Process for preparing aldehyde compounds

Details Process for preparing aldehyde compounds Process for preparing aldehyde compounds

2002-08-29

2003-12-16

Richter, Johann (Department: 1621)

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

Organic compounds

Oxygen containing

C568S014000, C568S015000, C568S017000

Reexamination Certificate

active

06664427

ABSTRACT:

FIELD OF THE INVENTION
The invention relates to a process for making organic aldehyde compounds from an unsaturated compounds by hydroformylation and in the presence of a catalyst system comprising a Group VIII metal and a bidentate phosphorus ligand having two trivalent phosphorus atoms bound to salicylanilide groups.
BACKGROUND OF THE INVENTION
Ligands that have trivalent phosphorus atoms are characterized in that each trivalent phosphorus atom is bonded with three organic groups. Phosphorus amide compounds are characterized in that the phosphorus atom is linked to the organic group with at least one P—N bond and one or two P-0 bonds (also known respectively as phosphorodiamidites and phosphoramidites). Bidentate phosphorus ligands are furthermore characterized in that two phosphorus atoms are present in the molecule and that one organic bridging group (Q) links both phosphorus atoms. The other organic groups bonded to a single phosphorus atom are often called termini groups (R).
Numerous patents (U.S. Pat. No. 4,769,498, etc.) and other literature describe olefin hydroformylation processes in which an active homogeneous hydroformylation catalyst system is formed by combining rhodium with an organic bidentate phosphite ligand containing two phosphorus atoms linked with an organic dihydroxyl bridging group. The termini groups in these phosphite ligands are most commonly substituted phenol or organic dihydroxyl groups similar to the bridging groups.
Fewer examples of organic bidentate phosphoramidite ligands have been discovered for olefin hydroformylation with rhodium (WO 9616923, U.S. Pat. No. 5,710,344, etc.). Phosphoramidite ligand examples includes those drawn below.
However, no prior art has been found that describes an homogeneous rhodium catalyst system for olefin hydroformylation using an organic bidentate phosphite or phosphoramidite ligand comprised of two phosphorus atoms linked by an organic dihydroxyl bridging group with salicylanilide termini groups. Salicylanilides are resonance hybrids of the following two structures.
SUMMARY OF THE INVENTION
Disclosed herein is a hydroformylation process for preparing an organic aldehyde compound from an unsaturated organic compound, said method comprising: contacting an unsaturated organic compound with carbon monoxide, hydrogen gas, and a catalyst system, said catalyst system comprising a Group VIII metal, and at least one or a combination of at least two bidentate organic ligands having two trivalent phosphorus atoms, said ligand selected from the group consisting of structure I, II, III, IV, V, and VI:
where X
1
-X
4
are C1-C6 alkyl, alkoxy, aryloxy, NR
6
R
7
, Cl, F, or CF
3
; R
1
is independently selected from the group consisting of substituted aryl, phenyl, or fused aromatic ring systems; R
2
and R
3
are independently selected from the group consisting of hydrogen, alkyl, aryl, triarylsilyl, trialkylsilyl, carboalkoxy, carboaryloxy, aryloxy, alkoxy, alkylcarbonyl, arylcarbonyl, or nitrile; R
4
and R
5
are independently selected from the group consisting of hydrogen, alkyl, alkoxy; R
6
and R
7
are independently chosen from alkyl and aryl.
Also disclosed are the novel bidentate ligand compositions having two trivalent phosphorus atoms represented by Structures I through VI above.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a hydroformylation process for preparing organic aldehydes using high performing catalyst systems (i.e., selectivity and/or activity) and novel bidentate ligands. A hydroformylation process is used to make the aldehyde from an ethylenically unsaturated compound in the presence of catalyst system that comprises a Group VIII metal or a compound comprising a Group VIII metal, a bidentate ligand having two trivalent phosphorous atoms. When the process according the present invention is used, high selectivities to aldehydes are achieved, combined with a relatively high catalyst activity.
