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Heterogeneous conversion of acyclic compounds to pyridine bases - a review
1
Applied CatuZysis, 23 (1986) l-14 Elsevier Science Publishers B.V., Amsterdam -Printed
HETEROGENEOUS
Stanislaw
CONVERSION
OF ACYCLIC
in The Netherlands
COMPOUNDS
TO PYRIDINE
BASES
- A REVIEW
E. GOLUNSKI*
St. John's
College,
Southsea
PO5 3QW, U.K.
and David JACKSON Frewen
Library,
Portsmouth
* To whom correspondence
(Received
12 August
Polytechnic,
should
Portsmouth
PO1 ZST, U.K.
be addressed.
1985, accepted
2 December
1985)
ABSTRACT A large and growing demand for the derivatives of pyridine exists because of their many chemical, pharmaceutical and agricultural uses. The commercial products gasare derived from pyridine bases, which can be prepared by the heterogeneous phase cyclisation of simple organic molecules in the presence of ammonia. Alumino-silicates are catalytically active in the conversion of carbonyl compounds to pyridine bases. It is probable that the reactants are adsorbed at acidic sites and that the formation of imines precedes cyclisation. The catalysts, with the exception of certain zeolites, lose activity with prolonged use, probably as a result of consecutive reactions that lead to the blocking of narrow pore openings. Alkenes can be converted to pyridine bases in two stages: partial oxidation over a mixed-metal oxide, followed by cyclisation in the presence of ammonia over direct ammoxidation can be achieved using cataalumino-silicates. Alternatively, lysts based on Te-Al-Si-0. These catalysts retain their activity during prolonged use, but are limited by their lack of selectivity. Potential new routes include the conversions of alkynes, epoxides and alcohols. Metal phosphates are active in the formation of pyridine bases from both alkynes and epoxides. The former process may involve the formation of adsorbed tautomeric intermediates. A most recent innovation is the condensation of aliphatic alcohols with ammonia, over a zeolitic catalyst.
INTRODUCTION Apart
from the long established
collectively
as pyridine
scavengers
[2], there
formation
of medicines
infectants
small amounts inadequate
ethyne
[cl. By contrast,
Economic
0166-9834/86/$03.50
[l-41,
Community
bases now produced
(acetylene)
the growth
catalysts
(known
[2] and acid
for them as intermediates herbicides
over the last forty years,
[1,5]. At the same time,
have superseded
supplements
and alkylpyridines
in the
[1,2], dis-
[I].
of the European
of pyridine
[1,2],
large demand
[l-4], dietary
of the decline,
states
as solvents
is now a very
[Z] and pesticides
As a result the member
bases)
uses of pyridine
in the use of coal in
and in North America,
by pyrolysis
the exploitation as the primary
of the petrochemical
of coal are vastly
of oil has meant
source
that alkenes
of many organic
industry
0 1966 Elsevier Science Publishers B.V.
the
has been
compounds
less rapid
in
the countries substantial continued
reserves
to the Council
will need to make
as their supplies
Although
molecules
alkanes
[ll], alkenes (notably
achieved
industrial
catalytic
[12] and alkynes
methods
This review
application.
that are already
ensure
[6,9,10]
synthesis
that
gas and
a limited
being employed,
the rBle of the catalyst are discussed.
pyridine
bases from
[2,11,13],
with ammonia
concentrates
changes
class of reaction,
USING CARBONYL
dicarbonyls
[5,13,14]),only
surface
SYNTHESIS
[7,8], but
should
predicted
for preparing
of aldehydes
in light of the expected
mechanisms
Siberia,
use of alkanes,
[2,11-131,
the condensations
cyclisations
show potential
greater
possible
(such as carbonyls
processes
in western
Assistance
of crude oil diminish.
there are numerous
acyclic
Economic
[71. It is, however,
for some years
nations
for Mutual
of oil, particularly
expansion
the western ethyne,
belonging
dicyano-
number
of these
[3,4,12])
have
on those gas-phase, and those
in available
is considered
that appear
feedstocks.
to
For each
and, wherever
possible,
COMPOUNDS
Conditions
In the process hyde),
ethanal
catalyst, pyridine
that is usually
(acetaldehyde)
at temperatures (B-picoline)
feed is important.
attributed
and ammonia
between
to Chichibabin
are condensed
300 and 55O'C,
as the major
In its absence
products.
The inclusion
the total yield
10.8) can result
of over 70% [16]. This appears
in a yield
NH3 and vaporised
that have indicated aqueous
been considered
[17,18].
in the reaction
mixture
of oxidative
HCHO),
a maximum
possible
but in these studies
dealkylation
the formation
bases
can be less
the effect
[19,20]
= 1:2:2.7:
to contradict yield
results
of 66% (from CH3CH0, of steam
that the presence
of pyridine,
of the methylpyridine
in the gas-
(HCHO:CH3CHO:NH3:H20
It has also been shown favours
and 3-methyl-
of steam
of pyridine
proportion
studies
of steam
(formalde-
over an alumino-silicate
to give pyridine
than 50% [14]; a high molar
of kinetic
[15], methanal
[20],but
possibly it also
has not of oxygen
as a result
reduces
the
life of the catalyst. The alumino-silicate
catalyst
is best employed
Its performance
can be improved
oxides
and also by retaining
126,271,
1231. Alternative alumino-silicate zeolite useful
catalysts zeolites
C31a1, which as it allows
pyridines
include [30].
In particular,
high conversion
(lutidines)
by a cheaper
ZSM-5
advantage
to be excluded
[28,29]
[31,32]
from the gas-feed
(e.g. methanol
[ZO]).
during
reaction
and crystalline siliceous
may prove
that include
of all these
1211.
or metal
(a highly
[33,34]),
(up to 93%) to bases
reactor
[20,22-251
deposited
phosphates
with silicalite
[31b]. A further
reagent
in a fluidised-bed
of halides
some of the carbon
mixed-metal
is isostructural
is that they allow methanal replaced
by the addition
very
dimethyl-
improved [20,26-311
catalysts or to be
3
a) Formation
of imines
(i) Homogeneous
R = CH3 or H
reaction
R
R
I C
hew:N~3 F HO"'
(ii) Heterogeneous
-H 0 2 NH
H
R-CH=NH
2
reaction H
/,O R-C, H-
-.e----:NH3(ads) &H(ads)
H+(surf)
•-
3
bH
H
H 'C=NH(ads)4 R' b) Formation
of pyridine
(i) Homogeneously
'P+-+H2
3
R-;-NH;
(ads)
bases
catalysed
cyclisation
of allylamines
-2NH
(ii) Heterogeneously
Sb
-HP
catalysed
cyclisation
of imines
H=NH HC 3
H C=NH 2
-2NH 3
A
HC 3 'CH II NH
FIGURE
1 Condensations
N
of carbonyl
compounds
with ammonia.
