DE1913732C3 - Verfahren zur Herstellung von Bipyridylen - Google Patents

Verfahren zur Herstellung von Bipyridylen

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Publication number
DE1913732C3
DE1913732C3 DE1913732A DE1913732A DE1913732C3 DE 1913732 C3 DE1913732 C3 DE 1913732C3 DE 1913732 A DE1913732 A DE 1913732A DE 1913732 A DE1913732 A DE 1913732A DE 1913732 C3 DE1913732 C3 DE 1913732C3
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Prior art keywords
pyridyl
meoh
pentane
diol
bipyridyls
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Expired
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DE1913732A
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DE1913732A1 (de
DE1913732B2 (de
Inventor
R D Bowden
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Publication of DE1913732B2 publication Critical patent/DE1913732B2/de
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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
    • C07D213/06—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
    • C07D213/22—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 containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/32—Sulfur atoms
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/51—Acetal 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/56—Amides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

20
25
Es ist bekannt, daß Bipyridyle aus Pyridylen durch ^Umsetzung mit einem Metall und Oxidation des so Erhaltenen Zwischenprodukts hergestellt werden kön-Hen. So ist beispielsweise in der DE-OS 14 45 944 ein Verfahren zur Herstellung von 4,4'-Bipyridyl durch tJmsetzung von Pyridin mit Natrium beschrieben.
Gemäß der Erfindung wurde festgestellt, daß sich (Bipyridyle durch ein besonders zweckmäßiges Verfahfen auch aus leicht zugänglichen Ausgangsstoffen ^erstellen lassen, wobei nicht mit gefährlichen Stoffen fcde metallischem Natrium gearbeitet werden muß.
Demgemäß betrifft die Erfindung also ein Verfahren Jiur Herstellung von Bipyridylen, das dadurch gekenn-Zeichnet ist, daß man das entsprechende
4-Pyridyl-tetrahydropyran,
2-Pyridyl-tetrahydropyran,
3-Pyridyl-pentan-1,5-diol,
3-(4-Pyridyl)-pentan-1,5-dithiol, 3-(4-Pyridyl)-pentan-1 -thiol-5-ol,
3-(4-Pyridyl)-l,l-diäthoxypentan-5-ol,
3-(4-Pyridyl)-5,5-diäthoxypentan-l -thiol oder
[3-(4-Pyridyl)-glutaraldehyd-tetraäthylacetal]
Init. Ammoniak in der Dampfphase bei einer Tempera- |ur im Bereich von 250 bis 45O0C in Gegenwart eines t>ehydrierungskatalysators umsetzt.
Geeignete Katalysatoren sind Aluminiumoxid, Siliciumdioxid, Siliciumdioxid-Aluminiumoxid, Magnesium-Oxid, Chromoxid und Gemische daraus. Diese Katalysaloren können Platin und/oder Palladium (als Metall oder $\s Oxid) in fein verteilter Form enthalten. Besonders geeignete Katalysatoren sind die bekannten Dehydrieftingskatalysatoren Nickel, Cobalt, Kupfer, Chrom und ICupferchromit.
Vorzugsweise enthält das Reaktionsgemisch molekularen Sauerstoff, wie z. B. Sauerstoffgas, welcher in zweckmäßiger Weise in Form von Luft zugesetzt wird. Wenn die Reaktion in Abwesenheit von Sauerstoff ausgeführt wird, dann kann das Reaktionsprodukt anschließend mit molekularem Sauerstoff in das Bipyridyl oxidiert werden:
