DE71261C - Process for the preparation of amidoantipyrine and acetamidoantipyrine - Google Patents

Process for the preparation of amidoantipyrine and acetamidoantipyrine

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Publication number
DE71261C
DE71261C DENDAT71261D DE71261DA DE71261C DE 71261 C DE71261 C DE 71261C DE NDAT71261 D DENDAT71261 D DE NDAT71261D DE 71261D A DE71261D A DE 71261DA DE 71261 C DE71261 C DE 71261C
Authority
DE
Germany
Prior art keywords
amidoantipyrine
hydrochloric acid
solution
benzene
water
Prior art date
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 - Lifetime
Application number
DENDAT71261D
Other languages
German (de)
Original Assignee
FARBWERKE VORM. MEISTER LUCIUS & BRÜNING in Höchst a. M
Publication of DE71261C publication Critical patent/DE71261C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C07D231/50—Acylated on said nitrogen atom
    • 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
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C07D231/48—Oxygen atom in position 3 or 5 and nitrogen atom in position 4 with hydrocarbon radicals attached to said nitrogen atom

Description

KAISERLICHES A IMPERIAL A

Aus dem Nitrosoantipyrin, welches leicht gewonnen wird durch Einwirkung von Nitrit 'auf Antipyrin in saurer Lösung, erhielt Knorr (Bor. 17, 2039) durch Einwirkung reducirender Agcnticn ein Product, von dem er es dahin-•gcstellt sein liifst, ob dasselbe als Amidoantipyrin zu betrachten sei. Bei weiterer Untersuchung dieser Reaction hat sich gezeigt, dafs thatsa'chlich dabei Amidoantipyrin gebildet wird, und wurde nun weiter gefunden, dafs aus dem Amidoantipyrin durch Behandlung mit Essigsa'ureanhydrid ein Acetyldcrivat entsteht, das in der Medicin seiner antifebrilen Eigenschaften halber Verwendung finden kann. Dabei ist hervorzuheben, dafs man zur Isolirung des Amidoantipyrins mit Vortheil sich derBenzylidenverbindung bedient. Dieselbe bildet sich leicht bei Einwirkung von Benzaldehyd auf die wässerige neutrale oder alkalische Lösung des Amidoantipyrins. From nitrosoantipyrine, which is easily obtained through the action of nitrite 'on antipyrine in acidic solution, Knorr received (Bor. 17, 2039) by the action of reducing agents a product, of which he puts it there whether it is to be regarded as amidoantipyrine. Upon further investigation This reaction has shown that amidoantipyrine is actually formed in the process, and it has now been found that amidoantipyrine can be obtained by treatment with acetic anhydride an acetyl derivative arises, which in the medicin its antifebrile properties can be used halfway. It should be emphasized that in order to isolate the Amidoantipyrins makes advantageous use of the benzylidene compound. It forms easily on the action of benzaldehyde on the aqueous neutral or alkaline solution of the amidoantipyrine.

Man verfahrt z. B. wie folgt:
100 Theile Nitrosoantipyrin werden in 100 Theilen Wasser, 500 Theilen Sprit, 200 Theilen verdünnter Essigsäure (5oproccntig) suspendirt und unter Rühren allmälig Zinkstaub eingetragen. Zugleich wird durch Einstellen in kaltes Wasser dafür gesorgt, dafs die Temperatur nicht über 40 ° steigt. Ist alles Nitrosoantipyrin verschwunden und die Flüssigkeit nur noch wenig gefärbt, so wird in eine Lösung von 48 Theilen Benzaldehyd in 200 Theilen verdünnter Essigsäure und der nöthigen Menge (ca. 20 ecm) Sprit hineinfiltrirt. Zur Vollendung der alsbald beginnenden Abscheidung des Condensationsproductes wird noch einige Zeit stehen ge- ; lassen und dann der entstandene Krystallbrei : abgesaugt. Zur Entfernung des nicht ver-One travels z. B. as follows:
100 parts of nitrosoantipyrine are suspended in 100 parts of water, 500 parts of gasoline, 200 parts of dilute acetic acid (5%), and zinc dust is gradually added with stirring. At the same time, by placing it in cold water, it is ensured that the temperature does not rise above 40 °. When all the nitrosoantipyrine has disappeared and the liquid is only slightly colored, filter into a solution of 48 parts of benzaldehyde in 200 parts of dilute acetic acid and the necessary amount (about 20 ecm) of fuel. There will be some time before the separation of the condensation product, which will soon begin, will be completed; and then the resulting crystal pulp : sucked off. To remove the not

