Hydroformylation of acyclic monoethylenically unsaturated...

Details Hydroformylation of acyclic monoethylenically unsaturated... Hydroformylation of acyclic monoethylenically unsaturated...

1999-09-20

2001-10-23

Padmanabhan, Sreeni (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S451000, C502S155000

Reexamination Certificate

active

06307107

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a process for the preparation of linear aldehydes by hydroformylation of C
2
to C
20
monoethylenically unsaturated organic compounds in the presence of a Group VIII transition metal and selected multidentate phosphite ligands. The invention also relates to the selected multidentate phosphite ligands themselves, as well as hyroformylation catalysts made therefrom.
BACKGROUND OF THE INVENTION
Phosphorus-based ligands are ubiquitous in catalysis and are used for a number of commercially important chemical transformations. Phosphorus-based ligands commonly used in catalysis include phosphines and phosphites. These ligands include monophosphine and monophosphite ligands, which are compounds that contain a single phosphorus atom that serves as a donor to a transition metal, and bisphosphine, bisphosphite, and bis(phosphorus) ligands, which contain two phosphorus donor atoms and normally form cyclic chelate structures with transition metals.
An industrially important catalytic reaction using phosphorus-based ligands is olefin hydroformylation. Phosphite ligands are particularly good ligands for these reactions. For example, U.S. Pat. 5,235,113 describes a hydroformylation process in which an organic bidentate ligand containing two phosphorus atoms linked with an organic dihydroxyl bridging group is used in a homogeneous hydroformylation catalyst system also comprising rhodium. This patent describes a process for preparing aldehydes by hydroformylation of ethylenically unsaturated organic compounds, for example 1-octene or dimerized butadiene, using the above catalyst system. The use of phosphite ligands with rhodium has been disclosed in the hydroformylation of functionalized ethylenically unsaturated compounds. See for example Cuny et al.,
J. Am. Chem. Soc.,
1993, 115, 2066; U.S. Pat. Nos. 4,769,498, 4,668,651, 4,885,401, 5,113,022, 5,059,710, 5,235,113, 5,264,616, and 4,885,401; and published international applications WO9303839, and WO9518089.
Hydroformylation processes involving organic bidentate ligands containing an aromatic dihydroxyl bridging group and terminal aryl groups bearing heteroatom substituents are described in German Patent Application DE 19717359 A1.
Hydroformylation processes involving organic bidentate ligands containing two trivalent phosphorus atoms, in which the two phosphorous atoms are linked with a 2,2′-dihydroxyl-1,1′-binaphthalene bridging group, are described in U.S. Pat. No. 5,874,641 and the prior art referenced therein. U.S. Pat. No. 5,874,641 describes ligands containing substituents such as esters or ketones on the 3,3′-positions of the 2,2′-dihydroxyl-1,1′-binaphthalene bridging group. Such ligands provide reasonably good selectivity in the hydroformylation of internal olefins to terminal aldehydes.
Although some of these prior art systems involve commercially viable catalysts, there remains a need for even more effective catalyts to achieve even greater commercial potential. An object of this invention is to provide such improved catalysts for hydroformylation.
SUMMARY OF THE INVENTION
In one aspect, the present invention is a process for converting a C
2
to C
20
acyclic monoethylenically unsaturated compound to its corresponding terminal aldehyde, comprising reacting the compound with CO and H
2
in the presence of a Group VIII transition metal and at least one multidentate phosphite ligand of the following formulae I,II or III:
wherein:
each R
1
independently is C
1
to C
12
alkyl, C
6
to C
20
aryl, F, Cl, —CO
2
R
4
, —OR
4
, or —R
3
Z, provided that at least one R
1
is —R
3
Z;
each R
2
independently is H, F, Cl, C
1
to C
12
alkyl, C
6
to C
20
aryl, —OR
4
, —CO
2
R
4
, —C(O)R
4
, —CHO, —CN, or -CF
3
;
each R
3
independently is C
1
to C
10
alkylene;
each R