Das Ausgangsmaterial kann einfach durch Erhitzen auf die erforderliche Temperatur verdampft werden. Eine besonders geeignete Technik besteht darin, das Material in einem TYöpfchenstrom auf eine heiße Oberfläche fallen zu lassen, wie z. B. auf einen Verdampfer oder auf den Katalysator für die Reaktion mit Ammoniak. Das Material kann zweckmäßig vor der Berührung mit dem Katalysator in einem Verdampfer verdampft werden. Einige Ausgangsmaterialien sind jedoch bei gewöhnlichen Temperaturen klebrige viskose Flüssigkeiten oder Feststoffe. Diese werden zweckmäßig vor dem Verdampfen in einem geeigneten Lösungsmittel aufgelöst Beispiele für geeignete Lösungsmittel für diesen Zweck sind Wasser und Alkohole, insbesondere niedrige aliphatische Alkohole und ganz besonders Methanol.
Die durch das Verfahren gebildeten Bipyridyle können aus den Reaktionsprodukten durch bekannte Techniken isoliert werden. Beispielsweise können die gasförmigen Reaktionsprodukte kondensiert werden, worauf das Bipyridyl dann aus dem Kondensat durch Lösungsmittelextraktion und/oder fraktionierte Destillation, ggf. unter vermindertem Druck, isoliert werden kann. Wenn Wasser im Reaktionsprodukt anwesend ist, dann können die Bipyridyle durch Filtration abgetrennt werden.
Das Verfahren kann, ob nun in einer einzigen Stufe oder in zwei Stufen, absatzweise ausgeführt werden, eignet sich aber besonders für einen kontinuierlichen Betrieb.
Das Verfahren eignet sich besonders zur Herstellung von 4,4'-Bipyridylen, obwohl auch andere Isomere (mit Ausnahme von 3,3'-Isomeren), d. h. 2,2'-, 2,4'-, 2,3'- und 3,4'-Bipyridyle durch eine geeignete Auswahl der Ausgangsmaterialien erhalten werden können.
Die Erfindung wird durch die folgenden Beispiele erläutert:
Beispiele 1 bis 34
Das Verfahren war in jedem Beispiel wie folgt:
Ein Katalysatorbett wurde aus einer pelletisieren Form des Katalysators (siehe unten) bis zu einer bestimmten Tiefe in einem vertikalen Glasreaktionsrohr mit einem Innendurchmesser von 25 mm hergestellt. Das Rohr war mit einer zentralen Thermoelementtasche ausgerüstet und enthielt über dem Katalysatorbett Raschig-Ringe. Die Raschig-Ringe füllten das Rohr nicht vollständig. Das Rohr war in einem vertikalen Ofen angeordnet, der auf der entsprechenden Temperatur gehalten wurde.
Das substituierte Pyridin wurde in Wasser oder Methanol oder (Beispiel 30) Pyridin aufgelöst, und die Lösung wurde zur Oberseite des Reaktionsrohrs geführt, wo sie beim Kontakt mit den Raschig-Ringen verdampft. Die Dämpfe wurden nach unten durch das Katalysatorbett geführt. Die Dämpfe wurden mit Sauerstoff, Stickstoff oder Ammoniak, wie in der Tabelle angegeben, für den Durchgang durch das Katalysatorbett gemischt. In einigen Fällen wurde das Mischen jedoch unterhalb der Oberfläche des Katalysatorbetts ausgeführt.
Der Abstrom aus dem Reaktor wurde kondensiert, und das Kondensat wurde, sofern es flüssig war (was für die meisten Experimente gilt), durch Gas/Flüssigkeits-Chromatografie analysiert, wobei Standardtechniken verwendet wurden. Wenn das Kondensat ein Feststoff war, dann wurde dieser in Methanol aufgelöst, worauf die Lösung analysiert wurde.
der Tabelle 3 Pellets von 3x1 1 9 13 S Silicium- I I Substituiertes
Pyridin		 Katalysator E= E 152 102 Temp.
("C)		 732 4 - In der Tabelle gelten folgende Abkürzungen: Verd. Lösungs
mittel		 4,4'-Bipyridyl, sofern nichts anderes 830 Lösungsmittel
I I 2 I 8 Kntuly·
süior		 76 0 38 mm 340-360 3,5/25 MeOH angegeben ist
I In mit den j I 3-(4-Pyridyl)- A A 76 »Bipyridyl« = Länge des Katalysatorbetts
ein Bett aus 13% Aiuminiumoxid-Siliciumdioxid + 1 1,1-diäthoxy- Temperatur des Katalysatorbetts 830
! mm aus Aluminiumoxid, ein gesondertes Bett aus Aluminiumoxid. I 3 1 9 pentan-5-ol 76 A 350-380 »Länge« = 3,0/25 HiO/MeOH g Ausgangsmaterial/m! c: ^