■ brauchten Bittermandelöles wird zuerst mit ver-, dünntem Alkohol 1 : 1 gewaschen und dann■ The bitter almond oil needed is first mixed with diluted alcohol 1: 1 and then washed

zur Lösung von aiiskrystallisirtem Zinkacetat ; mit essigsäurehaltigem Wasser angerührt und mit Wasser zinkfrei gewaschen; Nach dem . Trocknen wird aus heifsem Sprit umkrystallisirt.for the solution of crystallized zinc acetate ; mixed with water containing acetic acid and washed zinc-free with water; After this . Drying is recrystallized from hot fuel.

Das BenzylidenamidoantipyrinThe benzylideneamidoantipyrine

/C11 ZbT11 JV2 O)N= C HC0H5 bildet schöne gelbe glänzende Blättchen und schmilzt bei 1730, in Wasser ist es unlöslich, reichlich/ C 11 ZbT 11 JV 2 O) N = C HC 0 H 5 forms beautiful yellow, shiny leaflets and melts at 173 0 , in water it is insoluble, plentiful

■ löslich in heifsem Alkohol. Von verdünnter Salzsäure wird es leicht unter Abspaltung von Benzaldehyd gelöst.■ soluble in hot alcohol. Dilute hydrochloric acid easily splits off Benzaldehyde dissolved.

Zur Darstellung des salzsauren Amidoantipyrins bringt man reines Benzylidenamidoantipyrin (vom Schmelzpunkt 1730) in einen Scheidetrichter, übergiefst es mit Aether (oder Benzol) und verdünnter Salzsäure und schüttelt, bis alles in Lösung gegangen ist; dann trennt man die salzsaure Lösung von der Aetherschicht und dampft auf dem Wasserbade ein. Aus der concentrirten syrupdicken Lösung scheiden sich beim Stehen im Exsiccator schöne Prismen von salzsaurem Amidoantipyrin ab, die von der Mutterlauge durch Absaugen getrennt und darauf getrocknet werden. Die gesättigte wässerige Lösung des salzsauren Salzes scheidet auf Zusatz von absolutem Alkohol Krystalle ab; die Abscheidung wird durch Zufügen von Aether befördert. Man saugt den Krystallbrei ab und wäscht mit Alkoholäther nach.For the presentation of the hydrochloric Amidoantipyrins bringing pure Benzylidenamidoantipyrin (of melting point 173 0) into a separating funnel, it drenched with ether (or benzene) and dilute hydrochloric acid and shakes, everything has gone up in solution; then the hydrochloric acid solution is separated from the ether layer and evaporated on the water bath. From the concentrated syrupy solution, on standing in the desiccator, beautiful prisms of hydrochloric acid amidoantipyrine separate, which are separated from the mother liquor by suction and then dried. The saturated aqueous solution of the hydrochloric acid salt separates crystals on the addition of absolute alcohol; the separation is promoted by adding ether. The crystal pulp is sucked off and washed with alcohol ether.

Man erhält das freie Amidoantipyrin aus der Lösung des salzsauren Salzes durch Zusatz von überschüssiger Natronlauge und AufnehmenThe free amidoantipyrine is obtained from the solution of the hydrochloric acid salt by addition of excess caustic soda and absorbing

Claims (2)

