BE859767R - PROCESS FOR THE CATALYTIC PREPARATION OF PYRIDINES SUBSTITUTED IN POSITION 2 - Google Patents

PROCESS FOR THE CATALYTIC PREPARATION OF PYRIDINES SUBSTITUTED IN POSITION 2

Info

Publication number
BE859767R
BE859767R BE181780A BE181780A BE859767R BE 859767 R BE859767 R BE 859767R BE 181780 A BE181780 A BE 181780A BE 181780 A BE181780 A BE 181780A BE 859767 R BE859767 R BE 859767R
Authority
BE
Belgium
Prior art keywords
emi
catalytic preparation
pyridines substituted
cobaltocene
pyridines
Prior art date
Application number
BE181780A
Other languages
French (fr)
Original Assignee
Lonza Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lonza Ag filed Critical Lonza Ag
Application granted granted Critical
Publication of BE859767R publication Critical patent/BE859767R/en

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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
    • C07D213/24—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
    • C07D213/36—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)

Description

       

  "Procédé de préparation catalytique de pyridines substituées en position 2."   <EMI ID=1.1> 

  
tir des dérivés cyano correspondants et d'acétylène et il est caractérisé en ce que l'on effectue la réaction à température élevée en présence de cobaltocène comme catalyseur.

  
La présente addition concerne un procédé de préparation catalytique de 2-éthyl-pyridines &#65533; substituées à partir des dérivés

  
 <EMI ID=2.1> 

  
lène et ce procédé est caractérisé en ce que la réaction a lieu en présence de cobaltocëne. Ici aussi un avantage spécial de l'utilisation du cobaltocène comme catalyseur consiste dans le fait que l'on peut utiliser ce catalyseur à des températures élevées, supérieures à 80[deg.]C.

  
 <EMI ID=3.1> 

  
le cobaltocëne, de préférence les alcools aliphatiques ayant un nombre de carbone petit.

  
 <EMI ID=4.1> 

  
 <EMI ID=5.1> 

  
ridine, du méthanol.

  
 <EMI ID=6.1> 

  
 <EMI ID=7.1> 

  
 <EMI ID=8.1> 

  
 <EMI ID=9.1> 

  
choix approprié des quantités de ce catalyseur, de la pression

  
 <EMI ID=10.1> 

  
 <EMI ID=11.1> 

  
talyseur et par heure. Pour des transformations allant jusqu'à

  
 <EMI ID=12.1> 

  
tillation. On peut réutiliser un distillat de tête apparaissant  <EMI ID=13.1> 

  
Pour la mise en oeuvre de la réaction, il n'est normalement pas nécessaire d'avoir recours à un solvant, mais toutefois on peut, pour avoir une meilleure dissipation de la chaleur lors de

  
 <EMI ID=14.1> 

  
ple le bensène ou le dérivé de pyridine faisant l'objet de la préparation, comme agents de dilution. On peut introduire les composés cyanoëthylês soit à l'état de produits purs, soit également à l'état de produits bruts en mélange avec l'aminé ou l'alcool utilisé.

  
On peut également mettre en oeuvre le procédé en continu, par exemple dans un tube à écoulement.

  
 <EMI ID=15.1> 

  
 <EMI ID=16.1> 

  
se rapportant aux composés cyano utilisés ou les transfor-

  
 <EMI ID=17.1> 

Exemple 1

  
 <EMI ID=18.1> 

  
175 g de ,3 -diéthylaminopropionitrile (1,4 M) et on sature, dans un autoclave de un litre &#65533; 20[deg.]C, par de l'acétylène sous 12 atmosphères. On chauffe à 125[deg.]C, on observe une réaction exother-

  
 <EMI ID=19.1> 

  
agite pendant 6 heures sous une pression d'acétylène constante de 12 atmosphères et une température de 175[deg.]C. Après avoir laissé refroidir et après détente, on distille sous colonne. on obtient, après une tête de benzène et d'une petite quantité de produit de

  
 <EMI ID=20.1> 

  
de 99,3%, correspondant à un rendement de 84,7%.

