DE713469C - Process for the preparation of 3-cyano-2-pyridones - Google Patents

Process for the preparation of 3-cyano-2-pyridones

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Publication number
DE713469C
DE713469C DEB189523D DEB0189523D DE713469C DE 713469 C DE713469 C DE 713469C DE B189523 D DEB189523 D DE B189523D DE B0189523 D DEB0189523 D DE B0189523D DE 713469 C DE713469 C DE 713469C
Authority
DE
Germany
Prior art keywords
cyano
parts
weight
alcohol
pyridones
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
Application number
DEB189523D
Other languages
German (de)
Inventor
Dr Paul Baumgarten
Dr Alfred Dornow
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.)
PAUL BAUMGARTEN DR
ALFRED DORNOW DR
Original Assignee
PAUL BAUMGARTEN DR
ALFRED DORNOW DR
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by PAUL BAUMGARTEN DR, ALFRED DORNOW DR filed Critical PAUL BAUMGARTEN DR
Priority to DEB189523D priority Critical patent/DE713469C/en
Application granted granted Critical
Publication of DE713469C publication Critical patent/DE713469C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Hydrogenated Pyridines (AREA)

Description

Verfahren zur Herstellung von 3-Cyan-2-pyridonen Es wurde gefunden, daß das ß-Äthoxyacroleindiäthylacetal sich mit Cyanacetami,d zu 3-Cyan-2-pyridon zu kondensieren vermag. Die Kondensation erfolgt in Gegenwart von geeigneten Katälysatoren, wie sekundären Aminen, z. B. Diäthylamin, Piperidin o. dgl. Im Falle der Verwendung von Piperidi.n z. B. wird nach dem Schema zunächst ein beständiges Anlagerungsprodukt von P.iperidin an 3-Cyan-2-pyridon erhalten, das aber durch Behandeln mit Al:kalilauge leicht in das freie Cyanpyridon übergeführt werden kann.Process for the preparation of 3-cyano-2-pyridones It has been found that the β-ethoxyacroleindiethylacetal is able to condense with cyanoacetami, d to give 3-cyano-2-pyridone. The condensation takes place in the presence of suitable Katälysatoren, such as secondary amines, z. B. diethylamine, piperidine o. The like. In the case of using Piperidi.n z. B. is according to the scheme initially a stable addition product of P.iperidine with 3-cyano-2-pyridone was obtained, but this can easily be converted into the free cyanopyridone by treatment with aluminum potassium hydroxide solution.

In ähnlicher Weise wie Äthoxyacroleindiäthylacetal vermag auch sein Methylderivat, das ß-Äthoxycrotonal-dehyddiäthylacetal, mit zCyanacetamid zu reagieren. Hierbei entsteht das :bisher unbekannte 6-Methyl-3-cyan-2-pyri don.In a similar way as Äthoxyacroleindiethylacetal can also be Methyl derivative, the ß-ethoxycrotonal dehydrogenated diethylacetal, reacts with cyanoacetamide. This creates the: previously unknown 6-methyl-3-cyano-2-pyridone.

Die Umsetzung wird durch Erhitzen der Komponenten für sich oder besser in Gegenwart eines Lösungsmittels, wie z. B. Alkohol, vorgenommen.The implementation is done by heating the components by themselves or better in the presence of a solvent, such as. B. alcohol.

Die erhaltenen Verbindungen sind mannigfachen Umwandlungen' zugänglich. So kann z. B. die Cyangruppe zur Säureamid- oder Carboxyl,gruppe verseift und die Carboxyl- gruppe weiterhin verestert oder anders _t@tr=- ändert werden. @`f Die Produkte sollen therapeutische Verw dung finden. Beispiele i. Eine Lösung von 1,75 Gewicht. rlen /i-Äthoxyacroleindiäthylacetal, 0,9 G@@ts- teilen Cyanacetamid und o,9 Gewicht ilen Piperidin in i o Raumteilen 95 °/oigem Alkohol wird etwa 3 Stunden auf dem Wasserbade erhitzt. Nach Abkühlen scheidet sich die Hauptmenge der Piperidinanlagerungsverbindung ab; der Rest wird durch Einengender Mutterlauge erhalten. Das Produkt kristallisiert aus Wasser nach Klären mit Tierkohle in breiten Prismen vom Schmelzpunkt 1971.The compounds obtained are amenable to various transformations. So z. B. the cyano group to the acid amide or Carboxyl, group saponified and the carboxyl group still esterified or different _t @ tr = - will be changed. @ `f The products are intended for therapeutic use find application. Examples i. A solution of 1.75 weight. rlen / i-Ethoxyacroleindiethylacetal, 0.9 G @@ ts- share cyanacetamide and o.9 weight ilen Piperidine in 10 parts by volume of 95% alcohol is heated on the water bath for about 3 hours. After cooling, most of the piperidine addition compound separates out; the remainder is obtained by concentrating the mother liquor. The product crystallizes from water after clarification with animal charcoal in broad prisms with a melting point of 1971.

