Preparation of pyrrole and pyridine

Details Preparation of pyrrole and pyridine Preparation of pyrrole and pyridine

2002-09-05

2003-03-25

Morris, Patricia L. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C548S564000

Reexamination Certificate

active

06538139

ABSTRACT:

The present invention relates to the preparation of pyrroles from pyrrolidines and of pyridines from piperidines by dehydrogenation over noble metal catalysts.
It is known that pyrrolidine and piperidine can be dehydrogenated over palladium- and/or platinum-containing supported catalysts to give pyrrole and pyridine, respectively.
U.S. Pat. No. 3 522 269 describes the dehydrogenation of pyrrolidine to pyrrole over Pd catalysts at relatively high temperatures, preferably 400-450° C.
GB-A 1 393 086 describes the dehydrogenation of piperidine to pyridine by means of catalysts comprising palladium on SiO
2
as a support.
EP-A 67 360 and 155 649 describe Pd catalysts for dehydrogenating pyrrolidines, which are effective at lower temperatures of from 160 to 400° C.
In the dehydrogenation of pyrrolidine to pyrrole, a certain amount of byproducts, such as butylamine, N-butylpyrrole and butyronitrile, is formed. Among these, butyronitrile, which is generally formed in amounts of from 0.3 to 3% by weight, is particularly troublesome. Owing to the very similar boiling points of pyrrole and butyronitrile, butyronitrile can be separated from pyrrole by distillation only with considerable effort. Columns having a large number of theoretical plates are required for this purpose, and a high reflux ratio has to be employed. The distillative separation is associated with a large loss of desired product. However, the use of the pyrroles in the preparation of pharmaceutical active compounds or in electronic components requires very high purity of the pyrroles.
It i s a n object of the present invention to provide an improved process for the preparation of pyrroles and pyridines in which byproducts are formed to a smaller extent.
We have found that this object is achieved by a process for the preparation of pyrroles of the formula (I)
where
R
1
and R
2
, independently of one another, are hydrogen or an aliphatic radical of 1 to 6 carbon atoms,
by dehydrogenating pyrrolidines of the formula (II)
where R
1
and R
2
have the abovementioned meanings,
in the presence of a supported noble metal catalyst, wherein the dehydrogenation is carried out in the presence of from 1 to 50% by weight, based on pyrrolidine and water, of water.
It has been found that the formation of (substituted) butyronitrile is greatly suppressed by the presence of water during the dehydrogenation of (substituted) pyrrolidine. The amount of butyronitrile in the crude discharge of the dehydrogenation of pyrrolidine is in general <0.2, preferably <0. 1, % by weight. As a result, the subsequent purification of pyrrole by distillation is considerably simplified. Large losses of desired product do not occur, making the preparation of pyrrole as a whole more economical.
Suitable pyrrolidines (I) are unsubstituted pyrrolidine and pyrrolidine which is substituted in the 3- and/or 4-position by an aliphatic radical of 1 to 6 carbon atoms. The aliphatic radicals may be substituted by groups which are inert under the reaction conditions. Preferred aliphatic radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and isomeric pentyl and hexyl radicals. A preferred starting compound of the novel dehydrogenation is unsubstituted pyrrolidine.
In the same way, the preparation of pyridines of the formula (III)
can be carried out by dehydrogenating piperidines of the formula (IV)
Therein, R
3
, R
4
and R
5
, independently of one another, may have the same meanings as R
1
and R
2
. Unsubstituted piperidine is preferred. As a result of the presence of water during the dehydrogenation, the formation of (substituted) valeronitrile as a byproduct is accordingly suppressed.
The dehydrogenation is carried out in the presence of from 1 to 50, preferably from 5 to 50, particularly preferably from 5 to 25, % by weight of water. The percentage data are based on the sum of pyrrolidine or piperidine and water, which gives 100% by weight. The water may have been admixed with the pyrrolidine or piperidine feedstock stream or may be fed into the reactor during the dehydrogenation in the corresponding ratio.