Exemple 2

  
 <EMI ID=21.1>   <EMI ID=22.1> 

  
Exemple 

  
Sous atmosphère d'azote, on prépare une solution à partir de 166,5 g de benzène sec et 27,9 g de ^ -mëthoxypropionitrile

  
 <EMI ID=23.1> 

  
 <EMI ID=24.1> 

  
tes par de l'acétylène sous 12 atmosphères et on chauffe à 155[deg.]C

  
 <EMI ID=25.1> 

  
de 77,7%.

Exemple 5

  
 <EMI ID=26.1> 

  
 <EMI ID=27.1> 

  
ras à 155[deg.]C. Apres refroidissement et détente, on soudât le pro-

  
 <EMI ID=28.1> 

  
de lira%.

Exemple 6 

  
 <EMI ID=29.1> 

  
 <EMI ID=30.1> 

  
Ceci étant et quel que soit le mode de réalisation adopté,  <EMI ID=31.1> 

  
 <EMI ID=32.1> 

  
résultent suffisamment de ce qui précède pour qu'il soit inutile d'insister à ce sujet et qui présente, par rapport à ce qui existe déjà, de nombreux avantages, notamment : <EMI ID=33.1>  en général supérieurs à 90%, et une sélectivité des 2-êthyl-

  
 <EMI ID=34.1> 

  
 <EMI ID=35.1> 

  
de ce qui précède, l'invention ne se limite nullement à ceux de ses modes d'application et de réalisation qui ont été plus spécialement envisagés ; elle en embrasse, au contraire, toutes les variantes. 

  
 <EMI ID=36.1> 

  
 <EMI ID=37.1> 

  
d'aminés et d'alcools et d'acétylène, caractérisé par le fait que la réaction est effectuée en présence de cobaltocëne.



  "Process for the catalytic preparation of pyridines substituted in position 2." <EMI ID = 1.1>

  
shooting of the corresponding cyano derivatives and acetylene and it is characterized in that the reaction is carried out at high temperature in the presence of cobaltocene as catalyst.

  
The present addition relates to a process for the catalytic preparation of 2-ethyl-pyridines &#65533; substituted from derivatives

  
 <EMI ID = 2.1>

  
lene and this process is characterized in that the reaction takes place in the presence of cobaltocene. Here also a special advantage of using cobaltocene as a catalyst consists in the fact that this catalyst can be used at high temperatures, above 80 [deg.] C.

  
 <EMI ID = 3.1>

  
cobaltocene, preferably aliphatic alcohols having a low carbon number.

  
 <EMI ID = 4.1>

  
 <EMI ID = 5.1>

  
ridine, methanol.

  
 <EMI ID = 6.1>

  
 <EMI ID = 7.1>

  
 <EMI ID = 8.1>

  
 <EMI ID = 9.1>

  
appropriate choice of the quantities of this catalyst, the pressure

  
 <EMI ID = 10.1>

  
 <EMI ID = 11.1>

  
analyzer and per hour. For transformations up to

  
 <EMI ID = 12.1>

  
tillation. You can reuse an overhead that appears <EMI ID = 13.1>

  
For carrying out the reaction, it is normally not necessary to have recourse to a solvent, but it is however possible, in order to have a better dissipation of the heat during

  
 <EMI ID = 14.1>

  
ple the bensene or the pyridine derivative forming the subject of the preparation, as diluting agents. The cyanoethyl compounds can be introduced either in the form of pure products, or also in the form of crude products, mixed with the amine or the alcohol used.

  
The process can also be carried out continuously, for example in a flow tube.

  
 <EMI ID = 15.1>

  
 <EMI ID = 16.1>

  
relating to cyano compounds used or transforming them

  
 <EMI ID = 17.1>

Example 1

  
 <EMI ID = 18.1>

  
175 g of, 3 -diethylaminopropionitrile (1.4 M) and saturated, in a one-liter autoclave &#65533; 20 [deg.] C, with acetylene at 12 atmospheres. Heated to 125 [deg.] C, an exothermic reaction is observed.