sind die Katalysatoren aktiviertes Kupferoxid/Chromoxid, I Tabelle I 3-(4-Pyridyf)- A »Temp.« = (1:1) Methanol Umwand!
in 4,4'-Bi-
pyridyl (c
I Buchstaben A, B, C oder D bezeichnet: 0,5% Platin auf 50% Aluminiumoxid/50°/c I NrP' I 1,1-diäthoxy- »Verd.« = 830 24
i dioxid-Aluminiumoxid, 4 I 1° pentan-5-ol .76 350-390 »MeOH« = 2,66/25 MeOH
I A. 1 3-(4-Pyridyl)- A Gasbeschickung
S R %. glularaldehyd- Lufl
(ml/min)
N:
(nil min)		 830 39
5 I 11 tetraäthylacetal 76 370-490 Flüssigkeitsbeschickung 1,85/25 HO/MeOH 100 -
I I 3-(4-Pyridyl)- A Zeit
(min)		 (50:50)
1 D. % glutaraldehyd- 45 830 86
I 6 I 12 tetraäthylacetal 76 360-400 1,82/25 MeOH 100 -
I 3-(4-Pyridyl)- A
5,5-diäthoxy- 45 830 70
7 & pentan-1-thiol 76 380-415 2,1/25 MeOH 100 -
ι 14 3-(4-Pyridyl)- A
1 5-hydroxy- 60 830 58
I 15 pentan-1-thiol 76 350-400 1,3/25 MeOH 100 -
I 3-(4-Pyridyl)- A
I I6 peman-!,5-di- 77 830 19
I thiol 76 380-420 1,1/25 MeOH 100 -
I 17 2-(2-PyridyI)- A
tetrahydro- 52 500 3
I is pyran 76 370 2,1/10 H2O 100 -
4-(4-Pyridyl)- A
V 19 tetrahydro- 75 500 2,2'-Bi-
pyran 76 370 2,5/12,5 H2O 1OP - pyridyl 13
I 20 4-(4-Pyridyl)- A
I tetrahydro- 67 830 20
I 21 pyran 76 370 4,5/25 MeOH 100 -
I 4-(4-Pyridyl)- A
1 22 tetrahydro- 34 300 6
I pyran 63 340-360 2,9/16,3 50 -
4-(4-Pyridyl)-
tetrahydro-
pyran		 A 830
4-(4-PyridyI)-
tetrahydro-
pyran		 76 360-370 30 4,4/25 MeOH 15
4-(4-Pyridy!)-
telrahydro-
pyran		 B — — 830
3-(2-Pyridyl)- 76 360-370 4,4/25 MeOH
penlan-l,5-diol B 35 830 10
3-(2-Pyridyl)- 76 360-380 3,6/18 MeOH 100 -
pentan-1,5-diol A 830 9
3-(3-Pyridyl)- 89 340-360 56 15/75 MeOH
pentan-l,5-diol B 50 - 830 1 I
3-(3-Pyridyl)- 102 370-400 5/25 MeOH
pentan-l,5-diol A 50 100 - 830 2,4'-Bi-
3-(4-Pyridyl)- 76 370-390 1,95/25 MeOH pyridyl 10
pentan-l,5-diol B 60 - 100 830 2,4'-Bi-
3-(4-Pyridyl)- 102 360-380 4,8/25 MeOH pyridyl 22
pentan-l,5-diol C 0 38 mm 60 100 - 830 3,4'-Bi-
3-(4-Pyridyl)- B 360-364 5/25 MeOH pyridyl 10
pentan-l,5-diol 60 100 - 500 3,4'-Bi-
3-(4-Pyridyl)- 400 2,6/18 H2O pyridyl 18
pentan-l,5-diol 120 100 - 830 46
400 15/75 MeOH
60 100 - 75
120 100 67 8
50 100 100 20
50 - 100
50 100 -
180
Fortsetzung Substituiertes A nuKs;„..r go Hüssigkeiisbeschi Vcrcl. ekung Uiisbcschickung ZS ZS SJj
Hsp.
Nr.		 O
5 Ξ?ξ		 400 NI S 3,8/19 M Lufl
(ml/niin)		 500
3-(4-Pyridy1)- A 7ö 80 H2O 100 20
23 pentan-l,5-diol 0 300-340 5/25 60 830
3-(4-Pyridyl)- D 165 66 MeOH 135 30
24 pentan-l,5-diol 0 38 mm 325-375 6,4/25 100 830
3-(4-Pyridyl)- D 76 + 76 59 MeOH 100 Io
25 pentan-1,5-dio! 0 38 mm 330-370 5/25 300 830
3-(4-Pyridyi)-
pentan-l,5-diol		 A 76 + 76 51 MeOH 100 13
26 3-(4-Pyridyl)- 38 mm 320-330 5/25 — 830
pentan-13-diol A 152 82 MeOH 100 26
27 3-(4-Pyridyl)- 350-390 51,4/260 — 830
pentan-1,5-diol D 76 hauptsächl.
^70		 11 St MeOH 100 18
28 3-(4-Pyridyl)- 320-380 8,6/43 500
pentan-lp-diol A 76 30 H2O 100 12
29 3-(4-Pyridyl)- 370-400 1,8/39 — 500
pentan-l,5-diol B 76 30 Pyridin 60 5
30 3-(4-Pyridyl)- 0 360-380 35/125 100 830
pentan-l,5-diol B 152 7 st MeOH 100 60
31 3-(4-Pyridyl)- 0 38 mm 360-380 10/50 60 830
pentan-l,5-diol B 152 100 MeOH — 67
32 3-(4-Pyridyl)- 0 38 mm 360-380 5/25 60 830
pentan-l,5-diol B 152 40 MeOH 35 84
33 3-(4-Pyridyl)- 0 38 mm 360-390 2,5/25 67 830
pentan-l,5-diol 152 42 H2O 100 17
34 38 mm
In der obigen Tabelle sind die angegebenen Produkte die Hauptprodukte. In vielen Beispielen wurden jedoch auch andere Produkte identifiziert wie folgt:
Beispiele Nrn.
5,6, 7, 19 bis 34 15, Ib 17, 18
Andere Produkte
4-(4-Pyridyl)-tetrahydropyran 4-(2-Pyridyl)-tetrahydropyran 4-(3-Pyridyl)-tetrahydropyran und 3'-Methyl-3,4'-bipyridyl

