Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2001-08-23
2002-06-25
Padmanabhan, Sreeni (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S451000, C568S909000
Reexamination Certificate
active
06410799
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved process for hydroformylation of olefinically unsaturated compounds using a catalyst based on cobalt and/or rhodium used in a two-phase medium. One of the phases is constituted by a non-aqueous ionic solvent comprising at least one quaternary ammonium and/or phosphonium cation Q
+
and at least one anion A
−
. The catalyst comprises at least one complex of cobalt and/or rhodium co-ordinated with at least one ligand selected from the group formed by nitrogen-containing or phosphorus-containing ligands also carrying an ionic function (Q′)
+
(A′)
−
where Q and Q′ and/or A and A′ are chemically identical.
2. Description of the Prior Art
Hydroformylation of olefinic compounds is a reaction of great industrial importance and the majority of processes use homogeneous catalysts dissolved in an organic phase constituted by the reactants, products and possibly an excess of ligand, although difficulties are encountered in separating and recovering the catalyst, in particular when it is used in relatively large quantities, as is the case with catalysts based on cobalt, or with a noble metal, as is the case with rhodium based catalysts.
One solution to resolving that problem has been suggested by Bartik et al.: Organometallics (1993) 12 164-170, J. Organometal. Chem. (1994) 480 15-21, and by Beller et al.: J. Molecular Catal. A: Chemical (1999) 143 31-39. It consists of carrying out hydroformylation in the presence of an aqueous solution containing a cobalt complex which is rendered water-soluble by the presence of a phosphine-sulfonate ligand such as the sodium salt of trisulfonated triphenylphosphine or a trisulfonated tris-(alkylphenyl)phosphine. International patent application WO-A-97/00 132 describes clusters of cobalt substituted by trialkoxysilylmethyl groups, which render them water-soluble. In that manner, the organic phase containing the aldehydes is readily separated from the aqueous phase containing the catalyst.
A further solution to the problem has been described in U.S. Pat. No. 4,248,802. It consists of carrying out hydroformylation in the presence of an aqueous solution containing a rhodium complex which is rendered water-soluble by the presence of a sulfonated phosphine ligand which is itself water-soluble, such as the sodium salt of trisulfonated triphenylphosphine. In that manner, the organic phase containing the aldehydes is readily separated from the aqueous phase containing the catalyst. This technique has formed the subject matter of a considerable number of studies which have been discussed in an article by W. A. Herrmann in “Angewandte Chemie International”, 1993, volume 32, page 1524 ff.
Despite the huge industrial interest of such techniques in the hydroformylation of propylene, such two-phase systems suffer from a lack of solubility of the olefins in water, which leads to relatively low reaction rates which renders them unsuitable for long chain olefins.
Further, United States patent U.S. Pat. No. 3,565,823 describes a technique consisting of dispersing a transition metal compound in a quaternary ammonium or phosphonium tin or germanium salt with formula (R
1
R
2
R
3
R
4
Z)YX
3
, where R
1
, R
2
, R
3
and R
4
are hydrocarbyl residues containing up to 18 carbon atoms, Z is nitrogen or phosphorus, Y is tin or germanium and X is a halogen, for example chlorine or bromine. U.S. Pat. No. 3,832,391 describes a process for carbonylating olefins using such a composition. Those compositions have the disadvantage of having a relatively high melting point, for example more than 90° C., which complicates manipulation of the solutions of catalyst and reaction products.
The Applicant's patent U.S. Pat. No. 5,874,638 describes benefiting both from the advantages of two-phase processing and avoiding the disadvantages connected firstly with using water and secondly with using compounds with high melting points, by dissolving certain catalytic compounds of transition metals from groups 8, 9 or 10, known to catalyze hydroformylation, in non-aqueous ionic solvents which are constituted by organic-inorganic salts which are liquid at ambient temperature.
