DE1913732B2 - Verfahren zur Herstellung von Bipyridylen - Google Patents

Verfahren zur Herstellung von Bipyridylen

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Publication number
DE1913732B2
DE1913732B2 DE1913732A DE1913732A DE1913732B2 DE 1913732 B2 DE1913732 B2 DE 1913732B2 DE 1913732 A DE1913732 A DE 1913732A DE 1913732 A DE1913732 A DE 1913732A DE 1913732 B2 DE1913732 B2 DE 1913732B2
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DE
Germany
Prior art keywords
pyridyl
pentane
meoh
diol
bipyridyls
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.)
Granted
Application number
DE1913732A
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DE1913732C3 (de
DE1913732A1 (de
Inventor
Roy Dennis Runcorn Cheshire 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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Publication of DE1913732C3 publication Critical patent/DE1913732C3/de
Expired legal-status Critical Current

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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

Es ist bekannt, daß Bipyridyle aus Pyridylen durch Umsetzung mit einem Metall und Oxidation des so erhaltenen Zwischenprodukts hergestellt werden können. So ist beispielsweise in der DE-OS 14 45 944 ein Verfahren zur Herstellung von 4,4'-Bipyridyl durch Umsetzung von Pyridin mit Natrium beschrieben.
Gqmäß der Erfindung wurde festgestellt, daß sich Bipyridyle durch ein besonders zweckmäßiges Verfahren auch aus leicht zugänglichen Ausgangsstoffen herstellen lassen, wobei nicht mit gefährlichen Stoffen wie metallischem Natrium gearbeitet werden muß.
Demgemäß betrifft die Erfindung also ein Verfahren zur Herstellung von Bipyridylen, das dadurch gekennzeichnet ist, daß man das entsprechende
4- Pyridyl-tetrahydropyran,
2-Pyridyl-tetrahydropyran,
3- Pyridyl-pentan-1,5-diol,
3-(4-Pyridyl)-pentan-l,5-dithiol,
3-(4-Pyridyl)-pentan-l-thioI-5-oI,
3-(4-Pyridyl)-l,l-diäthoxypentan-5-ol,
3-(4-Pyridyl)-5,5-diäthoxypentan-1 -thiol oder
[3-(4-Pyridyl)-glutaraIdehyd-tetraäthylacetal]
mit Ammoniak in der Dampfphase bei einer Temperatur im Bereich von 250 bis 450eC in Gegenwart eines Dehydrierungskatalysators umsetzt
Geeignete Katalysatoren sind Aluminiumoxid, Siliciumdioxid, Siliciumdioxid-Aluminiumoxid, Magnesiumoxid, Chromoxid und Gemische daraus. Diese Katalysatoren können Platin und/oder Palladium (als Metall oder als Oxid) in fein verteilter Form enthalten. Besonders geeignete Katalysatoren sind die bekannten Dehydrierungskatalysatoren Nickel, Cobalt, Kupfer, Chrom und KupferchromiL
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 dje erforderliche Temperatur verdampft werden, E|ne besonders geeignete Technik besteht darin, das Material in einem Tröpfi;hetistrora auf eine heiße Oberfläche fallen zu lasjsen, wie ζ,Β, 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 visko-
se Flüssigkeiten oder Feststoffe. Diese werden zweckmäßig vor dem Verdampfen in einem geeigneten Lösungsmittel aufgelöst Beispiele für geeignete Lösungsmittel für diesen Zwecjic sind Wasser und Alkohole, insbesondere niedrige aliplptische Alkohole und ganz
besonders Methanol
Die durch das Verfahren gebildeten Bipyridyle können aus den Reaktionsprodukten durch bekannte Techniken isoliert werden. Beispielsweise tonnen 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 Realctionsprodukt anwesend ist, dann können die Bipyridyle durch Filtration abgetrennt werden.
Das Verfahren kann, ob raun 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'-Isoineren), d. h. 2£'-, 2,4'-, 23'- 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
4u Das Verfahren war in jedem Beispiel wie folgt:
Ein Katalysatorbett wurde aus einer pelletisierten 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 Ober dem Katalysatorbett Raschig-Ringe. Die Raschig-Ringe füllten das Rohr nicht vollständig. Das Rohr war in einem vertikalen Ofen angeordnet, der auf der entsprechenden Temperatür gehalten wurde.