Zur Herstellung des freien 3-Cyan-2-pyridons wird die Piperidinanlagerungsverbindung mit 5 Raumteilen normaler Natronlauge etwa 5 Stunden am Rückflußkühler erhitzt. Nach Ausziehen mit Äther und :Neutralisieren mit Salzsäure wird eingedampft und der Rückstand mit heißem Alkohol extrahiert. Beim Einengen der mit Tierkohle geklärten alkoholischen Lösung kristallisiert das 3-Cyan-2-pyridon in farblosen --Nadeln vom Schmelzpunkt 225 bis 226° aus.The piperidine addition compound is used to produce the free 3-cyano-2-pyridone heated with 5 parts by volume of normal sodium hydroxide solution for about 5 hours on the reflux condenser. After taking off with ether and: neutralizing with hydrochloric acid is evaporated and the residue extracted with hot alcohol. When concentrating the clarified with animal charcoal alcoholic solution, the 3-cyano-2-pyridone crystallizes in colorless needles from Melting point 225 to 226 °.

2. 0,95 Gewichtsteile ß-Äthoxycrotonaldehyddiäthvlacetalwerden mit 0,5 Gewichtsteil-en Cyanacetaanid und o,5 Gewichtsteilen Piperidin in 4 Raumteilen 95 °/aigem. Alkohol 3 Stunden auf dem Wasserbade erhitzt. Beim Abkühlen kristallisiert die Piperidinanlagerungsverbindung aus. :;ach Umlösen aus Wasser werden Blättchen vom Schmelzpunkt i92° erhalten.2. 0.95 parts by weight of ß-ethoxycrotonaldehyde dietary acetal are added with 0.5 part by weight of cyanacetaanide and 0.5 parts by weight of piperidine in 4 parts by volume of 95%. Alcohol heated on a water bath for 3 hours. The piperidine addition compound crystallizes out on cooling. After dissolving in water, leaflets with a melting point of 192 ° are obtained.

0,2 Gewichtsteile dieser Substanz werden mit i Raumteil normaler Natronlauge 4 Stunden am Rückflußküh.ler erhitzt. Es wird ausgeäthert; beim Neutralisieren der wäßrigen Lösung mit i Raumteil normaler Salzsäure fällt dann das freie 6-iMethy1-3-cyan-2-pyricion in Nadeln vorn Schmelzpunkt 295° aus. 3. o,9 Gewichtsteile ß-Äthoxyacroleindi- sithylacetal, o,45 Gewichtsteile Cyanacetamid . d 0,45 Gewichtsteile Diäthylamin werden in yaumteilen f. 95%igem Alkohol 5 Stunden auf dein Wasserbade erhitzt. Nach Abdampfen des #Ikohols wird mit 5 Raumteilen normaler N atronlauge 4 Stunden am Rückflußkühler erhitzt, darauf mit Äther extrahiert und nach Zugabe von 5 Rauanteilen normaler Salzsäure eingeengt. Der Rückstand wird mit Alkohol ausgezogen, die alkoholische Lösung eingedampft und das auskristallisierte 3-Cyan-2-pyridon aus Alkohol umgelöst.0.2 parts by weight of this substance are heated with 1 part by volume of normal sodium hydroxide solution on a reflux cooler for 4 hours. It is etherified; when the aqueous solution is neutralized with 1 part by volume of normal hydrochloric acid, the free 6-methyl-3-cyano-2-pyricione then precipitates in needles with a melting point of 295 °. 3. 0.9 parts by weight of ß-ethoxyacroleindi- sithylacetal, 0.45 parts by weight cyanoacetamide . d 0.45 parts by weight of diethylamine are in Divide up for 95% alcohol for 5 hours heated your water bath. After evaporation The alcohol is heated with 5 parts by volume of normal N atronlauge for 4 hours on the reflux condenser, then extracted with ether and concentrated after the addition of 5 parts of normal hydrochloric acid. The residue is extracted with alcohol, the alcoholic solution is evaporated and the 3-cyano-2-pyridone which has crystallized out is redissolved from alcohol.

