Processes for producing hydroxyaldehydes

This invention relates in part to processes for producing one or more substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, which comprise subjecting one or more substituted or unsubstituted alkadienes, e.g., butadiene, to hydrocarbonylation in the presence of a hydrocarbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and hydroformylation in the presence of a hydroformylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce one or more substituted or unsubstituted hydroxyaldehydes. The substituted and unsubstituted hydroxyaldehydes produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof, e.g., epsilon caprolactone. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted hydroxyaldehydes as principal product(s) of reaction.

This application claims the benefit of provisional U.S. patent application 
Ser. Nos. 60/016259, 60/016378, 60/016174 and 60/016263, all filed Apr. 
24, 1996, and all of the disclosures of which are incorporated herein by 
reference. 
BRIEF SUMMARY OF THE INVENTION 
1. Technical Field 
This invention relates in part to processes for selectively producing one 
or more substituted or unsubstituted hydroxyaldehydes, e.g., 
6-hydroxyhexanals. This invention also relates in part to reaction 
mixtures containing one or more substituted or unsubstituted 
hydroxyaldehydes, e.g., 6-hydroxyhexanals, as the principal product(s) of 
reaction. 
2. Background of the Invention 
Hydroxyaldehydes, e.g., 6-hydroxyhexanals, are valuable intermediates which 
are useful, for example, in the production of epsilon caprolactone, 
epsilon caprolactam, adipic acid and 1, 6-hexanediol. The processes 
currently used to produce hydroxyaldehydes have various disadvantages. For 
example, the starting materials used to produce 6-hydroxyhexanals are 
relatively expensive. In addition, the selectivity to 6-hydroxyhexanals in 
prior art processes has been low. Accordingly, it would be desirable to 
selectively produce hydroxyaldehydes from a relatively inexpensive 
starting material and by a process which can be employed commercially. 
DISCLOSURE OF THE INVENTION 
It has been discovered that alkadienes or pentenals can be converted to 
linear hydroxyaldehydes in high selectivities. It has also been discovered 
that unsaturated alcohols, e.g., alcohols possessing internal olefinic 
unsaturation, can be hydroformylated to hydroxyaldehydes, e.g., terminal 
aldehydes, in high normal:branched isomer ratios, e.g., 3-penten-1-ols 
hydroformylated to 6-hydroxyhexanals in high normal:branched isomer 
ratios. In particular, it has been surprisingly discovered that butadiene 
can be converted to linear 6-hydroxyhexanals, e.g., 6-hydroxyhexanal, by 
employing catalysts having 
hydrocarbonylation/hydroformylation/isomerization capabilities. It has 
further been discovered that high selectivities and high normal:branched 
isomer ratios may result from conducting the hydrocarbonylation in the 
presence of a metal-ligand complex catalyst and optionally free ligand in 
which the ligand is preferably of high basicity and low steric bulk and in 
the presence of a promoter, i.e., an organic or inorganic compound with an 
ionizable hydrogen of pKa of from about 1 to about 35. 
This invention relates to processes for producing one or more substituted 
or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, which comprise 
subjecting one or more substituted or unsubstituted alkadienes, e.g., 
butadiene, to hydrocarbonylation in the presence of a hydrocarbonylation 
catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and 
hydroformylation in the presence of a hydroformylation catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, to produce one or more 
substituted or unsubstituted hydroxyaldehydes. 
This invention also relates to processes for producing one or more 
substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, 
which comprise subjecting one or more substituted or unsubstituted 
pentenals to hydrocarbonylation in the presence of a hydrocarbonylation 
catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to 
produce one or more substituted or unsubstituted hydroxyaldehydes. 
This invention further relates to processes for producing one or more 
substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, 
which comprise subjecting one or more substituted or unsubstituted 
unsaturated alcohols, preferably having at least 4 carbon atoms, e.g., 
penten-1-ols, to hydroformylation in the presence of a hydroformylation 
catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to 
produce said one or more substituted or unsubstituted hydroxyaldehydes. 
This invention yet further relates to processes for producing one or more 
substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, 
which comprise: (a) subjecting one or more substituted or unsubstituted 
alkadienes, e.g., butadiene, to hydrocarbonylation in the presence of a 
hydrocarbonylation catalyst, e.g., a metal-organophosphorus ligand complex 
catalyst, to produce one or more substituted or unsubstituted unsaturated 
alcohols; and (b) subjecting said one or more substituted or unsubstituted 
unsaturated alcohols to hydroformylation in the presence of a 
hydroformylation catalyst, e.g., a metal-organophosphorus ligand complex 
catalyst, to produce said one or more substituted or unsubstituted 
hydroxyaldehydes. The hydrocarbonylation reaction conditions in step (a) 
and the hydroformylation reaction conditions in step (b) may be the same 
or different, and the hydrocarbonylation catalyst in step (a) and the 
hydroformylation catalyst in step (b) may be the same or different. 
This invention also relates to processes for producing one or more 
substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, 
which comprises reacting one or more substituted or unsubstituted 
alkadienes, e.g., butadienes, with carbon monoxide and hydrogen in the 
presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and a promoter and 
optionally free ligand to produce one or more substituted or unsubstituted 
unsaturated alcohols, e.g., penten-1-ols, and reacting said one or more 
substituted or unsubstituted unsaturated alcohols with carbon monoxide and 
hydrogen in the presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and optionally free ligand 
to produce said one or more substituted or unsubstituted hydroxyaldehydes. 
In a preferred embodiment, the metal-ligand complex catalysts are 
metal-organophosphorus ligand complex catalysts and the promoter is the 
one or more starting materials, intermediates or products of the process. 
This invention further relates to processes for producing one or more 
substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, 
which comprises reacting one or more substituted or unsubstituted 
pentenals with carbon monoxide and hydrogen in the presence of a 
metal-ligand complex catalyst, e.g., a metal-organophosphorus ligand 
complex catalyst, and a promoter and optionally free ligand to produce one 
or more substituted or unsubstituted hydroxyaldehydes. In a preferred 
embodiment, the metal-ligand complex catalyst is a metal-organophosphorus 
ligand complex catalyst and the promoter is the one or more starting 
materials, intermediates or products of the process. 
This invention yet further relates to processes for producing one or more 
substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, 
which comprise reacting one or more substituted or unsubstituted 
unsaturated alcohols, preferably having at least 4 carbon atoms, e.g., 
penten-1-ols, with carbon monoxide and hydrogen in the presence of a 
metal-ligand complex catalyst, e.g., a metal-organophosphorus ligand 
complex catalyst, and optionally free ligand to produce said one or more 
substituted or unsubstituted hydroxyaldehydes. 
This invention also relates to processes for producing one or more 
substituted or unsubstituted hydroxyaldehydes, e.g., 6-hydroxyhexanals, 
which comprises: (a) reacting one or more substituted or unsubstituted 
alkadienes, e.g., butadienes, with carbon monoxide and hydrogen in the 
presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and a promoter and 
optionally free ligand to produce one or more substituted or unsubstituted 
unsaturated alcohols, e.g., penten-1-ols, and (b) reacting said one or 
more substituted or unsubstituted unsaturated alcohols with carbon 
monoxide and hydrogen in the presence of a metal-ligand complex catalyst, 
e.g., a metal-organophosphorus ligand complex catalyst, and optionally 
free ligand to produce said one or more substituted or unsubstituted 
hydroxyaldehydes. The hydrocarbonylation reaction conditions in step (a) 
and the hydroformylation reaction conditions in step (b) may be the same 
or different, and the hydrocarbonylation catalyst in step (a) and the 
hydroformylation catalyst in step (b) may be the same or different. 
This invention further relates in part to a process for producing a 
batchwise or continuously generated reaction mixture comprising: 
(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 
6-hydroxyhexanal; 
(2) optionally one or more substituted or unsubstituted penten-1-ols, e.g., 
cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 
trans-3-penten-1-ol and/or 4-penten-1-ol; 
(3) optionally one or more substituted or unsubstituted 5-hydroxypentanals 
and/or cyclic lactol derivatives thereof, e.g., 
2-methyl-5-hydroxypentanal; 
(4) optionally one or more substituted or unsubstituted 4-hydroxybutanals 
and/or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; 
(5) optionally one or more substituted or unsubstituted pentan-1-ols; 
(6) optionally one or more substituted or unsubstituted valeraldehydes; 
(7) optionally one or more substituted or unsubstituted pentenals, e.g., 
cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and/or 
4-pentenal; 
(8) optionally one or more substituted or unsubstituted 1,6-hexanedials, 
e.g., adipaldehyde; 
(9) optionally one or more substituted 1, 5-pentanedials, e.g., 
2-methylglutaraldehyde; 
(10) optionally one or more substituted 1,4-butanedials, e.g., 
2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and 
(11) one or more substituted or unsubstituted butadienes, e.g., butadiene; 
wherein the weight ratio of component (1) to the sum of components (2), 
(3), (4), (5), (6), (7), (8), (9) and (10) is greater than about 0.1, 
preferably greater than about 0.25, more preferably greater than about 
1.0; and the weight ratio of component (11) to the sum of components (1), 
(2), (3), (4), (5), (6), (7), (8), (9) and (10) is about 0 to about 100, 
preferably about 0.001 to about 50; 
which process comprises reacting one or more substituted or unsubstituted 
butadienes, e.g., butadiene, with carbon monoxide and hydrogen in the 
presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and a promoter and 
optionally free ligand to produce one or more substituted or unsubstituted 
penten-1-ols and reacting said one or more substituted or unsubstituted 
penten-1-ols with carbon monoxide and hydrogen in the presence of a 
metal-ligand complex catalyst, e.g., a metal-organophosphorus ligand 
complex catalyst, and optionally free ligand to produce said batchwise or 
continuously generated reaction mixture. In a preferred embodiment, the 
metal-ligand complex catalysts are metal-organophosphorus ligand complex 
catalysts and the promoter is the one or more starting materials, 
intermediates or products of the process. 
This invention yet further relates in part to a process for producing a 
batchwise or continuously generated reaction mixture comprising: 
(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 
6-hydroxyhexanal; 
(2) optionally one or more substituted or unsubstituted penten-1-ols, e.g., 
cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 
trans-3-penten-1-ol and/or 4-penten-1-ol; 
(3) optionally one or more substituted or unsubstituted 5-hydroxypentanals 
and/or cyclic lactol derivatives thereof, e.g., 
2-methyl-5-hydroxypentanal; 
(4) optionally one or more substituted or unsubstituted 4-hydroxybutanals 
and/or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; 
(5) optionally one or more substituted or unsubstituted pentan-1-ols; 
(6) optionally one or more substituted or unsubstituted valeraldehydes; and 
(7) one or more substituted or unsubstituted pentenals, e.g., 
cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and/or 
4-pentenal; 
wherein the weight ratio of component (1) to the sum of components (2), 
(3), (4), (5) and (6) is greater than about 0.1, preferably greater than 
about 0.25, more preferably greater than about 1.0; and the weight ratio 
of component (7) to the sum of components (1), (2), (3), (4), (5) and (6) 
is about 0 to about 100, preferably about 0.001 to about 50; which process 
comprises reacting one or more substituted or unsubstituted pentenals with 
carbon monoxide and hydrogen in the presence of a metal-ligand complex 
catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and a 
promoter and optionally free ligand to produce said batchwise or 
continuously generated reaction mixture. In a preferred embodiment, the 
metal-ligand complex catalyst is a metal-organophosphorus ligand complex 
catalyst and the promoter is the one or more starting materials, 
intermediates or products of the process. 
This invention also relates in part to a process for producing a batchwise 
or continuously generated reaction mixture comprising: 
(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 
6-hydroxyhexanal; 
(2) one or more substituted or unsubstituted penten-1-ols, e.g., 
cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 
trans-3-penten-1-ol and/or 4-penten-1-ol; 
(3) optionally one or more substituted or unsubstituted 5-hydroxypentanals 
and/or cyclic lactol derivatives thereof, e.g., 
2-methyl-5-hydroxypentanal; 
(4) optionally one or more substituted or unsubstituted 4-hydroxybutanals 
and/or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; 
and 
(5) optionally one or more substituted or unsubstituted valeraldehydes; 
wherein the weight ratio of component (1) to the sum of components (3), (4) 
and (5) is greater than about 0.1, preferably greater than about 0.25, 
more preferably greater than about 1.0; and the weight ratio of component 
(2) to the sum of components (1), (3), (4) and (5) is about 0 to about 
100, preferably about 0.001 to about 50; 
which process comprises reacting one or more substituted or unsubstituted 
penten-1-ols with carbon monoxide and hydrogen in the presence of a 
metal-ligand complex catalyst, e.g., a metal-organophosphorus ligand 
complex catalyst, and optionally free ligand to produce said batchwise or 
continuously generated reaction mixture. 
This invention further relates in part to a process for producing a 
batchwise or continuously generated reaction mixture comprising: 
(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 
6-hydroxyhexanal; 
(2) optionally one or more substituted or unsubstituted penten-1-ols, e.g., 
cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 
trans-3-penten-1-ol and/or 4-penten-1-ol; 
(3) optionally one or more substituted or unsubstituted 5-hydroxypentanals 
and/or cyclic lactol derivatives thereof, e.g., 
2-methyl-5-hydroxypentanal; 
(4) optionally one or more substituted or unsubstituted 4-hydroxybutanals 
and/or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; 
(5) optionally one or more substituted or unsubstituted pentan- 1-ols; 
(6) optionally one or more substituted or unsubstituted valeraldehydes; 
(7) optionally one or more substituted or unsubstituted pentenals, e.g., 
cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and/or 
4-pentenal; 
(8) optionally one or more substituted or unsubstituted 1,6-hexanedials, 
e.g., adipaldehyde; 
(9) optionally one or more substituted 1,5-pentanedials, e.g., 
2-methylglutaraldehyde; 
(10) optionally one or more substituted 1,4-butanedials, e.g., 
2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and 
(11) one or more substituted or unsubstituted butadienes, e.g., butadiene; 
wherein the weight ratio of component (1) to the sum of components (2), 
(3), (4), (5), (6), (7), (8), (9) and (10) is greater than about 0.1, 
preferably greater than about 0.25, more preferably greater than about 
1.0; and the weight ratio of component (11) to the sum of components (1), 
(2), (3), (4), (5), (6), (7), (8), (9) and (10) is about 0 to about 100, 
preferably about 0.001 to about 50; 
which process comprises: (a) reacting one or more substituted or 
unsubstituted butadienes, e.g., butadiene, with carbon monoxide and 
hydrogen in the presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and a promoter and 
optionally free ligand to produce one or more substituted or unsubstituted 
penten-1-ols, and (b) reacting said one or more substituted or 
unsubstituted penten-1-ols with carbon monoxide and hydrogen in the 
presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and optionally free ligand 
to produce said batchwise or continuously generated reaction mixture. The 
hydrocarbonylation reaction conditions in step (a) and the 
hydroformylation reaction conditions in step (b) may be the same or 
different, and the hydrocarbonylation catalyst in step (a) and the 
hydroformylation catalyst in step (b) may be the same or different. 
This invention yet further relates to a process for producing a reaction 
mixture comprising one or more substituted or unsubstituted 
hydroxyaldehydes, e.g., 6-hydroxyhexanals, which process comprises 
reacting one or more substituted or unsubstituted alkadienes, e.g., 
butadienes, with carbon monoxide and hydrogen in the presence of a 
metal-ligand complex catalyst, e.g., a metal-organophosphorus ligand 
complex catalyst, and a promoter and optionally free ligand to produce one 
or more substituted or unsubstituted unsaturated alcohols, e.g., 
penten-1-ols, and reacting said one or more substituted or unsubstituted 
unsaturated alcohols with carbon monoxide and hydrogen in the presence of 
a metal-ligand complex catalyst, e.g., a metal-organophosphorus ligand 
complex catalyst, and optionally free ligand to produce said reaction 
mixture comprising one or more substituted or unsubstituted 
hydroxyaldehydes. In a preferred embodiment, the metal-ligand complex 
catalysts are metal-organophosphorus ligand complex catalysts and the 
promoter is the one or more starting materials, intermediates or products 
of the process. 
This invention also relates to a process for producing a reaction mixture 
comprising one or more substituted or unsubstituted hydroxyaldehydes, 
e.g., 6-hydroxyhexanals, which process comprises reacting one or more 
substituted or unsubstituted pentenals with carbon monoxide and hydrogen 
in the presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and a promoter and 
optionally free ligand to produce said reaction mixture comprising one or 
more substituted or unsubstituted hydroxyaldehydes. In a preferred 
embodiment, the metal-ligand complex catalyst is a metal-organophosphorus 
ligand complex catalyst and the promoter is the one or more starting 
materials, intermediates or products of the process. 
This invention further relates to a process for producing a reaction 
mixture comprising one or more substituted or unsubstituted 
hydroxyaldehydes, e.g., 6-hydroxyhexanals, which process comprises 
reacting one or more substituted or unsubstituted unsaturated alcohols, 
preferably having at least 4 carbon atoms, e.g., penten-1-ols, with carbon 
monoxide and hydrogen in the presence of a metal-ligand complex catalyst, 
e.g., a metal-organophosphorus ligand complex catalyst, and optionally 
free ligand to produce said reaction mixture comprising one or more 
substituted or unsubstituted hydroxyaldehydes. 
This invention yet further relates to a process for producing a reaction 
mixture comprising one or more substituted or unsubstituted 
hydroxyaldehydes, e.g., 6-hydroxyhexanals, which process comprises: (a) 
reacting one or more substituted or unsubstituted alkadienes, e.g., 
butadienes, with carbon monoxide and hydrogen in the presence of a 
metal-ligand complex catalyst, e.g., a metal-organophosphorus ligand 
complex catalyst, and a promoter and optionally free ligand to produce one 
or more substituted or unsubstituted unsaturated alcohols, e.g., 
penten-1-ols, and (b) reacting said one or more substituted or 
unsubstituted unsaturated alcohols with carbon monoxide and hydrogen in 
the presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and optionally free ligand 
to produce said reaction mixture comprising one or more substituted or 
unsubstituted hydroxyaldehydes. The hydrocarbonylation reaction conditions 
in step (a) and the hydroformylation reaction conditions in step (b) may 
be the same or different, and the hydrocarbonylation catalyst in step (a) 
and the hydroformylation catalyst in step (b) may be the same or 
different. 
The processes of this invention can achieve high selectivities of 
alkadienes, pentenals and penten-1-ols to 6-hydroxyhexanals, i.e., 
selectivities of penten-1-ols to 6-hydroxyhexanals of at least 10% by 
weight and up to 85% by weight or greater may be achieved by the processes 
of this invention. Also, the processes of this invention can achieve high 
normal:branched isomer ratios, e.g., butadiene 
hydrocarbonylated/hydroformylated to 6-hydroxyhexanals in high 
normal:branched isomer ratios. 
This invention also relates in part to a batchwise or continuously 
generated reaction mixture comprising: 
(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 
6-hydroxyhexanal; 
(2) one or more substituted or unsubstituted penten-1-ols, e.g., 
cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 
trans-3-penten-1-ol and/or 4-penten-1-ol; 
(3) optionally one or more substituted or unsubstituted 5-hydroxypentanals 
and/or cyclic lactol derivatives thereof, e.g., 
2-methyl-5-hydroxypentanal; 
(4) optionally one or more substituted or unsubstituted 4-hydroxybutanals 
and/or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; 
and 
(5) optionally one or more substituted or unsubstituted valeraldehydes; 
wherein the weight ratio of component (1) to the sum of components (3), (4) 
and (5) is greater than about 0.1, preferably greater than about 0.25, 
more preferably greater than about 1.0; and the weight ratio of component 
(2) to the sum of components (1), (3), (4) and (5) is about 0 to about 
100, preferably about 0.001 to about 50. 
This invention further relates in part to a batchwise or continuously 
generated reaction mixture comprising: 
(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 
6-hydroxyhexanal; 
(2) optionally one or more substituted or unsubstituted penten-1-ols, e.g., 
cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 
trans-3-penten-1-ol and/or 4-penten-1-ol; 
(3) optionally one or more substituted or unsubstituted 5-hydroxypentanals 
and/or cyclic lactol derivatives thereof, e.g., 
2-methyl-5-hydroxypentanal; 
(4) optionally one or more substituted or unsubstituted 4-hydroxybutanals 
and/or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; 
(5) optionally one or more substituted or unsubstituted pentan-1-ols; 
(6) optionally one or more substituted or unsubstituted valeraldehydes; and 
(7) optionally one or more substituted or unsubstituted pentenals, e.g., 
cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and/or 
4-pentenal; 
wherein the weight ratio of component (1) to the sum of components (2), 
(3), (4), (5) and (6) is greater than about 0.1, preferably greater than 
about 0.25, more preferably greater than about 1.0; and the weight ratio 
of component (7) to the sum of components (1), (2), (3), (4), (5) and (6) 
is about 0 to about 100, preferably about 0.001 to about 50. 
