CH216945A - Process for the preparation of 2-methyl-4-ethoxymethyl-6-oxy-pyridine-5-carboxylic acid ethyl ester. - Google Patents

Process for the preparation of 2-methyl-4-ethoxymethyl-6-oxy-pyridine-5-carboxylic acid ethyl ester.

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Publication number
CH216945A
CH216945A CH216945DA CH216945A CH 216945 A CH216945 A CH 216945A CH 216945D A CH216945D A CH 216945DA CH 216945 A CH216945 A CH 216945A
Authority
CH
Switzerland
Prior art keywords
oxy
pyridine
methyl
ethoxymethyl
carboxylic acid
Prior art date
Application number
Other languages
German (de)
Inventor
F Hoffmann- Aktiengesellschaft
Original Assignee
Hoffmann La Roche
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 Hoffmann La Roche filed Critical Hoffmann La Roche
Publication of CH216945A publication Critical patent/CH216945A/en

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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  

  Verfahren zur Darstellung von     2-bZethyl-4-äthoxymethyl-6-oxy-pyridin-          5-carbonsäureäthylester.       In den     2-Methyl-4-alkoxymethyl-6-oxy-          pyridin-5-carbonsäureäthylestern    wurden für  die Herstellung von     Adermin    wichtige Zwi  schenprodukte gefunden. Man gelangt zu  diesen     bis    jetzt unbekannten     Estern,    wenn  man     2-Amino-4-oxo-5-alkoxypenten-(2)    mit       Malonester    bei Gegenwart von N     atriumäthy-          lat    kondensiert.  



  Die     2-Methyl-4-alkoxymethyl-6-oxy-pyri-          3        din-5-carbonsäureäthylester    lösen sich ziem  lich schwer in kaltem, leicht in heissem Was  ser. In den gebräuchlichen organischen Lö  sungsmitteln sind sie leicht löslich. Sowohl  Säuren wie Alkalien bilden mit ihnen leicht  wasserlösliche Salze, aus welchen durch       Neuträlisieren    die unveränderten Ester wie  der gewonnen werden können.  



  Gegenstand des vorliegenden Patentes  ist ein Verfahren zur Darstellung von 2  a     i#lethyl-4-äthoxymethyl-6-oxy-pyridin-5-car-          bonsä.ureäthylester,    welches dadurch gekenn  zeichnet ist, dass man 2-Amino-4-oxo-5-äthoxy-         penten-(2)    mit     Malonsäurediäthylester    bei  Gegenwart von     Natriumäthylat    kondensiert.  



  Der     2-Methyl-4-äthoxymethyl-6-oxy-pyri-          din-5-carbonsäureäthylester    bildet farblose  Kristalle vom     Schmelzpunkt        117-118'.        In.     kaltem Wasser     ist    er     ziemlich    schwer löslich,  leicht in heissem Wasser. Die gebräuchlichen  organischen Lösungsmittel lösen leicht. Mit  Säuren und Basen bildet er wasserlösliche  Salze.     Durch        Verseifung    erhält man die freie  Säure vom Schmelzpunkt     182-183'.     



  Der neue Ester bildet ein Zwischenpro  dukt für die     Herstellung    von     Arzenimitteln.     <I>Beispiel:</I>  In 255 Gewichtsteilen absolutem     Äthyl-          alkohol    löst man 23 Gewichtsteile Natrium.

    Zu der Lösung gibt man auf einmal 143 Ge  wichtsteile     2-Amino-4-oxo-5-äthoxy-penten-          (2)    und 160 Gewichtsteile     Malonsäurediäthyl-          ester    und kocht das Ganze 4 bis 5     Stunden     unter     Rückfluss.    Der entstehende 2-Methyl-4-           äthoxvrnethyl    - 6     -oxy-pyridin    - 5     -carbonsäure-          äthylester    bleibt als     Natriumsalz    in Lösung.

    Zur Vervollständigung der Reaktion wird der  Alkohol zuerst bei gewöhnlichem Druck und  zuletzt im Vakuum     abdestilliert.    Das Na  triumsalz bleibt als gelblicher, zähflüssiger  Sirup zurück. Dieser wird durch Schütteln  mit<B>150</B> Gewichtsteilen Wasser in Lösung ge  bracht. Beim Abkühlen kristallisiert das Na  triumsalz des     2-141ethyl-4-äthoxy        inethyl-6-          oxy-pyridin-5-carbonsäure < -it.hylesters    in farb  losen, glänzenden Plättchen. Dieses wird ab  getrennt. Man löst das     Natriumsalz    durch  leichtes Erwärmen in 300 Gewichtsteilen  Wasser und neutralisiert mit 3 n Salzsäure.

    Der     2-11ethy1-4-äthoxymethyl-6-oxy-pyridin-          5-carbonsäureäthvlester    fällt in farblosen  Kristallen aus. Er wird von der Mutterlauge       befreit    und mit wenig eiskaltem     Wasser    ge  waschen und getrocknet.