3,5 Gewichtsteile ß-Äthoxyacroleindiäthylacetalwerden mit i,7 Gewichtsteilen Cyanacetamid und o,5 Gewichtsteilen wass-erfreiern Natriuniacetat in io Gewichtsteilen absol. Alkohol etwa 15 Stunden lang auf dem Wasserbad erhitzt. Der Alkohol wird abgedampft und das zurückbleibende 3-Cyan-2-pyridon gleich mit konz. Salzsäure zur 2-Oxynicotinsäure verseift. F. 255°.3.5 parts by weight of ß-ethoxyacroleindiethylacetal become with 1.7 parts by weight Cyanoacetamide and 0.5 parts by weight of water-liberating sodium acetate in 10 parts by weight absolute Alcohol heated on a water bath for about 15 hours. The alcohol will evaporated and the remaining 3-cyano-2-pyridone equal to conc. Hydrochloric acid for 2-oxynicotinic acid saponified. F. 255 °.

5. 1,75 Gewichtsteile ß-Äthoxyacroleindiäthylacetal werden mit o,85 Gewichtsteilen Cyanacetamid und 0,85 Gewichtsteilen Piperidin 4 Stunden lang auf dem Wasserbad erhitzt. Das erhaltene Anlagerungsprodukt von 3-Cyan-2-pyridon an Piperidin wird aus Alkohol und schließlich aus Wasser umkristallisiert. F. r97°.5. 1.75 parts by weight of ß-ethoxyacroleindiethylacetal are heated for 4 hours on a water bath with 0.85 parts by weight of cyanoacetamide and 0.85 parts by weight of piperidine. The resulting adduct of 3-cyano-2-pyridone with piperidine is recrystallized from alcohol and finally from water. F. r97 °.

Claims (1)

PATENTANSPRUCH: "erfahren zur Herstellung von 3-Cyan-2-py ridonen, dadurch gekennzeichnet, daß ß-Äthoxyacroleindiäthylacetal oder ß _Äthoxycrotonal,dehyddiäthylacetal in Gegenwart von geeigneten Katalysatoren, wie sekundären Aminen, mit Cyairacetaniid umgesetzt und gegebenenfalls die zunächst erhaltenen Anlagerungsverbindungen der Cy anpy ridone mit sekundären Aminen durch Erhitzen mit Alkalilauge in die freien Cyanpyridone übergeführt werden.PATENT CLAIM: "Experienced in the production of 3-cyano-2-pyridones, characterized in that ß-Äthoxyacroleindiethylacetal or ß _Äthoxycrotonal, dehyddiäthylacetal in the presence of suitable catalysts, such as secondary amines, with Cyairacetaniid implemented and optionally the addition compounds initially obtained Cy anpy ridone with secondary amines by heating with alkali in the free Cyanpyridone are transferred.
DEB189523D 1940-01-10 1940-01-10 Process for the preparation of 3-cyano-2-pyridones Expired DE713469C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEB189523D DE713469C (en) 1940-01-10 1940-01-10 Process for the preparation of 3-cyano-2-pyridones

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEB189523D DE713469C (en) 1940-01-10 1940-01-10 Process for the preparation of 3-cyano-2-pyridones

Publications (1)

Publication Number Publication Date
DE713469C true DE713469C (en) 1941-11-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3108112A (en) * 1963-10-22 Method for the production of z-methyl-

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3108112A (en) * 1963-10-22 Method for the production of z-methyl-

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