N
4 Surface
reactions
Accounts depicted
of the conversion
the overall
35,361:
e.g. the conversion
represented
of carbonyl
changes
compounds
to pyridine
in the form of simple
reaction
of an ethanal-methanal
mixture
bases have often
schemes
[3a,4,11,12,14,
to pyridine
may be
as
H3C
\ 0
CHs
CHO
CHO
t 3H_,o + Hz
(1)
I
l
N
NH3
and the conversion
of ethanal
to 4-methylpyridine
as
CH3
CH3
H3C
I
I
CHO
CHO
Although first
mechanistic
stages
Antonova
schemes
The nucleophilic
have proposed,
therefore,
near or at acidic Nucleophilic
sites,
addition
by loss of water
groups;
of stable
forming
of intermediates
at higher
readily
surface
adsorb
imines
ammonia
catalysed
[43] has shown that two molecules and loss of a hydrogen
and heterogeneous (Figure
l,b,ii).
for the latter
15,411 conversions
et al. [40]
are adsorbed
ions (Figure
l,a,ii)
and is followed
[37,40-421.
have yet to be examined
in the homogeneously
have been proposed
[38] and are known
[39]. Vetrova
and carbonium
in the liquid-phase
processes
bases.
homogeneously
of the catalyst,
before
ring closure
(350-4OO"C),
of pyridine
step the reactants
at the surface
of cyclisation
ammonia
carbocations
the first
adsorbed
can occur
(80-lOO"C),
to form compounds
temperatures
to the formation
to an aldehyde
that during
thus occurs
stages
the
to the publication
of alumino-silicates
leading
of ammonia
to leave adsorbed
The subsequent analysis
and amino
but alumino-silicates
the formation
they have allowed
leading
that even at low temperatures
in the presence
immediately,
addition
l,a,i),
to promote
to be elucidated,
[37] have found
both hydroxyl occurs
have been far from extensive, reaction
(2)
[5,373.
and coworkers
reaction
(Figure
studies
react with ammonia
containing further
t 3H20 t Hz
of the surface
of more detailed
aldehydes
CH3
molecule stages
of carbonyl
in detail,
reaction
but
of allylamines
of annnonia are eliminated occur
(Figure
l,b,i).
of both the homogeneous
compounds
to pyridine
Similar [44]
bases
Alternative
reaction
include
the formation
2CH3CHO
+
schemes
for the conversion
of but-Z-enal
CH3CH=CHCHO
of ethanal-methanal
as an intermediate
mixtures
[11,45,46]:
(3)
+ Hz0
then. either
H/" II CH / H3C
CH3
\
CHO NH3
+ HZ
t 2H2.0
(4)
+ H2
t 2H20
(5)
,
+cl H3C
PI
or CH3 yCH CH I CHO
.
CH3
YH3 CHO
\ I
d-l N
NH3
Apart
from the evidence
ammonia,
When but-2-enal of pyridine cracking
ethanal
additional
and ammonia
a complex
is sometimes bases
included
is likely
[47], which
over aluminate
of the catalyst.
Furthermore, which
incorporated
instead
reaction
schemes
are usually
catalysts
[48,49],
attack
products,
catalyst
(3-5).
at 350°C, yields cyclisation,
its conversion
from ammonia
unless metal
thermal
Although
steam and the formation
(3-5) show the formation
minor
in the alumino-silicate
schemes
and carbon monoxide.
with
nucleophilic
ions with adsorbed
of the expected
in the gas-feed
then undergoes
carbonium
for discounting
of hydrocarbons
to involve
methylpyridines,
Nature
are passed
mixture
of surface
reasons
bases are low [47] because,
yields
but-2-enal pyridine
for the reaction
there are several
to of
at the surface
of 2- and 4phosphates
are
[29].
of catalyst
Previously,
it had been observed,
(Mo03-A1203)
was a more
(CaO-A1203),
but it has subsequently
and acid strength
is not simple
in order of decreasing 8.4% A1203
effective
by Butler
condensation been found
[37], as shown
[47], that an acidic catalyst
that the relationship by the following
activity:
+ 91.6% Si02 > 20% H3P04 + 80% A1203-Si02
40% H3P04 + 60% SiO2 > ZnO-A1203
> y-AlEO
aluminate
than a basic aluminate
>
between
catalysts
rate
arranged
6 Antonova
and coworkers
reaction
is retarded
seems,
therefore,
the nature proposed
(Figure
unreactive
then a large number doped with alumina
If the concentration
of inert ammonium
Furthermore,
sites
to depend
Some information been derived against
conical
of Brdnsted
sites
is too great,
formed
be obviated prising
greatly
appears
Lewis
by interaction
or fluorides,
studies
the formation either
[38,52!
of the catalyst
channel
hysteresis
between
systems
which
possesses
aromatic
to
of carbonyl
of the openings
or even
are
than the opening.
of the catalysts
compounds
by deposits
of
[53b]. This problem a pore structure
dimensions
is a shape-selective
channels
for mercury
of the pores can be
the pores
of different
of large polycyclic
in the narrow
has
that the pores
the condensation
within
catalysts
the curves
suggests
the formulation
during
ZSM-5,
of carbon
with
[53]. Plots of pore volume
the dimensions
reactions
by using the zeolite
involving
of preparation
equilibrium
of alumino-silicate
to be due to the blocking
be formed
gels
pro-
sites
the base of each pore being wider
by consecutive
that the formation
of silica
by conditions
on the following
[53a]. This
that, by changing
oxides
two intersecting
believed
to exhibit
[53a]. The loss of activity,
ammonia,
carbon,
surface
and adsorption
[53a], with
other metal
increased
the active
have been found
It has also been shown
Studies
in of
use.
and those for its evacuation
in shape
include
be formed
or during
from porosimetry
radius
penetration
with
the formation
the availability of Lewis sites would be expected 3+ . ions and on the morphology of the surface, of Al
sites would
about
be involved
allow
>
before
sites would
temperature/-H20
therefore,
Brdnsted
as
From the mechanism
[51] have shown that the relative
(
either
vapour,
It
sites would
the ratio depends
on the concentration
mobile
the
ions are formed.
ions may be formed.