This invention yet further relates in part to a batchwise or continuously 
generated reaction mixture comprising: 
(1) one or more substituted or unsubstituted 6-hydroxyhexanals, e.g., 
6-hydroxyhexanal; 
(2) optionally one or more substituted or unsubstituted penten-1-ols, e.g., 
cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol, 
trans-3-penten-1-ol and/or 4-penten-1-ol; 
(3) optionally one or more substituted or unsubstituted 5-hydroxypentanals 
and/or cyclic lactol derivatives thereof, e.g., 
2-methyl-5-hydroxypentanal; 
(4) optionally one or more substituted or unsubstituted 4-hydroxybutanals 
and/or cyclic lactol derivatives thereof, e.g., 2-ethyl-4-hydroxybutanal; 
(5) optionally one or more substituted or unsubstituted pentan- 1-ols; 
(6) optionally one or more substituted or unsubstituted valeraldehydes; 
(7) optionally one or more substituted or unsubstituted pentenals, e.g., 
cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, trans-3-pentenal and/or 
4-pentenal; 
(8) optionally one or more substituted or unsubstituted 1,6-hexanedials, 
e.g., adipaldehyde; 
(9) optionally one or more substituted 1,5-pentanedials, e.g., 
2-methylglutaraldehyde; 
(10) optionally one or more substituted 1,4-butanedials, e.g., 
2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and 
(11) one or more substituted or unsubstituted butadienes, e.g., butadiene; 
wherein the weight ratio of component (1) to the sum of components (2), 
(3), (4), (5), (6), (7), (8), (9) and (10) is greater than about 0.1, 
preferably greater than about 0.25, more preferably greater than about 
1.0; and the weight ratio of component (11) to the sum of components (1), 
(2), (3), (4), (5), (6), (7), (8), (9) and (10) is about 0 to about 100, 
preferably about 0.001 to about 50. 
This invention also relates in part to a reaction mixture comprising one or 
more substituted or unsubstituted hydroxyaldehydes, e.g., 
6-hydroxyhexanals, in which said reaction mixture is prepared by a process 
which comprises reacting one or more substituted or unsubstituted 
alkadienes, e.g., butadienes, with carbon monoxide and hydrogen in the 
presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and a promoter and 
optionally free ligand to produce one or more substituted or unsubstituted 
unsaturated alcohols, e.g., penten-1-ols, and reacting said one or more 
substituted or unsubstituted unsaturated alcohols with carbon monoxide and 
hydrogen in the presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and optionally free ligand 
to produce said reaction mixture comprising one or more substituted or 
unsubstituted hydroxyaldehydes. In a preferred embodiment, the 
metal-ligand complex catalysts are metal-organophosphorus ligand complex 
catalysts and the promoter is the one or more starting materials, 
intermediates or products of the process. 
This invention further relates in part to a reaction mixture comprising one 
or more substituted or unsubstituted hydroxyaldehydes, e.g., 
6-hydroxyhexanals, in which said reaction mixture is prepared by a process 
which comprises reacting one or more substituted or unsubstituted 
pentenals with carbon monoxide and hydrogen in the presence of a 
metal-ligand complex catalyst, e.g., a metal-organophosphorus ligand 
complex catalyst, and a promoter and optionally free ligand to produce 
said reaction mixture comprising one or more substituted or unsubstituted 
hydroxyaldehydes. In a preferred embodiment, the metal-ligand complex 
catalyst is a metal-organophosphorus ligand complex catalyst and the 
promoter is the one or more starting materials, intermediates or products 
of the process. 
This invention yet further relates in part to a reaction mixture comprising 
one or more substituted or unsubstituted hydroxyaldehydes, e.g., 
6-hydroxyhexanals, in which said reaction mixture is prepared by a process 
which comprises reacting one or more substituted or unsubstituted 
unsaturated alcohols, preferably having at least 4 carbon atoms, e.g., 
penten-1-ols, with carbon monoxide and hydrogen in the presence of a 
metal-ligand complex catalyst, e.g., a metal-organophosphorus ligand 
complex catalyst, and optionally free ligand to produce said reaction 
mixture comprising one or more substituted or unsubstituted 
hydroxyaldehydes. 
This invention also relates in part to a reaction mixture comprising one or 
more substituted or unsubstituted hydroxyaldehydes, e.g., 
6-hydroxyhexanals, in which said reaction mixture is prepared by a process 
which comprises: (a) reacting one or more substituted or unsubstituted 
alkadienes, e.g., butadienes, with carbon monoxide and hydrogen in the 
presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and a promoter and 
optionally free ligand to produce one or more substituted or unsubstituted 
unsaturated alcohols, e.g., penten-1-ols, and (b) reacting said one or 
more substituted or unsubstituted unsaturated alcohols with carbon 
monoxide and hydrogen in the presence of a metal-ligand complex catalyst, 
e.g., a metal-organophosphorus ligand complex catalyst, and optionally 
free ligand to produce said reaction mixture comprising one or more 
substituted or unsubstituted hydroxyaldehydes. The hydrocarbonylation 
reaction conditions in step (a) and the hydroformylation reaction 
conditions in step (b) may be the same or different, and the 
hydrocarbonylation catalyst in step (a) and the hydroformylation catalyst 
in step (b) may be the same or different. 
The reaction mixtures of this invention are distinctive insofar as the 
processes for their preparation achieve the generation of high 
selectivities of 6-hydroxyhexanals in a manner which can be suitably 
employed in a commercial process for the manufacture of 6-hydroxyhexanals. 
In particular, the reaction mixtures of this invention are distinctive 
insofar as the processes for their preparation allow for the production of 
6-hydroxyhexanals in relatively high yields without generating large 
amounts of byproducts, e.g., pentanols and valeraldehyde. 
Detailed Description 
Hydrocarbonylation Stage or Step 
The hydrocarbonylation stage or step of this invention involves converting 
one or more substituted or unsubstituted alkadienes to one or more 
substituted or unsubstituted unsaturated alcohols and/or converting one or 
more substituted or unsubstituted pentenals to one or more substituted or 
unsubstituted hydroxyaldehydes. The hydrocarbonylation stage or step of 
this invention may be conducted in one or more steps or stages, preferably 
a one step process. As used herein, the term "hydrocarbonylation" is 
contemplated to include all permissible hydrocarbonylation processes which 
involve converting one or more substituted or unsubstituted alkadienes to 
one or more substituted or unsubstituted unsaturated alcohols and/or 
converting one or more substituted or unsubstituted pentenals to one or 
more substituted or unsubstituted hydroxyaldehydes. In general, the 
hydrocarbonylation step or stage comprises reacting one or more 
substituted or unsubstituted alkadienes, e.g., butadienes, with carbon 
monoxide and hydrogen in the presence of a metal-ligand complex catalyst, 
e.g., a metal-organophosphorus ligand complex catalyst, and a promoter and 
optionally free ligand to produce one or more substituted or unsubstituted 
unsaturated alcohols, e.g., penten-1-ols and/or reacting one or more 
substituted or unsubstituted pentenals with carbon monoxide and hydrogen 
in the presence of a metal-ligand complex catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, and a promoter and 
optionally free ligand to produce one or more substituted or unsubstituted 
hydroxyaldehydes, e.g., 6-hydroxyhexanal. A preferred hydrocarbonylation 
process useful in this invention is disclosed in U.S. patent application 
Ser. No. (D-17761), filed on an even date herewith, the disclosure of 
which is incorporated herein by reference. 
The hydrocarbonylation stage or step involves the production of unsaturated 
alcohols or hydroxyaldehydes by reacting an alkadiene or pentenals with 
carbon monoxide and hydrogen in the presence of a metal-ligand complex 
catalyst and optionally free ligand in a liquid medium that also contains 
a promoter. The reaction may be carried out in a continuous single pass 
mode in a continuous gas recycle manner or more preferably in a continuous 
liquid catalyst recycle manner as described below. The hydrocarbonylation 
processing techniques employable herein may correspond to any known 
processing techniques. 
The hydrocarbonylation process mixtures employable herein includes any 
solution derived from any corresponding hydrocarbonylation process that 
may contain at least some amount of four different main ingredients or 
components, i.e., the unsaturated alcohol or hydroxyaldehyde product, a 
metal-ligand complex catalyst, a promoter and optionally free ligand, said 
ingredients corresponding to those employed and/or produced by the 
hydrocarbonylation process from whence the hydrocarbonylation process 
mixture starting material may be derived. By "free ligand" is meant 
organophosphorus ligand that is not complexed with (tied to or bound to) 
the metal, e.g., rhodium atom, of the complex catalyst. It is to be 
understood that the hydrocarbonylation process mixture compositions 
employable herein can and normally will contain minor amounts of 
additional ingredients such as those which have either been deliberately 
employed in the hydrocarbonylation process or formed in situ during said 
process. Examples of such ingredients that can also be present include 
unreacted alkadiene or pentenal starting materials, carbon monoxide and 
hydrogen gases, and in situ formed type products, such as saturated 
alcohols and/or unreacted isomerized olefins corresponding to the 
alkadiene or pentenal starting materials, and high boiling liquid 
byproducts, as well as other inert co-solvent type materials or 
hydrocarbon additives, if employed. 
The catalysts useful in the hydrocarbonylation stage or step include 
metal-ligand complex catalysts. The permissible metals which make up the 
metal-ligand complexes include Group 8, 9 and 10 metals selected from 
rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel 
(Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, 
with the preferred metals being rhodium, cobalt, iridium and ruthenium, 
more preferably rhodium, cobalt and ruthenium, especially rhodium. The 
permissible ligands include, for example, organophosphorus, organoarsenic 
and organoantimony ligands, or mixtures thereof, preferably 
organophosphorus ligands. The permissible organophosphorus ligands which 
make up the metal-organophosphorus ligand complexes and free 
organophosphorus ligand include mono-, di-, tri- and higher 
poly-(organophosphorus) compounds, preferably those of high basicity and 
low steric bulk. Illustrative permissible organophosphorus ligands 
include, for example, organophosphines, organophosphites, 
organophosphonites, organophosphinites, organophosphorus 
nitrogen-containing ligands, organophosphorus sulfur-containing ligands, 
organophosphorus silicon-containing ligands and the like. Other 
permissible ligands include, for example, heteroatom-containing ligands 
such as described in U.S. patent application Ser. No. (D-17646-1), filed 
Mar. 10, 1997, the disclosure of which is incorporated herein by 
reference. Mixtures of such ligands may be employed if desired in the 
metal-ligand complex catalyst and/or free ligand and such mixtures may be 
the same or different. It is to be noted that the successful practice of 
this invention does not depend and is not predicated on the exact 
structure of the metal-ligand complex species, which may be present in 
their mononuclear, dinuclear and/or higher nuclearity forms. Indeed, the 
exact structure is not known. Although it is not intended herein to be 
bound to any theory or mechanistic discourse, it appears that the 
catalytic species may in its simplest form consist essentially of the 
metal in complex combination with the ligand and carbon monoxide when 
used. 
The term "complex" as used herein and in the claims means a coordination 
compound formed by the union of one or more electronically rich molecules 
or atoms capable of independent existence with one or more electronically 
poor molecules or atoms, each of which is also capable of independent 
existence. For example, the ligands employable herein, i.e., 
organophosphorus ligands, may possess one or more phosphorus donor atoms, 
each having one available or unshared pair of electrons which are each 
capable of forming a coordinate covalent bond independently or possibly in 
concert (e.g., via chelation) with the metal. Carbon monoxide (which is 
also properly classified as a ligand) can also be present and complexed 
with the metal. The ultimate composition of the complex catalyst may also 
contain an additional ligand, e.g., hydrogen or an anion satisfying the 
coordination sites or nuclear charge of the metal. Illustrative additional 
ligands include, e.g., halogen (Cl, Br, I), alkyl, aryl, substituted aryl, 
acyl, CF.sub.3, C.sub.2 F.sub.5, CN, (R).sub.2 PO and RP(O)(OH)O (wherein 
each R is the same or different and is a substituted or unsubstituted 
hydrocarbon radical, e.g., the alkyl or aryl), acetate, acetylacetonate, 
SO.sub.4, BF.sub.4, PF.sub.6, NO.sub.2, NO.sub.3, CH.sub.3 O, CH.sub.2 
.dbd.CHCH.sub.2, CH.sub.3 CH.dbd.CHCH.sub.2, C.sub.6 H.sub.5 CN, CH.sub.3 
CN, NO, NH.sub.3, pyridine, (C.sub.2 H.sub.5).sub.3 N, mono-olefins, 
diolefins and triolefins, tetrahydrofuran, and the like. It is of course 
to be understood that the complex species are preferably free of any 
additional organic ligand or anion that might poison the catalyst and have 
an undue adverse effect on catalyst performance. It is preferred in the 
metal-ligand complex catalyzed hydrocarbonylation process that the active 
catalysts be free of halogen and sulfur directly bonded to the metal, 
although such may not be absolutely necessary. Preferred metal-ligand 
complex catalysts include rhodium-organophosphine ligand complex 
catalysts. 
The number of available coordination sites on such metals is well known in 
the art. Thus the catalytic species may comprise a complex catalyst 
mixture, in their monomeric, dimeric or higher nuclearity forms, which are 
preferably characterized by at least one phosphorus-containing molecule 
complexed per metal, e.g., rhodium. As noted above, it is considered that 
the catalytic species of the preferred catalyst employed in the 
hydrocarbonylation process may be complexed with carbon monoxide and 
hydrogen in addition to the organophosphorus ligands in view of the carbon 
monoxide and hydrogen gas employed by the hydrocarbonylation process. 
Among the organophosphines that may serve as the ligand of the 
metal-organophosphine complex catalyst and/or free organophosphine ligand 
of the hydrocarbonylation process mixture starting materials are mono-, 
di-, tri- and poly-(organophosphines) such as triorganophosphines, 
trialkylphosphines, alkyldiarylphosphines, dialkylarylphosphines, 
dicycloalkylarylphosphines, cycloalkyldiarylphosphines, 
triaralkylphosphines, tricycloalkylphosphines, and triarylphosphines, 
alkyl and/or aryl diphosphines and bisphosphine mono oxides, as well as 
ionic triorganophosphines containing at least one ionic moiety selected 
from the salts of sulfonic acid, of carboxylic acid, of phosphonic acid 
and of quaternary ammonium compounds, and the like. Of course any of the 
hydrocarbon radicals of such tertiary non-ionic and ionic organophosphines 
may be substituted if desired, with any suitable substitutent that does 
not unduly adversely affect the desired result of the hydrocarbonylation 
process. The organophosphine ligands employable in the hydrocarbonylation 
process and/or methods for their preparation are known in the art. 
Illustrative triorganophosphine ligands may be represented by the formula: 
##STR1## 
wherein each R.sup.1 is the same or different and is a substituted or 
unsubstituted monovalent hydrocarbon radical, e.g., an alkyl, cycloalkyl 
or aryl radical. In a preferred embodiment, each R.sup.1 is the same or 
different and is selected from primary alkyl, secondary alkyl, tertiary 
alkyl and aryl. Suitable hydrocarbon radicals may contain from 1 to 24 
carbon atoms or greater. Illustrative substituent groups that may be 
present on the hydrocarbon radicals include, e.g., substituted or 
unsubstituted alkyl radicals, substituted or unsubstituted alkoxy 
radicals, substituted or unsubstituted silyl radicals such as 
--Si(R.sup.2).sub.3 ; amino radicals such as --N(R.sup.2).sub.2 ; acyl 
radicals such as --C(O)R.sup.2 ; carboxy radicals such as --C(O)OR.sup.2 ; 
acyloxy radicals such as --OC(O)R.sup.2 ; amido radicals such as 
--C(O)N(R.sup.2).sub.2 and --N(R.sup.2)C(O)R.sup.2 ; ionic radicals such 
as --SO.sub.3 M wherein M represents inorganic or organic cationic atoms 
or radicals; sulfonyl radicals such as --SO.sub.2 R.sup.2 ; ether radicals 
such as --OR.sup.2 ; sulfinyl radicals such as --SOR.sup.2 ; selenyl 
radicals such as --SeR.sup.2 ; sulfenyl radicals such as --SR.sup.2 as 
well as halogen, nitro, cyano, trifluoromethyl and hydroxy radicals, and 
the like, wherein each R.sup.2 individually represents the same or 
different substituted or unsubstituted monovalent hydrocarbon radical, 
with the proviso that in amino substituents such as --N(R.sup.2).sub.2, 
each R.sup.2 taken together can also represent a divalent bridging group 
that forms a heterocyclic radical with the nitrogen atom and in amido 
substituents such as C(O)N(R.sup.2).sub.2 and --N(R.sup.2)C(O)R.sup.2 each 
--R.sup.2 bonded to N can also be hydrogen. Illustrative alkyl radicals 
include, e.g., methyl, ethyl, propyl, butyl, octyl, cyclohexyl, isopropyl 
and the like. Illustrative aryl radicals include, e.g., phenyl, naphthyl, 
fluorophenyl, difluorophenyl, benzoyloxyphenyl, carboethoxyphenyl, 
acetylphenyl, ethoxyphenyl, phenoxyphenyl, hydroxyphenyl; carboxyphenyl, 
trifluoromethylphenyl, methoxyethylphenyl, acetamidophenyl, 
dimethylcarbamylphenyl, tolyl, xylyl, 4-dimethylaminophenyl, 
2,4,6-trimethoxyphenyl and the like. 
Illustrative specific organophosphines include, e.g., trimethylphosphine, 
triethylphosphine, tributylphosphine, trioctylphosphine, 
diethylbutylphosphine, diethyl-n-propylphosphine, 
diethylisopropylphosphine, diethylbenzylphosphine, 
diethylcyclopentylphosphine, diethylcyclohexylphosphine, 
triphenylphosphine, tris-p-tolylphosphine, tris-p-methoxyphenylphosphine, 
tris-dimethylaminophenylphosphine, propyldiphenylphosphine, 
t-butyldiphenylphosphine, n-butyldiphenylphosphine, 
n-hexyldiphenylphosphine, cyclohexyldiphenylphosphine, 
dicyclohexylphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, 
DIOP, i.e., (4R,5R)-(-)-O-isopropylidene-2,3-dihydroxy- 
1,4-bis(diphenylphosphino)butane and/or (4S,5S 
)-(+)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane 
and/or 
(4S,5R)-(-)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butan 
e, substituted or unsubstituted bicyclic bisphosphines such as 
1,2-bis(1,4-cyclooctylenephosphino)ethane, 
1,3-bis(1,4-cyclooctylenephosphino)propane, 
1,3-bis(1,5-cyclooctylenephosphino)propane and 
1,2-bis(2,6-dimethyl-1,4-cyclooctylenephosphino)ethane, substituted or 
unsubstituted bis(2,2'-diphenylphosphinomethyl)biphenyl such as 
bis(2,2'-diphenylphosphinomethyl)biphenyl and bis2,2'-di(4-fluorophenyl 
)phosphinomethyl)biphenyl, MeC(CH.sub.2 PPh.sub.2).sub.3 (triphos), 
NaO.sub.3 S(C.sub.6 H.sub.4)CH.sub.2 C(CH.sub.2 PPh.sub.2).sub.3 
(sulphos), bis(diphenylphosphino)ferrocene, 
bis(diisopropylphosphino)ferrocene, bis(diphenylphosphino)ruthenocene, as 
well as the alkali and alkaline earth metal salts of sulfonated 
triphenylphosphines, e.g., of (tri-m-sulfophenyl)phosphine and of 
(m-sulfophenyl)diphenyl-phosphine and the like. 
The preferred organophosphorus ligands which make up the 
metal-organophosphorus ligand complex catalysts and free organophosphorus 
ligands are high basicity ligands. In general, the basicity of the 
organophosphorus ligands should be greater than or equal to the basicity 
of triphenylphosphine (pKb of 2.74), e.g., from about 2.74 to about 15. 
Suitable organophosphorus ligands have a pKb of about 3 or greater, 
preferably a pKb of about 3 to about 12, and more preferably a pKb of 
about 5 to about 12. pKb values for illustrative organophosphorus ligands 
useful in this invention are given in the Table I below. In addition, the 
organophosphorus ligands useful in this invention have a steric bulk 
sufficient to promote the hydrocarbonylation reaction. The steric bulk of 
monodentate organophosphorus ligands should be lower than or equal to a 
Tolman cone angle of 210.degree., preferably lower than or equal to the 
steric bulk of tricyclohexylphosphine (Tolman cone angle=170.degree.). 
Organophosphorus ligands having desired basicity and steric bulk include, 
for example, substituted or unsubstituted tri-primary-alkylphosphines 
(e.g., trioctylphosphine, diethylbutylphosphine, 
diethylisobutylphosphine), di-primary-alkylarylphosphines (e.g., 
diethylphenylphosphine, diethyl-p-N,N-dimethylphenylphosphine), 
di-primary-alkyl-mono-secondary-alkylphosphines (e.g., 
diethylisopropylphosphine, diethylcyclohexylphosphine), 
di-primary-alkyl-tert-alkylphosphines (e.g., diethyl-tert-butylphosphine), 
mono-primary-alkyl-diarylphosphines (e.g., diphenylmethylphosphine), 
mono-primary-alkyl-di-secondary-alkylphosphines (e.g., 
dicyclohexylethylphosphine), triarylphosphines (e.g., 
tri-para-N,N-dimethylaminophenylphosphine), tri-secondarylalkylphosphines 
(e.g., tricyclohexylphosphine), 
mono-primaryalkyl-mono-secondaryalkyl-mono-tertiary alkylphosphines (e.g., 
ethylisopropyltert-butylphosphine) and the like. The permissible 
organophosphorus ligands may be substituted with any suitable 
functionalities and may include the promoter as described hereinbelow. 
