DE710396C - Verfahren zur Herstellung von Cyanverbindungen der Pyridinreihe - Google Patents
Verfahren zur Herstellung von Cyanverbindungen der PyridinreiheInfo
- Publication number
- DE710396C DE710396C DEI64027D DEI0064027D DE710396C DE 710396 C DE710396 C DE 710396C DE I64027 D DEI64027 D DE I64027D DE I0064027 D DEI0064027 D DE I0064027D DE 710396 C DE710396 C DE 710396C
- Authority
- DE
- Germany
- Prior art keywords
- methyl
- alkoxy
- preparation
- cyano compounds
- pyridine series
- 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 7
- 125000004093 cyano group Chemical group *C#N 0.000 title claims description 3
- 150000003222 pyridines Chemical class 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- -1 carboxylic acid nitriles Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical class N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical class N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 1
- 150000003929 3-aminopyridines Chemical class 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 235000019988 mead Nutrition 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
- Verfahren zur Herstellung von Cyänverbindungen der Pyridinreihe Nach dem Patent 699 555 gelangt man zu 2- Methyl - 3 - alkoxy - ¢ - alkoxymethylpyridin-(5)-carbonsäuren dadurch, daß man 31AJkoxychinaldin-q.-carbonsäuren in 3-Alkoxychinaldin - q. - carbonsäureamide überführt, diese unter Einwirkung von wasserentziehenden Mitteln in entsprechende Carbonsäurenitrile umwandelt, letztere zu 3 - Alkoxyq. - aminomethylchinaldinen reduziert, diese durch Einwirken von salpetriger Säure in 3-Alkoxy-q.-,oxymethylchinaldine umwandelt, in diesen Verbindungen die Oxymethylbaruppe, gegebenenfalls auf dem Wege über die entsprechende Halogenmethylverbindung -oder nach sonst üblichen Verätherungsmethoden, veräthert, die so erhältlichen 3-Alkoxy-4.-alkoxymethylchinaldine nitriert, die Nitroverbindungen zu entsprechenden Aminoverbindungen reduziert, letztere durch Oxydation in 2 - Methyl - 3 - alkoxy - 4 - alkoxymethylpyridin-5, 6-dicarbonsäuren umwandelt und diese durch. Erhitzen zu 2-Methyl-3-alkOxy-q.-alkoxymethylpyridin-5-carbonsäuren decarboxyliert.
- Es hat sich nun weiter gezeigt, daß man die 2-Methyl-3-alkoxy-q.-alkoxymethylpyridin-(5)-carbonsäuren in die entsprechenden 5-Nitrilverbindungen `umwandeln kann, ohne daß die Substituenten in 3- und q.-Stellung Veränderungen erleiden, wenn man die 2 - Methyl - 3 - alkoxy - q - alkoxymethylpyridin-(5)-carhonsäuren zunächst in die zugehörigen Carbonsäurehalogenide überführt und die Carbonsäurehalogenide durch Einwirken von Ammoniak in die Carbonsäureamide umwandelt. Läßt man auf die Carbonsäureamide wasserentziehende Mittel einwirken, erhält man die 2-Methyl-3-alkoxy-q.-alkoxymethyl-5-cyanpyridine. Bei der Umwandlung der Carbonsäuten in die Carb,onsäurehalogenide arbeitet man vorteilhaft unter Innehaltung milder Reaktionsbedingungen mit Thionylchl:orid; als wasserentziehende Mittel verwendet man vorzugsweise Phosphoroxychlorid ,oder Säureanhydride, wie Phosphorpe@g@<d und Essigsäureanhydrid.
- Man hat bereits Cyanpyridine, die; 'ih; Gegensatz zu den Verfahrensprodukten jidoch im Kern keine weiteren Substituenten tragen, aus den entsprechenden Pyridincarcarbonsäuren über die zugehörigen Säurechloride und -amide erhalten, während man 3-Cyanpyridine, die noch weitere Kernsubstituenten tragen, aus entsprechend substituierten 3-Aminopyridinen auf dem Diazowege hergestellt hat. Auf Grund der bekannten Vorgänge war nicht vorauszusehen, daß die Carboxylgruppe der mehrere, zum Teil leicht aufspaltbare Kernsubstituenten tragenden 2 - Methyl - 3 - alkoxy - 4. - alkoxymethylpyridin-(5),-carbonsäuren auf dem oben angegebenen Wege in die Cyangruppe umgewandelt werden kann, ohne daß die leicht aufspaltbaren Substituenten bei der Umsetzung eine Veränderung erleiden. Das Vorhandensein dieser Substituenten in den Verfahrensprodukten ist für deren Verwertbarkeit bei der Herstellung von Verbindungen von der Art des Vitamins Br, von entscheidender Bedeutung.