1501 and of zeolites
In alumino-silicates,
water
that Brbnsted Lewis
is too great,
is not as important
of acid sites at its surface.
increasing Brdnsted
ammonium
of the solid
of the two types of site are affected
and calcination.
whereas
adsorbed
acidity
ions, whereas
ammonia.
that if the acidity
it is apparent
l,a,ii),
of carbonium
adsorbed
portions
because
that the overall
and distribution
the creation labile
[37] have deduced
molecules
in the wider
com-
[31,54].
process
may
It is
[32,55],
[56], which intersections
cannot within
the zeolite.
SYNTHESES
USING ALCOHOLS
The condensation over metals
and metal
36%, over Pd-A1203 higher yields mechanism
or prop-2-en-l-01 gives fairly
[57]).
poor yields
with ammonia,
of pyridine
bases
been shown recently
over zeolitic
catalysts
(e.g. that
[58]. The
has yet to be investigated.
have also been used to catalyse [59], but the
(piperazine):
(ally1 alcohol)
It has, however,
(ca. 45X), can be achieved
with ammonia
pyrazine
oxides,
at 310°C
for this reaction
Zeolites oxide)
OR EPOXIDES
of ethanol
major
the reaction
product
of epoxyethane
(ethylene
has been found to be hexahydro-
7
t 2H20
a catalyst
If, however,
[60], epoxyethane reaction
comprising
can be converted
that appears
to proceed
SYNTHESES
selectively
oxidation,
Traditionally,
For example,
propene oxide
can be partially
(e.g. Bi-MO-0
can allow almost
class of catalyst
with high selectivity,
the precise
mechanism
invariably
[61]):
depends
CHz=CH-CHB --=%
,,/“’
HC//cHi I gCH
[64,65],
(acrolein)
Sn-Sb-0
of 90% are not unusual
of the catalyst
of an allylic
ions from the catalyst
CHz ;T;-;-;CHT;T;TCH2(ads) Lol.
stage requires
to propenal
[66,67]
Fe Co Zr 0 [68]). The 10 2 8 0.1Ca0.1Ti0.2 x complete conversion of the alkene to
on the nature
leads to the formation
The second
U-Sb-0
in two separate
(e.g. BiMo
so that yields
which may then react with oxide
NH30
in a
(ethylenimine
from alkenes
oxidised
[62,63],
latter
HC \\ 0
of aziridine
is used
(7)
bases have been prepared
catalyst
I
to Z- and 4-methylpyridine
-2NH, -Hz
or over a multicomponent
propene
chloride
condensation
pyridine
over a binary-metal
propenal
and cobalt
USING ALKENES
Two steps:
stages.
phosphate
via the formation
a 3HzC L2-CHz
-3n,o + 3NH3-
0
3H&&Hz
calcium
(6)
the condensation
. XT ,
N
[52], adsorption
intermediate
of
[6,52],
[62,69,70]:
CH*=CHCHO
of propenal
[52]. Although
(8)
with
ammonia:
CH3 t 2H20
(9)
8 Acidic
catalysts
yields
of methylpyridines
are again catalytically are often
improved
by using alumino-silicate
ensuring
that the reactants
preventing reach
homogeneous
the reactor.
either
(supported
between yields
According
should
More pyridine
oxygen
participation
of adsorbed/lattice
reaction
steam
with
of methylbenzene occurs
because
hydroxyl
species,
and hydrogen. Butene
which
Subsequent silicate
generates
to pyridine
by the support
addition
yields
studies
of adsorbed
of allylimine
the case
propenal [77].
is present takes
[77],
place.
Even
by the
as the result
of
that dealkylation
on alumina,
material
to form surface
to produce
carbon
monoxide
to the dealkylation
of methylpyridines.
bases
Allylic
in two steps.
oxidation
butadiene:
(ads) =S
and 3_methylpyridine,
no mechanistic
between
[81] have suggested
groups
[76].
[77], possibly
probably,
of the diene with methanal
pyridine
44% [84]. Although
to the formation
may apply
[6,82,83]
such as
(Pt, Rh or Pd) supported
CH2 T-TTTF CH-CHT-XTCH~
condensation
that nucleophilic
and coworkers
mechanism
oxide
CH2=CH-CH2CH3 -H
or, more
oxygen
are adsorbed
can also be converted
over a mixed-metal
is formed
they
by using
compound,
when oxygen
of the product
SO
or platinum
of the reaction
then react with the methyl
A similar
before
in the gas-feed
is formed [78,79]
over metals
water molecules
carbonyl
[74al,
[74b,c,d]
but this is not always
some pyridine
[80]. Duprez
(toluene),
and ammonia
II elements)
another
product
derivative
dealkylation
of gaseous
+ Group
but
can be
C731, and by
of over 70% can be achieved
(propionaldehyde),
be 3-methylpyridine,
that oxidative
[71,72],
of the catalyst
the propenal
(Al-F-O
(9), the major
than the methyl
in the absence
of low bulk density
and by including
or propanal
to equation
and ammonia
suggesting
catalyst
in this reaction
in the presence
reactions
on Al-Si-0)[75], (acetone)
pellets
meet only
Alternatively,
a multicomponent
propanone
active
less than 30% [71]. The selectivity
CH2=CH-CH=CHp
and ammonia
ammonia
intermediates,
over an alumino-
in a combined
have been reported, to surface which
(10)
yield
of up to
it seems likely
carbonium
then undergo
ions leads
ring closure.
One step: ammoxidation Early merely
patents
describe
two different achieve
[85,86], improved
catalysts.
the conversion
More recently,
oxide
maximum
of pyridine
yield
carbon
[87,88].
that yields
dioxide,
direct
to pyridine
and condensation
bases, using
it has been shown that it is possible
the original
bases over Te-Al-Si-0
propanone
of alkenes
oxidation
step, over a catalyst
Although
of less than
ethanal,
conversion
for consecutive
in a single
and tellurium
have found
claiming methods
patent
and ethanoic
[87] shows
that the
is 17.5%, Forni and coworkers
10% are achieved
usually
acid).
to
based on alumino-silicate
(by-products
[SS]
include
9 The composition effect
and method
on the conversion
pyridine
bases
cipitation
at 400°C
[82a,b].
oxidising the latter
sites;
leads to its partial
to an acidic [88a,b].
A similar
Al-Si-0.
mechanism
for adsorption
of gaseous
of the alkene
retain
design
conditions
during
occur
over Sn-Sb-Te
oxides
in the allylic
oxidation
reactor
catalysts
catalysts
is clearly
have been shown,
use and to withstand
are important
factors
however,
sudden
when
limited
changes
considering
by
to in
the
[89].
