DE595361C - Process for the preparation of pyridine compounds - Google Patents
Process for the preparation of pyridine compoundsInfo
- Publication number
- DE595361C DE595361C DEC46811D DEC0046811D DE595361C DE 595361 C DE595361 C DE 595361C DE C46811 D DEC46811 D DE C46811D DE C0046811 D DEC0046811 D DE C0046811D DE 595361 C DE595361 C DE 595361C
- Authority
- DE
- Germany
- Prior art keywords
- methyl
- preparation
- chloropyridine
- pyridine compounds
- compounds
- 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
Classifications
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- 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
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
-
- 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
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- 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
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
- C07D213/77—Hydrazine radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/38—Nitrogen atoms
Description
Verfahren zur Darstellung von Pyridinverbindungen Es ist bekannt, daß 2-Chlorchinolin und 2-Chlorpyridin beim Behandeln mit überschüssigem jodmethyl unter Ersatz des Chloratoms durch ein Jodatom in 2-Jodchinolin- bzw. 2-Jodpyridin-N-methyljodid übergehen, deren 2-ständiges Jodatom leicht beweglich ist und sich z. B. gegen Amine und Hydrazine austauschen läßt (vgl. Annalen 282 [I894] S. 373ff- - Berichte 32 1, S. 130o). Ferner ist bekannt, daß einige der bei dieser Umsetzung erhaltenen quaternären Jodide bei der Behandlung mit Alkalien Basen von der Struktur der N-Methyl-2-pyridonimide geben (Journal f. prakt. Ch. 93 [1916] S.387ff).Process for the preparation of pyridine compounds It is known that 2-chloroquinoline and 2-chloropyridine when treated with excess iodomethyl replacing the chlorine atom with an iodine atom in 2-iodoquinoline or 2-iodopyridine-N-methyl iodide pass over, the 2-position iodine atom is easily mobile and z. B. against amines and hydrazines can be exchanged (cf. Annalen 282 [I894] p. 373ff - reports 32 1, p. 130o). It is also known that some of the obtained in this reaction quaternary iodides when treated with alkalis bases on the structure of N-methyl-2-pyridonimide give (Journal f. Prakt. Ch. 93 [1916] p.387ff).
Diese Gewinnungsweise von 2-Pyridonimiden ist ohne technische Bedeutung, da das Verfahren zufolge der Verwendung von Jodverbindungen zu unwirtschaftlich ist.This way of obtaining 2-pyridonimides is of no technical importance, because the process results from the use of iodine compounds too uneconomical is.
Es wurde nun gefunden, daß auch die Anlagerungsv erbindungen von Dialkylsulfaten oder Sulfonsäureestern an 2-Chlorpyridin oder 2-Chlorchinolin überraschend leicht mit Ammoniak, primären Aminen oder Hydrazinen der allgemeinen Formel R' R2 - N - N H2 oder mit deren Salzen, z. B. mit schwachen Säuren, reagieren. Diese Anlagerungsverbindungen unterscheiden sich von den mit Jodalkylen erhaltenen wesentlich, da sie noch das in 2-Stellung befindliche Chlor enthalten. Ein Austausch desselben gegen den Säurerest der Dialkylsulfate, die zwar vielfach an Stelle der Jodalkyle zum Alkylieren verwendet werden, findet also nicht statt. Das Verhalten der nach der vorliegenden Erfindung herzustellenden Anlagerungsverbindungen gegenüber Ammoniak usw. ließ sich daher keineswegs voraussehen. Denn bekanntlich setzt sich im Pyridinkern in 2-Stellung befindliches Chlor im Vergleich zu -Jod z. B. mit- Aminen so schwierig um, daß es zwecks Bildung von Pyridylaminen der Anwendung von Katalysatoren sowie der Wärmezufuhr bedarf.It has now been found that the addition compounds of dialkyl sulfates or sulfonic acid esters of 2-chloropyridine or 2-chloroquinoline surprisingly easily with ammonia, primary amines or hydrazines of the general formula R 'R2 - N - N H2 or their salts, e.g. B. react with weak acids. These addition compounds differ significantly from those obtained with iodoalkylenes, since they still have the contain chlorine in the 2-position. An exchange of the same for the acid residue the dialkyl sulfates, which are often used instead of iodine alkyls for alkylation will not take place. The behavior of the according to the present invention addition compounds to be produced with respect to ammonia, etc., could therefore be by no means foresee. Because it is well known that it is in the 2-position in the pyridine nucleus present chlorine compared to iodine z. B. with amines so difficult that it for the purpose of the formation of pyridylamines, the use of catalysts and the supply of heat requirement.