TABLE I 
______________________________________ 
Organophosphorus Ligand pKb 
______________________________________ 
Trimethylphosphine 8.7 
Triethylphosphine 8.7 
Tri-n-propylphosphine 8.7 
Tri-n-butylphosphine 8.4 
Tri-n-octylphosphine 8.4 
Tri-tert-butylphosphine 11.4 
Diethyl-tert-butylphosphine 
10.1 
Tricyclohexylphosphine 10 
Diphenylmethylphosphine 4.5 
Diethylphenylphosphine 6.4 
Diphenylcyclohexylphosphine 
5 
Diphenylethylphosphine 4.9 
Tri(p-methoxyphenyl)phosphine 
4.6 
Triphenylphosphine 2.74 
Tri(p-N,N-dimethylaminophenyl)phosphine 
8.65 
Tri(p-methylphenyl)phosphine 
3.84 
______________________________________ 
More particularly, illustrative metal-organophosphine complex catalysts and 
illustrative free organophosphine ligands include, for example, those 
disclosed in U.S. Pat. Nos. 3,239,566, 3,527,809; 4,148,830; 4,247,486; 
4,283,562; 4,400,548; 4,482,749, 4,861,918 and U.S. patent application 
Ser. No. (D-17459-1), filed on an even date herewith, the disclosures of 
which are incorporated herein by reference. 
Other illustrative permissible organophosphorus ligands which may make up 
the metal-organophosphorus ligand complexes and free organophosphorus 
ligands include, for example, those disclosed in U.S. Pat. Nos. 4,567,306, 
4,599,206, 4,668,651, 4,717,775, 3,415,906, 4,567,306, 4,599,206, 
4,748,261, 4,769,498, 4,717,775, 4,885,401, 5,202,297, 5,235,113, 
5,254,741, 5,264,616, 5,312,996, 5,364,950 and 5,391,801, the disclosures 
of which are incorporated herein by reference. Still other illustrative 
permissible organophosphorus ligands which may make up the 
metal-organophosphorus ligand complexes and free organophosphorus ligands 
include those described in the hydroformylation section below. 
The metal-ligand complex catalysts employable in the hydrocarbonylation 
step or stage may be formed by methods more fully disclosed in the 
hydroformylation section hereinbelow. The metal-ligand complex catalysts 
may be in homogeneous or heterogeneous form as more fully disclosed in the 
hydroformylation section hereinbelow. 
As noted the hydrocarbonylation stage or step involves the use of a 
metal-ligand complex catalyst as described herein. Of course mixtures of 
such catalysts can also be employed if desired. The amount of metal-ligand 
complex catalyst present in the reaction medium of a given 
hydrocarbonylation process need only be that minimum amount necessary to 
provide the given metal concentration desired to be employed and which 
will furnish the basis for at least the catalytic amount of metal 
necessary to catalyze the particular hydrocarbonylation process involved 
such as disclosed, for example, in the above-mentioned patents. In 
general, the catalyst concentration can range from several parts per 
million to several percent by weight. Organophosphorus ligands can be 
employed in the above-mentioned catalysts in a molar ratio of generally 
from about 0.5:1 or less to about 1000:1 or greater. The catalyst 
concentration will be dependent on the hydrocarbonylation process 
conditions and solvent employed. 
In general, the organophosphorus ligand concentration in hydrocarbonylation 
process mixtures may range from between about 0.005 and 25 weight percent 
based on the total weight of the reaction mixture. Preferably the ligand 
concentration is between 0.01 and 15 weight percent, and more preferably 
is between about 0.05 and 10 weight percent on that basis. 
In general, the concentration of the metal in the hydrocarbonylation 
process mixtures may be as high as about 2000 parts per million by weight 
or greater based on the weight of the reaction mixture. Preferably the 
metal concentration is between about 50 and 1500 parts per million by 
weight based on the weight of the reaction mixture, and more preferably is 
between about 70 and 1200 parts per million by weight based on the weight 
of the reaction mixture. 
In addition to the metal-ligand complex catalyst, free ligand (i.e., ligand 
that is not complexed with the rhodium metal) may also be present in the 
hydrocarbonylation stage or step medium. The free ligand may correspond to 
any of the above-defined phosphorus-containing ligands discussed above as 
employable herein. It is preferred that the free ligand be the same as the 
ligand of the metal-ligand complex catalyst employed. However, such 
ligands need not be the same in any given process. The hydrocarbonylation 
process may involve up to 100 moles, or higher, of free ligand per mole of 
metal in the hydrocarbonylation process medium. Preferably the 
hydrocarbonylation stage or step is carried out in the presence of from 
about 1 to about 50 moles of coordinatable phosphorus, more preferably 
from about 1 to about 20 moles of coordinatable phosphorus, and most 
preferably from about 1 to about 8 moles of coordinatable phosphorus, per 
mole of metal present in the reaction medium; said amounts of 
coordinatable phosphorus being the sum of both the amount of coordinatable 
phosphorus that is bound (complexed) to the rhodium metal present and the 
amount of free (non-complexed) coordinatable phosphorus present. Of 
course, if desired, make-up or additional coordinatable phosphorus can be 
supplied to the reaction medium of the hydrocarbonylation process at any 
time and in any suitable manner, e.g. to maintain a predetermined level of 
free ligand in the reaction medium. 
The substituted and unsubstituted alkadiene starting materials useful in 
the hydrocarbonylation stage or step include, but are not limited to, 
conjugated aliphatic diolefins represented by the formula: 
##STR2## 
wherein R.sub.1 and R.sub.2 are the same or different and are hydrogen, 
halogen or a substituted or unsubstituted hydrocarbon radical. The 
alkadienes can be linear or branched and can contain substituents (e.g., 
alkyl groups, halogen atoms, amino groups or silyl groups). Illustrative 
of suitable alkadiene starting materials are butadiene, isoprene, dimethyl 
butadiene, cyclopentadiene and chloroprene. Most preferably, the alkadiene 
starting material is butadiene itself (CH.sub.2 .dbd.CH-CH.dbd.CH.sub.2). 
For purposes of this invention, the term "alkadiene" is contemplated to 
include all permissible substituted and unsubstituted conjugated 
diolefins, including all permissible mixtures comprising one or more 
substituted and unsubstituted conjugated diolefins. Illustrative of 
suitable substituted and unsubstituted alkadienes (including derivatives 
of alkadienes) include those permissible substituted and unsubstituted 
alkadienes described in Kirk-Othmer, Encyclopedia of Chemical Technology, 
Fourth Edition, 1996, the pertinent portions of which are incorporated 
herein by reference. 
Illustrative substituted and unsubstituted pentenal starting materials that 
can be used in the processes of this invention include one or more of the 
following: cis-2-pentenal, trans-2-pentenal, cis-3-pentenal, 
trans-3-pentenal, and/or 4-pentenal, including mixtures of one or more of 
the above pentenals. Illustrative of suitable substituted and 
unsubstituted pentenals (including derivatives of pentenals) include those 
permissible substituted and unsubstituted pentenals which are described in 
Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition, 1996, 
the pertinent portions of which are incorporated herein by reference. 
The particular hydrocarbonylation reaction conditions are not narrowly 
critical and can be any effective hydrocarbonylation procedures sufficient 
to produce one or more unsaturated alcohols or hydroxyaldehydes. The exact 
reaction conditions will be governed by the best compromise between 
achieving high catalyst selectivity, activity, lifetime and ease of 
operability, as well as the intrinsic reactivity of the starting materials 
in question and the stability of the starting materials and the desired 
reaction product to the reaction conditions. The hydrocarbonylation stage 
or step conditions may include any suitable type hydrocarbonylation 
conditions heretofore employed for producing alcohols or hydroxyaldehydes. 
The total pressure employed in the hydrocarbonylation process may range in 
general from about 1 to about 10,000 psia, preferably from about 20 to 
3000 psia and more preferably from about 50 to about 2000 psia. The total 
pressure of the hydrocarbonylation process will be dependent on the 
particular catalyst system employed. 
More specifically, the carbon monoxide partial pressure of the 
hydrocarbonylation process in general may range from about 1 to about 3000 
psia, and preferably from about 3 to about 1500 psia, while the hydrogen 
partial pressure in general may range from about 1 to about 3000 psia, and 
preferably from about 3 to about 1500 psia. In general, the molar ratio of 
carbon monoxide to gaseous hydrogen may range from about 100:1 or greater 
to about 1:100 or less, the preferred carbon monoxide to gaseous hydrogen 
molar ratio being from about 1:10 to about 10:1. The carbon monoxide and 
hydrogen partial pressures will be dependent in part on the particular 
catalyst system employed. It is understood that carbon monoxide and 
hydrogen can be employed separately, either alone or in mixture with each 
other, i.e., synthesis gas, or may be produced in situ under reaction 
conditions and/or be derived from the promoter or solvent (not necessarily 
involving free hydrogen or carbon monoxide). In an embodiment, the 
hydrogen partial pressure and carbon monoxide partial pressure are 
sufficient to prevent or minimize derivatization, e.g., hydrogenation of 
penten-1-ols or further hydrocarbonylation of penten-1-ols or 
hydrogenation of alkadienes. The hydrocarbonylation is preferably 
conducted at a hydrogen partial pressure and carbon monoxide partial 
pressure sufficient to prevent or minimize formation of substituted or 
unsubstituted pentan-1-ols, and/or substituted or unsubstituted 
valeraldehydes. 
Further, the hydrocarbonylation process may be conducted at a reaction 
temperature from about 20.degree. C. to about 200.degree. C., preferably 
from about 50.degree. C. to about 150.degree. C., and more preferably from 
about 65.degree. C. to about 115.degree. C. The temperature must be 
sufficient for reaction to occur (which may vary with catalyst system 
employed), but not so high that ligand or catalyst decomposition occurs. 
At high temperatures (which may vary with catalyst system employed), 
conversion of penten-1-ols to undesired byproducts may occur. 
Of course, it is to be also understood that the hydrocarbonylation process 
conditions employed will be governed by the type of unsaturated alcohol or 
hydroxyaldehyde product desired. 
To enable maximum levels of 3-penten-1-ols and/or 4-penten-1-ols and 
minimize 2-penten-1-ols, it is desirable to maintain some alkadiene 
partial pressure or when the alkadiene conversion is complete, the carbon 
monoxide and hydrogen partial pressures should be sufficient to prevent or 
minimize derivatization, e.g., hydrogenation of penten-1-ols or further 
hydrocarbonylation of penten-1-ols or hydrogenation of alkadienes. 
In a preferred embodiment, the alkadiene hydrocarbonylation is conducted at 
an alkadiene partial pressure and/or a carbon monoxide and hydrogen 
partial pressures sufficient to prevent or minimize derivatization, e.g., 
hydrogenation of penten-1-ols or further hydrocarbonylation of 
penten-1-ols or hydrogenation of alkadienes. In a more preferred 
embodiment, the alkadiene, e.g., butadiene, hydrocarbonylation is 
conducted at an alkadiene partial pressure of greater than 0 psi, 
preferably greater than 5 psi, and more preferably greater than 9 psi; at 
a carbon monoxide partial pressure of greater than 0 psi, preferably 
greater than 25 psi, and more preferably greater than 40 psi; and at a 
hydrogen partial pressure of greater than 0 psi, preferably greater than 
25 psi, and more preferably greater than 80 psi. 
The hydrocarbonylation process is also conducted in the presence of a 
promoter. As used herein, "promoter" means an organic or inorganic 
compound with an ionizable hydrogen of pKa of from about 1 to about 35. 
Illustrative promoters include, for example, protic solvents, organic and 
inorganic acids, alcohols, water, phenols, thiols, thiophenols, 
nitroalkanes, ketones, nitriles, amines (e.g., pyrroles and 
diphenylamine), amides (e.g., acetamide), mono-, di- and trialkylammonium 
salts, and the like. Approximate pKa values for illustrative promoters 
useful in this invention are given in the Table II below. The promoter may 
be present in the hydrocarbonylation reaction mixture either alone or 
incorporated into the ligand structure, either as the metal-ligand complex 
catalyst or as free ligand, or into the alkadiene structure. The desired 
promoter will depend on the nature of the ligands and metal of the 
metal-ligand complex catalysts. In general, a catalyst with a more basic 
metal-bound acyl or other intermediate will require a lower concentration 
and/or a less acidic promoter. 
Although it is not intended herein to be bound to any theory or mechanistic 
discourse, it appears that the promoter may function to transfer a 
hydrogen ion to or otherwise activate a catalyst-bound acyl or other 
intermediate. Mixtures of promoters in any permissible combination may be 
useful in this invention. A preferred class of promoters includes those 
that undergo hydrogen bonding, e.g., NH, OH and SH-containing groups and 
Lewis acids, since this is believed to facilitate hydrogen ion transfer to 
or activation of the metal-bound acyl or other intermediate. In general, 
the amount of promoter may range from about 10 parts per million or so up 
to about 99 percent by weight or more based on the total weight of the 
hydrocarbonylation process mixture starting materials. 
TABLE II 
______________________________________ 
Promoter pKa 
______________________________________ 
ROH (R = alkyl) 15-19 
ROH (R = aryl) 8-11 
RCONHR (R = hydrogen or alkyl, 
15-19 
e.g., acetamide) 
R.sub.3 NH.sup.+, R.sub.2 NH.sub.2 .sup.+ (R = alkyl) 
10-11 
RCH.sub.2 NO.sub.2 8-11 
RCOCH.sub.2 R (R = alkyl) 
19-20 
RSH (R = alkyl) 10-11 
RSH (R = aryl) 8-11 
CNCH.sub.2 CN 11 
Diarylamine 21-24 
Pyrrole 20 
Pyrrolidine 34 
______________________________________ 
The concentration of the promoter employed will depend upon the details of 
the catalyst system employed. Without wishing to be bound by theory, the 
promoter component must be sufficiently acidic and in sufficient 
concentration to transfer a hydrogen ion to or otherwise activate the 
catalyst-bound acyl or other intermediate. It is believed that a promoter 
component acidity or concentration which is insufficient to transfer a 
hydrogen ion to or otherwise activate the catalyst-bound acyl or other 
intermediate will result in the formation of pentenal products, rather 
than the preferred penten-1-ol products. The ability of a promoter 
component to transfer a hydrogen ion to or otherwise activate the 
catalyst-bound acyl or other intermediate may be governed by several 
factors, for example, the concentration of the promoter component, the 
intrinsic acidity of the promoter component (the pKa), the composition of 
the reaction medium (e.g., the reaction solvent) and the temperature. 
Promoters are chosen on the basis of their ability to transfer a hydrogen 
ion to or otherwise activate such a catalyst-bound acyl or other 
intermediate under reaction conditions sufficient to result in the 
formation of alcohol or hydroxyaldehyde products, but not so high as to 
result in detrimental side reactions of the catalyst, reactants or 
products. In cases where the promoter component acidity or concentration 
is insufficient to do so, aldehyde products (e.g., pentenals) are 
initially formed which may or may not be subsequently converted to 
unsaturated alcohols, e.g., penten-1-ols, or hydroxyaldehydes, e.g., 
6-hydroxyhexanal. 
In general, a less basic metal-bound acyl will require a higher 
concentration of the promoter component or a more acidic promoter 
component to protonate or otherwise activate it fully, such that the 
products are more desired penten-1-ols, rather than pentenals. This can be 
achieved by appropriate choice of promoter component. For example, an 
enabling concentration of protonated or otherwise activated catalyst-bound 
acyl or other intermediate can be achieved though the use of a large 
concentration of a mildly acidic promoter component, or through the use of 
a smaller concentration of a more acidic component. The promoter component 
is selected based upon its ability to produce the desired concentration of 
protonated or otherwise activated catalyst-bound acyl or other 
intermediate in the reaction medium under reaction conditions. In general, 
the intrinsic strength of an acidic material is generally defined in 
aqueous solution as the pKa, and not in reaction media commonly employed 
in hydrocarbonylation. The choice of the promoter and its concentration is 
made based in part upon the theoretical or equivalent pH that the promoter 
alone at such concentration gives in aqueous solution at 22.degree. C. The 
desired theoretical or equivalent pH of promoter component solutions 
should be greater than 0, preferably from about 1-12, more preferably from 
about 2-10 and most preferably from 4-8. The theoretical or equivalent pH 
can be readily calculated from values of pKa's at the appropriate promoter 
component concentration by reference to standard tables such as those 
found in "Ionization Constants of Organic Acids in Aqueous Solution" 
(IU Chemical Data Series--No. 23) by E. P Serjeant and Boyd Dempsey, 
Pergamon Press (1979) and "Dissociation Constants of Inorganic Acids and 
Bases in Aqueous Solution" (IU Chemical Data Series--No. 19, by D. D. 
Perrin, Pergamon Press. 
Depending on the particular catalyst and reactants employed, suitable 
promoters preferably include solvents, for example, alcohols (e.g., the 
unsaturated alcohol or hydroxyaldehyde products such as penten-1-ols or 
6-hydroxyhexanals), thiols, thiophenols, selenols, tellurols, alkenes, 
alkynes, aldehydes, higher boiling byproducts, ketones, esters, amides, 
primary and secondary amines, alkylaromatics and the like. Any suitable 
promoter which does not unduly adversely interfere with the intended 
hydrocarbonylation process can be employed. Permissible protic solvents 
have a pKa of about 1-35, preferably a pKa of about 3-30, and more 
preferably a pKa of about 5-25. Mixtures of one or more different solvents 
may be employed if desired. 
In general, with regard to the production of unsaturated alcohols or 
hydroxyaldehydes, it is preferred to employ unsaturated alcohol or 
hydroxyaldehyde promoters corresponding to the unsaturated alcohol or 
hydroxyaldehyde products desired to be produced and/or higher boiling 
byproducts as the main protic solvents. Such byproducts can also be 
preformed if desired and used accordingly. Illustrative preferred protic 
solvents employable in the production of unsaturated alcohols, e.g., 
penten-1-ols, or hydroxyaldehydes, e.g., 6-hydroxyhexanal, include 
alcohols (e.g., pentenols, octanols, hexanediols), amines, thiols, 
thiophenols, ketones (e.g. acetone and methylethyl ketone), 
hydroxyaldehydes (e.g., 6-hydroxyaldehyde), lactols (e.g., 
2-methylvalerolactol), esters (e.g. ethyl acetate), hydrocarbons (e.g. 
diphenylmethane, triphenylmethane), nitrohydrocarbons (e.g. nitromethane), 
1,4-butanediols and sulfolane. Suitable protic solvents are disclosed in 
U.S. Pat. No. 5,312,996. 
As indicated above, the promoter may be incorporated into the 
organophosphorus ligand structure, either as the metal-ligand complex 
catalyst or as free ligand. Suitable organophosphorus ligand promoters 
which may be useful in this invention include, for example, 
tris(2-hydroxyethyl)phosphine, tris(3-hydroxypropyl)phosphine, 
tris(2-hydroxyphenylphosphine), tris(4-hydroxyphenylphosphine), 
tris(3-carboxypropyl)phosphine, tris(3-carboxamidopropyl)phosphine, 
diphenyl(2-hydroxyphenyl)phosphine, diethyl(2-anilinophenyl)phosphine, and 
tris(3-pyrroyl)phosphine. The use of ligand promoters may by particularly 
beneficial in those instances when the unsaturated alcohol or 
hydroxyaldehyde product is not effective as a promoter. As with the 
organophosphorus ligands which make up the metal-organophosphorus ligand 
complex catalysts and free organophosphorus ligands, the organophosphorus 
ligand promoters preferably are high basicity ligands having a steric bulk 
lower than or equal to a Tolman cone angle of 210.degree., preferably 
lower than or equal to the steric bulk of tricyclohexylphosphine (Tolman 
cone angle=170.degree.). Indeed, the organophosphorus ligand promoters may 
be employed as organophosphorus ligands which make up the 
metal-organophosphorus ligand complex catalysts and free organophosphorus 
ligands. Mixtures of promoters comprising one or more organophosphorus 
ligand promoters and mixtures comprising one or more organophosphorus 
ligand promoters and one or more other promoters, e.g., protic solvents, 
may be useful in this invention. 
In an embodiment of the invention, the hydrocarbonylation process mixture 
may consist of one or more liquid phases, e.g. a polar and a nonpolar 
phase. Such processes are often advantageous in, for example, separating 
products from catalyst and/or reactants by partitioning into either phase. 
In addition, product selectivities dependent upon solvent properties may 
be increased by carrying out the reaction in that solvent. An application 
of this technology is the aqueous-phase hydrocarbonylation of alkadienes 
employing sulfonated phosphine ligands, hydroxylated phosphine ligands and 
aminated phosphine ligands for the rhodium catalyst. A process carried out 
in aqueous solvent is particularly advantageous for the preparation of 
alcohols or hydroxyaldehydes because the products may be separated from 
the catalyst by extraction into a solvent. 
As described herein, the phosphorus-containing ligand for the rhodium 
hydrocarbonylation catalyst may contain any of a number of substituents, 
such as cationic or anionic substituents, which will render the catalyst 
soluble in a polar phase, e.g. water. Optionally, a phase-transfer 
catalyst may be added to the reaction mixture to facilitate transport of 
the catalyst, reactants, or products into the desired solvent phase. The 
structure of the ligand or the phase-transfer catalyst is not critical and 
will depend on the choice of conditions, reaction solvent, and desired 
products. 
