CH222990A - Process for the preparation of 2-methyl-3-carbethoxyamino-4-phenoxymethyl-5-cyano-6-chloropyridine. - Google Patents

Process for the preparation of 2-methyl-3-carbethoxyamino-4-phenoxymethyl-5-cyano-6-chloropyridine.

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Publication number
CH222990A
CH222990A CH222990DA CH222990A CH 222990 A CH222990 A CH 222990A CH 222990D A CH222990D A CH 222990DA CH 222990 A CH222990 A CH 222990A
Authority
CH
Switzerland
Prior art keywords
methyl
phenoxymethyl
cyano
pyridine
chloro
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 CH222990A publication Critical patent/CH222990A/en

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  • Pyridine Compounds (AREA)

Description

  

  Verfahren zur Darstellung von     2-1Vlethyl-3-carbäthoxyamino-4-phenoxymethyl-          5-cyan-6-elilor-pyridin.       Die     2-Methyl-3-carbalkoxyamino-4-phen-          oxymethyl    - 5 -     cyan    - 6 -chlor -     pyridine    bilden  Zwischenprodukte für die Herstellung phar  mazeutisch wertvoller Verbindungen.

   Sie       können    dadurch erhalten werden,     da,ss    man  auf 2 -     Methyl    - 4 -     phenoxymethyl    - 5 -Cyan -     6-          chlor-pyridin-3-carbonsäurehydrazid,    welches  seinerseits aus dem entsprechenden     Carbon-          säurechlorid    durch Umsetzung mit     Hydrazin     gewonnen wird, salpetrige Säure     bezw.     Stoffe, aus welchen sich während der Reak  tion salpetrige Säure bildet, einwirken lässt  und das entstehende     Azid    mit Alkoholen ver  kocht.  



  Es wurde nun gefunden, dass man in  einfacher Weise unter Umgehung des     Säure-          hydrazids    zu dem     2-Methyl-3-carbäthoxy-          amino-4-phenoxymethyl-5-cyan    - 6-     chlor-pyri-          din    gelangen kann, wenn man auf das     2-Me-          thyl    - 4 -     phenoxymethyl    - 5 -     eyan-6-chlor-pyri-          din-3-carbonsäurechlorid        Natriumazid    in  einem geeigneten Lösungsmittel einwirken  lässt und das gebildete     Azid    mit Äthylalko-    hol vorkocht,

   wobei man das     2-Methyl-3-          carbäthoxyamino-4-phenoxymethyl    -     5-cyan-6-          chlor-pyridin    sofort rein mit vorzüglicher       Ausbeute    erhält.  



  Das     2-Methyl-3-carbäthoxyamino-4-phen-          oxymethyl    - 5 -     cyan    - 6 -     chlorpyridin    ist eine  gutkristallisierende Verbindung,, die bei<B>167'</B>  schmilzt und sich in Alkohol, Benzol, Essig  ester, Eisessig in der     Wärme    leicht löst. Es  ist mässig löslich in Äther, in Wasser und  in     Petroläther    löst es sich schwer.  



  Die neue     Verbindung    bildet ein Zwi  schenprodukt für die Herstellung eines Arz  neimittels.         Beispiel:       Man löst 32 Gewichtsteile     2-Methyl-4-          phenoxymethyl    -     5-cyan-6-chlor-pyridin-3-car-          bonsäurechlorid    in 200 Gewichtsteilen     Di-          oxan    unter Rühren und kühlt gut in Eis  wasser. Dazu tropft man eine Lösung von  10 Gewichtsteilen     Natriumazid    in 50 Ge  wichtsteilen Wasser und verrührt unter fort-      währendem Kühlen während 1 Stunde. Das       Säureazid    fällt allmählich aus.

   Darauf tropft  man zur völligen     Abscheidung    100 Gewichts  teile Wasser zu und putscht nach weiterem  Rühren während 30 Minuten. Man wäscht  einmal mit Wasser und zweimal mit eiskal  tem absolutem Alkohol nach. Das     reinweisse          Azid    wird unter Rühren in 240 Gewichts  teilen absolutem Alkohol aufgeschlämmt und  auf etwa<B>50'</B> erwärmt, wobei eine allmäh  lich stärker werdende Stickstoffentwicklung  eintritt. Die Temperatur steigt von selbst bis  gegen 70  . Man hält 15 Minuten     bei    die  ser Temperatur, filtriert und versetzt mit  wenig Wasser bis zur beginnenden     Trübung.     Nach gründlichem Kühlen wird geputscht  und mit eiskaltem 50 %     igem    Alkohol gewa  schen.

   Man erhält     reinweisses    2-Methyl-3       carbäthoxyamino-4-phenoxymethyl-5-cyan-6-          chlorpyridin    vom Schmelzpunkt 167  .



  Process for the preparation of 2-1Vlethyl-3-carbäthoxyamino-4-phenoxymethyl-5-cyano-6-elilor-pyridine. The 2-methyl-3-carbalkoxyamino-4-phenoxymethyl-5-cyano-6-chloro-pyridines form intermediates for the production of pharmaceutically valuable compounds.