Vorliegendes Verfahren zeigt mithin einen neuen technisch brauchbaren Weg, der die N-Alkyf-2-pyridonimide zu leicht zugänglichen Stoffen macht. Beispiele i. N-Methyl-2-pyridonimid. 5o g der kristallisierten Anlagerungsverbindung von Dimethylsulfat an 2-Chlorpyridin werden in wenig Methylalkohol gelöst und zu der Lösung von 8 g trockenem Ammoniak in absolutem Methylalkohol zugesetzt. Unter starker Erwärmung tritt Umsetzung ein. Der Methylalkohol wird abgedampft, der Rückstand mit wenig Natronlauge alkalisch gemacht und mehrfach mit Benzol ausgeschüttelt. Nach dem Abdampfen des Benzols bleibt ein Öl übrig, das im Vakuum fraktioniert wird; Kp" 1o8 bis iog°. Die Verbindung ist ein schwach gelbes 01: Die Ausbeute ist, ebenso wie in den folgenden Beispielen, ausgezeichnet.The present process therefore shows a new technically useful way which makes the N-alkyf-2-pyridonimide easily accessible substances. Examples i. N-methyl-2-pyridonimide. 50 g of the crystallized addition compound of dimethyl sulfate and 2-chloropyridine are dissolved in a little methyl alcohol and added to the solution of 8 g of dry ammonia in absolute methyl alcohol. Reaction occurs under strong warming. The methyl alcohol is evaporated, the residue is made alkaline with a little sodium hydroxide solution and extracted several times with benzene. After the benzene has evaporated, an oil remains which is fractionated in vacuo; Kp "1o8 to 10 °. The compound is a pale yellow 01: the yield, as in the following examples, is excellent.
Nach derselben Methode wurden noch folgende Verbindungen dargestellt: 2. N-Methyl-2-pyridonmethylimid: schwach gelbes Öl, Kpg$ z38°, aus der Anlagerungsverbindung von Dimethylsulfat an Chlorpyridin und Methylamin.Using the same method, the following compounds were also shown: 2. N-Methyl-2-pyridonmethylimide: pale yellow oil, Kpg $ z38 °, from the addition compound of dimethyl sulfate to chloropyridine and methylamine.
3. N-Methyl-2-pyridonisoamylimid: hellgelbes 01, Kp" 122 bis i25°, aus der Anlagerungsverbindung von Dimethylsulfat an Chlorpyridin@und Isoamylamin.3. N-methyl-2-pyridonisoamylimide: light yellow oil , bp "122 to 125 °, from the addition compound of dimethyl sulfate with chloropyridine @ and isoamylamine.
4. N-Methyl-2-pyridonphenylimid: hellgelbe Kristalle, F. 69 bis 70°, aus der Anlagerungsverbindung von Dimethylsulfat an Chlorpyridin und Anilin.4. N-methyl-2-pyridonophenylimide: light yellow crystals, m.p. 69 to 70 °, from the addition of dimethyl sulfate to chloropyridine and aniline.
5. N-Methyl-2-pyridon-p-äthoxyphenylimid: kräftig gelbe Kristalle, F. 88 bis 89°, aus der Anlagerungsverbindung von Dimethylsulfat an Chlorpyridin und p-Phenetidin.5. N-methyl-2-pyridon-p-ethoxyphenylimide: bright yellow crystals, F. 88 to 89 °, from the addition compound of dimethyl sulfate to chloropyridine and p-phenetidine.