When the catalyst is present in a multiphasic system, the catalyst may be 
separated from the reactants and/or products by conventional methods such 
as extraction or decantation. The reaction mixture itself may consist of 
one or more phases; alternatively, the multiphasic system may be created 
at the end of the reaction by for example addition of a second solvent to 
separate the products from the catalyst. See, for example, U.S. Pat. No. 
5,180,854, the disclosure of which is incorporated herein by reference. 
In an embodiment of this invention, an olefin can be hydrocarbonylated 
along with an alkadiene or pentenal using the above-described metal-ligand 
complex catalysts. In such cases, an alcohol derivative of the olefin is 
also produced along with the unsaturated alcohols, e.g., penten-1-ols, or 
hydroxyaldehydes, e.g., 6-hydroxyhexanal. Mixtures of such olefinic 
starting materials are described more fully in the hydroformylation 
section hereinbelow. 
In those instances where the promoter is not the solvent, the 
hydrocarbonylation process is conducted in the presence of an organic 
solvent for the metal-ligand complex catalyst and free organophosphorus 
ligand. The solvent may also contain dissolved water up to the saturation 
limit. Depending on the particular catalyst and reactants employed, 
suitable organic solvents include, for example, alcohols, alkanes, 
alkenes, alkynes, ethers, aldehydes, higher boiling hydrocarbonylation 
byproducts, ketones, esters, amides, tertiary amines, aromatics and the 
like. Any suitable solvent which does not unduly adversely interfere with 
the intended hydrocarbonylation reaction can be employed. Mixtures of one 
or more different solvents may be employed if desired. Illustrative 
preferred solvents employable in the production of alcohols or 
hydroxyaldehydes include ketones (e.g. acetone and methylethyl ketone), 
esters (e.g. ethyl acetate), hydrocarbons (e.g. toluene), 
nitrohydrocarbons (e.g. nitrobenzene), ethers (e.g. tetrahydrofuran (THF) 
and sulfolane. Suitable solvents are disclosed in U.S. Pat. No. 5,312,996. 
The amount of solvent employed is not critical to the subject invention 
and need only be that amount sufficient to solubilize the catalyst and 
free ligand of the hydrocarbonylation reaction mixture to be treated. In 
general, the amount of solvent may range from about 5 percent by weight up 
to about 99 percent by weight or more based on the total weight of the 
hydrocarbonylation reaction mixture starting material. 
Illustrative substituted and unsubstituted unsaturated alcohol 
intermediates/starting materials that can be prepared by and/or used in 
the processes of this invention include one or more of the following: 
alkenols such as cis-3-penten-1-ol, trans-3-penten-1-ol, 4-penten-1-ol, 
cis-2-penten-1-ol and/or trans-2-penten-1-ol, including mixtures 
comprising one or more of the above unsaturated alcohols. The preferred 
unsaturated alcohols have at least 4 carbon atoms, preferably 4 to about 
30 carbon atoms, and more preferably 4 to about 20 carbon atoms. 
Illustrative of suitable substituted and unsubstituted unsaturated 
alcohols (including derivatives of unsaturated alcohols) include those 
permissible substituted and unsubstituted unsaturated alcohols which are 
described in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth 
Edition, 1996, the pertinent portions of which are incorporated herein by 
reference. 
As indicated above, it is generally preferred to carry out the 
hydrocarbonylation stage or step in a continuous manner. In general, 
continuous hydrocarbonylation process may involve: (a) hydrocarbonylating 
the alkadiene or pentenal starting material(s) with carbon monoxide and 
hydrogen in a liquid homogeneous reaction mixture comprising a solvent, a 
metal-ligand complex catalyst, and free ligand; (b) maintaining reaction 
temperature and pressure conditions favorable to the hydrocarbonylation of 
the alkadiene or pentenal starting material(s); (c) supplying make-up 
quantities of the alkadiene or pentenal starting material(s), carbon 
monoxide and hydrogen to the reaction medium as those reactants are used 
up; and (d) recovering the desired unsaturated alcohol or hydroxyaldehyde 
product(s) in any manner desired. The continuous reaction can be carried 
out in a single pass mode, i.e., wherein a vaporous mixture comprising 
unreacted alkadiene or pentenal starting material(s) and vaporized alcohol 
or hydroxyaldehyde product is removed from the liquid reaction mixture 
from whence the alcohol or hydroxyaldehyde product is recovered and 
make-up alkadiene or pentenal starting material(s), carbon monoxide and 
hydrogen are supplied to the liquid reaction medium for the next single 
pass through without recycling the unreacted alkadiene or pentenal 
starting material(s). However, it is generally desirable to employ a 
continuous reaction that involves either a liquid and/or gas recycle 
procedure. Such types of recycle procedure are known in the art and may 
involve the liquid recycling of the metal-ligand complex catalyst solution 
separated from the desired alcohol or hydroxyaldehyde reaction product(s). 
As indicated above, the hydrocarbonylation stage or step may involve a 
liquid catalyst recycle procedure. Such liquid catalyst recycle procedures 
are known in the art. For instance, in such liquid catalyst recycle 
procedures it is commonplace to continuously or intermittently remove a 
portion of the liquid reaction product medium, containing, e.g., the 
alcohol or hydroxyaldehyde product, the solubilized metal-ligand complex 
catalyst, free ligand, and organic solvent, as well as byproducts produced 
in situ by the hydrocarbonylation and unreacted alkadiene or pentenal 
starting material, carbon monoxide and hydrogen (syn gas) dissolved in 
said medium, from the hydrocarbonylation reactor, to a distillation zone, 
e.g., a vaporizer/separator wherein the desired alcohol or hydroxyaldehyde 
product is distilled in one or more stages under normal, reduced or 
elevated pressure, as appropriate, and separated from the liquid medium. 
The vaporized or distilled desired alcohol or hydroxyaldehyde product so 
separated may then be condensed and recovered in any conventional manner 
as discussed above. The remaining non-volatilized liquid residue which 
contains metal-ligand complex catalyst, solvent, free organophosphorus 
ligand and usually some undistilled alcohol or hydroxyaldehyde product is 
then recycled back, with or with out further treatment as desired, along 
with whatever by-product and non-volatilized gaseous reactants that might 
still also be dissolved in said recycled liquid residue, in any 
conventional manner desired, to the hydrocarbonylation reactor, such as 
disclosed e.g., in the above-mentioned patents. Moreover the reactant 
gases so removed by such distillation from the vaporizer may also be 
recycled back to the reactor if desired. 
Recovery and purification of unsaturated alcohols or hydroxyaldehydes may 
be by any appropriate means, and may include distillation, phase 
separation, extraction, precipitation, absorption, crystallization, 
membrane separation, derivative formation and other suitable means. For 
example, a crude reaction product can be subjected to a 
distillation-separation at atmospheric or reduced pressure through a 
packed distillation column. Reactive distillation may be useful in 
conducting the hydrocarbonylation reaction. Suitable recovery and 
purification methods are described more fully in the hydroformylation 
section hereinbelow. The subsequent hydroformylation of the unsaturated 
alcohol may be conducted without the need to separate the unsaturated 
alcohol from the other components of the crude reaction mixtures. 
While not wishing to be bound to any particular reaction mechanism, it is 
believed that the overall hydrocarbonylation reaction generally proceeds 
in one step, e.g., the one or more substituted or unsubstituted alkadienes 
(e.g., butadiene) are converted to one or more substituted or 
unsubstituted unsaturated alcohols (e.g., a 3-pentenol and/or 4-pentenol) 
either directly or through one or more intermediates (e.g., a 3-pentenal 
and/or 4-pentenal). This invention is not intended to be limited in any 
manner by any particular reaction mechanism, but rather encompasses all 
permissible reaction mechanisms involved in hydrocarbonylating one or more 
substituted or unsubstituted alkadienes with carbon monoxide and hydrogen 
in the presence of a metal-ligand complex catalyst and a promoter and 
optionally free ligand to produce one or more substituted or unsubstituted 
unsaturated alcohols or hydrocarbonylating one or more substituted or 
unsubstituted pentenals with carbon monoxide and hydrogen in the presence 
of a metal-ligand complex catalyst and a promoter and optionally free 
ligand to produce one or more substituted or unsubstituted 
hydroxyaldehydes. 
Hydroformylation Step or Stage 
The hydroformylation step or stage involves the production of 
hydroxyaldehydes, e.g., 6-hydroxyhexanals, by reacting an olefinic 
compound, e.g., penten-1-ols, with carbon monoxide and hydrogen in the 
presence of a metal-ligand complex catalyst and optionally free ligand in 
a liquid medium that also contains a solvent for the catalyst and ligand 
or the production of pentenals by reacting an alkadiene compound, e.g., 
butadiene, with carbon monoxide and hydrogen in the presence of a 
metal-ligand complex catalyst and optionally free ligand in a liquid 
medium that also contains a solvent for the catalyst and ligand. The 
processes may be carried out in a continuous single pass mode in a 
continuous gas recycle manner or more preferably in a continuous liquid 
catalyst recycle manner as described below. The hydroformylation 
processing techniques employable herein may correspond to any known 
processing techniques such as preferably employed in conventional liquid 
catalyst recycle hydroformylation reactions. As used herein, the term 
"hydroformylation" is contemplated to include, but is not limited to, all 
permissible hydroformylation processes which involve converting one or 
more substituted or unsubstituted unsaturated alcohols, e.g., alcohols 
possessing internal olefinic unsaturation, to one or more substituted or 
unsubstituted hydroxyaldehydes or converting one or more substituted or 
unsubstituted alkadienes to one or more substituted or unsubstituted 
pentenals. In general, the hydroformylation step or stage comprises 
reacting one or more substituted or unsubstituted penten-1-ols with carbon 
monoxide and hydrogen in the presence of a catalyst to produce one or more 
substituted or unsubstituted 6-hydroxyhexanals or reacting one or more 
substituted or unsubstituted alkadienes with carbon monoxide and hydrogen 
in the presence of a catalyst to produce one or more substituted or 
unsubstituted pentenals. 
The hydroformylation reaction mixtures employable herein include any 
solution derived from any corresponding hydroformylation process that may 
contain at least some amount of four different main ingredients or 
components, i.e., the hydroxyaldehyde or pentenal product, a metal-ligand 
complex catalyst, optionally free ligand and an organic solubilizing agent 
for said catalyst and said free ligand, said ingredients corresponding to 
those employed and/or produced by the hydroformylation process from whence 
the hydroformylation reaction mixture starting material may be derived. By 
"free ligand" is meant organophosphorus ligand that is not complexed with 
(tied to or bound to) the metal, e.g., rhodium atom, of the complex 
catalyst. It is to be understood that the hydroformylation reaction 
mixture compositions employable herein can and normally will contain minor 
amounts of additional ingredients such as those which have either been 
deliberately employed in the hydroformylation process or formed in situ 
during said process. Examples of such ingredients that can also be present 
include unreacted unsaturated alcohol or alkadiene starting material, 
carbon monoxide and hydrogen gases, and in situ formed type products, such 
as saturated hydrocarbons and/or unreacted isomerized olefins 
corresponding to the unsaturated alcohol or alkadiene starting materials, 
and high boiling liquid aldehyde condensation byproducts, as well as other 
inert co-solvent type materials or hydrocarbon additives, if employed. 
The catalysts useful in the hydroformylation process include metal-ligand 
complex catalysts. The permissible metals which make up the metal-ligand 
complexes include Group 8, 9 and 10 metals selected from rhodium (Rh), 
cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), 
palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, with the 
preferred metals being rhodium, cobalt, iridium and ruthenium, more 
preferably rhodium, cobalt and ruthenium, especially rhodium. The 
permissible ligands include, for example, organophosphorus, organoarsenic 
and organoantimony ligands, or mixtures thereof, preferably 
organophosphorus ligands. The permissible organophosphorus ligands which 
make up the metal-ligand complexes include organophosphines, e.g., mono-, 
di-, tri- and poly-(organophosphines), and organophosphites, e.g., 
mono-,di-,tri- and poly-(organophosphites). Other permissible 
organophosphorus ligands include, for example, organophosphonites, 
organophosphinites, amino phosphines and the like. Still other permissible 
ligands include, for example, heteroatom-containing ligands such as 
described in U.S. patent application Ser. No. (D-17646-1), filed Mar. 10, 
1997, the disclosure of which is incorporated herein by reference. 
Mixtures of such ligands may be employed if desired in the metal-ligand 
complex catalyst and/or free ligand and such mixtures may be the same or 
different. This invention is not intended to be limited in any manner by 
the permissible organophosphorus ligands or mixtures thereof. It is to be 
noted that the successful practice of this invention does not depend and 
is not predicated on the exact structure of the metal-ligand complex 
species, which may be present in their mononuclear, dinuclear and/or 
higher nuclearity forms. Indeed, the exact structure is not known. 
Although it is not intended herein to be bound to any theory or 
mechanistic discourse, it appears that the catalytic species may in its 
simplest form consist essentially of the metal in complex combination with 
the ligand and carbon monoxide when used. 
The term "complex" as used herein and in the claims means a coordination 
compound formed by the union of one or more electronically rich molecules 
or atoms capable of independent existence with one or more electronically 
poor molecules or atoms, each of which is also capable of independent 
existence. For example, the ligands employable herein, i.e., 
organophosphorus ligands, may possess one or more phosphorus donor atoms, 
each having one available or unshared pair of electrons which are each 
capable of forming a coordinate covalent bond independently or possibly in 
concert (e.g., via chelation) with the metal. Carbon monoxide (which is 
also properly classified as a ligand) can also be present and complexed 
with the metal. The ultimate composition of the complex catalyst may also 
contain an additional ligand, e.g., hydrogen or an anion satisfying the 
coordination sites or nuclear charge of the metal. Illustrative additional 
ligands include, e.g., halogen (Cl, Br, I), alkyl, aryl, substituted aryl, 
acyl, CF.sub.3, C.sub.2 F.sub.5, CN, (R).sub.2 PO and RP(O)(OH)O (wherein 
each R is the same or different and is a substituted or unsubstituted 
hydrocarbon radical, e.g., the alkyl or aryl), acetate, acetylacetonate, 
SO.sub.4, BF.sub.4, PF.sub.6, NO.sub.2, NO.sub.3, CH.sub.3 O, CH.sub.2 
.dbd.CHCH.sub.2, CH.sub.3 CH.dbd.CHCH.sub.2, C.sub.6 H.sub.5 CN, CH.sub.3 
CN, NO, NH.sub.3, pyridine, (C.sub.2 H.sub.5).sub.3 N, mono-olefins, 
diolefins and triolefins, tetrahydrofuran, and the like. It is of course 
to be understood that the complex species are preferably free of any 
additional organic ligand or anion that might poison the catalyst and have 
an undue adverse effect on catalyst performance. It is preferred in the 
metal-ligand complex catalyzed hydroformylation reactions that the active 
catalysts be free of halogen and sulfur directly bonded to the metal, 
although such may not be absolutely necessary. Preferred metal-ligand 
complex catalysts include rhodium-organophosphine ligand complex catalysts 
and rhodium-organophosphite ligand complex catalysts. 
The number of available coordination sites on such metals is well known in 
the art. Thus the catalytic species may comprise a complex catalyst 
mixture, in their monomeric, dimeric or higher nuclearity forms, which are 
preferably characterized by at least one phosphorus-containing molecule 
complexed per metal, e.g., rhodium. As noted above, it is considered that 
the catalytic species of the preferred catalyst employed in the 
hydroformylation reaction may be complexed with carbon monoxide and 
hydrogen in addition to the organophosphorus ligands in view of the carbon 
monoxide and hydrogen gas employed by the hydroformylation reaction. 
Among the organophosphines that may serve as the ligand of the 
metal-organophosphine complex catalyst and/or free organophosphine ligand 
of the hydroformylation reaction mixture starting materials are 
triorganophosphines, trialkylphosphines, alkyldiarylphosphines, 
dialkylarylphosphines, dicycloalkylarylphosphines, 
cycloalkyldiarylphosphines, triaralkylphosphines, tricycloalkylphosphines, 
and triarylphosphines, alkyl and/or aryl diphosphines and bisphosphine 
mono oxides, as well as ionic triorganophosphines containing at least one 
ionic moiety selected from the salts of sulfonic acid, of carboxylic acid, 
of phosphonic acid and of quaternary ammonium compounds, and the like. Of 
course any of the hydrocarbon radicals of such tertiary non-ionic and 
ionic organophosphines may be substituted if desired, with any suitable 
substituent that does not unduly adversely affect the desired result of 
the hydroformylation reaction. The organophosphine ligands employable in 
the hydroformylation reaction and/or methods for their preparation are 
known in the art. 
Illustrative triorganophosphine ligands may be represented by the formula: 
##STR3## 
wherein each R.sup.1 is the same or different and is a substituted or 
unsubstituted monovalent hydrocarbon radical, e.g., an alkyl or aryl 
radical. Suitable hydrocarbon radicals may contain from 1 to 24 carbon 
atoms or greater. Illustrative substituent groups that may be present on 
the aryl radicals include, e.g., alkyl radicals, alkoxy radicals, silyl 
radicals such as --Si(R.sup.2).sub.3 ; amino radicals such as 
--N(R.sup.2).sub.2 ; acyl radicals such as --C(O)R.sup.2 ; carboxy 
radicals such as --C(O)OR.sup.2 ; acyloxy radicals such as --OC(O)R.sup.2 
; amido radicals such as --C(O)N(R.sup.2).sub.2 and 
--N(R.sup.2)C(O)R.sup.2 ; ionic radicals such as --SO.sub.3 M wherein M 
represents inorganic or organic cationic atoms or radicals; sulfonyl 
radicals such as --SO.sub.2 R.sup.2 ; ether radicals such as --OR.sup.2 ; 
sulfinyl radicals such as --SOR.sup.2 ; sulfenyl radicals such as 
--SR.sup.2 as well as halogen, nitro, cyano, trifluoromethyl and hydroxy 
radicals, and the like, wherein each R.sup.2 individually represents the 
same or different substituted or unsubstituted monovalent hydrocarbon 
radical, with the proviso that in amino substituents such as 
--N(R.sup.2).sub.2, each R.sup.2 taken together can also represent a 
divalent bridging group that forms a heterocyclic radical with the 
nitrogen atom and in amido substituents such as C(O)N(R.sup.2).sub.2 and 
--N(R.sup.2)C(O)R.sup.2 each --R.sup.2 bonded to N can also be hydrogen. 
Illustrative alkyl radicals include, e.g., methyl, ethyl, propyl, butyl 
and the like. Illustrative aryl radicals include, e.g., phenyl, naphthyl, 
diphenyl, fluorophenyl, difluorophenyl, benzoyloxyphenyl, 
carboethoxyphenyl, acetylphenyl, ethoxyphenyl, phenoxyphenyl, 
hydroxyphenyl; carboxyphenyl, trifluoromethylphenyl, methoxyethylphenyl, 
acetamidophenyl, dimethylcarbamylphenyl, tolyl, xylyl, and the like. 
Illustrative specific organophosphines include, e.g., triphenylphosphine, 
tris-p-tolyl phosphine, tris-p-methoxyphenylphosphine, 
tris-p-fluorophenylphosphine, tris-p-chlorophenylphosphine, 
tris-dimethylaminophenylphosphine, propyldiphenylphosphine, 
t-butyldiphenylphosphine, n-butyldiphenylphosphine, 
n-hexyldiphenylphosphine, cyclohexyldiphenylphosphine, 
dicyclohexylphenylphosphine, tricyclohexylphosphine, tribenzylphosphine, 
DIOP, i.e., 
(4R,5R)-(-)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butan 
e and/or (4S ,5S)-( 
+)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane and/or 
(4S,5R)-(-)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butan 
e, substituted or unsubstituted bicyclic bisphosphines such as 
1,2-bis(1,4-cyclooctylenephosphino)ethane, 
1,3-bis(1,4-cyclooctylenephosphino)propane, 
1,3-bis(1,5-cyclooctylenephosphino)propane and 
1,2-bis(2,6-dimethyl-1,4-cyclooctylenephosphino)ethane, substituted or 
unsubstituted bis(2,2'-diphenylphosphinomethyl)biphenyl such as 
bis(2,2'-diphenylphosphinomethyl)biphenyl and 
bis{2,2'-di(4-fluorophenyl)phosphinomethyl}biphenyl, xantphos, 
thixantphos, bis(diphenylphosphino)ferrocene, 
bis(diisopropylphosphino)ferrocene, bis(diphenylphosphino)ruthenocene, as 
well as the alkali and alkaline earth metal salts of sulfonated 
triphenylphosphines, e.g., of (tri-m-sulfophenyl)phosphine and of 
(m-sulfophenyl)diphenyl-phosphine and the like. 
More particularly, illustrative metal-organophosphine complex catalysts and 
illustrative free organophosphine ligands include, e.g., those disclosed 
in U.S. Pat. Nos. 3,527,809; 4,148,830; 4,247,486; 4,283,562; 4,400,548; 
4,482,749, 4,861,918; 4,694,109; 4,742,178; 4,851,581; 4,824,977; 
5,332,846; 4,774,362; and WO Patent Application No. 95/30680, published 
Nov. 16, 1995; the disclosures of which are incorporated herein by 
reference. 
