Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2002-04-09
2004-11-02
Chang, Ceila (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S374000, C549S426000, C549S427000, C549S428000, C549S452000, C549S491000, C558S338000
Reexamination Certificate
active
06812352
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to certain multidentate phosphite ligands, the catalyst compositions made therefrom and catalytic processes which employ such multidentate phosphite ligands. In particular, the ligands have heteroatom-containing substituents on the carbon attached to the ortho position of the terminal phenol group. The catalytic processes exemplified herein are hydrocyanation and isomerization.
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.
U.S. Pat. No. 5,512,696 to Kreutzer, et al. discloses a hydrocyanation process using a multidentate phosphite ligand, and the patents and publications referenced therein describe hydrocyanation catalyst systems pertaining to the hydrocyanation of thylenically unsaturated compounds. U.S. Pat. Nos. 5,723,641, 5,663,369, 5,688,986 and 5,847,191 disclose processes and catalyst compositions for the hydrocyanation of monoethylenically unsaturated compounds using zero-valent nickel and multidentate phosphite ligands, and Lewis acid promoters.
U.S. Pat. No. 5,821,378 to Foo, et al. discloses a liquid phase process for the hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitriles as well as a liquid phase process for the isomerization of those nitriles to 3- and/or 4-monoalkene linear nitrites where the reactions are carried out in the presence of zero-valent nickel and a multidentate phosphite ligand. Other catalytic processes for the hydrocyanation of olefins and the isomerization of monoalkene nitrites are described in the patents and publications referenced therein. Commonly assigned, published PCT Application WO99/06357 discloses multidentate phosphite ligands 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 to produce nonconjugated acyclic nitrites as well as a liquid phase process for the isomerization of those nitrites to 3- and/or 4monoalkene linear nitrites.
While the catalyst systems described above may represent commercially viable catalysts, 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. The effectiveness and/or performance may be achieved in any or all of rapidity, selectivity, efficiency or stability, depending on the reaction performed. It is also desirable to provide such improved catalyst systems and/or processes which may be optimized for one or more commercially important reactions such as hydroformylation, hydrocyanation or isomerization. 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 hydrocyanation process comprising reacting an acyclic, aliphatic, monoethylenically unsaturated compound in which the ethylenic double bond is not conjugated to any other olefinic group in the molecule with a source of HCN in the presence of a catalyst precursor composition comprising a Lewis acid, a zero-valent nickel 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 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′
, 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, dialkylamnino, 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
,R CNR
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
, wherein R
14
is H, C
1
-C
18
alkyl, cycoalkyl, or aryl, (CR
14
2
)
n
—OR
14
, (CR
14
2
)
n
—NHR
15
, wherein n=0-3, 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 tile group consisting of (CR
14
2
)
n
—OR
14
wherein n=0-3 and R
14
is defined as above.
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 l, 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
Boyles John Ronald
Garner J. Michael
Kreutzer Kristina Ann
Tam Wilson
Chang Ceila
Invista North America S.a.r.l.
Langworthy John A.
Sackey Ebenezer
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