The novel catalytic dehydrogenation can be carried out in the liquid phase or in the gas phase.
The novel catalytic dehydrogenation can be carried out in the liquid phase. For this purpose, pyrrolidine or piperidine and the noble metal-containing supported catalyst, if required in a solvent, are kept at the reaction temperature, for example for from 1 to 10 hours. The catalyst is separated from the resulting product mixture by filtration, and pyrrole or pyridine is obtained by fractional distillation. Preferred solvents are toluene, xylenes, diethylbenzene, ethanol, n-butanol, methyl glycol, ethylene glycol and 1,2-dimethoxyethane. The dehydrogenation in the liquid phase is usually carried out in the presence of small amounts of hydrogen in order to activate the catalyst.
The novel dehydrogenation is preferably carried out continuously in the gas phase, it being possible to arrange the catalyst in a fixed bed or as a fluidized bed.
If the novel dehydrogenation is carried out in the gas phase, the pyrrolidine/steam mixture or piperidine/steam mixture is preferably present in a carrier gas stream comprising nitrogen and/or hydrogen. The volume ratio carrier gas: pyrrolidine or piperidine is as a rule from 1:1 to 100:1, preferably from 2:1 to 50:1, particularly preferably from 3:1 to 40:1. The volume ratio of nitrogen to hydrogen may be from 0.01:1 to 100:1, preferably from 0.1:1 to 10:1, particularly preferably from 0.5:1 to 5:1.
The novel dehydrogenation can be carried out in the presence of all noble metal-containing supported catalysts which are customary for this dehydrogenation reaction. In general, temperatures of from 150 to 400° C. and pressures of from 0.01 to 50 bar are employed.
The novel dehydrogenation can be carried out, for example, in the presence of the palladium supported catalysts which are described in EP-A 0 067 360 and contain basic compounds and/or elements of group 11, group 12 and group 7, cobalt and/or nickel. Supports are, for example, alumina, silica, aluminum silicate, magnesium silicate or spinels of aluminum, of chromium or of iron. Preferred activating additional elements of groups 7, 11 and 12 are manganese, zinc and silver. Preferred basic compounds are the oxides, hydroxides or carbonates of the alkali metals, preferably of lithium, of the alkaline earth metals, preferably of magnesium and of calcium, and of the lanthanides, preferably of cerium, of praesodynium and of neodynium.
However, noble metal-containing catalysts which contain from 30 to 100% by weight of
a) palladium on an oxide of a rare earth metal or an oxide of an element of group 4 or
b) a platinum/palladium mixture on alumina, an oxide of a rare earth metal or an oxide of an element of group 4
and from 0 to 70% by weight of alkali metal oxide or alkaline earth metal oxide are preferred. In the presence of these catalysts, the novel dehydrogenation is generally carried out at from 150 to 300° C., preferably from 170 to 270° C., particularly preferably from 180 to 250° C., and from 0.01 to 50, preferably from 0.1 to 5, particularly preferably from 1 to 1.5, bar.
In the context of this description, suitable rare earth metals are the elements of the lanthanide and the actinide group of the Periodic Table of the Elements, such as lanthanum, cerium, neodynium, samarium, gadolinium, ytterbium, actinium, thorium, uranium and neptunium, cerium, praesodynium, neodynium, samarium, europium, terbium, ytterbium, thorium and protactinium being preferred, and cerium, praesodynium, neodynium and thorium being particularly preferred.
Suitable metals of group 4 are titanium, zirconium and hafnium, titanium and zirconium being preferred, and zirconium being particularly preferred. Suitable alkali metals or alkaline earth metals are lithium, sodium, potassium, cesium, beryllium, magnesium, calcium, strontium and barium, sodium, potassium, magnesium, calcium and barium being preferred.
The active components of the catalyst (noble metals) ar

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