  Process for the preparation of 2-bZethyl-4-ethoxymethyl-6-oxy-pyridine-5-carboxylic acid ethyl ester. In the 2-methyl-4-alkoxymethyl-6-oxy-pyridine-5-carboxylic acid ethyl esters, important inter mediate products were found for the production of Adermin. These up to now unknown esters are obtained if 2-amino-4-oxo-5-alkoxypentene- (2) is condensed with malonic ester in the presence of sodium ethilate.



  The 2-methyl-4-alkoxymethyl-6-oxy-pyri- 3 din-5-carboxylic acid ethyl esters dissolve with difficulty in cold, slightly in hot water. They are easily soluble in common organic solvents. Both acids and alkalis form easily water-soluble salts with them, from which the unchanged esters can be obtained by neutralization.



  The subject of the present patent is a process for the preparation of 2 ai # lethyl-4-ethoxymethyl-6-oxy-pyridine-5-carboxylic acid ethyl ester, which is characterized in that 2-amino-4-oxo-5 -äthoxy- penten- (2) condensed with malonic acid diethyl ester in the presence of sodium ethylate.



  The ethyl 2-methyl-4-ethoxymethyl-6-oxy-pyridine-5-carboxylate forms colorless crystals with a melting point of 117-118 '. In. It is rather sparingly soluble in cold water and easily soluble in hot water. The common organic solvents dissolve easily. With acids and bases it forms water-soluble salts. The free acid with a melting point of 182-183 'is obtained by saponification.



  The new ester forms an intermediate product for the manufacture of pharmaceuticals. <I> Example: </I> 23 parts by weight of sodium are dissolved in 255 parts by weight of absolute ethyl alcohol.

    143 parts by weight of 2-amino-4-oxo-5-ethoxy-pentene- (2) and 160 parts by weight of diethyl malonate are added all at once to the solution and the whole is refluxed for 4 to 5 hours. The resulting 2-methyl-4-ethoxy-methyl-6-oxy-pyridine-5-carboxylic acid ethyl ester remains in solution as the sodium salt.

    To complete the reaction, the alcohol is first distilled off under normal pressure and finally in vacuo. The sodium salt remains as a yellowish, viscous syrup. This is brought into solution by shaking with <B> 150 </B> parts by weight of water. On cooling, the sodium salt of 2-141ethyl-4-ethoxy-methyl-6-oxy-pyridine-5-carboxylic acid <-it.hylesters crystallizes in colorless, shiny flakes. This is separated from. The sodium salt is dissolved in 300 parts by weight of water by gentle heating and neutralized with 3N hydrochloric acid.

    The ether 2-11ethy1-4-ethoxymethyl-6-oxy-pyridine-5-carboxylate precipitates in colorless crystals. It is freed from the mother liquor and washed ge with a little ice-cold water and dried.

Claims (1)

PATENTANSPIZUCI1 Verfahren zur Darstellung von 2-Methyl 4-äthoxymethyl-6-oxy-pyridin-5-carbonsäure- äthylester, dadurch gekennzeichnet, dass man 2-Amino-4-oxo-5-äthoxypenten-(2) mit Ma- lonsäurediäthylester bei Gegenwart von Na- triumä.thylat kondensiert. Der 2-Methyl-4-äthoxymethyl-6-oxy-pyri- din-5-carbonsäureäthylester bildet farblose Kristalle vom Schmelzpunkt 117-118 . In kaltem Wasser ist er ziemlich schwer löslich, leicht in heissem Wasser. PATENT INSPIZUCI1 Process for the preparation of 2-methyl-4-ethoxymethyl-6-oxy-pyridine-5-carboxylic acid ethyl ester, characterized in that 2-amino-4-oxo-5-ethoxypentene (2) with malonic acid diethyl ester in the presence condensed by sodium ethylate. The ethyl 2-methyl-4-ethoxymethyl-6-oxy-pyridine-5-carboxylate forms colorless crystals with a melting point of 117-118. It is rather sparingly soluble in cold water and easily soluble in hot water. Die gebräuchlichen organischen Lösungsmittel lösen leicht. Mit Säuren und Basen bildet er wasserlösliche Salze. Durch Verseifung erhält man die freie Säure vom Schmelzpunkt 182-183 . The common organic solvents dissolve easily. With acids and bases it forms water-soluble salts. The free acid with a melting point of 182-183 is obtained by saponification.
CH216945D 1940-10-04 1940-10-04 Process for the preparation of 2-methyl-4-ethoxymethyl-6-oxy-pyridine-5-carboxylic acid ethyl ester. CH216945A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH216945T 1940-10-04

Publications (1)

Publication Number Publication Date
CH216945A true CH216945A (en) 1941-09-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
CH216945D CH216945A (en) 1940-10-04 1940-10-04 Process for the preparation of 2-methyl-4-ethoxymethyl-6-oxy-pyridine-5-carboxylic acid ethyl ester.

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Country Link
CH (1) CH216945A (en)

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