The organophosphites that may serve as the ligand of the 
metal-organophosphite ligand complex catalyst and/or free ligand of the 
processes and reaction product mixtures of this invention may be of the 
achiral (optically inactive) or chiral (optically active) type and are 
well known in the art. 
Among the organophosphites that may serve as the ligand of the 
metal-organophosphite complex catalyst and/or free organophosphite ligand 
of the hydroformylation reaction mixture starting materials are 
monoorganophosphites, diorganophosphites, triorganophosphites and 
organopolyphosphites. The organophosphite ligands employable in this 
invention and/or methods for their preparation are known in the art. 
Representative monoorganophosphites may include those having the formula: 
##STR4## 
wherein R.sup.3 represents a substituted or unsubstituted trivalent 
hydrocarbon radical containing from 4 to 40 carbon atoms or greater, such 
as trivalent acyclic and trivalent cyclic radicals, e.g., trivalent 
alkylene radicals such as those derived from 1,2,2-trimethylolpropane and 
the like, or trivalent cycloalkylene radicals such as those derived from 
1,3,5-trihydroxycyclohexane, and the like. Such monoorganophosphites may 
be found described in greater detail, e.g., in U.S. Pat. No. 4,567,306, 
the disclosure of which is incorporated herein by reference. 
Representative diorganophosphites may include those having the formula: 
##STR5## 
wherein R.sup.4 represents a substituted or unsubstituted divalent 
hydrocarbon radical containing from 4 to 40 carbon atoms or greater and W 
represents a substituted or unsubstituted monovalent hydrocarbon radical 
containing from 1 to 18 carbon atoms or greater. 
Representative substituted and unsubstituted monovalent hydrocarbon 
radicals represented by W in the above formula (III) include alkyl and 
aryl radicals, while representative substituted and unsubstituted divalent 
hydrocarbon radicals represented by R.sup.4 include divalent acyclic 
radicals and divalent aromatic radicals. Illustrative divalent acyclic 
radicals include, e.g., alkylene, alkylene-oxy-alkylene, 
alkylene-NX-alkylene wherein X is hydrogen or a substituted or 
unsubstituted monovalent hydrocarbon radical, alkylene-S-alkylene, and 
cycloalkylene radicals, and the like. The more preferred divalent acyclic 
radicals are the divalent alkylene radicals such as disclosed more fully, 
e.g., in U.S. Pat. Nos. 3,415,906 and 4,567,302 and the like, the 
disclosures of which are incorporated herein by reference. Illustrative 
divalent aromatic radicals include, e.g., arylene, bisarylene, 
arylene-alkylene, arylene-alkylene-arylene, arylene-oxy-arylene, 
arylene-NX-arylene wherein X is as defined above, arylene-S-arylene, and 
arylene-S-alkylene, and the like. More preferably R.sup.4 is a divalent 
aromatic radical such as disclosed more fully, e.g., in U.S. Pat. Nos. 
4,599,206 and 4,717,775, and the like, the disclosures of which are 
incorporated herein by reference. 
Representative of a more preferred class of diorganophosphites are those of 
the formula: 
##STR6## 
wherein W is as defined above, each Ar is the same or different and 
represents a substituted or unsubstituted aryl radical, each y is the same 
or different and is a value of 0 or 1, Q represents a divalent bridging 
group selected from --C(R.sup.5).sub.2 --, --O--, --S--, --NR.sup.6-, 
Si(R.sup.7).sub.2 --and --CO--, wherein each R.sup.5 is the same or 
different and represents hydrogen, alkyl radicals having from 1 to 12 
carbon atoms, phenyl, tolyl, and anisyl, R.sup.6 represents hydrogen or a 
methyl radical, each R.sup.7 is the same or different and represents 
hydrogen or a methyl radical, and m is a value of 0 or 1. Such 
diorganophosphites are described in greater detail, e.g., in U.S. Pat. 
Nos. 4,599,206 and 4,717,775, the disclosures of which are incorporated 
herein by reference. 
Representative triorganophosphites may include those having the formula: 
##STR7## 
wherein each R.sup.8 is the same or different and is a substituted or 
unsubstituted monovalent hydrocarbon radical, e.g., an alkyl or aryl 
radical. Suitable hydrocarbon radicals may contain from 1 to 24 carbon 
atoms or greater and may include those described above for R.sup.1 in 
formula (I). 
Representative organopolyphosphites contain two or more tertiary 
(trivalent) phosphorus atoms and may include those having the formula: 
##STR8## 
wherein X.sup.1 represents a substituted or unsubstituted n-valent 
hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each 
R.sup.9 is the same or different and is a divalent hydrocarbon radical 
containing from 4 to 40 carbon atoms, each R.sup.10 is the same or 
different and is a substituted or unsubstituted monovalent hydrocarbon 
radical containing from 1 to 24 carbon atoms, a and b can be the same or 
different and each have a value of 0 to 6, with the proviso that the sum 
of a+b is 2 to 6 and n equals a+b. Of course it is to be understood that 
when a has a value of 2 or more, each R.sup.9 radical may be the same or 
different, and when b has a value of 1 or more, each R.sup.10 radical may 
also be the same or different. 
Representative n-valent (preferably divalent) hydrocarbon bridging radicals 
represented by X.sup.1, as well as representative divalent hydrocarbon 
radicals represented by R.sup.9 above, include both acyclic radicals and 
aromatic radicals, such as alkylene, alkylene-Q.sub.m -alkylene, 
cycloalkylene, arylene, bisarylene, arylene-alkylene, and 
arylene-(CH.sub.2).sub.y -Q.sub.m -(CH.sub.2).sub.y -arylene radicals, and 
the like, wherein Q, m and y are as defined above for formula (IV). The 
more preferred acyclic radicals represented by X.sup.1 and R.sup.9 above 
are divalent alkylene radicals, while the more preferred aromatic radicals 
represented by X.sup.1 and R.sup.9 above are divalent arylene and 
bisarylene radicals, such as disclosed more fully, e.g., in U.S. Pat. Nos. 
3,415,906; 4,567,306; 4,599,206; 4,769,498; 4,717,775; 4,885,401; 
5,202,297; 5,264,616 and 5,364,950, and the like, the disclosures of which 
are incorporated herein by reference. Representative monovalent 
hydrocarbon radicals represented by each R.sup.10 radical above include 
alkyl and aromatic radicals. 
Illustrative preferred organopolyphosphites may include bisphosphites such 
as those of formulas (VII) to (IX) below: 
##STR9## 
wherein each R.sup.9, R.sup.10 and X.sup.1 of formulas (VII) to (IX) are 
the same as defined above for formula (VI). Preferably, each R.sup.9 and 
X.sup.1 represents a divalent hydrocarbon radical selected from alkylene, 
arylene, arylene-alkylene-arylene, and bisarylene, while each R.sup.10 
represents a monovalent hydrocarbon radical selected from alkyl and aryl 
radicals. Phosphite ligands of such formulas (VI) to (IX) may be found 
disclosed, e.g., in said U.S. Pat. Nos. 4,668,651; 4,748,261; 4,769,498; 
4,885,401; 5,202,297; 5,235,113; 5,254,741; 5,264,616; 5,312,996; 
5,364,950; and 5,391,801; the disclosures of all of which are incorporated 
herein by reference. 
Representative of more preferred classes of organobisphosphites are those 
of the following formulas (X) to (XII): 
##STR10## 
wherein Ar, Q, R.sup.9, R.sup.10, X.sup.1, m and y are as defined above. 
Most preferably X.sup.1 represents a divalent aryl-(CH.sub.2).sub.y 
--(Q).sub.m --(CH.sub.2).sub.y -aryl radical wherein each y individually 
has a value of 0 or 1; m has a value of 0 or 1 and Q is --O--, --S--or 
--C(R.sup.5).sub.2 -- wherein each R.sup.5 is the same or different and 
represents a hydrogen or methyl radical. More preferably each alkyl 
radical of the above defined R.sup.10 groups may contain from 1 to 24 
carbon atoms and each aryl radical of the above-defined Ar, X.sup.1, 
R.sup.9 and R.sup.10 groups of the above formulas (VI) to (XII) may 
contain from 6 to 18 carbon atoms and said radicals may be the same or 
different, while the preferred alkylene radicals of X.sup.1 may contain 
from 2 to 18 carbon atoms and the preferred alkylene radicals of R.sup.9 
may contain from 5 to 18 carbon atoms. In addition, preferably the 
divalent Ar radicals and divalent aryl radicals of X.sup.1 of the above 
formulas are phenylene radicals in which the bridging group represented by 
--(CH.sub.2).sub.y --(Q).sub.m --(CH.sub.2).sub.y -- is bonded to said 
phenylene radicals in positions that are ortho to the oxygen atoms of the 
formulas that connect the phenylene radicals to their phosphorus atom of 
the formulas. It is also preferred that any substituent radical when 
present on such phenylene radicals be bonded in the para and/or ortho 
position of the phenylene radicals in relation to the oxygen atom that 
bonds the given substituted phenylene radical to its phosphorus atom. 
Moreover, if desired any given organophosphite in the above formulas (VI) 
to (XII) may be an ionic phosphite, i.e., may contain one or more ionic 
moieties selected from the group consisting of: 
SO.sub.3 M wherein M represents inorganic or organic cation, 
PO.sub.3 M wherein M represents inorganic or organic cation, 
N(R.sup.11).sub.3 X.sup.2 wherein each R.sup.11 is the same or different 
and represents a hydrocarbon radical containing from 1 to 30 carbon atoms, 
e.g, alkyl, aryl, alkaryl, aralkyl, and cycloalkyl radicals, and X.sup.2 
represents inorganic or organic anion, 
CO.sub.2 M wherein M represents inorganic or organic cation, 
as described, e.g., in U.S. Pat. Nos. 5,059,710; 5,113,022, 5,114,473 and 
5,449,653, the disclosures of which are incorporated herein by reference. 
Thus, if desired, such phosphite ligands may contain from 1 to 3 such 
ionic moieties, while it is preferred that only one such ionic moiety be 
substituted on any given aryl moiety in the phosphite ligand when the 
ligand contains more than one such ionic moiety. As suitable counter-ions, 
M and X.sup.2, for the anionic moieties of the ionic phosphites there can 
be mentioned hydrogen (i.e. a proton), the cations of the alkali and 
alkaline earth metals, e.g., lithium, sodium, potassium, cesium, rubidium, 
calcium, barium, magnesium and strontium, the ammonium cation, quaternary 
ammonium cations, phosphonium cations, arsonium cations and iminium 
cations. Suitable anionic groups include, for example, sulfate, carbonate, 
phosphate, chloride, acetate, oxalate and the like. 
Of course any of the R.sup.9, R.sup.10, X.sup.2 and Ar radicals of such 
non-ionic and ionic organophosphites of formulas (VI) to (XII) above may 
be substituted if desired, with any suitable substituent containing from 1 
to 30 carbon atoms that does not unduly adversely affect the desired 
result of the hydroformylation reaction. Substituents that may be on said 
radicals in addition of course to corresponding hydrocarbon radicals such 
as alkyl, aryl, aralkyl, alkaryl and cyclohexyl substituents, may include 
for example silyl radicals such as --Si(R.sup.12).sub.3 ; amino radicals 
such as --N(R.sup.12).sub.2 ; phosphine radicals such as 
-aryl-P(R.sup.12).sub.2 ; acyl radicals such as --C(O)R.sup.12 ; acyloxy 
radicals such as --OC(O)R.sup.12 ; amido radicals such as 
--CON(R.sup.12).sub.2 and --N(R.sup.12)COR.sup.12 ; sulfonyl radicals such 
as --SO.sub.2 R.sup.12 ; alkoxy radicals such as --OR.sup.12 ; sulfinyl 
radicals such as --SOR.sup.12 ; sulfenyl radicals such as --SR.sup.12 ; 
phosphonyl radicals such as --P(O)(R.sup.12).sub.2 ; as well as, halogen, 
nitro, cyano, trifluoromethyl, hydroxy radicals, and the like, wherein 
each R.sup.12 radical is the same or different and represents a monovalent 
hydrocarbon radical having from 1 to 18 carbon atoms (e.g., alkyl, aryl, 
aralkyl, alkaryl and cyclohexyl radicals), with the proviso that in amino 
substituents such as --N(R.sup.12).sub.2 each R.sup.12 taken together can 
also represent a divalent bridging group that forms a heterocyclic radical 
with the nitrogen atom, and in amido substituents such as 
--C(O)N(R.sup.12).sub.2 and --N(R.sup.12)COR.sup.12 each R.sup.12 bonded 
to N can also be hydrogen. Of course it is to be understood that any of 
the substituted or unsubstituted hydrocarbon radicals groups that make up 
a particular given organophosphite may be the same or different. 
More specifically illustrative substituents include primary, secondary and 
tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, 
sec-butyl, t-butyl, neo-pentyl, n-hexyl, amyl, sec-amyl, t-amyl, 
iso-octyl, decyl, octadecyl, and the like; aryl radicals such as phenyl, 
naphthyl and the like; aralkyl radicals such as benzyl, phenylethyl, 
triphenylmethyl, and the like; alkaryl radicals such as tolyl, xylyl, and 
the like; alicyclic radicals such as cyclopentyl, cyclohexyl, 
1-methylcyclohexyl, cyclooctyl, cyclohexylethyl, and the like; alkoxy 
radicals such as methoxy, ethoxy, propoxy, t-butoxy, --OCH.sub.2 CH.sub.2 
OCH.sub.3, --(OCH.sub.2 CH.sub.2).sub.2 OCH.sub.3, --(OCH.sub.2 
CH.sub.2).sub.3 OCH.sub.3, and the like; aryloxy radicals such as phenoxy 
and the like; as well as silyl radicals such as --Si(CH.sub.3).sub.3, 
--Si(OCH.sub.3).sub.3, --Si(C.sub.3 H.sub.7).sub.3, and the like; amino 
radicals such as --NH.sub.2, --N(CH.sub.3).sub.2, --NHCH.sub.3, 
--NH(C.sub.2 H.sub.5), and the like; arylphosphine radicals such as 
--P(C.sub.6 H.sub.5).sub.2, and the like; acyl radicals such as 
--C(O)CH.sub.3, --C(O)C.sub.2 H.sub.5, --C(O)C.sub.6 H.sub.5, and the 
like; carbonyloxy radicals such as --C(O)OCH.sub.3 and the like; 
oxycarbonyl radicals such as --O(CO)C.sub.6 H.sub.5, and the like; amido 
radicals such as --CONH.sub.2, --CON(CH.sub.3).sub.2, --NHC(O)CH.sub.3, 
and the like; sulfonyl radicals such as --S(O).sub.2 C.sub.2 H.sub.5 and 
the like; sulfinyl radicals such as --S(O)CH.sub.3 and the like; sulfenyl 
radicals such as --SCH.sub.3, --SC.sub.2 H.sub.5, --SC.sub.6 H.sub.5, and 
the like; phosphonyl radicals such as --P(O)(C.sub.6 H.sub.5).sub.2, 
--P(O)(CH.sub.3).sub.2, --P(O)(C.sub.2 H.sub.5).sub.2, --P(O)(C.sub.3 
H.sub.7).sub.2, --P(O)(C.sub.4 H.sub.9).sub.2, --P(O)(C.sub.6 
H.sub.13).sub.2, --P(O)CH.sub.3 (C.sub.6 H.sub.5), --P(O)(H)(C.sub.6 
H.sub.5), and the like. 
Specific illustrative examples of such organophosphite ligands include the 
following: 
2-t-butyl-4-methoxyphenyl(3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2' 
-diyl)phosphite having the formula: 
##STR11## 
methyl(3,3'-di-t-butyl-5,5 '-dimethoxy-1,1'-biphenyl-2,2'-diyl)phosphite 
having the formula: 
##STR12## 
6,6'-4,4'-bis(1,1-dimethylethyl)-1,1'-binaphthyl!-2,2'-diyl!bis(oxy)!bi 
s 
-dibenzo d,f!1,3,2!-dioxaphosphepin having the formula: 
##STR13## 
6,6'-3,3'-bis(1,1-dimethylethyl)-5,5'-dimethoxy-1,1'-biphenyl!-2,2'-diy 
l 
!bis(oxy)!bis-dibenzod,f!1,3,2!dioxaphosphepin having the formula: 
##STR14## 
6,6'-3,3',5,5'-tetrakis(1,1-dimethylpropyl)-1,1'-biphenyl!-2,2'-diyl!bi 
s 
(oxy)!bis-dibenzo d,f!1,3,2!dioxaphosphepin having the formula: 
##STR15## 
6,6'-3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl!-2,2'-diyl!bis( 
o 
xy)!bis-dibenzo d,f!1,3,2!-dioxaphosphepin having the formula: 
##STR16## 
(2R,4R)-di2,2'-(3,3',5,5'-tetrakis-tert-amyl-1, 
1'-biphenyl)!-2,4-pentyldiphosphite having the formula: 
##STR17## 
(2R,4R)-di2,2'-(3,3',5,5'-tetrakis-tert-butyl-1,1'-biphenyl)!-2,4-pentyld 
i 
phosphite having the formula: 
##STR18## 
(2R,4R)-di2,2'-(3,3'-di-amyl-5,5'-dimethoxy-1,1'-biphenyl)!-2,4-pentyldip 
h 
osphite having the formula: 
##STR19## 
(2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-dimethyl-1,1'-biphenyl)!-2,4-pent 
y 
ldiphosphite having the formula: 
##STR20## 
(2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-diethoxy-1,1'-biphenyl)!-2,4-pent 
y 
ldiphosphite having the formula: 
##STR21## 
(2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-diethyl-1,1'-biphenyl)!-2,4-penty 
l 
diphosphite having the formula: 
##STR22## 
(2R,4R)-di2,2'-(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl)!-2,4-pen 
t 
yldiphosphite having the formula: 
##STR23## 
6-2'-(4,6-bis(1,1-dimethylethyl)-1,3,2-benzodioxaphosphol-2-yl)oxy!-3,3 
' 
-bis(1,1-dimethylethyl)-5,5'-dimethoxy 
1,1'-biphenyl!-2-yl!oxy!-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxydibenzo 
d,f!1,3,2!dioxaphosphepin having the formula: 
##STR24## 
6-2'-1,3,2-benzodioxaphosphol-2-yl)oxy!-3,3'-bis(1,1-dimethylethyl)-5,5 
' 
-dimethoxy1,1'-biphenyl!-2-yl!oxy!-4,8-bis(1,1-dimethylethyl)-2,10-dimetho 
xydibenzod,f!1,3,2!dioxaphosphepin having the formula: 
##STR25## 
6-2'-(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl)oxy!-3,3'-bis 
(1,1-dimethylethyl)-5,5'-dimethoxy1,1'-biphenyl!-2-yl!oxy!-4,8-bis(1,1-di 
methylethyl)-2,10-dimethoxydibenzod,f!1,3,2!dioxaphosphepin having the 
formula: 
##STR26## 
2'-4,8-bis(1,1-dimethylethyl)-2,10-dimethoxydibenzod,f!1,3,2!-dioxapho 
s 
phepin-6-yl!oxyl!-3,3'-bis( 1,1-dimethylethyl)-5,5'-dimethoxyl 
1,1'-biphenyl!-2-yl bis(4-hexylphenyl)ester of phosphorous acid having 
the formula: 
##STR27## 
2-2-4,8,-bis(1,1-dimethylethyl), 
2,10-dimethoxydibenzo-d,f!1,3,2!dioxophosphepin-6-yl!oxy!-3-(1,1-dimethy 
lethyl)-5-methoxyphenyl!methyl!-4-methoxy, 6-(1,1-dimethylethyl)phenyl 
diphenyl ester of phosphorous acid having the formula: 
##STR28## 
3-methoxy-1,3-cyclohexamethylene 
tetrakis3,6-bis(1,1-dimethylethyl)-2-naphthalenyl!ester of phosphorous 
acid having the formula: 
##STR29## 
2,5-bis(1,1-dimethylethyl)-1,4-phenylene 
tetrakis2,4-bis(1,1-dimethylethyl)phenyl!ester of phosphorous acid having 
the formula: 
##STR30## 
methylenedi-2,1-phenylene tetrakis2,4-bis(1,1-dimethylethyl)phenyl!ester 
of phosphorous acid having the formula: 
##STR31## 
1,1'-biphenyl!-2,2'-diyl 
tetrakis2-(1,1-dimethylethyl)-4-methoxyphenyl!ester of phosphorous acid 
having the formula: 
##STR32## 
Still other illustrative organophosphorus ligands useful in this invention 
include those disclosed in U.S. patent application Ser. No. (D-17459-1), 
filed on an even date herewith, the disclosure of which is incorporated 
herein by reference. 