  
 <EMI ID = 19.1>

  
stirred for 6 hours under a constant acetylene pressure of 12 atmospheres and a temperature of 175 [deg.] C. After allowing to cool and after expansion, distillation is carried out in a column. we obtain, after a head of benzene and a small quantity of product of

  
 <EMI ID = 20.1>

  
of 99.3%, corresponding to a yield of 84.7%.

Example 2

  
 <EMI ID = 21.1> <EMI ID = 22.1>

  
Example

  
Under a nitrogen atmosphere, a solution is prepared from 166.5 g of dry benzene and 27.9 g of β-methoxypropionitrile

  
 <EMI ID = 23.1>

  
 <EMI ID = 24.1>

  
tes with acetylene under 12 atmospheres and heated to 155 [deg.] C

  
 <EMI ID = 25.1>

  
by 77.7%.

Example 5

  
 <EMI ID = 26.1>

  
 <EMI ID = 27.1>

  
ras at 155 [deg.] C. After cooling and relaxation, the pro

  
 <EMI ID = 28.1>

  
to read%.

Example 6

  
 <EMI ID = 29.1>

  
 <EMI ID = 30.1>

  
This being the case and whatever the embodiment adopted, <EMI ID = 31.1>

  
 <EMI ID = 32.1>

  
result sufficiently from the above for it to be unnecessary to dwell on this subject and which presents, compared to what already exists, many advantages, in particular: <EMI ID = 33.1> in general greater than 90%, and a selectivity of 2-ethyl-

  
 <EMI ID = 34.1>

  
 <EMI ID = 35.1>

  
of the foregoing, the invention is in no way limited to those of its modes of application and embodiments which have been more especially considered; on the contrary, it embraces all the variants.

  
 <EMI ID = 36.1>

  
 <EMI ID = 37.1>

  
of amines and alcohols and acetylene, characterized in that the reaction is carried out in the presence of cobaltocene.

Claims (1)

2. Procédé selon la revendication 1 , caractérisé en 02 <EMI ID=38.1> 2. Method according to claim 1, characterized in 02 <EMI ID = 38.1> <EMI ID=39.1> <EMI ID = 39.1> <EMI ID=40.1> <EMI ID = 40.1> cobaltocëne. cobaltocene. <EMI ID=41.1> <EMI ID = 41.1> <EMI ID=42.1> <EMI ID = 42.1> <EMI ID=43.1> <EMI ID = 43.1> 5. Procédé selon la revendication 1 ou 2, caractérisé en 5. Method according to claim 1 or 2, characterized in <EMI ID=44.1> <EMI ID = 44.1> cools sous forme de produits brut.3 en mélange avec 1'aminé ou l'alcool utilisé. cools as crude products mixed with the amine or alcohol used. 6. Procédé selon l'une quelconque des revendications 1 6. Method according to any one of claims 1 <EMI ID=45.1> <EMI ID = 45.1> quantités de 0,1 à 1 mole % par rapport au nitrile d'acide carboxylique. amounts of 0.1 to 1 mole% based on the carboxylic acid nitrile. 7. Procédé selon l'une quelconque des revendications 1 7. Method according to any one of claims 1 <EMI ID=46.1> <EMI ID = 46.1> <EMI ID=47.1> <EMI ID = 47.1>
BE181780A 1976-10-15 1977-10-14 PROCESS FOR THE CATALYTIC PREPARATION OF PYRIDINES SUBSTITUTED IN POSITION 2 BE859767R (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1307976A CH622008A5 (en) 1976-10-15 1976-10-15 Process for the catalytic preparation of beta-substituted 2-ethylpyridines

Publications (1)

Publication Number Publication Date
BE859767R true BE859767R (en) 1978-04-14

Family

ID=4389104

Family Applications (1)

Application Number Title Priority Date Filing Date
BE181780A BE859767R (en) 1976-10-15 1977-10-14 PROCESS FOR THE CATALYTIC PREPARATION OF PYRIDINES SUBSTITUTED IN POSITION 2

Country Status (2)

Country Link
BE (1) BE859767R (en)
CH (1) CH622008A5 (en)

Also Published As

Publication number Publication date
CH622008A5 (en) 1981-03-13

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Legal Events

Date Code Title Description
RE Patent lapsed

Owner name: LONZA S.A.

Effective date: 19880930