Bidentate phosphite and nickel catalyst compositions for...

Details Bidentate phosphite and nickel catalyst compositions for... Bidentate phosphite and nickel catalyst compositions for...

1995-11-29

2003-11-11

Stockton, Laura L. (Department: 1626)

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

Organic compounds

Phosphorus esters

C502S162000

Reexamination Certificate

active

06646148

ABSTRACT:

FIELD OF THE INVENTION
The invention generally relates to processes and catalyst precursor compositions useful for the hydrocyanation of monoolefins. In particular, the invention relates to the hydrocyanation of monoolefins using catalyst precursor compositions comprising zero-valent nickel and unsymmetrical bidentate phosphite ligands.
BACKGROUND OF THE INVENTION
Hydrocyanation catalyst systems, particularly pertaining to the hydrocyanation of olefins, are known in the art. For example, systems useful for the hydrocyanation of butadiene to form pentenenitrile (PN) and in the subsequent hydrocyanation of pentenenitrile (PN) to form adiponitrile (ADN), are known in the commercially important nylon synthesis field.
The hydrocyanation of olefins using transition metal complexes with monodentate phosphite ligand is documented in the prior art. See for example; U.S. Pat. Nos. 3,496,215, 3,631,191, 3,655,723 and 3,766,237, and Tolman, C. A.; McKinney, R. J.; Seidel, W. C.; Druliner, J. D.; and Stevens, W. R.; Advances in Catalysis, 33, 1, 1985.
The hydrocyanation of activated olefins such as with conjugated olefins (e.g., butadiene and styrene) and strained olefins (e.g., norbornene) proceeds without the use of a Lewis acid promoter, while hydrocyanation of unactivated olefins such as 1-octene and 3-pentene-nitrile requires the use of a Lewis acid promoter. Teachings regarding the use of a promoter in the hydrocyanation reaction appear, for example, in U.S. Pat. No. 3,496,217. This patent discloses an improvement in hydrocyanation using a promoter selected from a large number of metal cation compounds with a variety of anions as catalyst promoters.
U.S. Pat. No. 3,496,218 discloses a nickel hydrocyanation catalyst promoted with various boron-containing compounds, including triphenylboron and alkali metal borohydrides. U.S. Pat. No. 4,774,353 discloses a process for the preparation of dinitriles, including ADN, from unsaturated nitriles, including PN, in the presence of a zero-valent nickel catalyst and a triorganotin catalyst promoter. U.S. Pat. No. 4,874,884 discloses a process for producing ADN by the zero-valent nickel catalyzed hydrocyanation of pentenenitriles in the presence of a synergistic combination of promoters selected in accordance with the reaction kinetics of the ADN synthesis.
Bidentate phosphite ligands similar to those used in the present invention for the hydrocyanation of monoolefins have been shown to be useful ligands in the hydrocyanation of activated olefins. See, for example: Baker, M. J., and Pringle, P. G.; J. Chem. Soc., Chem. Commun., 1292, 1991; Baker, M. J.; Harrison, K. N.; Orpen, A. G.; Pringle, P. G.; and Shaw, G.; J. Chem. Soc.; Chem. Commun., 803, 1991, Union Carbide, WO 93,03839. Also, similar ligands have been disclosed with rhodium in the hydroformylation of functionalized olefins; Cuny et al., J. Am. Chem. Soc. 1993, 115, 2066.
The present invention provides novel processes and catalyst precursor compositions which are rapid, selective, efficient and stable in the hydrocyanation of monoolefins. 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 present invention provides a process for hydro-cyanation, comprising reacting a nonconjugated acyclic aliphatic monoolefin or a monoolefin conjugated to an ester group; e.g., methyl pent-2-eneoate, with a source of HCN in the presence of a catalyst precursor composition comprising zero-valent nickel and a bidentate phosphite ligand of Formula I,
wherein
each R
1
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms;
each R
2
is independently, H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
3
wherein R
3
is C
1
to C
12
alkyl;
to produce a terminal organonitrile. Preferably, the reaction is carried out in the presence of a Lewis acid promoter.
The present invention also provides a process for hydrocyanation comprising reacting a nonconjugated acyclic aliphatic monoolefin or a monoolefin conjugated to an ester group; e.g., methyl pent-2-eneoate, with a source of HCN in the presence of a catalyst precursor composition comprising zero-valent nickel and a bidentate phosphite ligand selected from the group consisting of Formulas II-VI as set forth below:
wherein
each R
6
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms; and
each R
7
is independently H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
8
wherein R
8
is C
1
to C
12
alkyl;
wherein
each R
9
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms;
each R
10
is independently H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
8
wherein R
8
is C
1
to C
12
alkyl; and
each R
11
is independently a branched or straight chain alkyl of up to 12 carbon atoms;
wherein
each R
12
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms;
each R
13
is independently H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
8
wherein R
8
is C
1
to C
12
alkyl; and
each R
14
is independently a branched or straight chain alkyl of up to 12 carbon atoms;
wherein
each R
15
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms; and
each R
16
is independently H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
8
wherein R
8
is C
1
to C
12
alkyl;
and
wherein
each R
17
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms; and
each R
18
is independently H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
8
wherein R
8
is C
1
to C
12
alkyl;
to produce a terminal organonitrile. Preferably, the reaction is carried out in the presence of a Lewis acid promoter.
The monoolefins of the above-identified processes are described by Formulas VII or IX, and the corresponding terminal organonitrile compounds produced are described by Formulas VIII or X, respectively.
wherein
R
19
is H, CN, CO
2
R
20
, or perfluoroalkyl;
y is 0 to 12;
x is 0 to 12 when R
19
is H, CO
2
R
20
or perfluoroalkyl;
x is 1 to 12 when R
19
is CN; and
R
20
is alkyl; or
wherein
R
19
is H, CN, CO
2
R
20
, or perfluoroalkyl;
x is 0 to 12 when R
19
is H, CO
2
R
20
or perfluoroalkyl;
x is 1 to 12 when R
19
is CN; and
R
20
is alkyl.
The present invention further provides a catalyst precursor composition comprising zero-valent nickel and an unsymmetrical bidentate phosphite ligand of Formula I,
wherein
each R
1
is independently a secondary or tertiary substituted hydrocarbon of 3 to 12 carbon atoms; and
each R
2
is independently H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
3
wherein R
3
is C
1
to C
12
alkyl.
The present invention further provides a catalyst precursor composition comprising zero-valent nickel and an unsymmetrical bidentate phosphite ligand selected from the group consisting of Formulas II-VI as set forth below:
wherein
each R
6
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms; and
each R
7
is independently H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
8
wherein R
8
is C
1
to C
12
alkyl;
wherein
each R
9
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms;
each R
10
is independently H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
8
wherein R
8
is C
1
to C
12
alkyl; and
each R
11
is independently a branched or straight chain alkyl of up to 12 carbon atoms;
wherein
each R
12
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms;
each R
13
is independently H, X wherein X is Cl, F or Br, a C
1
to C
12
alkyl, or OR
8
wherein R
8
is C
1
to C
12
alkyl; and
each R
14
is independently a branched or straight chain alkyl of up to 12 carbon atoms;
wherein
each R
15
is independently a secondary or tertiary substituted hydrocarbyl of 3 to 12 carbon atoms; and
each R
16
is independe

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