FROM ALKYNES
Cadmium of alkynes
[90,91]
and alumina
[92] are catalytically
with ammonia,
salts
but cadmium
sulphate
ethanonitrile
over cadmium
(acetonitrile).
phosphate,
of ethyne 39O"C,
415 - 45O"C,
2MP > 4MP > E;
450 - 46O"C,
2MP > E > 4MP;
above 46O"C,
E > 2MP > 4MP.
et al. [90b] have proposed
to form enamine
and imine molecules
react with another
molecule
or imine. Evidence
for the formation
products,
could
be formed
which
is liberated
The relative be determined of the initial
which
during
proportions
C90b1,
that adsorbed
to produce of these
reaction
with changes
in com-
for the
> 4_methylpyridine(4MP);
ethyne
and ammonia
an unsaturated
intermediates to include
between
tautomers
secondary
amine
comes from the analysis
diethylamine
adsorbed
combine may then
dienamine
[gob].
This
and hydrogen,
stage of cyclisation.
of the pyridine
by the equilibrium,
can be achieved
e.g. yields
2). Each of these
have been found
the final
bases
in the reaction C92] yield
orders:
(Figure
of ethyne
by an addition
reaction
considerably
> Z-methylpyridine(2MP)
2MP > E > 4MP;
of the minor
varies
are in the following
390 - 415"C,
Akhmerov
to pyridine
[90b] and in temperature
ethanonitrile(E)
active
C90al and y-alumina
Conversion
but selectivity
of the gas-feed
conversion below
of the aldehyde
and cyclisation
ions may act as centres
then participates
These
prolonged
[SSd], which
of a commercial
position
both
phase and
to the inner
by migration
ammonia
but Sb3+
tellurium-based
[88,a,b,e].
their activity
SYNTHESES
mostly
of the present
low selectivity
operating
which
possesses
of propene
to ammoxidation
is not clear,
containing
at 110°C and calcination
[70].
The usefulness their
with adsorbed
to
by the pre-
oxide,
(IV)
an inner Te-0
diffusion
Thus,
seems to apply
oxygen,
within
and is followed
reaction
1891. The role of the antimony
has been prepared
tellurium by drying
located
oxidation,
site, at which
have a considerable
of the reaction
[88b] that this catalyst
the former
in the surrounding
ground
followed
oxide,
It has been proposed
and acidic
catalyst
on finely
of antimony
of the catalyst
and on the selectivity
[88a]. The most effective
of alumino-silicate
a small proportion
phase
of preparation
of propene
equation
at the surface
bases
in the final products
(II), which
of the catalyst
is established [90b,93].
seem to
as a result
10 Cd'+(surf)
t C H 2 2
I
(surf)
H
+
C=CHNH (ads) ~ 2 2
H CCH=NH 3
(ads)
I
I
CH 2 2
CH 2 2
(ads)
(ads) I
ICII
L
N
N’
J
H -H
-H 2
2 CH 2 2
CH 2 2
(ads)
(ads) I
I
CH 3 . /
0
n
N
CH CN
., N
CH
3
FIGURE
2
Reactions
enamine
(ads)
Greater
stability
of ethyne with
1
3
ammonia
imine
over cadmium
(ads)
(11)
of the imine leads to the formation
than 4-methylpyridine.
Over cadmium
phosphate
at temperatures
tautomers
is favoured
below
sulphate,
of more
v-alumina
390°C or above
so that the major
phosphate.
product
46O"C,
Z-methylpyridine
and even over cadmium dehydrogenation
becomes
ethanonitrile.
of the
11 CONCLUSIONS Most patents of carbony
describing
compounds.
of both the catalyst relatjvefy
syntheses
They
of pyridine
show the many
and the gas-feed
fettdfundamental
have been reported.
Studies
A promising
mixture.
development
such examples
are zeo‘iites, which are widely
range of reactants
the oxidation aldehydes With
of nitrogen
the availability
[87-891.
are needed
publications
of pyridine.
Ethyne
Europe
Finally, gas suggests
the
is worthy
dependent
of greater
and ammonia
in the production
can be converted absence
should
organic ensure
for a
bases
for thefr
from
catalyst,
but detailed to ensure
cyclisations
manufacture
re-emerge
phase studies
in the western
an important
nations, of alkynes,
catalysts,
of selected feedstock
These
de-
in the
in that r$ie in those
on oil [9]. Therefore
the gas-phase
cycli-
investigation. in the use of alkanes
of pyridine
with ethanaf
over the versatile
reactant.
some
high selectivity.
[IOO] as homogeneous
however,
direct
catalysts
molecules
bases.
and synthesis
wiTI continue
It has been known for
and ammonia
~201, and with
but recently it has been shown that aliphatic
to wridines
of another
by zeolites
C90b1,
pyridine
of Te-Al-Si-Sb-0
of oxygen-containing
Some time that methanol will cyclise ethYne
bases
has shown that they possess
in the small-scale is stiil,
that the condensation
to PIa!4 a large Part
Two
is employed in
search
on the liquid-phase
LG,10,1011 increase
predicted
the
as a feedstock
[83, and it may well
that are at present
sation of alkynes
pyridine which
but will yield
oxides
[99] or a~uminjum
may find application
countries
towards
can be optimised
have concentrated
rivatives
of we]]-
Processes.
used for cracking and hydrocrackiv
from petroleum,
in the use of ethyne
processes
USSR and eastern
[96,97],
in an industrial
~onlpounds of cobalt
with other
that
reactionS
[98].
their composition
Since the decline
therefore,
and of Surface
for Pt-Rh alloy),
of these mixed
necessary
before
associated
has led to the formulation
Characterisation
of the qualities
using
compounds
of alkenes
to pyridines
structure
to be very selective
[75] and from ketones
conversion
recent
that are normally
1301, and platinum
the condensation in the comPosition
seems t0 be the UtilisatiOn
catalysts,
but have been found
concern
variations
It is Surprising,
of catalyst
characterised
194,951
bases
possible
Current
that this reaction
zeolite
interest
ZSM-5
~583, even
in all aspects
is examined
alcohols in the
of catalysis
in detail.
ACKNOWLEDGEMENT'S The authors
are grateful
to Professor
T.A. Crabb
and Dr. T.G. Nevell
for their
time and their opinions.