Claims (1)

  1. Patentanspruch:
    Verfahren zur Herstellung von Bipyridylen, dadurch gekennzeichnet, daß man das entsprechende
    4-Pyridyl-tetrahydropyran,
    2-Pyridyl-tetrahydropyran,
    3-Pyridyl-pentan-1,5-diol,
    3-.{4-Pyridyl)-pentan-1,5-dithiol,
    3-(4-Pyridyl)-pentan-l-thiol-5-ol,
    3-(4-Pyridyl)-2,l-diäthoxypentan-5-ol,
    3-(4-Pyridyl)-5,5-diäthoxypentan-l-thioIoder
    [3-(4-Pyridyl)-glutaraldehyd-tetraäthyl-
    acetal]
    mit Ammoniak in der Dampfphase bei einer Temperatur im Bereich von 250 bis 450° C in Gegenwart eines Dehydrierungskatalysators umsetzt
    H)
DE1913732A 1968-03-18 1969-03-18 Verfahren zur Herstellung von Bipyridylen Expired DE1913732C3 (de)

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
GB46736/71A GB1268194A (en) 1968-03-18 1968-03-18 Pyridine derivatives and their manufacture
GB1300868 1968-03-18
GB46739/71A GB1268196A (en) 1968-03-18 1968-05-29 Pyridine derivatives and their manufacture
GB2577368 1968-05-29
GB6071468 1968-12-20
GB6071568 1968-12-20
GB6071668 1968-12-20
GB4673771 1968-12-20
GB246/69A GB1268191A (en) 1968-03-18 1969-01-02 Process for the manufacture of bipyridyls
US17417571A 1971-08-23 1971-08-23
US412093A US3873555A (en) 1968-03-18 1973-11-02 Process for the manufacture of bipyridyls

Publications (3)

