DE944251C - Process for the preparation of compounds of the pyridine series - Google Patents
Process for the preparation of compounds of the pyridine seriesInfo
- Publication number
- DE944251C DE944251C DEB21045A DEB0021045A DE944251C DE 944251 C DE944251 C DE 944251C DE B21045 A DEB21045 A DE B21045A DE B0021045 A DEB0021045 A DE B0021045A DE 944251 C DE944251 C DE 944251C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- compounds
- preparation
- pyridine series
- solution
- 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
-
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
-
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/14—Preparation from compounds containing heterocyclic oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
Verfahren zur Herstellung von Verbindungen der Pyridinreihe Es wurde gefunden, daB man in guter Ausbeute Verbindungen der Pyridinreihe erhält, wenn man Glutardialdehyde als solche oder in Form ihrer Acetale, insbesondere in Form der cyclischen Enolacetale, d. h. der 2 Allcoxy-3, 4-dihydro-i, 2-pyrane, oder die entsprechenden- 2-Acyloxy-3, 4-dihydroi, 2-pyrane bei erhöhter Temperatur in Gegenwart von Oxydationsmitteln mit wäBrigen Lösungen von Ammoniumsalzen umsetzt.Process for the preparation of compounds of the pyridine series Es has been found that compounds of the pyridine series are obtained in good yield if one Glutaraldehyde as such or in the form of their acetals, especially in the form of cyclic enol acetals, d. H. the 2 allcoxy-3, 4-dihydro-i, 2-pyrans, or the corresponding 2-Acyloxy-3, 4-dihydroi, 2-pyrans at elevated temperature in the presence of oxidizing agents with aqueous solutions of ammonium salts.
Die Umsetzung verläuft z. B. nach folgendem Schema: beziehungsweise wobei R "eine -Alkyl- oder Acylgruppe, und X -ein einwertiges Anion oder das einwertige Äquivalent eines mehrwertigen Anions bedeutet.The implementation proceeds z. B. according to the following scheme: respectively where R "denotes an -alkyl or acyl group, and X -a monovalent anion or the monovalent equivalent of a polyvalent anion.
Man kann z. B. Ammoniumsulfat oder andere Ammoniumsalze verwenden.You can z. B. Use ammonium sulfate or other ammonium salts.
Geeignete Oxydationsmittel sind insbesondere Salze von Metallen höherer Wertigkeitsstufe, die zu solchen niedrigerer Wertigkeitsstufe reduzierbar sind, z. B. Salze des dreiwertigenEisens oderMangans, Kupfer(II)-salze; ferner Wasserstoffperoxyd in Gegenwart von Eisen- oder Kupfersalzen. Besonders vorteilhaft verwendet man für die Umsetzung z. B. _ Ferriammoniumsulfat, das zugleich als Ammoniumsalz und als Oxydationsmittel wirkt.Suitable oxidizing agents are, in particular, salts of higher metals Significance level, which can be reduced to such a lower level, z. B. salts of trivalent iron or manganese, copper (II) salts; also hydrogen peroxide in the presence of iron or copper salts. It is particularly advantageous to use for the implementation z. B. _ Ferriammonium sulfate, which is used both as an ammonium salt and as Oxidizing agent works.
Die Umsetzung kann in der Weise erfolgen, daß man die Reaktionskomponenten in wäßriger Lösung miteinander erhitzt, z. B. am Rückflußkühler zum Sieden bringt. Man kann aber auch besser "so verfahren, daß man den Glutardialdehyd bzw. das Dihydropyranderivat in eine erhitzte, z. B. siedende Lösung des Ammoniumsalzes und des Oxydationsmittels einfließen läßt. Das Verfahren kann auch unter erhöhtem Druck und bzw. oder kontinuierlich ausgeführt werden.The reaction can be carried out in such a way that the reaction components heated together in aqueous solution, e.g. B. brings to the boil at the reflux condenser. But it is also better to proceed in such a way that the glutaraldehyde or the dihydropyran derivative is used in a heated, e.g. B. boiling solution of the ammonium salt and the oxidizing agent can flow in. The process can also be carried out under increased pressure and / or continuously are executed.
Die in den Beispielen genannten Teile sind Gewichtsteile.The parts mentioned in the examples are parts by weight.