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88
NOTE ADDED Syntheses
IN PROOF using alkenes
The review processes, oxides
by Dewing
whereas
and Davies
the mechanism
was first reported
Oxidation
Communications,
[89] discusses
the economics
for the ammoxidation
in the following 5 (1983) 89.
paper:
of alkenes
J. Halasz,
of catalytic over Sn-Sb-Te
K. Varga and P. Fejes,
Applied CatuZysis, 23 (1986) l-14 Elsevier Science Publishers B.V., Amsterdam -Printed
HETEROGENEOUS
Stanislaw
CONVERSION
OF ACYCLIC
in The Netherlands
COMPOUNDS
TO PYRIDINE
BASES
- A REVIEW
E. GOLUNSKI*
St. John's
College,
Southsea
PO5 3QW, U.K.
and David JACKSON Frewen
Library,
Portsmouth
* To whom correspondence
(Received
12 August
Polytechnic,
should
Portsmouth
PO1 ZST, U.K.
be addressed.
1985, accepted
2 December
1985)
ABSTRACT A large and growing demand for the derivatives of pyridine exists because of their many chemical, pharmaceutical and agricultural uses. The commercial products gasare derived from pyridine bases, which can be prepared by the heterogeneous phase cyclisation of simple organic molecules in the presence of ammonia. Alumino-silicates are catalytically active in the conversion of carbonyl compounds to pyridine bases. It is probable that the reactants are adsorbed at acidic sites and that the formation of imines precedes cyclisation. The catalysts, with the exception of certain zeolites, lose activity with prolonged use, probably as a result of consecutive reactions that lead to the blocking of narrow pore openings. Alkenes can be converted to pyridine bases in two stages: partial oxidation over a mixed-metal oxide, followed by cyclisation in the presence of ammonia over direct ammoxidation can be achieved using cataalumino-silicates. Alternatively, lysts based on Te-Al-Si-0. These catalysts retain their activity during prolonged use, but are limited by their lack of selectivity. Potential new routes include the conversions of alkynes, epoxides and alcohols. Metal phosphates are active in the formation of pyridine bases from both alkynes and epoxides. The former process may involve the formation of adsorbed tautomeric intermediates. A most recent innovation is the condensation of aliphatic alcohols with ammonia, over a zeolitic catalyst.
INTRODUCTION Apart
from the long established
collectively
as pyridine
scavengers
[2], there
formation
of medicines
infectants
small amounts inadequate
ethyne
[cl. By contrast,
Economic
0166-9834/86/$03.50
[l-41,
Community
bases now produced
(acetylene)
the growth
catalysts
(known
[2] and acid
for them as intermediates herbicides
over the last forty years,
[1,5]. At the same time,
have superseded
supplements
and alkylpyridines
in the
[1,2], dis-
[I].
of the European
of pyridine
[1,2],
large demand
[l-4], dietary
of the decline,
states
as solvents
is now a very
[Z] and pesticides
As a result the member
bases)
uses of pyridine
in the use of coal in
and in North America,
by pyrolysis
the exploitation as the primary
of the petrochemical
of coal are vastly
of oil has meant
source
that alkenes
of many organic
industry
0 1966 Elsevier Science Publishers B.V.
the
has been
compounds
less rapid
in
the countries substantial continued
reserves
to the Council
will need to make
as their supplies
Although
molecules
alkanes
[ll], alkenes (notably
achieved
industrial
catalytic
[12] and alkynes
methods
This review
application.
that are already
ensure
[6,9,10]
synthesis
that
gas and
a limited
being employed,
the rBle of the catalyst are discussed.
pyridine
bases from
[2,11,13],
with ammonia
concentrates
changes
class of reaction,
USING CARBONYL
dicarbonyls
[5,13,14]),only
surface
SYNTHESIS
[7,8], but
should
predicted
for preparing
of aldehydes
in light of the expected
mechanisms
Siberia,
use of alkanes,
[2,11-131,
the condensations
cyclisations
show potential
greater
possible
(such as carbonyls
processes
in western
Assistance
of crude oil diminish.
there are numerous
acyclic
Economic
[71. It is, however,
for some years
nations
for Mutual
of oil, particularly
expansion
the western ethyne,
belonging
dicyano-
number
of these
[3,4,12])
have
on those gas-phase, and those
in available
is considered
that appear
feedstocks.
to
For each
and, wherever
possible,
COMPOUNDS
Conditions
In the process hyde),
ethanal
catalyst, pyridine
that is usually
(acetaldehyde)
at temperatures (B-picoline)
feed is important.
attributed
and ammonia
between
to Chichibabin
are condensed
300 and 55O'C,
as the major
In its absence
products.
The inclusion
the total yield
10.8) can result
of over 70% [16]. This appears
in a yield
NH3 and vaporised
that have indicated aqueous
been considered
[17,18].
in the reaction
mixture
of oxidative
HCHO),
a maximum
possible
but in these studies
dealkylation
the formation
bases
can be less
the effect
[19,20]
= 1:2:2.7:
to contradict yield
results
of 66% (from CH3CH0, of steam
that the presence
of pyridine,
of the methylpyridine
in the gas-
(HCHO:CH3CHO:NH3:H20
It has also been shown favours
and 3-methyl-
of steam
of pyridine
proportion
studies
of steam
(formalde-
over an alumino-silicate
to give pyridine
than 50% [14]; a high molar
of kinetic
[15], methanal
[20],but
possibly it also
has not of oxygen
as a result
reduces
the
life of the catalyst. The alumino-silicate
catalyst
is best employed
Its performance
can be improved
oxides
and also by retaining
126,271,
1231. Alternative alumino-silicate zeolite useful
catalysts zeolites
C31a1, which as it allows
pyridines
include [30].
In particular,
high conversion
(lutidines)
by a cheaper
ZSM-5
advantage
to be excluded
[28,29]
[31,32]
from the gas-feed
(e.g. methanol
[ZO]).
during
reaction
and crystalline siliceous
may prove
that include
of all these
1211.
or metal
(a highly
[33,34]),
(up to 93%) to bases
reactor
[20,22-251
deposited
phosphates
with silicalite
[31b]. A further
reagent
in a fluidised-bed
of halides
some of the carbon
mixed-metal
is isostructural
is that they allow methanal replaced
by the addition
very
dimethyl-
improved [20,26-311
catalysts or to be
3
a) Formation
of imines
(i) Homogeneous
R = CH3 or H
reaction
R
R
I C
hew:N~3 F HO"'
(ii) Heterogeneous
-H 0 2 NH
H
R-CH=NH
2
reaction H
/,O R-C, H-
-.e----:NH3(ads) &H(ads)
H+(surf)
•-
3
bH
H
H 'C=NH(ads)4 R' b) Formation
of pyridine
(i) Homogeneously
'P+-+H2
3
R-;-NH;
(ads)
bases
catalysed
cyclisation
of allylamines
-2NH
(ii) Heterogeneously
Sb
-HP
catalysed
cyclisation
of imines
H=NH HC 3
H C=NH 2
-2NH 3
A
HC 3 'CH II NH
FIGURE
1 Condensations
N
of carbonyl
compounds
with ammonia.