6. N-Methyl-2-pyridon-2'-äthoxypyridyl-5'-imid: kräftig gelbes Öl, Kp1a 2i9°, aus der Anlagerungsverbindung von Ditnethylsulfat an Chlorpyridin und 2-Äthoxy-5-aminopyridin.6. N-methyl-2-pyridon-2'-ethoxypyridyl-5'-imide: bright yellow oil, Kp1a 2i9 °, from the addition compound of diethyl sulfate and chloropyridine 2-ethoxy-5-aminopyridine.
7. N-Methyl-2-pyridon-ß-naphthylimid: orangegelbe Kristalle, F. 141 bis 1d.2°, aus der Anlagerungsverbindung von Dimethy 1-sulfat an Chlorpyridin und ß-Naphthylamin.7. N-methyl-2-pyridone-ß-naphthylimide: orange-yellow crystals, m.p. 141 to 1d.2 °, from the addition compound of dimethyl 1-sulfate to chloropyridine and ß-naphthylamine.
B. N-Methyl-2-pyridonsemicarbazon: orangefarbene Nadeln, F. 17o bis 171°, unter Zersetzung aus der Anlagerungsverbindung von Dirnethylsulfat an Chlorpyridin und Semicarbazidacetat (aus Setnicarbazidhydrochlorid und wasserfreiem Natriumacetat in Methvlalkohol).B. N-methyl-2-pyridone semicarbazone: orange needles, F. 17o bis 171 °, with decomposition from the addition compound of dimethyl sulfate to chloropyridine and semicarbazide acetate (from setnicarbazide hydrochloride and anhydrous sodium acetate in methyl alcohol).
N-Methyl-3, 5-dichlor-2-pyridonphenylimid: rotgelbes, zähes Öl, Kpi5 2I9°, aus der Anlagerungsverbindung von Dimethylsulfat an 2, 3, 5-Trichlorpyridin und Anilin.N-methyl-3, 5-dichloro-2-pyridonphenylimide: red-yellow, viscous oil, Kpi5 219 °, from the addition compound of dimethyl sulfate to 2, 3, 5-trichloropyridine and aniline.
io. 15- g 2-Chlorchinolin werden auf dem Dampfbad mit i i,6 g Dimethylsulfat umgesetzt. Dann wird in Alkohol gelöst und mit 9 g Anilin auf dem Wasserbad erwärmt. Nach beendeter Umsetzung wird aufgearbeitet wie üblich und im Hochvakuum fraktioniert. Kpo,ooS@,ol 16o bis i7o °. Man erhält ein zähes, stark gelbes Öl.ok 15 g of 2-chloroquinoline are mixed with 1.6 g of dimethyl sulfate on the steam bath implemented. Then it is dissolved in alcohol and heated with 9 g of aniline on a water bath. After the reaction has ended, it is worked up as usual and fractionated in a high vacuum. Kpo, ooS @, ol 16o to i7o °. A viscous, strongly yellow oil is obtained.
Sämtliche Beispiele können z. B. auch mit den entsprechenden p-Toluolsulfonsäureestern an Stelle von Dialkylsulfat ausgeführt werden.All examples can be e.g. B. also with the corresponding p-toluenesulfonic acid esters instead of dialkyl sulfate.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC46811D DE595361C (en) | 1932-08-20 | 1932-08-20 | Process for the preparation of pyridine compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC46811D DE595361C (en) | 1932-08-20 | 1932-08-20 | Process for the preparation of pyridine compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE595361C true DE595361C (en) | 1934-04-11 |
Family
ID=7026433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC46811D Expired DE595361C (en) | 1932-08-20 | 1932-08-20 | Process for the preparation of pyridine compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE595361C (en) |
-
1932
- 1932-08-20 DE DEC46811D patent/DE595361C/en not_active Expired
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