DE522272C - Process for the preparation of pyracridone - Google Patents
Process for the preparation of pyracridoneInfo
- Publication number
- DE522272C DE522272C DED56680D DED0056680D DE522272C DE 522272 C DE522272 C DE 522272C DE D56680 D DED56680 D DE D56680D DE D0056680 D DED0056680 D DE D0056680D DE 522272 C DE522272 C DE 522272C
- Authority
- DE
- Germany
- Prior art keywords
- pyracridone
- preparation
- chloropyridine
- temperature
- acid
- 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
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RMEDXVIWDFLGES-UHFFFAOYSA-N methyl 6-chloropyridine-3-carboxylate Chemical compound COC(=O)C1=CC=C(Cl)N=C1 RMEDXVIWDFLGES-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000005762 2-bromopyridine Chemical class 0.000 description 1
- 150000005749 2-halopyridines Chemical class 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000005755 iodopyridines Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- JNYYORRROUFDBG-UHFFFAOYSA-N n-phenylpyridin-3-amine Chemical compound C=1C=CN=CC=1NC1=CC=CC=C1 JNYYORRROUFDBG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Description
Verfahren zur Darstellung von Pyracridon Vor längerer Zeit hat R e i s s e r t (vgl. Berichte der deutschen Chem. Ges. 28 [t895], Seite 119) berichtet, daß er bei der Einwirkung von 2-Chlorpyridin-5-carbonsäuremethylester auf Anthranilsäure eine Verbindung erhalten hat, die er als ein Derivat des Pyracridons ansprach. In letzterer Zeit hat Seide (Annalen 440 [19241, Seite 311) nachzuweisen versucht, daß die von R e i s s e r t angenommene Konstitution zu Unrecht besteht.Process for the preparation of pyracridone Long ago R e issert (cf. reports of the German Chem. Ges. 28 [t895], page 119) reported that he obtained a compound when anthranilic acid was exposed to methyl 2-chloropyridine-5-carboxylate which he referred to as a derivative of pyracridone. Recently, Silk (Annalen 440 [19241, page 31 1) tried to prove that the constitution adopted by Rissert was wrong.
Es wurde nun gefunden, daß man in einfacher Weise und aus leicht zugänglichen Ausgangsstoffen zu einem Pyracridon der von R e i s s e r t angenommenen Zusammensetzung gelangt, wenn man Anthranilsäure mit 2-Halogenpyridinen bei einer Temperatur von von etwa 15o bis 16o° behandelt. Während in dem 2-Chlorpyridin-5-carbonsäuremethylester eine Verbindung zur Umsetzung gelangte, deren a-ständiges Halogenatom durch den in 5-Stellung befindlichen negativen Substituenten -neben der Carboxylgruppe kommt auch der Nitrogruppe und den Halogenen die gleiche Eigenschaft zu - bedeutend in seiner Austauschfiihigkeit erhöht wird, konnte festgestellt werden, daß auch die unsubstituierten cc-Halogenpyridine mit reaktionsträgeren Halogenatomen unter geeigneten Bedingungen leicht mit Anthranilsäure reagieren unter unmittelbarer Bildung von Pyracridon. Es ist selbstverständlich, daß das mit 2-Chlorpyridin durchgeführte Verfahren auch mit den reaktionsfähigeren 2-Brom- und -Jodpyridinen leicht ausführbar ist. -Bei der Durchführung des Verfahrens ist die Einhaltung der Reaktionsbedingungen von größter Wichtigkeit. So wurde gefunden, daß die Temperatur zwischen 15o bis 16o° gehalten werden muß, weil sonst aus der intermediär gebildeten a-Pyridylamino-o-benzoesäure unter Kohlensäureabspaltung 3-Pyridylphenylamin entsteht.It has now been found that one can in a simple manner and from easily accessible Starting materials for a pyracridone of the composition assumed by R e i s s e r t if you get anthranilic acid with 2-halopyridines at a temperature of treated from about 15o to 16o °. While in the 2-chloropyridine-5-carboxylic acid methyl ester a compound came to the implementation, the a-halogen atom through the Negative substituents in the 5-position -in addition to the carboxyl group the nitro group and the halogens also have the same property - significant in its interchangeability is increased, it was found that the unsubstituted cc-halopyridines with less reactive halogen atoms under suitable Conditions easily react with anthranilic acid with the immediate formation of Pyracridone. It goes without saying that this is done with 2-chloropyridine The process can also be carried out easily with the more reactive 2-bromo- and iodopyridines is. -When carrying out the process, compliance with the reaction conditions is essential of the utmost importance. It was found that the temperature was between 15o to 16o ° must be kept because otherwise from the intermediate formed a-pyridylamino-o-benzoic acid 3-pyridylphenylamine is formed with the elimination of carbonic acid.