N
4 Surface
reactions
Accounts depicted
of the conversion
the overall
35,361:
e.g. the conversion
represented
of carbonyl
changes
compounds
to pyridine
in the form of simple
reaction
of an ethanal-methanal
mixture
bases have often
schemes
[3a,4,11,12,14,
to pyridine
may be
as
H3C
\ 0
CHs
CHO
CHO
t 3H_,o + Hz
(1)
I
l
N
NH3
and the conversion
of ethanal
to 4-methylpyridine
as
CH3
CH3
H3C
I
I
CHO
CHO
Although first
mechanistic
stages
Antonova
schemes
The nucleophilic
have proposed,
therefore,
near or at acidic Nucleophilic
sites,
addition
by loss of water
groups;
of stable
forming
of intermediates
at higher
readily
surface
adsorb
imines
ammonia
catalysed
[43] has shown that two molecules and loss of a hydrogen
and heterogeneous (Figure
l,b,ii).
for the latter
15,411 conversions
et al. [40]
are adsorbed
ions (Figure
l,a,ii)
and is followed
[37,40-421.
have yet to be examined
in the homogeneously
have been proposed
[38] and are known
[39]. Vetrova
and carbonium
in the liquid-phase
processes
bases.
homogeneously
of the catalyst,
before
ring closure
(350-4OO"C),
of pyridine
step the reactants
at the surface
of cyclisation
ammonia
carbocations
the first
adsorbed
can occur
(80-lOO"C),
to form compounds
temperatures
to the formation
to an aldehyde
that during
thus occurs
stages
the
to the publication
of alumino-silicates
leading
of ammonia
to leave adsorbed
The subsequent analysis
and amino
but alumino-silicates
the formation
they have allowed
leading
that even at low temperatures
in the presence
immediately,
addition
l,a,i),
to promote
to be elucidated,
[37] have found
both hydroxyl occurs
have been far from extensive, reaction
(2)
[5,373.
and coworkers
reaction
(Figure
studies
react with ammonia
containing further
t 3H20 t Hz
of the surface
of more detailed
aldehydes
CH3
molecule stages
of carbonyl
in detail,
reaction
but
of allylamines
of annnonia are eliminated occur
(Figure
l,b,i).
of both the homogeneous
compounds
to pyridine
Similar [44]
bases
Alternative
reaction
include
the formation
2CH3CHO
+
schemes
for the conversion
of but-Z-enal
CH3CH=CHCHO
of ethanal-methanal
as an intermediate
mixtures
[11,45,46]:
(3)
+ Hz0
then. either
H/" II CH / H3C
CH3
\
CHO NH3
+ HZ
t 2H2.0
(4)
+ H2
t 2H20
(5)
,
+cl H3C
PI
or CH3 yCH CH I CHO
.
CH3
YH3 CHO
\ I
d-l N
NH3
Apart
from the evidence
ammonia,
When but-2-enal of pyridine cracking
ethanal
additional
and ammonia
a complex
is sometimes bases
included
is likely
[47], which
over aluminate
of the catalyst.
Furthermore, which
incorporated
instead
reaction
schemes
are usually
catalysts
[48,49],
attack
products,
catalyst
(3-5).
at 350°C, yields cyclisation,
its conversion
from ammonia
unless metal
thermal
Although
steam and the formation
(3-5) show the formation
minor
in the alumino-silicate
schemes
and carbon monoxide.
with
nucleophilic
ions with adsorbed
of the expected
in the gas-feed
then undergoes
carbonium
for discounting
of hydrocarbons
to involve
methylpyridines,
Nature
are passed
mixture
of surface
reasons
bases are low [47] because,
yields
but-2-enal pyridine
for the reaction
there are several
to of
at the surface
of 2- and 4phosphates
are
[29].
of catalyst
Previously,
it had been observed,
(Mo03-A1203)
was a more
(CaO-A1203),
but it has subsequently
and acid strength
is not simple
in order of decreasing 8.4% A1203
effective
by Butler
condensation been found
[37], as shown
[47], that an acidic catalyst
that the relationship by the following
activity:
+ 91.6% Si02 > 20% H3P04 + 80% A1203-Si02
40% H3P04 + 60% SiO2 > ZnO-A1203
> y-AlEO
aluminate
than a basic aluminate
>
between
catalysts
rate
arranged
6 Antonova
and coworkers
reaction
is retarded
seems,
therefore,
the nature proposed
(Figure
unreactive
then a large number doped with alumina
If the concentration
of inert ammonium
Furthermore,
sites
to depend
Some information been derived against
conical
of Brdnsted
sites
is too great,
formed
be obviated prising
greatly
appears
Lewis
by interaction
or fluorides,
studies
the formation either
[38,52!
of the catalyst
channel
hysteresis
between
systems
which
possesses
aromatic
to
of carbonyl
of the openings
or even
are
than the opening.
of the catalysts
compounds
by deposits
of
[53b]. This problem a pore structure
dimensions
is a shape-selective
channels
for mercury
of the pores can be
the pores
of different
of large polycyclic
in the narrow
has
that the pores
the condensation
within
catalysts
the curves
suggests
the formulation
during
ZSM-5,
of carbon
with
[53]. Plots of pore volume
the dimensions
reactions
by using the zeolite
involving
of preparation
equilibrium
of alumino-silicate
to be due to the blocking
be formed
gels
pro-
sites
the base of each pore being wider
by consecutive
that the formation
of silica
by conditions
on the following
[53a]. This
that, by changing
oxides
two intersecting
believed
to exhibit
[53a]. The loss of activity,
ammonia,
carbon,
surface
and adsorption
[53a], with
other metal
increased
the active
have been found
It has also been shown
Studies
in of
use.
and those for its evacuation
in shape
include
be formed
or during
from porosimetry
radius
penetration
with
the formation
the availability of Lewis sites would be expected 3+ . ions and on the morphology of the surface, of Al
sites would
about
be involved
allow
>
before
sites would
temperature/-H20
therefore,
Brdnsted
as
From the mechanism
[51] have shown that the relative
(
either
vapour,
It
sites would
the ratio depends
on the concentration
mobile
the
ions are formed.
ions may be formed.