Das substituierte Pyridin wurde in Wasser oder Methanol oder (Beispiel 30]' Pyridin aufgelöst, und die Lösung wurde zur Obenseite 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 d«r 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-
h5 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 sind 3 Pellets γοη 3 χ 3 nun aus Aluminiumoxid, 19 13 S 0,5% Platin auf 50% Aluminiumond/50% Silicium- Sqbstfariertes
Pyridin		 Katalysator H 152 102 Temp.
CC)		 -(- 732 4 Verd, in
Jl		 4,4'-BipyridyI, sofern nichts anderes i in 4,4'-B
pyridyl (
aktiviertes Kupferoxid/Chromoxid, . dioxid-AIuminiumoxid, Kataly
sator		 76 0 38 mm 340-360 3,5/25 MeOH angegeben ist 830 24
In mit den 1,1-dJäthoxy-
nan fan -5-λΙ		 A 76 A 76 350-380 3,0/25 HzO/MeOH Lange des Katalysatorbetts 830 39
dies Katalysstoren llWUlull >J^ll A Temperatur des Katalysatorbetts
Buchstaben A, B, C oder D bezeichnet; ein Bett aus 13% Aluminiumoxid-Siliciurndioxid pentan-5-ol 76 A 350-390 2,66/25 MeOH g Ausgangsmaterial/ml Lösungsmittel 830 86
ein gesondertes Bett aus Aluminiumoxid. 3-(4-Pyridyl)-
glutaraldehyd-		 A In der Tabelle gelten folgende Abkflrzungen; Methanol
A, Tabelle tetraathylacetal 76 370-490 135/25 H20/Me0H
(50:50)		 830 70
B, Bsp,
ΝγΓ		 3-<4-PyridyI)-
glutaraldehyd-		 A »Bipyridyl« =
C, tetraäthylacetal 76 360-400 132/25 MeOH Gasbeschickung 830 58
1 3-(4-PyridyI)-
53^diäthoxy-		 A »Länge« = Luft
(ml/min)
N2
(ml/min)
D. 2 pentan-1-thiol 76 380-415 »Temp.« = 2,1/25 MeOH 100 — 830 19
3-{4-PyridyI)-
5-hydroxy-		 A »Verd.« = 100 -
3 pentan-1-thiol /6 350-400 »MeOH« = U/25 MeOH 830 8
3-<4-Pyridyl)- A 100 -
4 pentan-l^-di-
thiol		 76 380-420 1,1/25 MeOH 830 2,2'-Bi-
2-(2-Pyridyl)- A FIDssigkeitsbeschidcung 100 - pyridyl 13
5 tetrahydro- Zeit
(min)
pyran 76 370 45 2,1/10 H2O 100 500 20
6 4-(4-Pyridyl)- A 45
tetrahydro- 100 -
7 pyran 76 370 60 2,5/12 J H2O 500 6
4-(4-PyridyI)- A 100 -
8 tetrahydro- 77
pyran 76 370 4^/25 MeOH 100 - 830 15
4-{4-Pyridyl)- A 52
9 tetrahydro-
pyran 63 340-360 75 2,9/163 H2O 50 300 10
4-{4-Pyridyl)- A
10 pyran 76 360-370 67 4,4/25 MeOH 830 9
4-(4-Pyridyl)-
tctrflhvrfro-		 B _ _
ICVl QiIVUI ν
pyran		 76 360-370 34 4,4/25 MeOH 8JO 11
11 4-(4-Pyridyl)- B
pyrm 76 360-380 3,6/18 MeOH 100 - H?0 2,4'-Bi-
3-(2-Pyiidyl> A 30 pyridyl IO
12 pentan-l^-diol 89 340-360 15/75 MeOH 830 2.4'-Bi-
3-(3-Pyridyl)- B 50 - pyridyl 22
13 pentan-l^-diol 102 370-400 35 5/25 MeOH 1JiO 3,4-Bi
pyridyl 10
3-(3Pyridyl)-
pentan-l^-diol		 A 76 370-390 1,95/25 MeOH 100 - 830 3,4'Bi-
14 3-(3-Pyridyl)-
pentan-l,5-diol		 B pyridyl 18
3-(4-Pyridyl)- 102 360-380 56 4,8/25 MeOlI - 100 830 46