The metal-ligand complex catalysts employable in this invention may be 
formed by methods known in the art. The metal-ligand complex catalysts may 
be in homogeneous or heterogeneous form. For instance, preformed metal 
hydrido-carbonyl-organophosphorus ligand catalysts may be prepared and 
introduced into the reaction mixture of a hydroformylation process. More 
preferably, the metal-organophosphorus ligand complex catalysts can be 
derived from a metal catalyst precursor which may be introduced into the 
reaction medium for in situ formation of the active catalyst. For example, 
rhodium catalyst precursors such as rhodium dicarbonyl acetylacetonate, 
Rh.sub.2 O.sub.3, Rh.sub.4 (CO).sub.12, Rh.sub.6 (CO).sub.16, 
Rh(NO.sub.3).sub.3 and the like may be introduced into the reaction 
mixture along with the organophosphorus ligand for the in situ formation 
of the active catalyst. In a preferred embodiment of this invention, 
rhodium dicarbonyl acetylacetonate is employed as a rhodium precursor and 
reacted in the presence of a solvent with the organophosphorus ligand to 
form a catalytic rhodium-organophosphorus ligand complex precursor which 
is introduced into the reactor along with excess free organophosphorus 
ligand for the in situ formation of the active catalyst. In any event, it 
is sufficient for the purpose of this invention that carbon monoxide, 
hydrogen and organophosphorus compound are all ligands that are capable of 
being complexed with the metal and that an active metal-ligand catalyst is 
present in the reaction mixture under the conditions used in the 
hydroformylation reaction. 
More particularly, a catalyst precursor composition can be formed 
consisting essentially of a solubilized metal-ligand complex precursor 
catalyst, an organic solvent and free ligand. Such precursor compositions 
may be prepared by forming a solution of a metal starting material, such 
as a metal oxide, hydride, carbonyl or salt, e.g. a nitrate, which may or 
may not be in complex combination with a ligand as defined herein. Any 
suitable metal starting material may be employed, e.g. rhodium dicarbonyl 
acetylacetonate, Rh.sub.2 O.sub.3, Rh.sub.4 (CO).sub.12, Rh.sub.6 
(CO).sub.16, Rh(NO.sub.3).sub.3, and organophosphorus ligand rhodium 
carbonyl hydrides. Carbonyl and organophosphorus ligands, if not already 
complexed with the initial metal, may be complexed to the metal either 
prior to or in situ during the hydroformylation process. 
By way of illustration, the preferred catalyst precursor composition of 
this invention consists essentially of a solubilized rhodium carbonyl 
organophosphorus ligand complex precursor catalyst, a solvent and free 
organophosphorus ligand prepared by forming a solution of rhodium 
dicarbonyl acetylacetonate, an organic solvent and a ligand as defined 
herein. The organophosphorus ligand readily replaces one of the carbonyl 
ligands of the rhodium acetylacetonate complex precursor at room 
temperature as witnessed by the evolution of carbon monoxide gas. This 
substitution reaction may be facilitated by heating the solution if 
desired. Any suitable organic solvent in which both the rhodium dicarbonyl 
acetylacetonate complex precursor and rhodium organophosphorus ligand 
complex precursor are soluble can be employed. The amounts of rhodium 
complex catalyst precursor, organic solvent and organophosphorus ligand, 
as well as their preferred embodiments present in such catalyst precursor 
compositions may obviously correspond to those amounts employable in the 
hydroformylation process of this invention. Experience has shown that the 
acetylacetonate ligand of the precursor catalyst is replaced after the 
hydroformylation process has begun with a different ligand, e.g., 
hydrogen, carbon monoxide or organophosphorus ligand, to form the active 
complex catalyst as explained above. In a continuous process, the 
acetylacetone which is freed from the precursor catalyst under 
hydroformylation conditions is removed from the reaction medium with the 
product aldehyde and thus is in no way detrimental to the hydroformylation 
process. The use of such preferred rhodium complex catalytic precursor 
compositions provides a simple economical and efficient method for 
handling the rhodium precursor metal and hydroformylation start-up. 
Accordingly, the metal-ligand complex catalysts used in the process of this 
invention consists essentially of the metal complexed with carbon monoxide 
and a ligand, said ligand being bonded (complexed) to the metal in a 
chelated and/or non-chelated fashion. Moreover, the terminology "consists 
essentially of", as used herein, does not exclude, but rather includes, 
hydrogen complexed with the metal, in addition to carbon monoxide and the 
ligand. Further, such terminology does not exclude the possibility of 
other organic ligands and/or anions that might also be complexed with the 
metal. Materials in amounts which unduly adversely poison or unduly 
deactivate the catalyst are not desirable and so the catalyst most 
desirably is free of contaminants such as metal-bound halogen (e.g., 
chlorine, and the like) although such may not be absolutely necessary. The 
hydrogen and/or carbonyl ligands of an active metal-ligand complex 
catalyst may be present as a result of being ligands bound to a precursor 
catalyst and/or as a result of in situ formation, e.g., due to the 
hydrogen and carbon monoxide gases employed in hydroformylation process of 
this invention. 
As noted the hydroformylation reactions involve the use of a metal-ligand 
complex catalyst as described herein. Of course mixtures of such catalysts 
can also be employed if desired. Mixtures of hydroformylation catalysts 
and hydrocarbonylation catalysts may also be employed if desired. The 
amount of metal-ligand complex catalyst present in the reaction medium of 
a given hydroformylation reaction need only be that minimum amount 
necessary to provide the given metal concentration desired to be employed 
and which will furnish the basis for at least the catalytic amount of 
metal necessary to catalyze the particular hydroformylation reaction 
involved such as disclosed e.g. in the above-mentioned patents. In 
general, the catalyst concentration can range from several parts per 
million to several percent by weight. Organophosphorus ligands can be 
employed in the above-mentioned catalysts in a molar ratio of generally 
from about 0.5:1 or less to about 1000:1 or greater. The catalyst 
concentration will be dependent on the hydroformylation reaction 
conditions and solvent employed. 
In general, the organophosphorus ligand concentration in hydroformylation 
reaction mixtures may range from between about 0.005 and 25 weight percent 
based on the total weight of the reaction mixture. Preferably the ligand 
concentration is between 0.01 and 15 weight percent, and more preferably 
is between about 0.05 and 10 weight percent on that basis. 
In general, the concentration of the metal in the hydroformylation reaction 
mixtures may be as high as about 2000 parts per million by weight or 
greater based on the weight of the reaction mixture. Preferably the metal 
concentration is between about 50 and 1000 parts per million by weight 
based on the weight of the reaction mixture, and more preferably is 
between about 70 and 800 parts per million by weight based on the weight 
of the reaction mixture. 
In addition to the metal-ligand complex catalyst, free ligand (i.e., ligand 
that is not complexed with the rhodium metal) may also be present in the 
hydroformylation reaction medium. The free ligand may correspond to any of 
the above-defined phosphorus-containing ligands discussed above as 
employable herein. It is preferred that the free ligand be the same as the 
ligand of the metal-ligand complex catalyst employed. However, such 
ligands need not be the same in any given process. The hydroformylation 
reaction may involve up to 100 moles, or higher, of free organophosphorus 
ligand per mole of metal in the hydroformylation reaction medium. 
Preferably the hydroformylation reaction is carried out in the presence of 
from about 0.25 to about 50 moles of coordinatable phosphorus, and more 
preferably from about 0.5 to about 30 moles of coordinatable phosphorus, 
per mole of metal present in the reaction medium; said amounts of 
coordinatable phosphorus being the sum of both the amount of coordinatable 
phosphorus that is bound (complexed) to the rhodium metal present and the 
amount of free (non-complexed) coordinatable phosphorus present. Of 
course, if desired, make-up or additional coordinatable phosphorus can be 
supplied to the reaction medium of the hydroformylation reaction at any 
time and in any suitable manner, e.g. to maintain a predetermined level of 
free ligand in the reaction medium. 
As indicated above, the hydroformylation catalyst may be in heterogeneous 
form during the reaction and/or during the product separation. Such 
catalysts are particularly advantageous in the hydroformylation of olefins 
or alkadienes to produce high boiling or thermally sensitive aldehydes, so 
that the catalyst may be separated from the products by filtration or 
decantation at low temperatures. For example, the rhodium catalyst may be 
attached to a support so that the catalyst retains its solid form during 
both the hydroformylation and separation stages, or is soluble in a liquid 
reaction medium at high temperatures and then is precipitated on cooling. 
As an illustration, the rhodium catalyst may be impregnated onto any solid 
support, such as inorganic oxides, (e.g., alumina, silica, titania, or 
zirconia) carbon, or ion exchange resins. The catalyst may be supported 
on, or intercalated inside the pores of, a zeolite or glass; the catalyst 
may also be dissolved in a liquid film coating the pores of said zeolite 
or glass. Such zeolite-supported catalysts are particularly advantageous 
for producing one or more regioisomeric aldehydes in high selectivity, as 
determined by the pore size of the zeolite. The techniques for supporting 
catalysts on solids, such as incipient wetness, which will be known to 
those skilled in the art. The solid catalyst thus formed may still be 
complexed with one or more of the ligands defined above. Descriptions of 
such solid catalysts may be found in for example: J. Mol. Cat. 1991, 70, 
363-368; Catal. Lett. 1991, 8, 209-214; J. Organomet. Chem, 1991, 403, 
221-227; Nature, 1989, 339, 454-455; J. Catal. 1985, 96, 563-573; J. Mol. 
Cat. 1987, 39, 243-259. 
The rhodium catalyst may be attached to a thin film or membrane support, 
such as cellulose acetate or polyphenylenesulfone, as described in for 
example J. Mol. Cat. 1990, 63, 213-221. 
The rhodium catalyst may be attached to an insoluble polymeric support 
through an organophosphorus-containing ligand, such as a phosphine or 
phosphite, incorporated into the polymer. Such polymer-supported ligands 
are well known, and include such commercially available species as the 
divinylbenzene/polystyrene-supported supported triphenylphosphine. The 
supported ligand is not limited by the choice of polymer or 
phosphorus-containing species incorporated into it. Descriptions of 
polymer-supported catalysts may be found in for example: J. Mol. Cat. 
1993, 83, 17-35; Chemtech 1983, 46; J. Am. Chem. Soc. 1987, 109, 
7122-7127. 
In the heterogeneous catalysts described above, the catalyst may remain in 
its heterogeneous form during the entire hydroformylation and catalyst 
separation process. In another embodiment of the invention, the catalyst 
may be supported on a polymer which, by the nature of its molecular 
weight, is soluble in the reaction medium at elevated temperatures, but 
precipitates upon cooling, thus facilitating catalyst separation from the 
reaction mixture. Such "soluble" polymer-supported catalysts are described 
in for example: Polymer, 1992, 33, 161; J. Org. Chem. 1989, 54, 2726-2730. 
When the rhodium catalyst is in a heterogeneous or supported form, the 
reaction may be carried out in the gas phase. More preferably, the 
reaction is carried out in the slurry phase due to the high boiling points 
of the products, and to avoid decomposition of the product aldehydes. The 
catalyst may then be separated from the product mixture by filtration or 
decantation. 
The hydroformylation reaction conditions may include any suitable type 
hydroformylation conditions heretofore employed for producing aldehydes. 
For instance, the total gas pressure of hydrogen, carbon monoxide and 
olefin or alkadiene starting compound of the hydroformylation process may 
range from about 1 to about 10,000 psia. In general, the hydroformylation 
process is operated at a total gas pressure of hydrogen, carbon monoxide 
and olefin or alkadiene starting compound of less than about 1500 psia and 
more preferably less than about 1000 psia, the minimum total pressure 
being limited predominately by the amount of reactants necessary to obtain 
a desired rate of reaction. The total pressure employed in the 
hydroformylation reaction may range in general from about 20 to about 3000 
psia, preferably from about 50 to 1500 psia. The total pressure of the 
hydroformylation process will be dependent on the particular catalyst 
system employed. 
More specifically, the carbon monoxide partial pressure of the 
hydroformylation process in general may range from about 1 to about 3000 
psia, and preferably from about 3 to about 1500 psia, while the hydrogen 
partial pressure in general may range from about 1 to about 3000 psia, and 
preferably from about 3 to about 1500 psia. In general, the molar ratio of 
carbon monoxide to gaseous hydrogen may range from about 100:1 or greater 
to about 1:100 or less, the preferred carbon monoxide to gaseous hydrogen 
molar ratio being from about 1:10 to about 10:1. The carbon monoxide and 
hydrogen partial pressures will be dependent in part on the particular 
catalyst system employed. 
Carbon monoxide partial pressure should be sufficient for the 
hydroformylation reaction, e.g., of an unsaturated alcohol, to 
6-hydroxyhexanal to occur at an acceptable rate. Hydrogen partial pressure 
must be sufficient for the hydroformylation reaction to occur at an 
acceptable rate, but not so high that hydrogenation of butadiene or 
isomerization of penten-1-ols to undesired isomers occurs. It is 
understood that carbon monoxide and hydrogen can be employed separately, 
in mixture with each other, i.e., synthesis gas, or may in part be 
produced in situ under reaction conditions. 
Further, the hydroformylation process may be conducted at a reaction 
temperature from about 20.degree. C. to about 200.degree. C. may be 
employed, preferably from about 50.degree. C. to about 150.degree. C., and 
more preferably from about 65.degree. C. to about 115.degree. C. The 
temperature must be sufficient for reaction to occur (which may vary with 
catalyst system employed), but not so high that ligand or catalyst 
decomposition occurs. At high temperatures (which may vary with catalyst 
system employed), isomerization of penten-1-ols to undesired isomers may 
occur. 
Of course, it is to be also understood that the hydroformylation reaction 
conditions employed will be governed by the aldehyde product desired. 
In the penten-1-ol hydroformylation step of this invention, the penten-1-ol 
hydroformylation reaction can be conducted at a penten-1-ol conversion 
and/or carbon monoxide partial pressure sufficient to selectively produce 
the 6-hydroxyhexanals. In the penten-1-ol hydroformylation reaction, the 
penten-1-ol conversion may be complete or incomplete, and the partial 
pressure of carbon monoxide may be higher or lower than the partial 
pressure of hydrogen as described above. 
The hydroformylation reaction is also conducted in the presence of water or 
an organic solvent for the metal-ligand complex catalyst and free ligand. 
Depending on the particular catalyst and reactants employed, suitable 
organic solvents include, for example, alcohols, alkanes, alkenes, 
alkynes, ethers, aldehydes, higher boiling aldehyde condensation 
byproducts, ketones, esters, amides, tertiary amines, aromatics and the 
like. Any suitable solvent which does not unduly adversely interfere with 
the intended hydroformylation reaction can be employed and such solvents 
may include those disclosed heretofore commonly employed in known metal 
catalyzed hydroformylation reactions. Mixtures of one or more different 
solvents may be employed if desired. In general, with regard to the 
production of aldehydes, it is preferred to employ aldehyde compounds 
corresponding to the aldehyde products desired to be produced and/or 
higher boiling aldehyde liquid condensation byproducts as the main organic 
solvents as is common in the art. Such aldehyde condensation byproducts 
can also be preformed if desired and used accordingly. Illustrative 
preferred solvents employable in the production of aldehydes include 
ketones (e.g. acetone and methylethyl ketone), esters (e.g. ethyl 
acetate), hydrocarbons (e.g. toluene), nitrohydrocarbons (e.g. 
nitrobenzene), ethers (e.g. tetrahydrofuran (THF) and glyme), 
1,4-butanediols and sulfolane. Suitable solvents are disclosed in U.S. 
Pat. No. 5,312,996. The amount of solvent employed is not critical to the 
subject invention and need only be that amount sufficient to solubilize 
the catalyst and free ligand of the hydroformylation reaction mixture to 
be treated. In general, the amount of solvent may range from about 5 
percent by weight up to about 99 percent by weight or more based on the 
total weight of the hydroformylation reaction mixture starting material. 
In an embodiment of the invention, the hydroformylation reaction mixture 
may consist of one or more liquid phases, e.g. a polar and a nonpolar 
phase. Such processes are often advantageous in, for example, separating 
products from catalyst and/or reactants by partitioning into either phase. 
In addition, product selectivities dependent upon solvent properties may 
be increased by carrying out the reaction in that solvent. An application 
of this technology is the aqueous-phase hydroformylation of olefins or 
alkadienes employing sulfonated phosphine ligands for the rhodium 
catalyst. A process carried out in aqueous solvent is particularly 
advantageous for the preparation of aldehydes because the products may be 
separated from the catalyst by extraction into an organic solvent. 
Alternatively, aldehydes which tend to undergo self-condensation 
reactions, are expected to be stabilized in aqueous solution as the 
aldehyde hydrates. 
As described herein, the phosphorus-containing ligand for the rhodium 
hydroformylation catalyst may contain any of a number of substituents, 
such as cationic or anionic substituents, which will render the catalyst 
soluble in a polar phase, e.g. water. Optionally, a phase-transfer 
catalyst may be added to the reaction mixture to facilitate transport of 
the catalyst, reactants, or products into the desired solvent phase. The 
structure of the ligand or the phase-transfer catalyst is not critical and 
will depend on the choice of conditions, reaction solvent, and desired 
products. 
When the catalyst is present in a multiphasic system, the catalyst may be 
separated from the reactants and/or products by conventional methods such 
as extraction or decantation. The reaction mixture itself may consist of 
one or more phases; alternatively, the multiphasic system may be created 
at the end of the reaction by for example addition of a second solvent to 
separate the products from the catalyst. See, for example, U.S. Pat. No. 
5,180,854, the disclosure of which is incorporated herein by reference. 
In an embodiment of the process of this invention, an olefin can be 
hydroformylated along with an unsaturated alcohol or alkadiene using the 
above-described metal-ligand complex catalysts. In such cases, an aldehyde 
derivative of the olefin is also produced along with the hydroxyaldehydes 
or pentenals. It has been found that the unsaturated alcohol reacts to 
form a complex with the metal more rapidly than certain of the olefins and 
requires more forcing conditions to be hydroformylated itself than certain 
of the olefins. 
Mixtures of different olefinic or alkadiene starting materials can be 
employed, if desired, in the hydroformylation reactions. More preferably 
the hydroformylation reactions are especially useful for the production of 
6-hydroxyhexanals, by hydroformylating unsaturated alcohols in the 
presence of alpha olefins containing from 2 to 30, preferably 4 to 20, 
carbon atoms, including isobutylene, and internal olefins containing from 
4 to 20 carbon atoms as well as starting material mixtures of such alpha 
olefins and internal olefins. Commercial alpha olefins containing four or 
more carbon atoms may contain minor amounts of corresponding internal 
olefins and/or their corresponding saturated hydrocarbon and that such 
commercial olefins need not necessarily be purified from same prior to 
being hydroformylated. 
Illustrative of other olefinic starting materials include alpha-olefins, 
internal olefins, 1,3-dienes, alkyl alkenoates, alkenyl alkanoates, 
alkenyl alkyl ethers, alkenols, alkenals, and the like, e.g., ethylene, 
propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 
1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 
1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 
2-butene, 2-methyl propene (isobutylene), 2-methylbutene, 2-pentene, 
2-hexene, 3-hexane, 2-heptene, cyclohexene, propylene dimers, propylene 
trimers, propylene tetramers, piperylene, isoprene, 2-ethyl-1-hexene, 
2-octene, styrene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene, 
3-cyclohexyl-1-butene, allyl alcohol, allyl butyrate, hex-1-en-4-ol, 
oct-1-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl acetate, vinyl 
propionate, allyl propionate, methyl methacrylate, vinyl ethyl ether, 
vinyl methyl ether, vinyl cyclohexene, allyl ethyl ether, methyl 
pentenoate, n-propyl-7-octenoate, pentenals, e.g., 2-pentenal, 3-pentenal 
and 4-pentenal; penten-1-ols, e.g., 2-penten-1-ol, 3-penten-1-ol and 
4-penten-1-ol; 3-butenenitrile, 3-pentenenitrile, 5-hexenamide, 4-methyl 
styrene, 4-isopropyl styrene, 4-tert-butyl styrene, alpha-methyl styrene, 
4-tert-butyl-alpha-methyl styrene, 1,3-diisopropenylbenzene, eugenol, 
iso-eugenol, safrole, iso-safrole, anethol, 4-allylanisole, indene, 
limonene, beta-pinene, dicyclopentadiene, cyclooctadiene, camphene, 
linalool, and the like. Other illustrative olefinic compounds may include, 
for example, p-isobutylstyrene, 2-vinyl-6-methoxynaphthylene, 
3-ethenylphenyl phenyl ketone, 4-ethenylphenyl-2-thienylketone, 
4-ethenyl-2-fluorobiphenyl, 4-(1,3-dihydro-1-oxo-2H-isoindol-2-yl)styrene, 
2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether, 
propenylbenzene, isobutyl-4-propenylbenzene, phenyl vinyl ether and the 
like. Other olefinic compounds include substituted aryl ethylenes as 
described in U.S. Pat. No. 4,329,507, the disclosure of which is 
incorporated herein by reference. 
