339

Hydroformylation
(Oxo Reaction, Oxo Process, Oxo
Synthesis)

A. GENERAL DESCRIPTION OF THE REACTION

This reaction was first reported by Smith et al. in 19301 and subsequently by Roelen
in 1938.2 It is an industrial process for synthesizing aldehydes and alcohols from olefins
and synthesis gas (i.e., carbon monoxide and hydrogen) in the presence of a cobalt or
rhodium catalyst at high pressures (100–200 atm) and high temperatures (115–190◦ C) with
the attachment of a new carbon to the less-substituted end of the double bonds.3 In the litera-
ture, this reaction is often known as hydroformylation,2b,2c,4 as well as oxo process,2b,4i,4j,5
oxo reaction2c,3,4l−4o,6 oxo synthesis,4k,7 and Roelen reaction.8 This reaction is one of the
most extensively used reactions in the field of organometallic chemistry,9 resulting in the
production of 2.6 million metric tons of aldehydes and alcohols in 1969. Generally, alde-
hydes dominate in the product mixtures at relatively low temperatures (e.g., 115–125◦ C),
whereas alcohols are almost the sole products at temperature >180◦ C.3 This process is
sometimes carried out in two stages: the production of aldehydes and the further reduction
of aldehydes into alcohols. In addition, the straight-chain terminal olefins often lead to
two isomeric aldehydes or alcohols,4m while ketones are the major product when ethylene
is subjected to the hydroformylation.4k However, α,β-unsaturated aldehydes and ketones
undergo direct reduction to saturated aldehydes and ketones without any hydroformylation
at 120–125◦ C and 200–300 atm, yet these unsaturated carbonyl compounds are completely
reduced under similar pressure, but at temperatures of 180–185◦ C. For comparison, con-
jugated dienes and furans undergo both types of reactions, by which one double bond is
reduced and the other is extended by a formyl group; in contrast, thiophene and phenan-
threne undergo only slow reductions, and benzene is inert under such hydroformylation

Comprehensive Organic Name Reactions and Reagents, by Zerong Wang

Copyright © 2010 John Wiley & Sons, Inc.

1516
 PROPOSED MECHANISMS 1517

conditions. For vinyl aromatics or vinyl heteroaromatics, the corresponding aldehydes

are the major products, except for 4-vinyl pyridine and 2-vinyl pyridine, which form either
hydrogenation or hydroformylation products, depending on the catalyst employed.10 For
rhodium-catalyzed hydroformylation, it has been found that hydrogen and formyl groups
add to both cis and trans internal olefins from the same side with high stereospecificity.11
Because of the high cost of rhodium catalyst, this process has been modified using a VIB
group metal (Cr, Mo, W) complex as the major component of the binary catalyst system in
combination with trace amounts of cobalt or rhodium carbonyl, which can be adjusted in
terms of catalytic activity and selectivity.4i

B. GENERAL REACTION SCHEME

Co/Rh catalyst R1 R3
R1 R2
R2 + CO + H2 and/or R
1
∆ R3 R2
R1 = H, alkyl, vinyl, aryl, R3 = CHO, CH2OH
R2 = H, alkyl

C. PROPOSED MECHANISMS

It is believed that this process involves the following steps: (a) formation of dicobaltoc-
tacarbonyl from cobalt and CO, which equilibrates with cobalt hydrocarbonyl by reaction
with hydrogen; (b) substitution of one carbon monoxide by olefin to form a π-complex;
(c) conversion of a π-complex to cobalt alkyltetracarbonyl via a cobalt tricarbonyl inter-
mediate after the addition of carbon monoxide; and (d) fast rearrangement of the cobalt
alkyltetracarbonyl compound into the acyl cobalt tricarbonyl compound, which reacts with
hydrogen to give aldehyde and cobalt hydrocarbonyls.4k A detailed mechanism is shown
below.
1518 HYDROFORMYLATION

D. MODIFICATION

This reaction has been modified using a group VIB metal complex as catalyst in combi-
nation with trace amounts of cobalt or rhodium carbonyl complex.4i

E. APPLICATIONS

This reaction has extensive application in the industrial production of aldehydes and
alcohols with carbon chains from C4 to C13 .12

F. RELATED REACTIONS

N/A

G. CITED EXPERIMENTAL EXAMPLES

CHO
Rh4(CO)12/PMe2Ph
+ CO + H2
Benzene
N N
> 94%
Reference 9.

A solution of 0.8 mL 4-vinyl pyridine (7.42 mmol), 3.0 mg Rh4 (CO)12 (0.004 mmol),
and 9.0 mg PMe2 Ph (0.064 mmol) in 4.0 mL benzene was introduced by suction into an
evacuated 25-mL stainless-steel autoclave equipped with a magnetic stirrer. The reactor
was transferred to an oil bath, and carbon monoxide was introduced; the autoclave was
then heated to 100◦ C (45 atm), and hydrogen was rapidly introduced up to 100 atm total
pressure (CO/H2 ,1:1). During the reaction, the drop in pressure was restored by injection of
a carbon monoxide–hydrogen mixture (1:1 from a high-pressure container). After 75 min,
GC analysis of a siphonated sample indicated that 4-vinyl pyridine had been completely
transformed into branched and linear aldehydes (96:4 isomeric ratio), and the hydrogenation
product was < 2%. The reactor was cooled, and the CO/H2 gas mixture was vented. After
evaporation of the solvent, a pure sample was obtained as a yellow-green oil by distillation
of the crude product at reduced pressure (0.1 mmHg, 120–125◦ C).

Reference 4k.
 REFERENCES 1519

A solution of 0.2 mol potassium tetracarbonylcobaltate(-I) in 300 mL water was placed in

a 1-L steel autoclave; then 120 mL concentrated phosphoric acid and 0.2 mol 1,4-pentadiene
were added without mixing, and the autoclave was closed, inverted to mix the reactants,
and rocked for 24 h. The vessel was opened under a stream of nitrogen, and 100 mL hexane
was added to extract the products. The hexane layer was separated, washed with distilled
water, dried over sodium sulfate, and transferred to a distillation apparatus. The hexane was
removed by aspirator vacuum; the product was distilled under high vacuum. The material
distilling at 45◦ C (1 mmHg) was collected as one fraction; the material distilling at 45◦ C
was predominantly π-(l-ethylallyl) tricarbonylcobaltate(-I). The first fraction was further
separated into two pure compounds in a Beckman Megchrom gas chromatograph equipped
with a silicone rubber column. The first component (8% yield) was identified as 5-hexenal.
The second component (22% yield) was identified as 2-methylcyclopentanone.

Other references related to the hydroformylation are cited in the literature.13

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