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.Info
- 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
Links
Landscapes
- 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)
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) |
-
1941
- 1941-07-04 CH CH222990D patent/CH222990A/en unknown
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