SUMMARY OF THE INVENTION
It has now been discovered that, in the hydroformylation reaction catalyzed by complexes based on cobalt and/or rhodium carried out in a non-aqueous ionic solvent comprising at least one quaternary ammonium and/or phosphonium cation Q
+
and at least one anion A
−
, which catalyst is liquid at a temperature of less than 90° C., the amount of metal retained in the ionic solvent is greatly improved when the catalyst comprises at least one cobalt and/or rhodium complex coordinated by at least one ligand selected from the group formed by nitrogen-containing or phosphorus-containing ligands also carrying an ionic function (Q′)
+
(A′)
−
where Q and Q′ and/or A and A′ are chemically identical.
More precisely, the invention provides a process for liquid phase hydroformylation of olefinically unsaturated compounds in which the reaction is carried out in the presence of at least one non-aqueous ionic solvent comprising at least one salt with general formula Q
+
A
−
, where Q
+
represents a quaternary ammonium and/or phosphonium cation, and A represents an anion, and at least one cobalt and/or rhodium complex coordinated by at least one ligand selected from the group formed by nitrogen-containing or phosphorus-containing ligands also carrying an ionic function (Q′)
+
(A′)
−
where at least the cation (Q′)
+
or anion (A′)
−
has the same chemical nature as the cation Q
+
or anion A
−
of the non-aqueous ionic solvent.
The non-aqueous ionic solvent is selected from the group formed by liquid salts with general formula Q
+
A
−
where Q
+
represents a quaternary ammonium and/or phosphonium and A
−
represents any anion which can form a liquid salt at low temperature, i.e., below 90° C., advantageously at most 85° C., preferably below 50° C. Preferred anions A
−
are nitrate, sulfate, phosphate, acetate, halogenoacetates, tetrafluoroborate, tetrachloroborate, hexafluorophosphate, hexafluoroantimonate, fluorosulfonate, perfluoroalkylsulfonates and arene-sulfonates, these latter optionally being substituted by halogen or halogenoalkyl groups.
The quaternary ammonium and/or phosphonium cations Q
+
preferably have general formula NR
1
R
2
R
3
R
4+
and PR
1
R
2
R
3
R
4+
or general formulae R
1
R
2
N═C R
3
R
4+
or R
1
R
2
P═C R
3
R
4+
where R
1
, R
2
, R
3
and R
4
, which may be identical or different, represent hydrogen (with the exception of the NH
4
+
cation for NR
1
R
2
R
3
R
4+
), preferably a single substituent represents hydrogen, or hydrocarbyl residues containing 1 to 30 carbon atoms, for example saturated or unsaturated, cycloalkyl or aromatic alkyl groups, or aryl or aralkyl groups, which may be substituted, containing 1 to 30 carbon atoms. The ammonium and/or phosphonium cation can also be derived from nitrogen-containing and/or phosphorus-containing heterocycles containing 1, 2 or 3 nitrogen and/or phosphorus atoms, in which the cycles are constituted by 4 to 10 atoms, preferably 5 or 6 atoms.
The quaternary ammonium and/or phosphonium cation can also be a cation with formula:
R
1
R
2+
N═CR
3
-R
5
-R
3
C═N
+
R
1
R
2
or
R
1
R
2+
P═CR
3
-R
5
-R
3
C═P
+
R
1
R
2
where R
1
, R
2
and R
3
, which may be identical or different, are defined as above and R
5
represents an alkylene or phenylene residue.
groups R
1
, R
2
, R
3
and R
4
include the following radicals: methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, amyl, methylene, ethylidene, phenyl or benzyl; R
5
can be a methylene, ethylene, propylene or phenylene group.
The ammonium and/or phosphonium cation Q
+
is preferably selected from the group
Commereuc Dominique
Favre Frédéric
Olivier-Bourbigou Helene
Saussine Lucien
Institut Francais du Pe'trole
Millen White Zelano & Branigan P.C.
Padmanabhan Sreeni
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