As indicated above, it is generally preferred to carry out the 
hydroformylation process of this invention in a continuous manner. In 
general, continuous hydroformylation processes are well known in the art 
and may involve: (a) hydroformylating the unsaturated alcohol or alkadiene 
starting material(s) with carbon monoxide and hydrogen in a liquid 
homogeneous reaction mixture comprising a solvent, the metal-ligand 
complex catalyst, and free ligand; (b) maintaining reaction temperature 
and pressure conditions favorable to the hydroformylation of the 
unsaturated alcohol or alkadiene starting material(s); (c) supplying 
make-up quantities of the unsaturated alcohol or alkadiene starting 
material(s), carbon monoxide and hydrogen to the reaction medium as those 
reactants are used up; and (d) recovering the desired aldehyde 
hydroformylation product(s) in any manner desired. The continuous process 
can be carried out in a single pass mode, i.e., wherein a vaporous mixture 
comprising unreacted unsaturated alcohol or alkadiene starting material(s) 
and vaporized aldehyde product is removed from the liquid reaction mixture 
from whence the aldehyde product is recovered and make-up unsaturated 
alcohol or alkadiene starting material(s), carbon monoxide and hydrogen 
are supplied to the liquid reaction medium for the next single pass 
through without recycling the unreacted unsaturated alcohol or alkadiene 
starting material(s). However, it is generally desirable to employ a 
continuous process that involves either a liquid and/or gas recycle 
procedure. Such types of recycle procedure are well known in the art and 
may involve the liquid recycling of the metal-ligand complex catalyst 
solution separated from the desired aldehyde reaction product(s), such as 
disclosed e.g., in U.S. Pat. No. 4,148,830 or a gas cycle procedure such 
as disclosed e.g., in U.S. Pat. No. 4,247,486, as well as a combination of 
both a liquid and gas recycle procedure if desired. The disclosures of 
said U.S. Pat. Nos. 4,148,830 and 4,247,486 are incorporated herein by 
reference thereto. The most preferred hydroformylation process of this 
invention comprises a continuous liquid catalyst recycle process. 
Illustrative substituted and unsubstituted hydroxyaldehydes that can be 
prepared by the processes of this invention include, for example, 
6-hydroxyhexanals such as 6-hydroxyhexanal and substituted 
6-hydroxyhexanals (e.g., 2-methyl-6-hydroxyhexanal and 
3,4-dimethyl-6-hydroxyhexanal) and the like, including mixtures of one or 
more of the above 6-hydroxyhexanals. Illustrative of suitable substituted 
and unsubstituted hydroxyaldehydes (including derivatives of 
hydroxyaldehydes) include those permissible substituted and unsubstituted 
hydroxyaldehydes which are described in Kirk-Othmer, Encyclopedia of 
Chemical Technology, Fourth Edition, 1996, the pertinent portions of which 
are incorporated herein by reference. As used herein, the term 
"hydroxyaldehydes" is contemplated to include, but is not limited to, 
6-hydroxyhexanals and its cyclic lactols, hydrates or oligomers. 
As indicated above, the hydroformylation reactions may involve a liquid 
catalyst recycle procedure. Such liquid catalyst recycle procedures are 
known as seen disclosed, e.g., in U.S. Pat. Nos. 4,668,651; 4,774,361; 
5,102,505 and 5,110,990. For instance, in such liquid catalyst recycle 
procedures it is common place to continuously or intermittently remove a 
portion of the liquid reaction product medium, containing, e.g., the 
aldehyde product, the solubilized metal-ligand complex catalyst, free 
ligand, and organic solvent, as well as byproducts produced in situ by the 
hydroformylation, e.g., aldehyde condensation byproducts etc., and 
unreacted unsaturated alcohol or alkadiene starting material, carbon 
monoxide and hydrogen (syn gas) dissolved in said medium, from the 
hydroformylation reactor, to a distillation zone, e.g., a 
vaporizer/separator wherein the desired aldehyde product is distilled in 
one or more stages under normal, reduced or elevated pressure, as 
appropriate, and separated from the liquid medium. The vaporized or 
distilled desired aldehyde product so separated may then be condensed and 
recovered in any conventional manner as discussed above. The remaining 
non-volatilized liquid residue which contains metal-ligand complex 
catalyst, solvent, free ligand and usually some undistilled aldehyde 
product is then recycled back, with or without further treatment as 
desired, along with whatever by-product and non-volatilized gaseous 
reactants that might still also be dissolved in said recycled liquid 
residue, in any conventional manner desired, to the hydroformylation 
reactor, such as disclosed e.g., in the above-mentioned patents. Moreover 
the reactant gases so removed by such distillation from the vaporizer may 
also be recycled back to the reactor if desired. 
In an embodiment of this invention, the hydroxyaldehyde mixtures may be 
separated from the other components of the crude reaction mixtures in 
which the aldehyde mixtures are produced by any suitable method. Suitable 
separation methods include, for example, solvent extraction, 
crystallization, distillation, vaporization, phase separation, wiped film 
evaporation, falling film evaporation and the like. It may be desired to 
remove the aldehyde products from the crude reaction mixture as they are 
formed through the use of trapping agents as described in published Patent 
Cooperation Treaty Patent Application WO 88/08835. A method for separating 
the aldehyde mixtures from the other components of the crude reaction 
mixtures is by membrane separation. Such membrane separation can be 
achieved as set out in U.S. Pat. No. 5,430,194 and copending U.S. patent 
application Ser. No. 08/430,790, filed May 5, 1995, both incorporated 
herein by reference. 
As indicated above, at the conclusion of (or during) the process of this 
invention, the desired hydroxyaldehydes may be recovered from the reaction 
mixtures used in the process of this invention. For example, the recovery 
techniques disclosed in U.S. Pat. Nos. 4,148,830 and 4,247,486 can be 
used. For instance, in a continuous liquid catalyst recycle process the 
portion of the liquid reaction mixture (containing 6-hydroxyhexanal 
product, catalyst, etc.) removed from the reactor can be passed to a 
vaporizer/separator wherein the desired aldehyde product can be separated 
via distillation, in one or more stages, under normal, reduced or elevated 
pressure, from the liquid reaction solution, condensed and collected in a 
product receiver, and further purified if desired. The remaining 
non-volatilized catalyst containing liquid reaction mixture may then be 
recycled back to the reactor as may, if desired, any other volatile 
materials, e.g., unreacted olefin or alkadiene, together with any hydrogen 
and carbon monoxide dissolved in the liquid reaction after separation 
thereof from the condensed 6-hydroxyhexanal product, e.g., by distillation 
in any conventional manner. It is generally desirable to employ an 
organophosphorus ligand whose molecular weight exceeds that of the higher 
boiling aldehyde oligomer byproduct corresponding to the hydroxyhexanals 
being produced in the hydroformylation process. Another suitable recovery 
technique is solvent extraction or crystallization. In general, it is 
preferred to separate the desired hydroxyhexanals from the 
catalyst-containing reaction mixture under reduced pressure and at low 
temperatures so as to avoid possible degradation of the organophosphorus 
ligand and reaction products. When an alpha-mono-olefin reactant is also 
employed, the aldehyde derivative thereof can also be separated by the 
above methods. 
More particularly, distillation and separation of the desired aldehyde 
product from the metal-ligand complex catalyst containing product solution 
may take place at any suitable temperature desired. In general, it is 
recommended that such distillation take place at relatively low 
temperatures, such as below 150.degree. C., and more preferably at a 
temperature in the range of from about 50.degree. C. to about 130.degree. 
C. It is also generally recommended that such aldehyde distillation take 
place under reduced pressure, e.g., a total gas pressure that is 
substantially lower than the total gas pressure employed during 
hydroformylation when low boiling aldehydes (e.g., C.sub.5 and C.sub.6) 
are involved or under vacuum when high boiling aldehydes (e.g. C.sub.7 or 
greater) are involved. For instance, a common practice is to subject the 
liquid reaction product medium removed from the hydroformylation reactor 
to a pressure reduction so as to volatilize a substantial portion of the 
unreacted gases dissolved in the liquid medium which now contains a much 
lower synthesis gas concentration than was present in the hydroformylation 
reaction medium to the distillation zone, e.g. vaporizer/separator, 
wherein the desired aldehyde product is distilled. In general, 
distillation pressures ranging from vacuum pressures on up to total gas 
pressure of about 50 psig should be sufficient for most purposes. 
Particularly when conducting the process of this invention in a continuous 
liquid recycle mode employing an organophosphite ligand, undesirable 
acidic byproducts (e.g., a hydroxy alkyl phosphonic acid) may result due 
to reaction of the organophosphite ligand and the hydroxyaldehydes over 
the course of the process. The formation of such byproducts undesirably 
lowers the concentration of the ligand. Such acids are often insoluble in 
the reaction mixture and such insolubility can lead to precipitation of an 
undesirable gelatinous byproduct and may also promote the autocatalytic 
formation of further acidic byproducts. The organopolyphosphite ligands 
used in the process of this invention have good stability against the 
formation of such acids. However, if this problem does occur, the liquid 
reaction effluent stream of a continuous liquid recycle process may be 
passed, prior to (or more preferably after) separation of the desired 
hydroxyhexanal product therefrom, through any suitable weakly basic anion 
exchange resin, such as a bed of amine Amberlyst.RTM. resin, e.g., 
Amberlyst.RTM. A-21, and the like, to remove some or all of the 
undesirable acidic byproducts prior to its reincorporation into the 
hydroformylation reactor. If desired, more than one such basic anion 
exchange resin bed, e.g. a series of such beds, may be employed and any 
such bed may be easily removed and/or replaced as required or desired. 
Alternatively if desired, any part or all of the acid-contaminated 
catalyst recycle stream may be periodically removed from the continuous 
recycle operation and the contaminated liquid so removed treated in the 
same fashion as outlined above, to eliminate or reduce the amount of 
acidic by-product prior to reusing the catalyst containing liquid in the 
hydroformylation process. Likewise, any other suitable method for removing 
such acidic byproducts from the hydroformylation process of this invention 
may be employed herein if desired such as by extraction of the acid with a 
weak base (e.g., sodium bicarbonate). 
The processes useful in this invention may involve improving the catalyst 
stability of any organic solubilized rhodium-organopolyphosphite complex 
catalyzed, liquid recycle hydroformylation process directed to producing 
aldehydes from olefinic unsaturated compounds which may experience 
deactivation of the catalyst due to recovery of the aldehyde product by 
vaporization separation from a reaction product solution containing the 
organic solubilized rhodium-organopolyphosphite complex catalyst and 
aldehyde product, the improvement comprising carrying out said 
vaporization separation in the presence of a heterocyclic nitrogen 
compound. See, for example, copending U.S. patent application Ser. No. 
08/756,789, filed Nov. 26, 1996, the disclosure of which is incorporated 
herein by reference. 
The processes useful in this invention may involve improving the hydrolytic 
stability of the organophosphite ligand and thus catalyst stability of any 
organic solubilized rhodium-organophosphite ligand complex catalyzed 
hydroformylation process directed to producing aldehydes from olefinic 
unsaturated compounds, the improvement comprising treating at least a 
portion of an organic solubilized rhodium-organophosphite ligand complex 
catalyst solution derived from said process and which also contains 
phosphorus acidic compounds formed during the hydroformylation process, 
with an aqueous buffer solution in order to neutralize and remove at least 
some amount of said phosphorus acidic compounds from said catalyst 
solution, and then returning the treated catalyst solution to the 
hydroformylation reactor. See, for example, copending U.S. patent 
application Ser. Nos. 08/756,501 and 08/753,505, both filed Nov. 26, 1996, 
the disclosures of which are incorporated herein by reference. 
In an embodiment of this invention, deactivation of 
metal-organopolyphosphorus ligand complex catalysts caused by an 
inhibiting or poisoning organomonophosphorus compound can be reversed or 
at least minimized by carrying out hydroformylation processes in a 
reaction region where the hydroformylation reaction rate is of a negative 
or inverse order in carbon monoxide and optionally at one or more of the 
following conditions: at a temperature such that the temperature 
difference between reaction product fluid temperature and inlet coolant 
temperature is sufficient to prevent and/or lessen cycling of carbon 
monoxide partial pressure, hydrogen partial pressure, total reaction 
pressure, hydroformylation reaction rate and/or temperature during said 
hydroformylation process; at a carbon monoxide conversion sufficient to 
prevent and/or lessen cycling of carbon monoxide partial pressure, 
hydrogen partial pressure, total reaction pressure, hydroformylation 
reaction rate and/or temperature during said hydroformylation process; at 
a hydrogen conversion sufficient to prevent and/or lessen cycling of 
carbon monoxide partial pressure, hydrogen partial pressure, total 
reaction pressure, hydroformylation reaction rate and/or temperature 
during said hydroformylation process; and at an olefinic unsaturated 
compound conversion sufficient to prevent and/or lessen cycling of carbon 
monoxide partial pressure, hydrogen partial pressure, total reaction 
pressure, hydroformylation reaction rate and/or temperature during said 
hydroformylation process. See, for example, copending U.S. patent 
application Ser. No. 08/756,499, filed Nov. 26, 1996, the disclosure of 
which is incorporated herein by reference. 
As indicated above, the substituted and unsubstituted penten-1-ols and 
6-hydroxyhexanals produced by the hydroformylation step of this invention 
can be separated by conventional techniques such as distillation, 
extraction, precipitation, crystallization, membrane separation, phase 
separation or other suitable means. For example, a crude reaction product 
can be subjected to a distillation-separation at atmospheric or reduced 
pressure through a packed distillation column. Reactive distillation may 
be useful in conducting the hydroformylation reaction step. 
A one-step process involving the reductive hydroformylation of one or more 
substituted or unsubstituted alkadienes to produce one or more substituted 
or unsubstituted 6-hydroxyhexanals is disclosed in copending U.S. patent 
application Ser. No. (D-17488-1), filed on an even date herewith, the 
disclosure of which is incorporated herein by reference. Another process 
involving the production of one or more substituted or unsubstituted 
hydroxyhexanals by reductive hydroformylation/hydroformylation is 
disclosed in copending U.S. patent application Ser. No. (D-17477-1), filed 
on an even date herewith, the disclosure of which is incorporated herein 
by reference. 
An embodiment of this invention relates to a process for producing one or 
more substituted or unsubstituted 6-hydroxyhexanals which comprises: 
(a) subjecting one or more substituted or unsubstituted alkadienes, e.g., 
butadiene, to hydrocarbonylation in the presence of a hydrocarbonylation 
catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and a 
promoter to produce one or more substituted or unsubstituted unsaturated 
alcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-ols; 
(b) optionally separating the 3-penten-1-ols, 4-penten-1-ol and/or 
2-penten-1-ols from the hydrocarbonylation catalyst; and 
(c) subjecting said one or more substituted or unsubstituted unsaturated 
alcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-ols to 
hydroformylation in the presence of a hydroformylation catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, to produce one or more 
substituted or unsubstituted 6-hydroxyhexanals. The reaction conditions in 
steps (a) and (c) may be the same or different, and the hydrocarbonylation 
catalyst in step (a) and the hydroformylation catalyst in step (c) may be 
the same or different. 
Yet another embodiment of this invention relates to a process for producing 
one or more substituted or unsubstituted 6-hydroxyhexanals which 
comprises: 
(a) subjecting one or more substituted or unsubstituted alkadienes, e.g., 
butadiene, to hydrocarbonylation in the presence of a hydrocarbonylation 
catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and a 
promoter to produce one or more substituted or unsubstituted unsaturated 
alcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or 2-penten-1-ols; 
(b) optionally separating the 3-penten-1-ols, 4-penten-1-ol and/or 
2-penten-1-ols from the hydrocarbonylation catalyst; 
(c) optionally subjecting the 2-penten-1-ols and/or 3-penten-1-ols to 
isomerization in the presence of a heterogeneous or homogeneous olefin 
isomerization catalyst to partially or completely isomerize the 
2-penten-1-ols and/or 3-penten-1-ols to 3-penten-1-ols and/or 
4-penten-1-ol; and 
(d) subjecting said one or more substituted or unsubstituted unsaturated 
alcohols comprising 2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-ol to 
hydroformylation in the presence of a hydroformylation catalyst, e.g., a 
metal-organophosphorus ligand complex catalyst, to produce one or more 
substituted or unsubstituted 6-hydroxyhexanals. The reaction conditions in 
steps (a) and (d) may be the same or different, and the hydrocarbonylation 
catalyst in step (a) and the hydroformylation catalyst in step (d) may be 
the same or different. 
The olefin isomerization catalyst in step (c) may be any of a variety of 
homogeneous or heterogeneous transition metal-based catalysts 
(particularly Ni, Rh, Pd, Pt, Co, Ru, or Ir), or may be a heterogeneous or 
homogeneous acid catalyst (particularly any acidic zeolite, polymeric 
resin, or source of H.sup.+, any of which may be modified with one or more 
transition metals). Such olefin isomerization catalysts are known in the 
art and the isomerization can be conducted by conventional procedures 
known in the art. As used herein, the term "isomerization" is contemplated 
to include, but are not limited to, all permissible isomerization 
processes which involve converting one or more substituted or 
unsubstituted 2-penten-1-ols and/or 3-penten-1-ols to one or more 
substituted or unsubstituted 4-penten-1-ols. 
When the processes of this invention are conducted in two stages (i.e., 
first producing 2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-ol under 
one set of conditions and then producing a 6-hydroxyhexanal from the 
2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-ol under another set of 
conditions), it is preferred to conduct the first stage at a temperature 
from 75.degree. C. to 110.degree. C. and at a total pressure from 250 psi 
to 1000 psi and to conduct the second stage at a temperature from 
60.degree. C. to 120.degree. C. and at a pressure from 5 psi to 500 psi. 
The same or different catalysts can be used in the first and second 
stages. The other conditions can be the same or different in both stages. 
The processes of this invention can be operated over a wide range of 
reaction rates (m/L/h=moles of product/liter of reaction solution/hour). 
Typically, the reaction rates are at least 0.01 m/L/h or higher, 
preferably at least 0.1 m/L/h or higher, and more preferably at least 0.5 
m/L/h or higher. Higher reaction rates are generally preferred from an 
economic standpoint, e.g., smaller reactor size, etc. 
The substituted and unsubstituted hydroxyaldehyde products (e.g., 
6-hydroxyhexanals) have a wide range of utilities that are well known in 
the art, e.g., they are useful as intermediates in the production of 
epsilon caprolactone, epsilon caprolactam, adipic acid and 1,6-hexanediol. 
A one-step process involving the preparation of one or more substituted or 
unsubstituted 6-hydroxyhexanals from one or more substituted or 
unsubstituted alkadienes is disclosed in copending U.S. patent application 
Ser. No. (D-17477), filed Apr. 24, 1996, the disclosure of which is 
incorporated herein by reference. 
The processes of this invention may be carried out using, for example, a 
fixed bed reactor, a fluid bed reactor, a continuous stirred tank reactor 
(CSTR) or a slurry reactor. The optimum size and shape of the catalysts 
will depend on the type of reactor used. In general, for fluid bed 
reactors, a small, spherical catalyst particle is preferred for easy 
fluidization. With fixed bed reactors, larger catalyst particles are 
preferred so the back pressure within the reactor is kept reasonably low. 
The processes of this invention can be conducted in a batch or continuous 
fashion, with recycle of unconsumed starting materials if required. The 
reaction can be conducted in a single reaction zone or in a plurality of 
reaction zones, in series or in parallel or it may be conducted batchwise 
or continuously in an elongated tubular zone or series of such zones. The 
materials of construction employed should be inert to the starting 
materials during the reaction and the fabrication of the equipment should 
be able to withstand the reaction temperatures and pressures. Means to 
introduce and/or adjust the quantity of starting materials or ingredients 
introduced batchwise or continuously into the reaction zone during the 
course of the reaction can be conveniently utilized in the processes 
especially to maintain the desired molar ratio of the starting materials. 
The reaction steps may be effected by the incremental addition of one of 
the starting materials to the other. Also, the reaction steps can be 
combined by the joint addition of the starting materials. When complete 
conversion is not desired or not obtainable, the starting materials can be 
separated from the product, for example by distillation, and the starting 
materials then recycled back into the reaction zone. 
The processes may be conducted in either glass lined, stainless steel or 
similar type reaction equipment. The reaction zone may be fitted with one 
or more internal and/or external heat exchanger(s) in order to control 
undue temperature fluctuations, or to prevent any possible "runaway" 
reaction temperatures. 
The processes of this invention may be conducted in one or more steps or 
stages. The exact number of reaction steps or stages will be governed by 
the best compromise between achieving high catalyst selectivity, activity, 
lifetime and ease of operability, as well as the intrinsic reactivity of 
the starting materials in question and the stability of the starting 
materials and the desired reaction product to the reaction conditions. 
In an embodiment, the processes useful in this invention may be carried out 
in a multistaged reactor such as described, for example, in copending U.S. 
patent application Ser. No.08/757,743, filed on Nov. 26, 1996, the 
disclosure of which is incorporated herein by reference. Such multistaged 
reactors can be designed with internal, physical barriers that create more 
than one theoretical reactive stage per vessel. In effect, it is like 
having a number of reactors inside a single continuous stirred tank 
reactor vessel. Multiple reactive stages within a single vessel is a cost 
effective way of using the reactor vessel volume. It significantly reduces 
the number of vessels that otherwise would be required to achieve the same 
results. Fewer vessels reduces the overall capital required and 
maintenance concerns with separate vessels and agitators. 
The substituted and unsubstituted hydroxyaldehydes, e.g., 
6-hydroxyhexanals, produced by the processes of this invention can undergo 
further reaction(s) to afford desired derivatives thereof. Such 
permissible derivatization reactions can be carried out in accordance with 
conventional procedures known in the art. Illustrative derivatization 
reactions include, for example, hydrogenation, esterification, 
etherification, amination, alkylation, dehydrogenation, reduction, 
acylation, condensation, carboxylation, carbonylation, oxidation, 
cyclization, silylation and the like, including permissible combinations 
thereof. Preferred derivatization reactions and derivatives of 
6-hydroxyhexanal include, for example, reductive amination to give 
hexamethylenediamine, oxidation to give adipic acid, oxidation and 
cyclization to give epsilon caprolactone, oxidation, cyclization and 
amination to give epsilon caprolactam, and hydrogenation or reduction to 
give 1,6-hexanediols. This invention is not intended to be limited in any 
manner by the permissible derivatization reactions or permissible 
derivatives of substituted and unsubstituted 6-hydroxyhexanals. 