Die nach dem Verfahren gewonnene Verbindung soll als solche oder als Ausgangsstoff für die Gewinnung therapeutisch wertvoller Verbindungen dienen. Beispiel 121 g Anthranilsäure und 1 o 1 g frisch .destilliertes 2-Chlorpyridin werden im ölbad langsam erhitzt. Bei einer Temperatur von 15o', die genau innezuhalten ist, verflüssigt sich der Kolbeninhalt und gerät allmählich unter Kohlensäureentwicklung ins Sieden. Nach 2 Stunden erstarrt die Flüssigkeit zu einer rotgelben Masse, die noch 1/2 Stunde auf der gleichen Temperatur gehalten wird. lach dem Erkalten wird das Reaktionsprodukt in konzentrierter Salzsäure aufgenommen und das entstandene Pyracridon durch Zusatz von Alkali ausgefällt. Der Niederschlag wird abfiltriert und mit ammoniakhaltigem Wasser gut ausgewaschen. Durch Umkristallisieren des Rückstandes aus Methylalkohol wird die gesuchte Verbindung von dein als.Nebenprodukt entstandenen:-a-Anilidopyriäin getrennt. Man erhält so das Pyracridon in hellgelben anthrachinonähnlichen Nadeln vom Schmelzpunkt 2 i o° in einer Ausbeute von etwa q.o @*o der Theorie. Die gleiche Ausbeute erhält man bei Verwendung von :!-Brom- bzw. 2-Jodpyridin.The compound obtained by the process should be as such or as Serve starting material for the production of therapeutically valuable compounds. example 121 g of anthranilic acid and 1 o 1 g of freshly distilled 2-chloropyridine are in the oil bath slowly heated. At a temperature of 15o ', which is to be paused carefully, the contents of the flask liquefy and gradually develop carbon dioxide to the boil. After 2 hours the liquid solidifies to a red-yellow mass, which is kept at the same temperature for another 1/2 hour. laughs cold the reaction product taken up in concentrated hydrochloric acid and the resulting Pyracridone through Addition of alkali precipitated. The precipitation is filtered off and washed well with ammonia-containing water. By recrystallization of the residue from methyl alcohol is the sought-after compound of your als.n byproduct resulting: -a-Anilidopyriäin separated. The pyracridone is thus obtained in light yellow Anthraquinone-like needles with a melting point of 20 ° in a yield of about q.o @ * o the theory. The same yield is obtained when using:! - bromine- and 2-iodopyridine, respectively.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED56680D DE522272C (en) | 1928-09-30 | 1928-09-30 | Process for the preparation of pyracridone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED56680D DE522272C (en) | 1928-09-30 | 1928-09-30 | Process for the preparation of pyracridone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE522272C true DE522272C (en) | 1931-04-04 |
Family
ID=7056955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED56680D Expired DE522272C (en) | 1928-09-30 | 1928-09-30 | Process for the preparation of pyracridone |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE522272C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1262970B (en) * | 1961-02-27 | 1968-03-14 | Us Stoneware Inc | Filler of saddle-like shape for treatment towers |
-
1928
- 1928-09-30 DE DED56680D patent/DE522272C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1262970B (en) * | 1961-02-27 | 1968-03-14 | Us Stoneware Inc | Filler of saddle-like shape for treatment towers |
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