Beispiel i .Example i.
Man läßt eine wäßrig-saure Lösung von, i14 Teilen ß-Methyl-glutardialdehyd, die durch Hydolyse von 128 Teilen 2-Methoxy-4-methyl 3,4 dihydro-i, 2-pyran mit 5oo Teilen 2 °/oiger Schwefelsäure erhalten wurde, allmählich in eine siedende Lösung von 964 Teilen kristallisiertem Ferriammoniumsulfat in iooo Teilen Wasser einlaufen. Nach Abdestillieren des Methanols macht man das Reaktionsgemisch alkalisch und destilliert dann das entstandene y-Picolin ab. Die Ausbeute beträgt 85 Teile = 9i °% der Theorie. Fügt man die Lösung des Ferriammoniumsulfats bei gewöhnlicher Temperatur zur Lösung des ß-Methylglutardialdehyds und erhitzt das Gemisch dann 2 Stunden am Rückflußkühler zum Sieden, so erhält man bei im übrigen gleicher Aufarbeitung 62 Teile y-Picohn.An aqueous-acidic solution of, 14 parts of ß-methyl-glutaraldehyde, by hydrolyzing 128 parts of 2-methoxy-4-methyl 3,4 dihydro-i, 2-pyran with 500 parts of 2% sulfuric acid was obtained gradually into a boiling solution of 964 parts of crystallized ferric ammonium sulfate run in 100 parts of water. After the methanol has been distilled off, the reaction mixture is made alkaline and distilled then the resulting y-picoline is removed. The yield is 85 parts = 91% of theory. The ferric ammonium sulfate solution is added to the solution at ordinary temperature of the ß-methylglutaraldehyde and then heated the mixture for 2 hours on the reflux condenser to boiling, 62 parts of y-Picohn are obtained with otherwise identical work-up.
Beispiel 2 Man läßt eine Lösung von Zoo Teilen Glutardialdehyd in 8oo Teilen 3 °%iger Schwefelsäure im Laufe von 2 Stunden in eine siedende Lösung von iiooTeilen kristallisiertem Ferrisulfat und Zoo Teilen Ammoniumsulfat in 15oo Teilen Wasser einlaufen. Bei der Aufarbeitung gemäß Beispiel i erhält man reines Pvridin in einer Ausbeute von 82 °/o "der Theorie.Example 2 A solution of zoo parts of glutaraldehyde in 800 parts of 3% sulfuric acid in the course of 2 hours in a boiling solution of 100 parts of crystallized ferric sulphate and zoo parts of ammonium sulphate in 1500 Pour in parts of water. When working up according to Example i, pure ones are obtained Pvridine in a yield of 82% of theory.
Beispiel 3 Man trägt 142 Teile2-Äthoxy-5-methyl-3, 4-dihydroi, 2-pyran, das aus a-Methacrolein und Vinyläthyläther durch Diensynthese hergestellt wurde, im Laufe von 2 Stunden in eine siedende Lösung von x32 Teilen Ammoniumsulfatund 5oo Teilen kristallisiertem Kupfersulfat in iooo Teilen i °/oiger Schwefelsäure ein. Bei der Aufarbeitung erhält man 45 Teile reines ß-Picolin.Example 3 142 parts of 2-ethoxy-5-methyl-3, 4-dihydroi, 2-pyran, which was produced from a-methacrolein and vinyl ethyl ether by diene synthesis, in the course of 2 hours in a boiling solution of x32 parts of ammonium sulfate and 500 parts of crystallized copper sulphate in 100 parts of 100% sulfuric acid a. Working up gives 45 parts of pure β-picoline.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB21045A DE944251C (en) | 1952-07-04 | 1952-07-04 | Process for the preparation of compounds of the pyridine series |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB21045A DE944251C (en) | 1952-07-04 | 1952-07-04 | Process for the preparation of compounds of the pyridine series |
Publications (1)
Publication Number | Publication Date |
---|---|
DE944251C true DE944251C (en) | 1956-06-14 |
Family
ID=6960498
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEB21045A Expired DE944251C (en) | 1952-07-04 | 1952-07-04 | Process for the preparation of compounds of the pyridine series |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE944251C (en) |
-
1952
- 1952-07-04 DE DEB21045A patent/DE944251C/en not_active Expired
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