedure leads to an almost quantitative yield an =, 2-diriethyl-3; phenylpyrazolon- (5) without the addition of. i-methyl-3-phenylpyrazolone- (5). The latter does not need to be isolated beforehand, as is the case with the one variant the iodomethyl process according to Michaelis and Dorn (Liebigs Annalen der Chemie, Vol. 352, p. 176, lines 4 to 8), because they succeed only with isolated i-methyl-3-phenylpyrazolone- (5) complete methylation to i, 2-dimethyl-3-phenylpyrazolone- (5) while taking it the same test conditions (loc. cit., paragraph 3, lines i to 7) of heating with iodomethyl and methanol in the melting tube on the steam bath directly from 3-phenylpyrazolone- (5) only a difficult to separate mixture of i-methyl-3-phenylpyrazolone- (5) and i, 2-dimethyl-3-phenylpyrazolone- (5).

Erst diese keineswegs vorherzusehende Erkenntnis der Notwendigkeit hoher Temperaturen führte zu einem praktisch brauchbaren Herstellungsverfahren, das große Vorteile gegenüber der wenig befriedigenden Literaturangabe über die Gewinnung von i, 2-Dimethyl-3-phenylpyrazolon-(5). aufweist.Only this by no means foreseeable knowledge of necessity high temperatures led to a practically useful manufacturing process, the great advantage over the unsatisfactory literature on the extraction of i, 2-dimethyl-3-phenylpyrazolone- (5). having.

Beispiel i In 50,4 Teile Dimethylsulfat werden bei 6o° Anfangstemperatur32 3~eile3-Phenylpyrazolon-(5) eingetragen. Die Temperatur steigt von selbst schnell auf etwa i50°. Hierauf wird auf etwa 2oo° angeheizt und 7 Stunden bei dieser Temperatur gehalten. Die etwas abgekühlte. Schmelze wird in 175 Teilen Wasser aufgenommen, 51/2 Stunden gekocht, nach Behandlung mit 3 Teilen Entfärbungskohle filtriert, mit 40,5 Teilen 33°/oiger Natronlauge alkalisch gestellt und nochmals 2 Stunden gekocht. Nun wird die Lösung.mit Chloroform ausgeschüttelt, die sich dabei bildenden Schichten werden getrennt, und die Chloroformlösung wird eingeengt, Man erhält 29 Teile i, 2-Dimethyl-3-phenylpyrazolon-(5), das aus Benzol umkristallisiert werden kann und bei 107 bis iio° schmilzt.Example i In 50.4 parts of dimethyl sulfate, at an initial temperature of 60 °, 32 3-eile3-phenylpyrazolone- (5) entered. The temperature rises quickly by itself to about 150 °. This is followed by heating to about 2oo ° and 7 hours at this temperature held. The slightly cooled one. Melt is absorbed in 175 parts of water, Boiled for 51/2 hours, filtered after treatment with 3 parts of decolorizing charcoal, with 40.5 parts of 33% sodium hydroxide solution made alkaline and boiled for another 2 hours. Now the solution is shaken out with chloroform, the layers that form in the process are separated, and the chloroform solution is concentrated, 29 parts of i are obtained 2-dimethyl-3-phenylpyrazolone- (5), which can be recrystallized from benzene and melts at 107 to 10 °.

Beispiel 2 Ein Gemisch von 24 Teilen 3-Phenylpyrazolon, 3o Teilen Brommethyl und ig Teilen Methanol wird im Autoklav 15 Stunden auf i45° erhitzt. Nach dem Erkalten wird die kristallinisch erstarrte Reaktionsmasse in i5o Teilen Wasser gelöst, die Lösung filtriert, mit überschüssiger Natronlauge versetzt und mehrmals bei 55 bis 6o° mit Benzol ausgerührt.- Die sich dabei bildenden Schichten werden getrennt, und die Benzollösung wird eingeengt. Die Ausbeute an i, 2-Dimethyl-3-phenylpyrazölon-(5) beträgt 26 Teile.Example 2 A mixture of 24 parts of 3-phenylpyrazolone, 30 parts Bromomethyl and ig parts of methanol are heated in the autoclave to i45 ° for 15 hours. After cooling, the crystalline solidified reaction mass becomes in 150 parts Dissolved water, the solution filtered, mixed with excess sodium hydroxide solution and Stirred out several times with benzene at 55 to 60 °. The layers formed in the process are separated and the benzene solution is concentrated. The yield of i, 2-dimethyl-3-phenylpyrazolone- (5) is 26 parts.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von i, 2-Dimethyl-3 -phenylpyrazolon - (5) durch Behandeln von 3-Phenylpyrazolon-(5) mit methylierenden Mitteln bei erhöhter Temperatur, dadurch gekennzeichnet, daß man - bezogen auf das 3-Phenylpyrazolon-(5) - mit der etwa theoretischen Menge Dimethylsulfat auf etwa 15o bis 2oo°, beziehungsweise mit Brommethyl und Methanol auf etwa i2o bis 15o° erhitzt und die so erhaltenen Schmelzen in an sich bekannter Weise aufarbeitet. In Betracht gezogene Druckschriften: Deutsche Patentschrift Nr. 516 534.PATENT CLAIM: Process for the production of i, 2-dimethyl-3-phenylpyrazolone - (5) by treating 3-phenylpyrazolone- (5) with methylating agents at elevated levels Temperature, characterized in that - based on the 3-phenylpyrazolone- (5) - With the approximately theoretical amount of dimethyl sulfate to about 15o to 2oo °, respectively heated with bromomethyl and methanol to about i2o to 15o ° and the resulting Melts worked up in a manner known per se. Considered publications: German patent specification No. 516 534.
DEF10233A 1952-10-26 1952-10-26 Process for the preparation of 1, 2-dimethyl-3-phenylpyrazolone- (5) Expired DE968560C (en)

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DEF10233A DE968560C (en) 1952-10-26 1952-10-26 Process for the preparation of 1, 2-dimethyl-3-phenylpyrazolone- (5)

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Application Number Priority Date Filing Date Title
DEF10233A DE968560C (en) 1952-10-26 1952-10-26 Process for the preparation of 1, 2-dimethyl-3-phenylpyrazolone- (5)

Publications (1)

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DE968560C true DE968560C (en) 1958-03-06

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE516534C (en) * 1924-11-26 1931-01-26 Curt Raeth Dr Process for the preparation of pyrazolone derivatives

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE516534C (en) * 1924-11-26 1931-01-26 Curt Raeth Dr Process for the preparation of pyrazolone derivatives

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