4
independently is C
1
to C
12
alkyl or C
6
to C
20
aryl;
each Z is —CO
2
R
4
, —CHO, —C(O)R
4
, —C(O)SR
4
, —SR
4
, —C(O)NR
5
R
6
, —OC(O)R
4
, —OC(O)OR
4
, —N═CR
5
R
6
, —C(R
5
)═NR
6
, —C(R
5
)═N—O—R
6
, —P(O) (OR
4
) (OR
4
), —S(O)
2
R
4
, —S(O)R
4
, —C(O)OC(O)R
4
, —NR
4
CO
2
R
4
, —NR
4
C(O)NR
5
R
6
, or —CN;
each R
4
independently is C
1
to C
12
alkyl or C
6
to C
20
aryl;
each R
5
independently is H, C
1
to C
12
alkyl, or C
6
to C
20
aryl;
each R
6
independently is H, C
1
to C
12
alkyl, or C
6
to C
20
aryl;
Q is a divalent bridging group of the formula:
 wherein:
each R
7
independently is H, F, Cl, C
1
to C
12
alkyl, C
6
to C
20
aryl, —OR
4
, —CO
2
R
4
, —C(O)R
4
, —C(R
5
)═N—O—R
6
, —CHO, —CN, —CF
3
, —C(R
5
)═NR
6
, —NR
5
R
6
or —R
3
Z; and
each R
8
is H, F, Cl, C
1
to C
12
alkyl, C
6
to C
20
aryl, —OR
4
, —CO
2
R
4
, —C(O)R
4
, —CN, or —CF
3
.
The term “aryl” is meant to denote an organic radical which is derived from an aromatic hydrocarbon by removal of one atom. Suitable aryl radicals are, for example, phenyl, benzyl, naphthyl, binaphthyl, and anthracenyl. The terms “alkyl” and “alkylene” are meant to denote both straight and branched groups.
In another aspect, this invention provides for the above multidentate phosphite ligands and catalyst compositions made therefrom.
Any of the above ligands optionally may be attached to a soluble or insoluble inert support. An example of an insoluble inert support is Merrifield's resin (a functionalized polystyrene resin commercially available from Aldrich Chemical Company).
DETAILED DESCRIPTION OF THE INVENTION
This invention provides a process for the preparation of terminal aldehydes with high catalyst performance (selectivity and/or activity). The advantages of the present process are particularly pronounced when the reactant is an internally monoethylenically unsaturated compound. Preparing terminal aldehydes starting from internally monoethylenically unsaturated compounds using previously known hydroformylation processes generally results in moderate selectivity to terminal aldehydes, some hydrogenation of the double bond and/or lower catalytic activity. An additional advantage of the process according to the present invention is that the linearity [terminal aldehydes/(terminal+branched aldehydes)] is high, facilitating the isolation of the desired terminal aldehyde from a mixture of terminal and branched aldehydes.
The catalyst compositions useful in the processes of the invention comprise selected multidentate phosphite ligands and a Group VIII transition metal, which is provided in the form of a chemical compound.
The multidentate phosphite ligand is of the formulae I,II or III:
wherein:
each R
1
independently is C
1
to C
12
alkyl, C
6
to C
20
aryl, F, Cl, —CO
2
R
4
, —OR
4
, or —R
3
Z, provided that at least one R
1
is —R
3
Z;
each R
2
independently is H, F, Cl, C
1
to C
12
alkyl, C
6
to C
20
aryl, —OR
4
, —CO
2
R
4
, —C(O)R
4
, —CHO, —CN, or —CF
3
;
each R
3
independently is C
1
to C
10
alkylene;
each R
4
independently is C
1
to C
12
alkyl or C
6
to C
20
aryl;
each Z is —CO
2
R
4
, —CHO, —C(O)R
4
, —C(O)SR
4
, —SR
4
, —C(O)NR
5
R
6
, —OC(O)R
4
, —OC(O)OR
4
, —N═CR
5
R
6
, —C(R
5
)═NR
6
, —C(R
5
)═N—O—R
6
, —P(O) (OR
4
) (OR
4
), —S(O)
2
R
4
, —S(O)R, —C(O)OC(O)R
4
, —NR
4
CO
2
R
4
, —NR
4
C(O)NR
5
R
6
, or —CN;
each R
4
independently is C
1
to C
12
alkyl or C
6
to C
20
aryl;
each R
5
independently is H, C
1
to C
12
alkyl, or C
6
to C
20
aryl;
each R
6
independently is H, C
1
to C
12
alkyl, or C
6
to C
20
aryl;
Q is a divalent bridging group of the formula:
 wherein:
each R
7
independently is H, F, Cl, C
1
to C
12
alkyl, C
6
to C
20
aryl, —OR
4
, —CO
2
R
4
, —C(O)R
4
, —C(R
5
)═N—O—R
6
, —CHO, —CN, —CF
3
, —C(R
5
)═NR
6
, —NR
5
R
6
or —R
3
Z; and
each R
8
is H, F, Cl, C
1
to C
12
alkyl, C
6
to C
20
aryl, OR
4
, —CO
2
R
4
, —C(O)R
4
, —CN, or —CF
3
.
Preferred multidentate phosphite ligands are of the following formula I:
wherein:
each R
1
independently is —R
3
Z;
each R
2
independently is H, F, Cl, C
1
to C
12
alkyl, C
6
to C
20
aryl, —OR
4
, —CO
2
R
4
, —C(O)R
4
, —CHO, —

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