in Benzol. Aus der Benzollösung krystallisirt die Base in schönen gelben Spiefsen vom Schmelzpunkt ioq°. Das Amidoantipyrin verbindet sich wie das im Pyrazolkern substituirte Amidomethylphenylpyrazolon mit nur ι Molecül Salzsäure, während das im Benzolkern substituirte Amidopyrazolon 2 Molecule Salzsäure bindet. Die Lösung des salzsauren Amidoantipyrins wird durch Eisenchlorid violettroth — wie Permanganat — gefärbt, gegen Dichromat und verdünnte Schwefelsäure verhält es sich ähnlich. In Wasser ist das Salz a'ufserst leicht löslich, die Lösung reagirt sauer; in Alkohol ist es zwar schwerer als in Wasser, aber auch sehr leicht löslich. Versetzt man eine Lösung des salzsauren Salzes in verdünntem Alkohol mit Natriumacetat und Benzaldehyd, so krystallisirt die Benzylidenverbindung vom Schmelzpunkt 1730 aus. Acetamidoantipyrin erhält man aus dem salzsauren Amidoantipyrin z. B. in folgender Weise: Man kocht gleiche Theile trockenes salzsaures Amidoantipyrin und entwässertes Natriumacetat mit der vierfachen Menge Essigsäure- anhydrid einige Stunden am Rückflnlskühlor. Zur Verjagung der überschüssigen Essigsäure wird auf dem Wasserbade zur Trockne verdampft. Aus dem Rückstand erhält man durch Umkrystallisiren aus Toluol das Acetylnmido-' antipyrin rein in derben Krystallen. Das Acetylamidoantipyrin schmilzt bei 197°; in Wasser und Alkohol ist es leicht löslich, schwer in Aether und Benzol. '■'-,. Patent-Ansprüche:in benzene. The base crystallizes out of the benzene solution in beautiful yellow pegs with a melting point of 10 °. The amidoantipyrine, like the amidomethylphenylpyrazolone substituted in the pyrazole nucleus, binds with only one molecule of hydrochloric acid, while the amidopyrazolone substituted in the benzene nucleus binds two molecules of hydrochloric acid. The solution of the hydrochloric acid amidoantipyrine is colored violet-red by iron chloride - like permanganate - it behaves similarly against dichromate and dilute sulfuric acid. The salt is extremely easily soluble in water, the solution is acidic; it is heavier in alcohol than in water, but also very easily soluble. If sodium acetate and benzaldehyde are added to a solution of the hydrochloric acid salt in dilute alcohol, the benzylidene compound crystallizes with a melting point of 1730. Acetamidoantipyrine is obtained from the hydrochloric acid amidoantipyrine z. B. in the following way: Equal parts of dry hydrochloric acid amidoantipyrine and dehydrated sodium acetate are boiled with four times the amount of acetic anhydride for a few hours on a reflux condenser. To drive away the excess acetic acid, evaporate to dryness on the water bath. Acetylnmido- 'antipyrine is obtained in solid crystals from the residue by recrystallization from toluene. The acetylamidoantipyrine melts at 197 °; it is easily soluble in water and alcohol, difficult in ether and benzene. '■' - ,. Patent Claims: 1. Verfahren zur Abscheidung von Amido-1. Process for the deposition of amido ■ antipyrin aus dem bei Einwirkung von Zink : und Essigsäure auf Nitrosoantipyrin ent- ·: stehenden Product, darin bestehend, dafs : man das Amidoantipyrin mit einem Aldehyd,■ antipyrine from the action of zinc: and acetic acid on nitrosoantipyrine ·: Standing product, consisting in the fact that: amidoantipyrine with an aldehyde, ■ wie Benzaldehyd, als Aldehydverbindung ': fällt und diese mittelst einer MineralsäureLike benzaldehyde, as an aldehyde compound: falls and this by means of a mineral acid zerlegt.disassembled. 2. Verfahren zur Darstellung von Acetamido-' antipyrin, darin bestehend, dafs man das ; nach dem durch Anspruch 1. geschützten ; Verfahren dargestellte salzsaure Amidoantipyrin durch Erhitzen mit Natriumacetat und Essigsäureanhydrid acetylirt. 2. Process for the preparation of acetamido- 'antipyrine, consisting in that one uses the; according to the protected by claim 1 ; Hydrochloric acid amidoantipyrine prepared in the process is acetylated by heating with sodium acetate and acetic anhydride.
DENDAT71261D Process for the preparation of amidoantipyrine and acetamidoantipyrine Expired - Lifetime DE71261C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4669338A (en) * 1985-10-11 1987-06-02 Collins Bobby W Ratcheting box wrench
WO2004106306A1 (en) * 2003-05-30 2004-12-09 Aston University Novel ureido - and amido-pyrazolone derivatives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4669338A (en) * 1985-10-11 1987-06-02 Collins Bobby W Ratcheting box wrench
WO2004106306A1 (en) * 2003-05-30 2004-12-09 Aston University Novel ureido - and amido-pyrazolone derivatives

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