1501 and of zeolites
In alumino-silicates,
water
that Brbnsted Lewis
is too great,
is not as important
of acid sites at its surface.
increasing Brdnsted
ammonium
of the solid
of the two types of site are affected
and calcination.
whereas
adsorbed
acidity
ions, whereas
ammonia.
that if the acidity
it is apparent
l,a,ii),
of carbonium
adsorbed
portions
because
that the overall
and distribution
the creation labile
[37] have deduced
molecules
in the wider
com-
[31,54].
process
may
It is
[32,55],
[56], which intersections
cannot within
the zeolite.
SYNTHESES
USING ALCOHOLS
The condensation over metals
and metal
36%, over Pd-A1203 higher yields mechanism
or prop-2-en-l-01 gives fairly
[57]).
poor yields
with ammonia,
of pyridine
bases
been shown recently
over zeolitic
catalysts
(e.g. that
[58]. The
has yet to be investigated.
have also been used to catalyse [59], but the
(piperazine):
(ally1 alcohol)
It has, however,
(ca. 45X), can be achieved
with ammonia
pyrazine
oxides,
at 310°C
for this reaction
Zeolites oxide)
OR EPOXIDES
of ethanol
major
the reaction
product
of epoxyethane
(ethylene
has been found to be hexahydro-
7
t 2H20
a catalyst
If, however,
[60], epoxyethane reaction
comprising
can be converted
that appears
to proceed
SYNTHESES
selectively
oxidation,
Traditionally,
For example,
propene oxide
can be partially
(e.g. Bi-MO-0
can allow almost
class of catalyst
with high selectivity,
the precise
mechanism
invariably
[61]):
depends
CHz=CH-CHB --=%
,,/“’
HC//cHi I gCH
[64,65],
(acrolein)
Sn-Sb-0
of 90% are not unusual
of the catalyst
of an allylic
ions from the catalyst
CHz ;T;-;-;CHT;T;TCH2(ads) Lol.
stage requires
to propenal
[66,67]
Fe Co Zr 0 [68]). The 10 2 8 0.1Ca0.1Ti0.2 x complete conversion of the alkene to
on the nature
leads to the formation
The second
U-Sb-0
in two separate
(e.g. BiMo
so that yields
which may then react with oxide
NH30
in a
(ethylenimine
from alkenes
oxidised
[62,63],
latter
HC \\ 0
of aziridine
is used
(7)
bases have been prepared
catalyst
I
to Z- and 4-methylpyridine
-2NH, -Hz
or over a multicomponent
propene
chloride
condensation
pyridine
over a binary-metal
propenal
and cobalt
USING ALKENES
Two steps:
stages.
phosphate
via the formation
a 3HzC L2-CHz
-3n,o + 3NH3-
0
3H&&Hz
calcium
(6)
the condensation
. XT ,
N
[52], adsorption
intermediate
of
[6,52],
[62,69,70]:
CH*=CHCHO
of propenal
[52]. Although
(8)
with
ammonia:
CH3 t 2H20
(9)
8 Acidic
catalysts
yields
of methylpyridines
are again catalytically are often
improved
by using alumino-silicate
ensuring
that the reactants
preventing reach
homogeneous
the reactor.
either
(supported
between yields
According
should
More pyridine
oxygen
participation
of adsorbed/lattice
reaction
steam
with
of methylbenzene occurs
because
hydroxyl
species,
and hydrogen. Butene
which
Subsequent silicate
generates
to pyridine
by the support
addition
yields
studies
of adsorbed
of allylimine
the case
propenal [77].
is present takes
[77],
place.
Even
by the
as the result
of
that dealkylation
on alumina,
material
to form surface
to produce
carbon
monoxide
to the dealkylation
of methylpyridines.
bases
Allylic
in two steps.
oxidation
butadiene:
(ads) =S
and 3_methylpyridine,
no mechanistic
between
[81] have suggested
groups
[76].
[77], possibly
probably,
of the diene with methanal
pyridine
44% [84]. Although
to the formation
may apply
[6,82,83]
such as
(Pt, Rh or Pd) supported
CH2 T-TTTF CH-CHT-XTCH~
condensation
that nucleophilic
and coworkers
mechanism
oxide
CH2=CH-CH2CH3 -H
or, more
oxygen
are adsorbed
can also be converted
over a mixed-metal
is formed
they
by using
compound,
when oxygen
of the product
SO
or platinum
of the reaction
then react with the methyl
A similar
before
in the gas-feed
is formed [78,79]
over metals
water molecules
carbonyl
[74al,
[74b,c,d]
but this is not always
some pyridine
[80]. Duprez
(toluene),
and ammonia
II elements)
another
product
derivative
dealkylation
of gaseous
+ Group
but
can be
C731, and by
of over 70% can be achieved
(propionaldehyde),
be 3-methylpyridine,
that oxidative
[71,72],
of the catalyst
the propenal
(Al-F-O
(9), the major
than the methyl
in the absence
of low bulk density
and by including
or propanal
to equation
and ammonia
suggesting
catalyst
in this reaction
in the presence
reactions
on Al-Si-0)[75], (acetone)
pellets
meet only
Alternatively,
a multicomponent
propanone
active
less than 30% [71]. The selectivity
CH2=CH-CH=CHp
and ammonia
ammonia
intermediates,
over an alumino-
in a combined
have been reported, to surface which
(10)
yield
of up to
it seems likely
carbonium
then undergo
ions leads
ring closure.
One step: ammoxidation Early merely
patents
describe
two different achieve
[85,86], improved
catalysts.
the conversion
More recently,
oxide
maximum
of pyridine
yield
carbon
[87,88].
that yields
dioxide,
direct
to pyridine
and condensation
bases, using
it has been shown that it is possible
the original
bases over Te-Al-Si-0
propanone
of alkenes
oxidation
step, over a catalyst
Although
of less than
ethanal,
conversion
for consecutive
in a single
and tellurium
have found
claiming methods
patent
and ethanoic
[87] shows
that the
is 17.5%, Forni and coworkers
10% are achieved
usually
acid).
to
based on alumino-silicate
(by-products
[SS]
include
9 The composition effect
and method
on the conversion
pyridine
bases
cipitation
at 400°C
[82a,b].
oxidising the latter
sites;
leads to its partial
to an acidic [88a,b].
A similar
Al-Si-0.
mechanism
for adsorption
of gaseous
of the alkene
retain
design
conditions
during
occur
over Sn-Sb-Te
oxides
in the allylic
oxidation
reactor
catalysts
catalysts
is clearly
have been shown,
use and to withstand
are important
factors
however,
sudden
when
limited
changes
considering
by
to in
the
[89].
