Organic compounds -- part of the class 532-570 series – Organic compounds – Nitriles
Reexamination Certificate
2000-08-30
2003-02-04
Shippen, Michael L. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitriles
C560S175000, C568S454000
Reexamination Certificate
active
06515161
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to a hydroformylation process using certain multidentate phosphite ligands. In particular, the ligands have heteroatom-containing substituents on the carbon attached to the ortho position of the terminal phenol group.
TECHNICAL BACKGROUND OF THE INVENTION
Phosphorus ligands are ubiquitous in catalysis and are used for a number of commercially important chemical transformations. Phosphorus ligands commonly encountered in catalysis include phosphines (A), and phosphites (B), shown below. In these representations, R can be virtually any organic group. Monophosphine and monophosphite ligands are compounds which contain a single phosphorus atom which serves as a donor to a metal. Bisphosphine, bisphosphite, and bis(phosphorus) ligands in general, contain two phosphorus donor atoms and normally form cyclic chelate structures with transition metals.
There are several industrially important catalytic processes employing phosphorus ligands. For example, U.S. Pat. No. 5,910,600 to Urata, et al. discloses that bisphosphite compounds can be used as a constituting element of a homogeneous metal catalyst for various reactions such as hydrogenation, hydroformylation, hydrocyanation, hydrocarboxylation, hydroamidation, hydroesterification and aldol condensation.
Some of these catalytic processes are used in the commercial production of polymers, solvents, plasticizers and other commodity chemicals. Consequently, due to the extremely large worldwide chemical commodity market, even small incremental advances in yield or selectivity in any of these commercially important reactions are highly desirable. Furthermore, the discovery of certain ligands that may be useful for applications across a range of these commercially important reactions is also highly desirable not only for the commercial benefit, but also to enable consolidation and focusing of research and development efforts to a particular group of compounds.
One industrially important catalytic reaction using phosphorus ligands of particular importance is olefin hydroformylation. For example, U.S. Pat. No. 5,235,113 to Sato, et al. discloses 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. 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 commonly assigned, copending application Ser. No. 60/087,151, filed May 29, 1998, and the patents and publications referenced therein.
Commonly assigned, published PCT Application W099/06357 discloses multidentate phosphite ligands with a structure having alkyl ether substituents on the carbon attached to the ortho position of the terminal phenol group for use in a liquid phase process for the hydrocyanation of diolefinic compounds.
It always remains desirable to provide even more effective, higher performing catalyst precursor compositions, catalytic compositions and catalytic processes to achieve full commercial potential for a desired reaction such as hydroformylation. The effectiveness and/or performance may be achieved in any or all of rapidity, selectivity, efficiency or stability. Other objects and advantages of the present invention will become apparent to those skilled in the art upon reference to the detailed description which hereinafter follows.
SUMMARY OF THE INVENTION
The invention provides for a hydroformylation process comprising reacting an acyclic, monoethylenically unsaturated compound with CO and H
2
in the presence of a catalyst precursor composition comprising a transition metal, and at least one multidentate phosphite ligand selected from the group represented by the following formulae I, I-A or I-B, in which all like reference characters have the same meaning, except as further explicitly limited.
The invention further provides for the hydroformylation of aromatic olefins comprising reacting an acyclic aromatic olefin compound with CO and H
2
in the presence of a catalyst precursor composition comprising a low-valent transition metal, and at least one multidentate phosphite ligand selected from the group represented by the following formulae I, I-A or I-B, in which all like reference characters have the same meaning, except as further explicitly limited.
wherein X
1
is a bridging group and is selected from the group consisting of:
wherein R
1
, R
2
, R
3
R
4
, R
5
, R
6
, R
7
, R
8
, R
1
′, and R
2
′ are independently selected from the group consisting of H, C
1
to C
18
alkyl, cycloalkyl, trialkylsilyl, triarylsilyl, halogen, nitrile, perfluoroalkyl, —SO
2
R
11
, —SO
2
NR
2
12
, acetal, ketal, dialkylamino, or diarylamino, —OR
11
, —CO
2
R
11
, —(CNR
11
)R
11
, —(CNOR
11
)R
11
, wherein R
11
is C
1
to C
18
alkyl, aryl, or substituted aryl, —C(O)R
12
, —C(O)NR
12
R
13
, —O—C(O)R
12
, —NR
12
—C(O)R
13
, wherein R
12
and R
13
are independently selected from the group of H, C
1
to C
18
alkyl, cycloalkyl, aryl, or substituted aryl; wherein positions other than R
1
through R
8
on the aromatic rings may also be substituted with C
1
to C
18
alkyl, cycloalkyl, trialkylsilyl, triarylsilyl, halogen, nitrile, perfluoroalkyl, sulfonyl, acetal, ketal, dialkylamino, diarylamino, —OR
11
, —CO
2
R
11
, RCNR
11
, or RCNOR
11
,
wherein R
9
and R
10
are independently selected from the group consisting of H, C
1
to C
18
alkyl, cycloalkyl, aryl, or substituted aryl;
wherein X
2
through X
5
are independently selected from the group consisting of:
wherein Y is independently selected from the group consisting of H, aryl, CR
14
3
, (CR
14
2
)n—OR
14
, (CR
14
2
)n—NR
15
, wherein R
14
is H, C
1
-C
18
alkyl, cycloalkyl, or aryl, wherein R
15
is selected from the group consisting of H, alkyl, aryl, —SO
2
R
11
, —SO
2
NR
12
2
, —COR
16
, wherein R
16
is H, C
1
-C
18
alkyl, cycloalkyl, aryl or perfluoroalkyl;
and Z is selected from the group consisting of (CR
14
2
)n—OR
14
wherein n=0-3.
In other embodiments of the invention a ligand of the structure of Formula I-A may be substituted for the ligand of Formula I, and in those embodiments an aromatic ring carbon in the ortho position to an O bonded to a P may be bonded through (Z
1
)n
1
to another aromatic ring carbon in the ortho position to the other O bonded to the P;
wherein Z
1
is independently
and each of R
17
and R
18
are independently selected from the group consisting of H, C
1
to C
18
alkyl, cycloalkyl, aryl, or substituted aryl, n
1
is either one or zero; and wherein it is understood that n
1
=0 represents a bond replacing the two aromatic ring hydrogens.
In other embodiments of the invention a ligand of the structure of Formula I-B may be substituted for the ligand of Formula I, and wherein an aromatic ring carbon in the ortho position to an O bonded to a P may be bonded through (Z
1
)n
1
to another aromatic ring carbon in the ortho position to the other O bonded to the P;
wherein Z
1
is independently
and each of R
17
and R
18
are independently selected from the group consisting of H, C
1
to C
18
alkyl, cycloalkyl, aryl, or substituted aryl, n
1
is either one or zero; and wherein it is understood that n
1
=0 represents a bond replacing the two aromatic ring hydrogens.
Furthermore, in embodiments of the invention utilizing Formula I, Formula I-A or Formula I-B, either one of the Y's may be linked with Z to form a cyclic ether.
The invention further provides for a hydroformylation process comprising reacting an acyclic, monoethylenically unsaturated compound with CO and H
2
in the presence of a catalyst precursor composition comprising a transition metal, and at least one multidentate phosphite ligand selected from the group represented by the following formulae II, II-A or II-B, in which all like reference characters have the same meaning, except as further explicitly limited.
The
Boyles John Ronald
Garner J Michael
Kreutzer Kristina Ann
Tam Wilson
E. I. du Pont de Nemours and Company
Shippen Michael L.
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