The advantages of this process are even more pronounced when starting from internally unsaturated organic compounds. In comparison to terminal olefins, preparing aldehydes starting from internally unsaturated compounds using previously known hydroformylation processes generally results in lower selectivity to the aldehydes, more hydrogenation of the olefinic double bond and/or lower catalytic activity. An additional advantage of the process according to this invention is that the linearity [linear aldehydes/(linear+branched aldehydes)] is higher.
This object of the present invention is achieved by using at least one ligand of the following formula in a Group VIII metal-catalyzed hydroformylation process:
where X
1
-X
4
are C1-C6 alkyl, alkoxy, aryloxy, NR
6
R
7
, Cl, F, or CF
3
;
R
1
is selected from the group consisting of substituted aryl, phenyl, or fused aromatic ring systems;
R
2
and R
3
each are independently selected from the group consisting of hydrogen, alkyl, aryl, triarylsilyl, trialkylsilyl, carboalkoxy, carboaryloxy, aryloxy, alkoxy, alkylcarbonyl, arylcarbonyl, or nitrile;
R
4
and R
5
are independently chosen from the group of hydrogen, alkyl, alkoxy;
R
6
and R
7
are independently chosen from alkyl and aryl.
Examples of the ligands of the present invention are:
Salicylanilides may be prepared by the amidation of phenyl salicylates with anilines or by treating salicyl chlorides (often prepared in situ with SOCl
2
, PCl
3
, or POCl
3
with anilines). Both chemistries can be extended to 1-hydroxy-2-naphthoic or 2-hydroxy-3-naphthoic acid derivatives to prepare the naphthyl analogs.
Salicylanilides can react with phosphorus trichloride (PCl
3
) to yield compounds where the salicylanilide acts as a dianionic chelate to the phosphorus atom. Two possible product structures (A and B) are shown below that differ in the salicylanilide atoms linked to phosphorus (linkage isomers). For the examples provided below, a single
31
P NMR peak in the region of 140 ppm was observed.
We have found that in the presence of a base, like triethylamine, the product A, B, or a combination of A and B, reacts with organic bridging groups (unsubstituted or substituted 2,2′-biphenol or 1,1′-bi-2-naphthols) to form a single or mixture of ligands that may be used in the process of the present invention. Dependent upon the bridging and salicylanilide groups, the 140 ppm
31
P NMR peak for A or B is converted to a single or multiple peaks in the 109-121 ppm region. For the ligand product mixtures, the NMR analysis distinguishes phosphorus atoms in different chemical environments.
The catalyst system of the present invention can be prepared by combining a suitable Group VIII metal or a Group VIII metal compound with a phosphorus-containing ligand, optionally in a suitable solvent, in accordance with methods known for forming complexes.
Examples of suitable Group VIII metals are ruthenium, rhodium, and iridium. Examples of suitable Group VIII metal compounds are, for example, Ru
3
(CO)
12
, Ru(NO
3
)
3
, RuCl
3
(Ph
3
P)
3
, Ru(acac)
3
, Ir
4
(CO)
12
, IrSO
4
, RhCl
3
, Rh(NO
3
)
3
, Rh(OAC)
3
, Rh
2
O
3
, Rh(acac)(CO)
2
, [Rh(OAc)(COD)]
2
, Rh
4
(CO)
12
, Rh
6
(CO)
16
, RhH(CO)(Ph
3
P)
3
, [Rh(OAc)(CO)
2
]
2
, and [RhCl(COD)]
2
(wherein “acac” is an acetylacetonate group; “Ac” is an acetyl group; “COD” is 1,5-cyclo-octadiene; and “Ph” is a phenyl group). However, it should be noted that the Group VIII metal compounds are not necessarily limited to the above listed compounds. The source for the Group VIII metal is preferably rhodium. The source for suitable Group VIII metal compounds include, but are not limited to, hydrides, halides, organic acid salts, acetylacetonates, inorganic acid salts, oxides, carbonyl compounds and amine compounds of Group VIII metals.
The unsaturated organic compound that is used in the present invention must have at least one “C═C” bond in the molecule, and preferably, 2 to 20 carbon atoms. Suitable ethylenically unsaturated organic compounds for use in the present invention include, but are not limited to,

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