FROM ALKYNES
Cadmium of alkynes
[90,91]
and alumina
[92] are catalytically
with ammonia,
salts
but cadmium
sulphate
ethanonitrile
over cadmium
(acetonitrile).
phosphate,
of ethyne 39O"C,
415 - 45O"C,
2MP > 4MP > E;
450 - 46O"C,
2MP > E > 4MP;
above 46O"C,
E > 2MP > 4MP.
et al. [90b] have proposed
to form enamine
and imine molecules
react with another
molecule
or imine. Evidence
for the formation
products,
could
be formed
which
is liberated
The relative be determined of the initial
which
during
proportions
C90b1,
that adsorbed
to produce of these
reaction
with changes
in com-
for the
> 4_methylpyridine(4MP);
ethyne
and ammonia
an unsaturated
intermediates to include
between
tautomers
secondary
amine
comes from the analysis
diethylamine
adsorbed
combine may then
dienamine
[gob].
This
and hydrogen,
stage of cyclisation.
of the pyridine
by the equilibrium,
can be achieved
e.g. yields
2). Each of these
have been found
the final
bases
in the reaction C92] yield
orders:
(Figure
of ethyne
by an addition
reaction
considerably
> Z-methylpyridine(2MP)
2MP > E > 4MP;
of the minor
varies
are in the following
390 - 415"C,
Akhmerov
to pyridine
[90b] and in temperature
ethanonitrile(E)
active
C90al and y-alumina
Conversion
but selectivity
of the gas-feed
conversion below
of the aldehyde
and cyclisation
ions may act as centres
then participates
These
prolonged
[SSd], which
of a commercial
position
both
phase and
to the inner
by migration
ammonia
but Sb3+
tellurium-based
[88,a,b,e].
their activity
SYNTHESES
mostly
of the present
low selectivity
operating
which
possesses
of propene
to ammoxidation
is not clear,
containing
at 110°C and calcination
[70].
The usefulness their
with adsorbed
to
by the pre-
oxide,
(IV)
an inner Te-0
diffusion
Thus,
seems to apply
oxygen,
within
and is followed
reaction
1891. The role of the antimony
has been prepared
tellurium by drying
located
oxidation,
site, at which
have a considerable
of the reaction
[88b] that this catalyst
the former
in the surrounding
ground
followed
oxide,
It has been proposed
and acidic
catalyst
on finely
of antimony
of the catalyst
and on the selectivity
[88a]. The most effective
of alumino-silicate
a small proportion
phase
of preparation
of propene
equation
at the surface
bases
in the final products
(II), which
of the catalyst
is established [90b,93].
seem to
as a result
10 Cd'+(surf)
t C H 2 2
I
(surf)
H
+
C=CHNH (ads) ~ 2 2
H CCH=NH 3
(ads)
I
I
CH 2 2
CH 2 2
(ads)
(ads) I
ICII
L
N
N’
J
H -H
-H 2
2 CH 2 2
CH 2 2
(ads)
(ads) I
I
CH 3 . /
0
n
N
CH CN
., N
CH
3
FIGURE
2
Reactions
enamine
(ads)
Greater
stability
of ethyne with
1
3
ammonia
imine
over cadmium
(ads)
(11)
of the imine leads to the formation
than 4-methylpyridine.
Over cadmium
phosphate
at temperatures
tautomers
is favoured
below
sulphate,
of more
v-alumina
390°C or above
so that the major
phosphate.
product
46O"C,
Z-methylpyridine
and even over cadmium dehydrogenation
becomes
ethanonitrile.
of the
11 CONCLUSIONS Most patents of carbony
describing
compounds.
of both the catalyst relatjvefy
syntheses
They
of pyridine
show the many
and the gas-feed
fettdfundamental
have been reported.
Studies
A promising
mixture.
development
such examples
are zeo‘iites, which are widely
range of reactants
the oxidation aldehydes With
of nitrogen
the availability
[87-891.
are needed
publications
of pyridine.
Ethyne
Europe
Finally, gas suggests
the
is worthy
dependent
of greater
and ammonia
in the production
can be converted absence
should
organic ensure
for a
bases
for thefr
from
catalyst,
but detailed to ensure
cyclisations
manufacture
re-emerge
phase studies
in the western
an important
nations, of alkynes,
catalysts,
of selected feedstock
These
de-
in the
in that r$ie in those
on oil [9]. Therefore
the gas-phase
cycli-
investigation. in the use of alkanes
of pyridine
with ethanaf
over the versatile
reactant.
some
high selectivity.
[IOO] as homogeneous
however,
direct
catalysts
molecules
bases.
and synthesis
wiTI continue
It has been known for
and ammonia
~201, and with
but recently it has been shown that aliphatic
to wridines
of another
by zeolites
C90b1,
pyridine
of Te-Al-Si-Sb-0
of oxygen-containing
Some time that methanol will cyclise ethYne
bases
has shown that they possess
in the small-scale is stiil,
that the condensation
to PIa!4 a large Part
Two
is employed in
search
on the liquid-phase
LG,10,1011 increase
predicted
the
as a feedstock
[83, and it may well
that are at present
sation of alkynes
pyridine which
but will yield
oxides
[99] or a~uminjum
may find application
countries
towards
can be optimised
have concentrated
rivatives
of we]]-
Processes.
used for cracking and hydrocrackiv
from petroleum,
in the use of ethyne
processes
USSR and eastern
[96,97],
in an industrial
~onlpounds of cobalt
with other
that
reactionS
[98].
their composition
Since the decline
therefore,
and of Surface
for Pt-Rh alloy),
of these mixed
necessary
before
associated
has led to the formulation
Characterisation
of the qualities
using
compounds
of alkenes
to pyridines
structure
to be very selective
[75] and from ketones
conversion
recent
that are normally
1301, and platinum
the condensation in the comPosition
seems t0 be the UtilisatiOn
catalysts,
but have been found
concern
variations
It is Surprising,
of catalyst
characterised
194,951
bases
possible
Current
that this reaction
zeolite
interest
ZSM-5
~583, even
in all aspects
is examined
alcohols in the
of catalysis
in detail.
ACKNOWLEDGEMENT'S The authors
are grateful
to Professor
T.A. Crabb
and Dr. T.G. Nevell
for their
time and their opinions.
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13
ii 50 51
52 53
54 ;: 57 58 59 60 61
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88
NOTE ADDED Syntheses
IN PROOF using alkenes
The review processes, oxides
by Dewing
whereas
and Davies
the mechanism
was first reported
Oxidation
Communications,
[89] discusses
the economics
for the ammoxidation
in the following 5 (1983) 89.
paper:
of alkenes
J. Halasz,
of catalytic over Sn-Sb-Te
K. Varga and P. Fejes,