Publication Number Publication Date
DE1913732A1 DE1913732A1 (de) 1970-02-19
DE1913732B2 DE1913732B2 (de) 1981-04-02
DE1913732C3 true DE1913732C3 (de) 1982-04-15

Family

ID=27581625

Family Applications (4)

Application Number Title Priority Date Filing Date
DE1913732A Expired DE1913732C3 (de) 1968-03-18 1969-03-18 Verfahren zur Herstellung von Bipyridylen
DE19691967049 Withdrawn DE1967049A1 (de) 1968-03-18 1969-03-18 Verfahren zur herstellung von 4-(pyridyl)-tetrahydropyranen
DE1967047A Expired DE1967047C3 (de) 1968-03-18 1969-03-18 Verfahren zur Herstellung von Bipyridylen
DE19691967048 Withdrawn DE1967048A1 (de) 1968-03-18 1969-03-18 Verfahren zur herstellung von 4-(pyridyl)-tetrahydropyranen

Family Applications After (3)

Application Number Title Priority Date Filing Date
DE19691967049 Withdrawn DE1967049A1 (de) 1968-03-18 1969-03-18 Verfahren zur herstellung von 4-(pyridyl)-tetrahydropyranen
DE1967047A Expired DE1967047C3 (de) 1968-03-18 1969-03-18 Verfahren zur Herstellung von Bipyridylen
DE19691967048 Withdrawn DE1967048A1 (de) 1968-03-18 1969-03-18 Verfahren zur herstellung von 4-(pyridyl)-tetrahydropyranen

Country Status (9)

Country Link
US (2) US3651071A (de)
AT (5) AT292705B (de)
BE (1) BE729987A (de)
CH (6) CH538506A (de)
DE (4) DE1913732C3 (de)
FR (1) FR2004163A1 (de)
GB (4) GB1268194A (de)
NL (1) NL167689C (de)
SE (2) SE392468B (de)

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CA2022886A1 (en) * 1989-08-08 1991-02-09 Raymond Baker Substituted pyridines, their preparation, formulations and use in dementia
DE19536652A1 (de) * 1995-09-30 1997-04-10 Judit Kirschke Kompresse zur Wärmetherapie unter Verwendung von temperaturregulierendem und/oder heilendem und/oder beschwerdelinderndem Material
JP4603646B2 (ja) * 1999-11-15 2010-12-22 富士フイルムファインケミカルズ株式会社 新規なジピリジル誘導体
WO2005082872A1 (ja) * 2004-03-02 2005-09-09 Dainippon Sumitomo Pharma Co., Ltd. ベンゾチアジン－３－オン化合物及びその製造中間体
JP5235947B2 (ja) * 2010-07-30 2013-07-10 富士フイルムファインケミカルズ株式会社 新規なジピリジル誘導体

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NL131727C (de) * 1963-08-08 1900-01-01

Also Published As

Publication number Publication date
AT292705B (de) 1971-09-10
GB1268194A (en) 1972-03-22
GB1268191A (en) 1972-03-22
FR2004163A1 (de) 1969-11-21
NL6903976A (de) 1969-09-22
DE1967047B2 (de) 1980-05-14
DE1913732A1 (de) 1970-02-19
NL167689B (nl) 1981-08-17
SE394111B (sv) 1977-06-06
CH530997A (de) 1972-11-30
DE1967048A1 (de) 1976-11-04
AT292706B (de) 1971-09-10
CH540910A (de) 1973-10-15
AT295535B (de) 1972-01-10
NL167689C (nl) 1982-01-18
DE1913732B2 (de) 1981-04-02
CH540255A (de) 1973-10-15
CH532051A (de) 1972-12-31
US3873555A (en) 1975-03-25
BE729987A (de) 1969-09-17
DE1967049A1 (de) 1976-11-04
CH542222A (de) 1973-11-15
DE1967047C3 (de) 1981-01-22
US3651071A (en) 1972-03-21
AT292704B (de) 1971-09-10
CH538506A (de) 1973-08-15
GB1268196A (en) 1972-03-22
GB1268195A (en) 1972-03-22
DE1967047A1 (de) 1976-10-07
AT289797B (de) 1971-05-10
SE392468B (sv) 1977-03-28

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