DE1215156B - Process for the preparation of pyridine aldehydes by catalytic hydrogenation of cyanopyridines - Google Patents
Process for the preparation of pyridine aldehydes by catalytic hydrogenation of cyanopyridinesInfo
- Publication number
- DE1215156B DE1215156B DEV24877A DEV0024877A DE1215156B DE 1215156 B DE1215156 B DE 1215156B DE V24877 A DEV24877 A DE V24877A DE V0024877 A DEV0024877 A DE V0024877A DE 1215156 B DE1215156 B DE 1215156B
- Authority
- DE
- Germany
- Prior art keywords
- cyanopyridines
- preparation
- catalytic hydrogenation
- pyridine aldehydes
- pyridine
- 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.)
- Pending
Links
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical class N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 title claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims description 6
- -1 pyridine aldehydes Chemical class 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 description 2
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 101100356682 Caenorhabditis elegans rho-1 gene Proteins 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- SRVJKTDHMYAMHA-WUXMJOGZSA-N thioacetazone Chemical compound CC(=O)NC1=CC=C(\C=N\NC(N)=S)C=C1 SRVJKTDHMYAMHA-WUXMJOGZSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
Int. Cl.:Int. Cl .:
C07dC07d
Deutsche Kl.: 12 ρ-1/01 German class: 12 ρ -1/01
Nummer: 1215 156Number: 1215 156
Aktenzeichen: V 24877IV d/12 ρFile number: V 24877IV d / 12 ρ
Anmeldetag: 15. November 1963Filing date: November 15, 1963
Auslegetag: 28. April 1966Opening day: April 28, 1966
Pyridinaldehyde sind wertvolle Zwischenprodukte für die Herstellung pharmazeutischer Präparate.Pyridine aldehydes are valuable intermediates for the manufacture of pharmaceutical preparations.
Es ist aus der deutschen Auslegeschrift 1088 958 bekannt, daß man durch katalytische Reduktion von Cyanpyridinen in einfacher Weise zu Pyridinaldehyden gelangen kann. Man führt dabei die Reduktion in stark saurer Lösung bei einem pH-Wert von 2 in Gegenwart eines Nickelkatalysators durch, um die als Zwischenstufe sich bildende Aldiminoverbindung zum Aldehyd zu hydrolysieren. Die Gegenwart starker anorganischer oder organischer Säuren bedingt jedoch die Verwendung korrosionsbeständiger Apparaturen aus Speziallegierungen. Durch die verwendeten Säuren wird außerdem der zugesetzte Nickelkatalysator während des Prozesses zerstört und somit unwirksam. Schließlich muß die überschüssige Säure nach Beendigung der Reduktion zwecks Freisetzens des Pyridinaldehyds sorgfältig neutralisiert werden.It is known from German Auslegeschrift 1088 958 that by catalytic reduction of Cyanopyridines can easily reach pyridine aldehydes. One leads the reduction in a strongly acidic solution at a pH of 2 in the presence of a nickel catalyst to hydrolyze the aldimino compound formed as an intermediate to the aldehyde. The present stronger however, inorganic or organic acids require the use of corrosion-resistant equipment made of special alloys. The acids used also cause the added nickel catalyst destroyed during the process and therefore ineffective. Finally, the excess must Acid carefully neutralized after the end of the reduction in order to liberate the pyridine aldehyde will.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Pyridinaldehyden durch katalytieche Hydrierung von Cyanpyridinen in Gegenwart eines Nickelkatalysators und eines hydrolysierenden Mittels, das dadurch gekennzeichnet ist, daß die Reduktion unter Zusatz von Kohlendioxyd und überschüssigem Wasserstoff unter Druck durchgeführt wird. Die Umsetzung kann bei Zimmertemperatur erfolgen. Neben einer Vermeidung von Korrosionserscheinungen hat diese Arbeitsweise den Vorteil, daß die Reaktionslösung infolge Bildung von Pyridinium- und Ammoniumcarbonat neutral bis schwach alkalisch reagiert, so daß eine zusätzliche Neutralisation nach Beendigung der Reaktion entfällt und die Abtrennung des Aldehyds unmittelbar durch Extraktion oder Wasserdampfdestillation durchgeführt werden kann.The invention relates to a process for the preparation of pyridine aldehydes by catalytic Hydrogenation of cyanopyridines in the presence of a nickel catalyst and a hydrolyzing agent, which is characterized in that the reduction with the addition of carbon dioxide and excess Hydrogen is carried out under pressure. The reaction can take place at room temperature. In addition to avoiding the appearance of corrosion, this mode of operation has the advantage of that the reaction solution is neutral to weak due to the formation of pyridinium and ammonium carbonate reacts alkaline, so that an additional neutralization is not necessary after the end of the reaction and the Separation of the aldehyde can be carried out directly by extraction or steam distillation can.
