OXO ALDEHYDES AND ALCOHOLS

(Hydroformylation Reaction)

• Hydroformylation of olefins (OXO reaction) produces aldehydes with one

more carbon than the reacting olefin.

• For example, when ethylene is used, propionaldehyde is produced.

• This reaction is especially important for the production of higher aldehydes

that are further hydrogenated to the corresponding alcohols.
• The reaction is catalyzed with cobalt or rhodium complexes.

• Olefins with terminal double bonds are more reactive and produce aldehydes which
are hydrogenated to the corresponding primary alcohols.

• With olefins other than ethylene, the hydroformylation reaction mainly produces a
straight chain aldehyde with variable amounts of branched chain aldehydes.

• The reaction of propylene with CO and H2 produces n-butyraldehyde as the main

product. Isobutyraldehyde is a by-product:
• n-Butyraldehyde (n-butanal) is either hydrogenated to n-butanol or
transformed to 2-ethyl-hexanol via aldol condensation and subsequent
hydrogenation.

• n-Butanol is primarily used as a solvent or as an esterifying agent.

• The ester with acrylic acid, for example, is used in the paint, adhesive, and
plastic industries.
 2-ETHYL HEXANOL
2-Ethylhexanol is a colorless liquid soluble in many organic solvents.

It is one of the chemicals used for producing PVC plasticizers (by reacting with
phthalic acid or phthalic anhydride; the product is di-2-ethylhexyl phthalate
(DOP).
• Other olefins applied in the hydroformylation process with subsequent
hydrogenation are propylene trimer and tetramer for the production of decyl
and tridecyl alcohols, respectively, and C7 olefins (from copolymers of C3 and
C4 olefins) for isodecyl alcohol production.

• Propylene trimer (Nonene is the more commonly accepted name for

propylene trimer) and tetramer are oligomers produced by the polymerization
of propylene (tetramer is the preferred name for the branched C12 olefin).
• Several commercial processes are currently operative. Some use a rhodium
catalyst complex incorporating phosphine ligands HRhCO(PPh3)2 at relatively
lower temperatures and pressures and produce less branched aldehydes.

• Older processes use a cobalt carbonyl complex HCo(CO)4 at higher pressures

and temperatures and produce a higher ratio of the branched aldehydes.
 ETHYLENE GLYCOL (EG)
Ethylene glycol could be produced directly from synthesis gas using an Rh
catalyst at 230°C at very high pressure. In theory, five moles synthesis gas
mixture are needed to produce one mole ethylene glycol:

• Other routes have been tried starting from formaldehyde. One process reacts
formaldehyde with carbon monoxide and H2 (hydroformylation? why?) at
approximately 110°C using a rhodium triphenyl phosphine catalyst with the
intermediate formation of glycolaldehyde. Glycolaldehyde is then reduced to
ethylene glycol:
❖The DuPont process (the oldest syn. gas process to produce ethylene glycol)
reacts formaldehyde with CO in the presence of a strong acid.

❖The intermediate is glycolic acid, which is esterified with methanol. The ester
is then hydrogenated to ethylene glycol and methanol, which is recovered.
The net reaction from either process could be represented as:
❖Ethylene glycol (EG) is colorless syrupy liquid, and is very soluble in water.
Current world production of ethylene glycol is approximately 15 billion pounds.
Most of that is used for producing polyethylene terephthalate (PET) resins (for
fiber, film, bottles), antifreeze, and other products (approximately 25% of
plastic bottles are made from PET).