   They can be obtained by adding nitrous acid to 2-methyl-4-phenoxymethyl-5-cyano-6-chloro-pyridine-3-carboxylic acid hydrazide, which in turn is obtained from the corresponding carboxylic acid chloride by reaction with hydrazine respectively Substances from which nitrous acid is formed during the reaction can take effect and the resulting azide is boiled with alcohols.



  It has now been found that you can get to the 2-methyl-3-carbethoxy-amino-4-phenoxymethyl-5-cyano-6-chloropyridine in a simple manner by bypassing the acid hydrazide if you use the 2-methyl - 4 - phenoxymethyl - 5 - eyan-6-chloro-pyridine-3-carboxylic acid chloride lets sodium azide act in a suitable solvent and pre-cooks the azide formed with ethyl alcohol,

   the 2-methyl-3-carbäthoxyamino-4-phenoxymethyl-5-cyano-6-chloro-pyridine is obtained immediately in pure form with excellent yield.



  The 2-methyl-3-carbäthoxyamino-4-phenoxymethyl - 5 - cyano - 6 - chloropyridine is a well-crystallizing compound, which melts at <B> 167 '</B> and dissolves in alcohol, benzene, ethyl acetate, Glacial acetic acid dissolves easily in the heat. It is moderately soluble in ether, it is difficult to dissolve in water and petroleum ether.



  The new compound forms an intermediate product for the manufacture of a medicament. Example: 32 parts by weight of 2-methyl-4-phenoxymethyl-5-cyano-6-chloro-pyridine-3-carboxylic acid chloride are dissolved in 200 parts by weight of dioxane with stirring and cooled well in ice water. A solution of 10 parts by weight of sodium azide in 50 parts by weight of water is added dropwise and the mixture is stirred for 1 hour with continued cooling. The acid azide will gradually precipitate.

   Then 100 parts by weight of water are added dropwise for complete separation and after further stirring for 30 minutes. Wash once with water and twice with ice-cold absolute alcohol. The pure white azide is slurried in 240 parts by weight of absolute alcohol while stirring and heated to about <B> 50 '</B>, with the evolution of nitrogen gradually increasing. The temperature rises by itself to around 70. It is kept at this temperature for 15 minutes, filtered and mixed with a little water until the onset of turbidity. After thorough cooling, the car is swept and washed with ice-cold 50% alcohol.

   Pure white 2-methyl-3-carbethoxyamino-4-phenoxymethyl-5-cyano-6-chloropyridine with a melting point of 167 is obtained.

Claims (1)

PATENTANSPRUCH: Verfahren zur Darstellung von 2-Methyl 3-carbäthoxyamino-4-phenoxymethyl-5-cyan- 6-chlor-pyridin, dadurch gekennzeichnet, dass man 2 - Methyl - 4 - phenoxymethyl - 5 - cyan-6- chlor-pyridin-3-carbonsäureehlorid mit Na triumazid umsetzt und das entstehende 2 Methyl - 4 -phenoxymethyl-5-eyan-6-chl or-py- ridin-3-carbonsäureazid mit Äthylalkohol er wärmt. PATENT CLAIM: Process for the preparation of 2-methyl 3-carbäthoxyamino-4-phenoxymethyl-5-cyano-6-chloro-pyridine, characterized in that 2-methyl-4-phenoxymethyl-5-cyano-6-chloro-pyridine 3-carboxylic acid chloride reacts with sodium azide and the resulting 2 methyl - 4 -phenoxymethyl-5-eyan-6-chloro-pyridine-3-carboxylic acid azide is heated with ethyl alcohol. Das 2-Methyl-3-carl>ätlioxyamino-4-phen- oxymethyl - 5 -Cyan - 6 - chlorpyridin ist eine gutkristallisierende Verbindung, die bei<B>167'</B> schmilzt und sich in Alkohol, Benzol, Essig ester, Eisessig in der Wärme leicht löst. Es ist mässig löslich in Äther, in Wasser und in Petroläther löst es sich schwer. The 2-methyl-3-carl> ätlioxyamino-4-phenoxy-methyl-5-cyano-6-chloropyridine is a well-crystallizing compound, which melts at <B> 167 '</B> and converts into alcohol, benzene, ethyl acetate , Glacial acetic acid dissolves easily in the heat. It is moderately soluble in ether, it is difficult to dissolve in water and petroleum ether.
CH222990D 1940-09-10 1941-07-04 Process for the preparation of 2-methyl-3-carbethoxyamino-4-phenoxymethyl-5-cyano-6-chloropyridine. CH222990A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH217229T 1940-09-10
CH222990T 1941-07-04

Publications (1)

Publication Number Publication Date
CH222990A true CH222990A (en) 1942-08-15

Family

ID=25725917

Family Applications (1)

Application Number Title Priority Date Filing Date
CH222990D CH222990A (en) 1940-09-10 1941-07-04 Process for the preparation of 2-methyl-3-carbethoxyamino-4-phenoxymethyl-5-cyano-6-chloropyridine.

Country Status (1)

Country Link
CH (1) CH222990A (en)

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