50 g 3-Cyanpyridin wurden in 800 ml Wasser gelöst und die Lösung in einen 2-1-Autoklav gebracht. Es wurden 5 g Rany-Nickel und 60 g Kohlendioxyd zugegeben und anschließend der Ge-50 g of 3-cyanopyridine were dissolved in 800 ml of water and the solution was placed in a 2-1 autoclave. 5 g of Rany nickel and 60 g of carbon dioxide were added and then the
Verfahren zur Herstellung von Pyridinaldehyden durch katalytische Hydrierung von CyanpyridinenProcess for the preparation of pyridine aldehydes by catalytic hydrogenation of cyanopyridines
Anmelder:Applicant:
VEB »Leuna-Werke »Walter Ulbricht«,
Leuna (Kr. Merseburg)VEB »Leuna-Werke» Walter Ulbricht «,
Leuna (Kr.Merseburg)
Als Erfinder benannt:
Dr. Dieter Eilhauer, Leipzig;
Dipl.-Chem. Wilhelm Höfling,
Leuna (Kr. Merseburg);
Gerhard Reckling, SpergauNamed as inventor:
Dr. Dieter Eilhauer, Leipzig;
Dipl.-Chem. Wilhelm Höfling,
Leuna (Kr. Merseburg);
Gerhard Reckling, Spergau
samtdruck durch Aufpressen von Wasserstoff auf ao 20 at erhöht. Die Reduktion wurde bei Zimmertemperatur durchgeführt. Die Reaktionslösung zeigtetotal pressure increased to ao 20 atm by forcing hydrogen. The reduction was at room temperature carried out. The reaction solution showed
nach 8 Stunden einen pH-Wert von 8.
Der gebildete 3-Pyridinaldehyd wurde ohne weitereafter 8 hours a pH value of 8.
The 3-pyridine aldehyde formed was without further
Neutralisation mit Wasserdampf übergetrieben. Zur Ausbeutebestimmung wurde das Thiosemicarbazon mit Thiosemicarbazid gefällt.Neutralization with steam overdone. The thiosemicarbazone was used to determine the yield like with thiosemicarbazide.
Es wurde eine Ausbeute von 72 °/o der Theorie anIt was a yield of 72% of theory
3-Pyridinaldehyd, bezogen auf das eingesetzte Cyanpyridin, ermittelt.3-pyridine aldehyde, based on the cyanopyridine used, determined.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEV24877A DE1215156B (en) | 1963-11-15 | 1963-11-15 | Process for the preparation of pyridine aldehydes by catalytic hydrogenation of cyanopyridines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEV24877A DE1215156B (en) | 1963-11-15 | 1963-11-15 | Process for the preparation of pyridine aldehydes by catalytic hydrogenation of cyanopyridines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1215156B true DE1215156B (en) | 1966-04-28 |
Family
ID=7581511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEV24877A Pending DE1215156B (en) | 1963-11-15 | 1963-11-15 | Process for the preparation of pyridine aldehydes by catalytic hydrogenation of cyanopyridines |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1215156B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0008323A1 (en) * | 1978-06-08 | 1980-03-05 | Ciba-Geigy Ag | Process for the preparation of pyridine aldehydes and their derivatives, and compounds made by this process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1088958B (en) * | 1957-04-12 | 1960-09-15 | Cfmc | Process for the preparation of pyridine aldehydes |
-
1963
- 1963-11-15 DE DEV24877A patent/DE1215156B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1088958B (en) * | 1957-04-12 | 1960-09-15 | Cfmc | Process for the preparation of pyridine aldehydes |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0008323A1 (en) * | 1978-06-08 | 1980-03-05 | Ciba-Geigy Ag | Process for the preparation of pyridine aldehydes and their derivatives, and compounds made by this process |
| US4322536A (en) | 1978-06-08 | 1982-03-30 | Ciba-Geigy Corporation | Process for producing pyridinaldehydes |
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