Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2000-01-06
2001-05-01
Richter, Johann (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S451000
Reexamination Certificate
active
06225509
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the hydroformylation of allyl alcohol to product comprising mainly 4-hydroxybutyraldehyde (herein HBA) using a rhodium complex catalyst and a bidendate diphosphine ligand such as a (isopropylindene-2,3-dihydroxy-1,4-diphenylphosphine)butane (herein DIOP) ligand having a bite angle of 100-120 degrees, under reaction conditions wherein a relatively high liquid phase concentration of carbon monoxide is maintained during the reaction.
2. Description of the Prior Art
It is known to react allyl alcohol with a carbon monoxide and hydrogen mixture to form hydroxybutyraldehyde; various catalyst formulations have been employed, most notably a rhodium complex together with a phosphine ligand. Commonly employed phosphine ligands are trisubstituted phosphines such as triphenyl phosphine. Patents which are illustrative of such technologies include U.S. Pat. Nos. 4,567,305, 4,215,077, 4,238,419 and the like.
The hydroformylation of allyl alcohol to hydroxybutyraldehyde using rhodium complex catalysts and DIOP ligand is shown in the art, notably in Japan Kokai 06-279345 and 06-279344.
Butanediol is produced commercially by a process which involves hydroformylation of allyl alcohol to 4-hydroxybutyraldehyde and hydrogenation of the 4-hydroxybutraldehyde to 1,4- butanediol (herein BDO). Usually some methyl propanediol (herein MPD), itself a useful material, is formed from methyl hydroxypropionaldehyde (HMPA) also formed in the hydroformylation. A severe disadvantage of prior processes has been the formation of C
3
products such as normal propanol, propionaldehyde, and the like during the hydroformylation. Formation of these materials effectively represents a yield loss in the process which can have a severe adverse effect on the process economics.
SUMMARY OF THE INVENTION
It has now been found that in the hydroformylation of allyl alcohol using a rhodium complex catalyst in combination with a bidendate diphosphine ligand having a bite angle in the range 100-120 degrees, such as DIOP ligand, unlike systems involving other ligands the concentration of carbon monoxide (CO) in the liquid reaction mixture is critical insofar as reducing the undesirable make of C
3
co-products. Specifically, the CO concentration must be maintained above about 4.5 mg. mols/liter of reaction liquid, preferably above about 5.0 mg. mols/liter in order to achieve high 4-hydroxybutyaldehyde selectivities.
REFERENCES:
patent: 4215077 (1980-07-01), Matsumoto et al.
patent: 4238419 (1980-12-01), Matsumoto et al.
patent: 4567305 (1986-01-01), Matsumoto et al.
patent: 4678857 (1987-07-01), Dureanleau et al.
patent: H6-279344 (1994-10-01), None
patent: H6-279345 (1994-10-01), None
Kamer et al, “Designing Ligands with the Right Bite” Sep., 1998, Chemtech P. 27-33.
Dubner Walter S.
Shum Wilfred Po-sum
Arco Chemical Technology L.P.
Long William C.
Parsa J.
Richter Johann
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