- Beispiel 1 Teil 2 - Methyl - 3 - methoxy - q. - methoxymethylpyridin-(5)-carbonsäure (F.134.", Methylester Kp2 135'', F. des Methylesterpikrats 129", aus°Alkohol) wird mit 5 Teilen Thionylchlorid behandelt. Die Verbindung geht unter Gasentwicklung und Erwärmung in Lösung. Nach i/.,stündigem Stehen bei Zimmertemperatur -wird das überschüssige Thionylchlorid unter vermindertem Druck abgedampft. Der Rückstand wird mit i o Teilen konzentrierter wäßriger Ammoniaklösung übergossen. Ein Teil des gebildeten Carbonsäureamids scheidet sich dabei aus. Die ganze Mischung wird nun unter vermindertem Druck eingedampft und der feste =weiße Rückstand mehrfach mit -warmem Met,@iylenchlorid extrahiert. Nach dem @erdampfen des Methylenchlorids erhält man das 2 - Methyl- 3 -methoxy-q.-methoxymethylpy ridin-(5)-carbonsäureamid in Kristallen vom F. 13o°.
- 1 Teil dieses Amids wird mit 5 Teilen Phosphoroxychl.orid unter Rückflußkühlung gekocht. Nach kurzer Zeit ist die Verbindung in Lösung gegangen. Es wird noch kurze Zeit nachgelocht und danach das Phosphor-,oxychl.orid unter vermindertem Druck abgedampft. Der Rückstand wird mit Eiswasser versetzt und die Mischung nach Zusatz von Ammoniakwasser bis zur alkalischen Reaktion mit Äther extrahiert. Die ätherische Lösung -wird über Kaliumcarbonat getrocknet, der Äther abgedampft und der Rückstand destilliert. Das 2-Methyl-3-methOxy-.l-methoxymethyl:5-cyanpyridin destilliert unter o,oi mm Druck bei einer Heizbadtemperatur von 8o bis 9o" als farbloses öl.
Claims (1)
- PATIi1'rANS1'1ZUC:11: Verfahren zur Herstellung von Cyanverbindungen der Pyridinreihe, dadurch gekennzeichnet, daß 'man 2 - Methyl-31 - alkoxy= q.-#alkoxymetliylpyridin- ( 5) -carb.onsäuren in die entsprechenden 5-Carbonsäurehalogenide und diese durch Einwirkung von Ammoniak in die zugehörigen Carbonsäureamide umwandelt und daß man die letzteren durch Einwirkung von wasserentziehenden Mitteln in die 2 -Methyl- 3:- alkoxy -4-alkoxymethyl- 5-cyanpyridine überführt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI64027D DE710396C (de) | 1939-03-10 | 1939-03-10 | Verfahren zur Herstellung von Cyanverbindungen der Pyridinreihe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI64027D DE710396C (de) | 1939-03-10 | 1939-03-10 | Verfahren zur Herstellung von Cyanverbindungen der Pyridinreihe |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE710396C true DE710396C (de) | 1941-09-12 |
Family
ID=7196036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEI64027D Expired DE710396C (de) | 1939-03-10 | 1939-03-10 | Verfahren zur Herstellung von Cyanverbindungen der Pyridinreihe |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE710396C (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5060488A (en) * | 1989-05-29 | 1991-10-29 | E.M.M. S.R.L. | Device for supporting and controlling stitch-pressing and stitch-retaining means in an automatic straight knitting machine |
-
1939
- 1939-03-10 DE DEI64027D patent/DE710396C/de not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5060488A (en) * | 1989-05-29 | 1991-10-29 | E.M.M. S.R.L. | Device for supporting and controlling stitch-pressing and stitch-retaining means in an automatic straight knitting machine |
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