15 pentan-l^-diol C 0 38 mm
3-(4-Pyridyl)- B 360-364 5/25 MeOH 100 8.W 75
16 pentan-14-diol 50
3-(4-Pyridyl)- 400 2,6/18 H2O 100 500 8
17 pentan-l^-diol 60
18 3-(4-Pyridyl)- 400 15/75 MeOH 100 830 20
Dentan-15-diol 60 100 -
19
60 100 67
20
120 100 100
21
60 - 100
22 120
100
50
50
50
180
Fortsetzung
Bsp, Substituiertes KflWlysstPr k Flfissif I JkHng Gasbeschickung C
E
£1		 i W ^ Nrn. Andere Produkte
ΝΓτ' PyrMin 400 3,8/19 - 500 M · ^
Kataly
sator
Länge
(mm)		 300—340 Zeil
(min)		 5/25 Lösungs
mittel		 Luft
(ml/min)		 60 830 3.E B
23 A 76 80 H2O 100 20
24 3^4-PyridyIV A 165 325-375 66 6,4/25 MeOH 135 100 830 30
pentan-l,5-oiol 0 33 mm
25 : 3-(4-PyridyJ)- P 76+76 330-370 59 5/25 MeOH 100 300 830 56
pentan-l,5-diol 0 38 mm
26 3^4-PyridyIV- ΓΛ 76+76 320-380 51 5/25 MeOH 100 — 830 13
pentan-l,5-diol 0 38 mm 350-390
hauptsächL
370		 51,4/260 — 830
27 3-{4-PyridyI)-
pentan-l^-diol		 A 152 320-380 82 8,6/43 MeOH 100 26
28 ^Pyridyl);
p'entan-l^-diol		 A 76 11 st MeOH 100 18
29 3-(4-Pyridyl)- D 76 370-400 30 1,8/39 H2O 100 — 50Ö 12
. pentan-l,5-d:ol 360-380 35/125 100 830
30 3-(4-Pyridyl)-
pentan-14-diol		 A 76 360-380 30 10/50 Pyridin 60 60 830 5
31 3-(4-Pyridyl):
pentan-lp-diol		 B 152
0 38 mm		 360-380 7 st 5/25 MeOH 100 60 830 60
32 3-(4-PyridyI)-
pentan-14-diol		 B 152
0 38 mm		 100 MeOH — 67
33 3-{4-PyridyI)- B 152 360-390 40 £5/25 MeOH 35 67 830 84
pentan-l,5-diol 0 38 mm
34 3-(4-Pyridyl)-
pentan-I^diol		 B 152
0 38 mm		 42 H2O 100 17
In der obigen Tabelle sind die angegebenen Produkte die Hauptprodukte. In vielen Beispielen wurden jedoch auch
andere Produkte identifiziert wie folgt:
Beispiele
5. 6, 7, 19 bis 34 15, 16 17, 18
4-(4-Pyridyl)-tetrahydropyran 4-(2-Pyridyl)-tetrahydropyran 4-(3-PyridyI)-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-PyridyI-tetrahydropyran,
    3-PyridyI-pentan-l^-dioL
    3-(4-Pyridyf)-pentan-l^-dithioi,
    3-(4-Pyridyf)-pentan-l-thioI-5-oL
    3-{4-Pyridyl)-2,l-diäthoxypentan-5-oL
    3-(4-Pyridyl)-5,5-diäthoxypentan-l-thioloder
    [3-(4-Pyridyl)-glutaraIdehyd-tetraäthyl-
    acetaTJ
    mit Ammoniak in der Dampfphase bei einer Temperatur im Bereich von 250 bis 4500C in Gegenwart eines Dehydrierungskatalysators umsetzt
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 true DE1913732B2 (de) 1981-04-02
DE1913732C3 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
DE1913732C3 (de) 1982-04-15
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
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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