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Catalytic hydrogenation
1) Catalytic hydrogenation is one of the most convenient available for reduction
of organic compounds. Reduction is carried out easily by stirring or shaking
the substrate with the catalyst in a suitable solvent or without a solvent if the
substance being reduced is a liquid in an atmosphere of hydrogen gas. Once
the reaction is completed, the catalyst is filtered off and the product is
recovered from the filtrate, often in a high state of purity.
2) In many cases reaction proceeds smoothly at room temperature and at
atmospheric or slightly elevated pressure. However, in some cases, high
temperatures (100–200°C) and pressures (100–300 atmospheres) are
necessary, requiring special high-pressure equipment.
3) Catalytic hydrogenation may result simply in the addition of hydrogen to one
or more unsaturated groups in the molecule, or it may be accompanied by
fission of a bond between atoms. The latter process is known as
hydrogenolysis.
4) Under appropriate conditions, catalytic hydrogenation can be used to reduce
unsaturated groups such as alkenes, alkynes, carbonyl groups, nitriles, nitro
groups and aromatic rings.
5) Certain groups, notably allylic and benzylic hydroxyl and amino groups and
carbon–halogen single bonds readily undergo hydrogenolysis, resulting in
cleavage of the bond between the carbon and the heteroatom.
H2,Pd/C
MeOH
100 %
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Catalyst for hydrogenation
H2,PtO2
AcOH
72 %
3) Most platinum metal catalysts (with the exception of Adams’ catalyst) are
stable and can be kept for many years without appreciable loss of activity,
but can be deactivated by many substances, particularly by compounds of
divalent sulphur.
4) Catalytic activity is sometimes increased by addition of small amounts of
platinum or palladium salts or mineral acid. The increase in the activity may
simply be the result of neutralization of alkaline impurities in the catalyst.
Reduction Selectivity
1) Many hydrogenations proceed satisfactorily under a wide range of
conditions, but where a selective reduction is wanted, conditions may be
more critical.
2) The choice of catalyst for a hydrogenation depends on the activity and
selectivity required. In general, the more active the catalyst the less
discriminating it is in its action and for greatest selectivity reactions should
be run with the least active catalyst and under the mildest possible
conditions consistent with a reasonable rate of reaction.
3) The rate of a given hydrogenation may be increased by raising the
temperature, by increasing the pressure or by an increase in the amount of
catalyst used, but all these factors may result in a decrease in selectivity.
4) Hydrogenation of ethyl benzoate with copper chromite catalyst under the
appropriate conditions leads to benzyl alcohol by reduction of the ester
group, while Raney nickel gives ethyl cyclohexane carboxylate by selective
attack on the benzene ring.
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H2,CuCr2O4 H2,Raney Nickel
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Hydrogenation of alkenes
Hydrogenation of carbon–carbon double bonds takes place easily and, in most
cases, can be done under mild conditions. Only a few highly hindered alkenes
are resistant to hydrogenation and even these can generally be reduced under
more vigorous conditions. Palladium and platinum are the most-frequently used
catalysts. Both are very active and the preference is determined by the nature
of other functional groups in the molecule and by the degree of selectivity
required.
H2,10 % Pd/C
EtOH
74 %
93 %
99 %
98 %
E-alkene Racemic
H2, Pd
EtOH
98 %
Z-alkene Meso
83 % 17 %
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The hydrogenation of substituted cyclic alkenes is irregular in many cases in
that substantial amounts of trans-addition products are formed, particular
with palladium catalysts.
For example, the bicyclic alkene on hydrogenation over palladium in acetic acid
gives mainly trans-decalin and the alkene 1,2-dimethylcyclohexene gives
variable mixtures of cis- and trans-1,2- dimethyl cyclohexane depending on the
conditions.
H2,Pd/C
AcOH
21 % 79 %
H2,Pd/C 46 %
16 %
AcOH
H2,PtO2
82 % 18 %
AcOH
The reason for the formation of the trans products is thought to be because of
migration of the double bond in a partially hydrogenated product on the
catalyst surface. Although catalytic hydrogenation of alkenes may be
accompanied by migration of the double bond, no evidence of migration
normally remains on completion of the reduction.
Hydrogenation of alkynes
Catalytic hydrogenation of alkynes takes place in a stepwise manner and both
the alkene and the alkane can be isolated. Complete reduction of alkynes to the
saturated compound is easily accomplished over platinum, palladium or Raney
nickel. A complication which sometimes arises, particularly with platinum
catalysts, is the hydrogenolysis of hydroxyl groups to the alkyne.
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H2, Pt
Lindlar catalyst
i) 55 atm,H2,EtOH
5 %Rh-Al2O3,AcOH
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H2,Rh-Al2O3
H2,Pd/C
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However, large amounts of secondary amines may also be formed as an impurity
due to the side reaction of the amine with the intermediate imine.
H2 H2
Catalyst Catalyst
H2
Catalyst
-NH3
Homogeneous hydrogenation
1) The stereochemistry of reduction may not be easy to predict, since it
depends on chemisorption and not on reactions between molecules. Some
of these difficulties have been overcome by the introduction of soluble
catalysts, which allow hydrogenation in homogeneous solution.
2) A number of soluble-catalyst systems have been used, but the most common
are based on rhodium and ruthenium complexes, such as [(Ph3P)3RhCl]
(Wilkinson’s catalyst) and [(Ph3P)3RuClH].
3) Wilkinson’s catalyst is an extremely efficient catalyst for the homogeneous
hydrogenation of non-conjugated alkenes and alkynes at ordinary
temperature and pressure. Functional groups such as carbonyl, cyano, nitro
and chloro are not reduced under these conditions. Mono- and disubstituted
double bonds are reduced much more rapidly than tri- or tetrasubstituted
ones, permitting the partial hydrogenation of compounds containing
different kinds of double bonds.
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H2, [(Ph3P)3RhCl]
benzene
80 %
H2, [(Ph3P)3RhCl]
benzene
H2, [(Ph3P)3RhCl]
benzene
93 %
5) Wilkinson’s catalyst has a strong affinity for carbon monoxide and
decarbonylates aldehydes, therefore alkene compounds containing
aldehyde groups cannot normally be hydrogenated with this catalyst under
the usual conditions. For example, cinnamaldehyde is converted into styrene
in 65% yield, and benzoyl chloride gives chlorobenzene in 90% yield.
6) Addition of hydrogen to Wilkinson’s catalyst promotes oxidative addition of
hydrogen. Dissociation of a bulky phosphine ligand and co-ordination of the
alkene is followed by stepwise stereospecific cis transfer of the two hydrogen
atoms from the metal to the alkene by way of an intermediate with a carbon–
metal bond.
7) Diffusion of the saturated substrate away from the transfer site allows the
released complex to combine with dissolved hydrogen and repeat the
catalytic reduction cycle.
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tetrasubstituted double bonds as well as mono- and disubstituted ones,
although not so rapidly, and it appears to be unaffected by sulphur in the
molecule. A valuable feature of this catalyst is the high degree of stereo
control that can be achieved in the hydrogenation of cyclic allylic and
homoallylic alcohols. (Hydrogens add from the same side as that of hydroxyl
group).
H2, [Ir(COD)py(Pcy3)]PF4
H2, [Ir(COD)py(Pcy3)]PF4
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