For purposes of this invention, the term "hydrocarbon" is contemplated to 
include all permissible compounds having at least one hydrogen and one 
carbon atom. Such permissible compounds may also have one or more 
heteroatoms. In a broad aspect, the permissible hydrocarbons include 
acyclic (with or without heteroatoms) and cyclic, branched and unbranched, 
carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds 
which can be substituted or unsubstituted. 
As used herein, the term "substituted" is contemplated to include all 
permissible substituents of organic compounds unless otherwise indicated. 
In a broad aspect, the permissible substituents include acyclic and 
cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic 
and nonaromatic substituents of organic compounds. Illustrative 
substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, 
hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like in which 
the number of carbons can range from 1 to about 20 or more, preferably 
from 1 to about 12. The permissible substituents can be one or more and 
the same or different for appropriate organic compounds. This invention is 
not intended to be limited in any manner by the permissible substituents 
of organic compounds. 
For purposes of this invention, the chemical elements are identified in 
accordance with the Periodic Table of the Elements reproduced in "Basic 
Inorganic Chemistry" by F. Albert Cotton, Geoffrey Wilkinson and Paul L. 
Gaus, published by John Wiley and Sons, Inc., 3rd Edition, 1995.

Certain of the following examples are provided to further illustrate this 
invention. 
EXAMPLES 1-19 
Into a 100 milliliter overhead stirred high pressure reactor was charged 
0.25 mmol of dicarbonylacetylacetonato rhodium (I), 0.9 mmol of a 
trialkylphosphine defined in Table A below, 3 milliliters of butadiene, 26 
milliliters of a solvent as defined in Table A, and 1 milliliter of 
diglyme as internal standard. The reactor was pressurized with 5-10 psi of 
hydrogen/carbon monoxide in 1/1 ratio and heated to the desired 
temperature set out in Table A. At the desired temperature, the reactor 
was pressurized to the desired hydrogen/carbon monoxide ratio set out in 
Table A and the gas uptake was monitored. After a decrease in pressure of 
10%, the reactor was re-pressurized to the initial value with 
hydrogen/carbon monoxide in 1/1 ratio. Samples of the reaction mixture 
were taken in dry ice cooled vials via the sampling line at scheduled 
intervals and analyzed by gas chromatography. At the end of the reaction 
period of 90 minutes, the gases were vented and the reaction mixture 
drained. Further details and results of analyses are set out in Table A. 
TABLE A 
__________________________________________________________________________ 
Ex. Temp. 
H.sub.2 /CO 
Butadiene 
Rate 
Selectivity (%) 
No. 
Solvent/Promoter 
Phosphine (.degree.C.) 
(psi) 
Conv. (%) 
m/L/h 
3 & 4 Pentenols 
__________________________________________________________________________ 
1 Ethanol Triethylphosphine 
60 300/300 
27 0.2 92 
2 Ethanol Triethylphosphine 
80 300/300 
90 1 .6 
87 
3 Ethanol Triethylphosphine 
80 500/500 
87 1.3 91 
4 Ethanol Triethylphosphine 
80 75/75 
75 0.3 71 
5 Octanol Trioctylphosphine 
80 600/200 
98 1.9 88 
6 3-Pentenol 
Trioctylphosphine 
80 600/200 
89 nd 90 
7 Hexanediol 
Trioctylphosphine 
80 300/300 
65 nd 93 
8 Pyrrole Trioctylphosphine 
80 600/200 
90 1.4 88 
9 Ethanol Tributylphosphine 
80 300/300 
55 1.0 70 
10 Phenol/THF 
Trioctylphosphine 
80 600/200 
84 2.0 55 
11 t-Butanol 
Triethylphosphine 
120 250/250 
99 nd 38 (15 min rxn. time) 
12 Ethanol Trimethylphosphine 
120 250/250 
97 nd 42 (2 h rxn. time) 
13 Ethanol Diethyl-para-N,N- 
80 600/200 
70 1.2 64 
dimethylphenylphosphine 
14 Ethanol/Acetonitrile 
Triethylphosphine 
80 300/300 
68 1.1 82 
15 Ethanol/Tetraglyme 
Triethylphosphine 
80 300/300 
64 1.0 91 
16 Diphenylamine 
Trioctylphosphine 
80 600/200 
80 0.8 54 
17 Acetamide 
Trioctylphosphine 
80 600/200 
85 0.9 34 
18 Methylacetamide 
Trioctylphosphine 
80 600/200 
73 0.8 59 
19 N-Methylformamide 
Trioctylphosphine 
80 600/200 
33 0.1 19 
__________________________________________________________________________ 
nd = not determined 
EXAMPLES 20-26 
Into a 100 milliliter overhead stirred high pressure reactor was charged 
0.25 mmol of dicarbonylacetylacetonato rhodium mmol of a trialkylphosphine 
defined in Table B below, 3 milliliters of butadiene, 26 milliliters of 
ethanol, and 1 milliliter of diglyme as internal standard. The reactor was 
pressurized with 5-10 psi of hydrogen/carbon monoxide in 1/1 ratio and 
heated to 80.degree. C. At the desired temperature, the reactor was 
pressurized to the desired hydrogen/carbon monoxide ratio set out in Table 
B and the gas uptake was monitored. After a decrease in pressure of 10%, 
the reactor was re-pressurized to the initial value with hydrogen/carbon 
monoxide in 1/1 ratio. Samples of the reaction mixture were taken in dry 
ice cooled vials via the sampling line at scheduled intervals and analyzed 
by gas chromatography. At the end of the reaction period of 120 minutes, 
the gases were vented and the reaction mixture drained. Further details 
and results of analyses are set out in Table B. 
TABLE B 
______________________________________ 
Buta 
diene Rate 
Ex. H.sub.2 /CO 
Conv (m/L/ 
Selectivity (%) 
No. Phosphine (psi) (%) h) 3 & 4 Pentenols 
______________________________________ 
20 t-butyldiethyl 
300/300 60 0.8 13 
phosphine 
21 t-butyldiethyl 
800/200 69 1.1 19 
phosphine 
22 cyclohexyldiethyl 
300/300 76 0.7 75 
phosphine 
23 cyclohexyldiethyl 
800/200 82 1.4 80 
phosphine 
24 n-butyldiethyl 
300/300 77 1.1 82 
phosphine 
25 diethylphenyl 
200/800 53 0.9 77 
phosphine 
26 ethyldiphenyl 
200/806 38 0.6 27 
phosphine 
______________________________________ 
EXAMPLE 27 
A 160 milliliter magnetically stirred autoclave was purged with 1:1 H.sub.2 
/CO and charged with a catalyst solution consisting of 0.1125 grams (0.44 
mmol) dicarbonylacetylacetonato rhodium (I), 0.3515 grams (2.94 mmol) 
P(CH.sub.2 CH.sub.2 CH.sub.2 OH).sub.3, and 44.1 grams tetrahydrofuran. 
The autoclave was pressurized with 40 psig 1:1 H.sub.2 /CO and heated to 
80.degree. C. 6 milliliters (3.73 grams) of 1,3-butadiene was charged with 
a metering pump and the reactor was pressurized to 1000 psig with 1:1 
H2/CO. The reaction mixture was maintained at 80.degree. C. under 1000 psi 
1:1 H.sub.2 /CO. Samples of the reaction mixture taken after 90 minutes 
and 170 minutes provided the following results: 
______________________________________ 
Time Butadiene 
(min- 
Temperature 
H.sub.2 /CO 
Conversion 
Rate Selectivity (%) 
utes) 
(.degree.C.) 
(psig) (%) (m/L/h) 
3 & 4 Pentenols 
______________________________________ 
90 80 500/500 81 0.7 66 
170 80 500/500 96 0.4 72 
______________________________________ 
EXAMPLE 28 
A 160 milliliter magnetically stirred autoclave was purged with 1:1 H.sub.2 
/CO and charged with a catalyst solution consisting of 0.1126 grams (0.44 
minol) dicarbonylacetylacetonato rhodium (I), 0.6120 grams (1.69 mmol) 
P(CH.sub.2 CH.sub.2 CH.sub.2 OH).sub.3, and 39.9 grams of ethanol. The 
autoclave was pressurized with 40 psig 1:1 H.sub.2 /CO and heated to 
80.degree. C. 6 milliliters (3.73 grams) of 1,3-butadiene was charged with 
a metering pump and the reactor pressurized to 1000 psig with 1:1 H.sub.2 
/CO. The reaction mixture was maintained at 80.degree. C. under 1000 psi 
1:1 H.sub.2 /CO. Samples of the reaction mixture taken after 15 and 43 
minutes provided the following results: 
______________________________________ 
Time Butadiene 
(min- 
Temperature 
H.sub.2 /CO 
Conversion 
Rate Selectivity (%) 
utes) 
(.degree.C.) 
(psig) (%) (m/L/h) 
3 & 4 Pentenols 
______________________________________ 
15 80 500/500 53 2.6 70 
43 80 500/500 89 1.5 78 
______________________________________ 
EXAMPLE 29 
A 100 milliliter overhead stirred high pressure reactor was charged with 
0.12 mmol rhodium(I) dicarbonyl acetylacetonate, 2.2 mmol 
triphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters of 
ethyl alcohol, and 1 milliliter of diglyme as internal standard. The 
reactor was pressurized with 5 psi carbon monoxide and hydrogen in a 1:1 
ratio, heated to 105.degree. C., and then pressurized to 30 psi carbon 
monoxide and hydrogen. A sample of the reaction mixture was after 0.5 
hours, and then analyzed by gas chromatography. Details of the reaction 
are set out in Table C below. 
EXAMPLE 30 
A 100 milliliter overhead stirred high pressure reactor was charged with 
0.25 mmol rhodium(I) dicarbonyl acetylacetonate, 4.9 mmol 
triphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters of 
tetrahydrofuran, and 1 milliliter of diglyme as internal standard. The 
reactor was pressurized with 10 psi carbon monoxide and hydrogen in a 1:1 
ratio, heated to 75.degree. C., and then pressurized to 50 psi carbon 
monoxide and hydrogen. Samples of the reaction mixture were taken at time 
zero and after 5.5 hours, and then analyzed by gas chromatography. At the 
end of the reaction (5.5 hours), the gases were vented and the reaction 
mixture drained. Details of the reaction are set out in Table C. 
EXAMPLE 31 
A 100 milliliter overhead stirred high pressure reactor was charged with 
0.22 mmol rhodium(I) dicarbonyl acetylacetonate, 4.4 mmol 
triphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters of 
ethyl alcohol, and 1 milliliter of diglyme as internal standard. The 
reactor was pressurized with 10 psi carbon monoxide and hydrogen in a 1:1 
ratio, heated to 75.degree. C., and then pressurized to 50 psi carbon 
monoxide and hydrogen. Samples of the reaction mixture were taken at time 
zero and after 20 hours, and then analyzed by gas chromatography. At the 
end of the reaction (20 hours), the gases were vented and the reaction 
mixture drained. Details of the reaction are set out in Table C. 
EXAMPLE 32 
A 100 milliliter overhead stirred high pressure reactor was charged with 
0.25 mmol rhodium(I) dicarbonyl acetylacetonate, 4.9 mmol 
triphenylphosphine, 1.5 milliliters of cis-3-pentenol, 26 milliliters of 
tetrahydrofuran, and 1 milliliter of diglyme as internal standard. The 
reactor was pressurized with 5 psi carbon monoxide and hydrogen in a 1:1 
ratio, heated to 100.degree. C., and then pressurized to 30 psi carbon 
monoxide and hydrogen. Samples of the reaction mixture were taken at time 
zero and after 1.5 hours, and then analyzed by gas chromatography. At the 
end of the reaction (1.5 hours), the gases were vented and the reaction 
mixture drained. Details of the reaction are set out in Table C. 
EXAMPLE 33 
A 100 milliliter overhead stirred high pressure reactor was charged with 
0.27 mmol rhodium(I) dicarbonyl acetylacetonate, 0.29 mmol 
(R)-(+)-2,2'-bis(diphenylphosphino)-1, 1'-binaphthyl, 1.5 milliliters of 
cis-3-pentenol, 26 milliliters of tetrahydrofuran, and 1 milliliter of 
diglyme as internal standard. The reactor was pressurized with 10 psi 
carbon monoxide and hydrogen in a 1:1 ratio, heated to 75.degree. C., and 
then pressurized to 120 psi carbon monoxide and hydrogen. Samples of the 
reaction mixture were taken at time zero and after 2 hours, and then 
analyzed by gas chromatography. At the end of the reaction (2 hours), the 
gases were vented and the reaction mixture drained. Details of the 
reaction are set out in Table C. 
TABLE C 
__________________________________________________________________________ 
Pent. 
Ex. Temp. 
CO/H.sub.2 
Con. 
Rate 
C5.sup.a 
C5.sup.b 
Et5L 
Me6L 
6-HH 
No. 
Metal 
Ligand 
Solvent 
(.degree.C.) 
(psi) 
(%) 
(M/l-h) 
(%) 
(%) 
(%) 
(%) (%) 
__________________________________________________________________________ 
29 Rh TPP EtOH 
105 15/15 
18 n.d. 
14 37 7 15 25 
30 Rh TPP THF 75 25/25 
63 0.06 
1 7 34 47 10 
31 Rh TPP EtOH 
75 25/25 
40 0.01 
2 12 36 34 14 
32 Rh TPP THF 100 15/15 
40 0.15 
13 47 3 11 15 
33 Rh BINAP 
THF 75 60/60 
35 0.10 
6 83 0 9 1 
__________________________________________________________________________ 
Pent. Conv. = cis3-pentenol conversion; C5.sup.a = 1pentanol + 
valeraldehyde + 2pentenol; C5.sup.b = trans3-pentenol + 4pentenol; Et5L = 
2ethylbutyrolactol; Me6L = 2methylvalerolactol; 6HH = 6hydroxyhexanal; TP 
= triphenylphosphine; BINAP = 
(R)(+)2,2bis(diphenylphosphino)-1,1binaphthyl; EtOH = ethyl alcohol; THF 
tetrahydrofuran. 
EXAMPLE 34 
A 100 milliliter overhead stirred high pressure reactor was charged with 
0.10 mmol of dicarbonylacetylacetonato rhodium (I), about 0.20 mmol of 
2,2'-(bisdiphenylphosphinomethyl)1,1'-biphenyl, 1 milliliter of 
4-pentenol, 26 milliliters of ethanol, and 1 milliliter of diglyme as 
internal standard. The reactor was pressurized with 5-10 psi of 1/1 
hydrogen/carbon monoxide, and heated to 90.degree. C. At 90.degree. C., 
the reactor was pressurized to 250 psi with 1/1 hydrogen/carbon monoxide 
at stirred for 1 hour. The reactor gases were vented and the reaction 
mixture drained and analyzed by gas chromatography. 6-Hydroxyhexanal was 
formed in 97% selectivity. 
EXAMPLES 35-38 
Into a 100 milliliter overhead stirred high pressure reactor was charged 
0.07 mmol of dicarbonylacetylacetonato rhodium (I), 0.35 mmol of a 
bisphosphite ligand as identified in Table D below and depicted in the 
above specification, 25 milliliters of tetrahydrofuran, and 0.5 milliliter 
of diglyme as internal standard. The reactor was pressurized with 50 psi 
of hydrogen/carbon monoxide in 1/1 ratio and heated to the temperature in 
Table D. At the desired temperature, 1.0 milliliter of 3-pentenol was 
added and the reactor was pressurized to the desired hydrogen/carbon 
monoxide pressures set out in Table D. After a 5% drop in the reactor 
pressure, the reactor was re-pressurized to the initial value with 
hydrogen/carbon monoxide in 1/1 ratio. At the end of the reaction period 
of 120 minutes, the gases were vented and the reaction mixture drained and 
analyzed by gas chromatography. Further details and results of analyses 
are set out in Table D. 
TABLE D 
______________________________________ 
Selectivity to 
3- 6- 
Ex. Bisphosphite 
Temp. H.sub.2 /CO 
Pentenol 
hydroxyhexanal 
No. ligand (.degree.C.) 
(psi) Conv. (%) 
(%) 
______________________________________ 
35 Ligand F 85 100/100 
68 60 
36 Ligand F 95 200/50 
94 59 
37 Ligand D 85 100/100 
44 65 
38 Ligand D 95 333/167 
52 58 
______________________________________ 
EXAMPLES 39-43 
Into a 100 milliliter overhead stirred high pressure reactor was charged 
0.07 mmol of dicarbonylacetylacetonato rhodium 0.35 mmol of a bisphosphite 
ligand as identified in Table E below and depicted below or in the above 
specification, 25 milliliters of tetrahydrofuran, and 0.5 milliliter of 
digylme as internal standard. The reactor was pressurized with 50 psi of 
hydrogen/carbon monoxide in 1/1 ratio and heated to 95.degree. C. At the 
desired temperature, 1.0 milliliter of 3-pentenol was added and the 
reactor was pressurized to 500 psi with hydrogen/carbon monoxide in 1/1 
ratio. After a 5% drop in the reactor pressure, the reactor was 
re-pressurized to the initial value with hydrogen/carbon monoxide in 1/1 
ratio. At the end of the reaction period of 120 minutes, the gases were 
vented and the reaction mixture drained and analyzed by gas 
chromatography. Further details and results of analyses are set out in the 
Table E. 
TABLE E 
______________________________________ 
3- Selectivity to 6- 
Ex. Pentenol hydroxyhexanal 
No. Bisphosphite ligand 
Conv. (%) 
(%) 
______________________________________ 
39 Ligand W 20 59 
40 Ligand X 50 59 
41 Ligand E 67 55 
42 Ligand Y 92 44 
43 ethylidene bis(di-t-butyl) 
54 29 
phenyl (phenylene glycol- 
P)2 
______________________________________ 
##STR33## 
##STR34## 
##STR35## 
##STR36## 
A 100 milliliter magnetically stirred autoclave was urged with N.sub.2 for 
30 minutes and charged with a solution consisting of 3 milliliters of 
3-pentenol, 26 milliliters of tetrahydrofuran, Ligand Z identified below 
and dicarbonylacetylacetonato Rh (I) in amounts listed in Table F below. 
The autoclave was pressurized with 60-80% of the total amount of 1:1 
hydrogen/carbon monoxide and heated to the temperature listed in Table F. 
The total amount of 1:1 hydrogen/carbon monoxide was as follows: Ex. 
44-100 psi hydrogen and 100 psi carbon monoxide; Ex. 45-100 psi hydrogen 
and 100 psi carbon monoxide; Ex. 46-50 psi hydrogen and 50 psi carbon 
monoxide; and Ex. 47-100 psi hydrogen and 100 psi carbon monoxide. After 
the appropriate temperature was reached, the autoclave was pressurized to 
the total amount of 1:1 hydrogen/carbon monoxide described above. The 
reaction mixture was maintained isothermally under 1:1 hydrogen/carbon 
monoxide. Samples of the reaction mixture taken after 150 minutes gave the 
results listed in Table F. Selectivities were determined by gas 
chromatography and referenced to standard response factors. 0.94 grams 
(7.02 mmol) of diglyme was used as an internal gas chromatography standard 
in the reaction mixture. 
TABLE F 
______________________________________ 
6-Hydroxy- 
Ligand Rh(CO).sub.2 
3-pentenol hexanal 
Ex. Temp Z (acac) Con- Rate Selec- 
No. (.degree.C.) 
(g) (g) version 
(m/L/h) 
tivity (%) 
______________________________________ 
44 85 0.355 0.02 13% 0.5 46.7 
45 90 1.07 0.07 74% 0.70 54.3 
46 105 0.14 0.02 96% 0.96 61.2 
47 95 0.35 0.02 38% 0.41 54.4 
______________________________________ 
##STR37## 
EXAMPLE 48 
Tetrarhodium dodecacarbonyl (52.3 milligrams) and Ligand F (1.17 grams) was 
dissolved in tetraglyme (80 milliliters). To this was added nonane (1.07 
grams) as gas chromatograph internal standard, and cis-3-pentenol (25.8 
grams). The mixture was charged to a 300 milliliter stirred Parr autoclave 
and 200 psig of synthesis gas was added (1:1 carbon monoxide:hydrogen). 
The reactor temperature was raised to 95.degree. C., synthesis gas was 
added to the reactor to bring the pressure to 500 psig. The reaction was 
run for 157 minutes, before being stopped. Gas chromatograph analysis of 
the reaction mixture showed the following composition: valeraldehyde 
(23.7%), trans-3-pentenol (8.7%), cis-3-pentenol (13.6%), branched 
hydroxyaldehyde (5.6%), and 6-hydroxyhexanal (52.2%). The identity of the 
linear and branched aldehydes was confirmed by gas chromatograph mass 
spectrometry/infrared spectroscopy. 
Although the invention has been illustrated by certain of the preceding 
examples, it is not to be construed as being limited thereby; but rather, 
the invention encompasses the generic area as hereinbefore disclosed. 
Various modifications and embodiments can be made without departing from 
the spirit and scope thereof.