Hydrocyanation processes and multidentate phosphite ligand...

Details Hydrocyanation processes and multidentate phosphite ligand... Hydrocyanation processes and multidentate phosphite ligand...

1999-07-13

2001-01-09

Tsang, Cecilia (Department: 1626)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C558S338000

Reexamination Certificate

active

06171996

ABSTRACT:

FIELD OF THE INVENTION
The invention generally relates to a process and catalyst precursor composition for the hydrocyanation of monoethylenically unsaturated compounds wherein zero-valent nickel and a multidentate phosphite ligand are used in the presence of a Lewis acid promoter.
BACKGROUND OF THE INVENTION
Hydrocyanation catalyst systems, particularly pertaining to the hydrocyanation of ethylenically unsaturated compounds, 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 to form adiponitrile (ADN), are known in the commercially important nylon synthesis field.
The hydrocyanation of ethylenically unsaturated compounds using transition metal complexes with monodentate phosphite ligands 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 et al., Advances in Catalysis, 1985, 33, 1. The hydrocyanation of activated ethylenically unsaturated compounds, such as with conjugated ethylenically unsaturated compounds (e.g., butadiene and styrene), and strained ethylenically unsaturated compounds (e.g., norbomene) proceeds without the use of a Lewis acid promoter, while hydrocyanation of unactivated ethylenically unsaturated compounds, such as 1-octene and 3-pentenenitrile, 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 nitrites, including PN, in the presence of a zero-valent nickel catalyst and a triorganotin catalyst promoter. Moreover, 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.
Phosphite ligands have been shown to be useful ligands in the hydrocyanation of activated ethylenically unsaturated compounds. See, for example, Baker, M. J., and Pringle, P. G.,
J Chem. Soc. Chem. Commun.,
1991, 1292; Baker et al.,
J Chem. Soc., Chem. Commun.,
1991, 803; Union Carbide, WO 93,03839. Also, phosphite ligands have been disclosed with rhodium in the hydroformylation of functionalized ethylenically unsaturated compounds: see, Cuny et al.,
J. Am. Chem. Soc.,
1993, 115, 2066.
U.S. Pat. No. 5,512,696, which issued Apr. 30, 1996, discloses processes and catalyst compositions for the hydrocyanation of monoethyleneically unsaturated compounds using zero-valent nickel and certain multidentate phosphite ligands, and Lewis acid promoters, which are similar to those encompassed by the present invention, except for the choice of the ortho substituent for the group or the phosphite phenyl termin.
Like U.S. Pat. No. 5,512,696, the present invention provides processes and catalyst precursor compositions which are more rapid, selective, efficient and stable than prior processes and catalyst complexes employed in the hydrocyanation of monoethylenically unsaturated compounds. Other objects and advantages of the present invention will become apparent to those skilled in the art upon reference to the detailed description of the invention which hereinafter follows.
SUMMARY OF THE INVENTION
The present 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, or a monoethylenically unsaturated compound in which the ethylenic double bond is conjugated to an organic ester group, 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 Formulas I, II, III, IV, V, VI, VII, VIII, and IX, in which all like reference characters have the same meaning, except as further explicitly limited.
wherein
each R
1
is independently a primary, secondary, or tertiary hydrocarbyl of 1 to 12 carbon atoms; with the proviso that at least one of R
1
must be a primary hydrocarbyl;
each R
2
is independently H, halogen, primary or secondary hydrocarbyl of 1 to 12 carbon atoms, OR
3
wherein R
3
is a C
1
to C
12
alkyl, or CO
2
R
3
′ wherein R
3
′ is an aryl or a C
1
to C
12
alkyl;
each R
2
′ is independently H, halogen, CHO, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR
3
wherein R
3
is a C
1
to C
12
alkyl, CO
2
R
3
′ wherein R
3
′ is an aryl or a C
1
to C
12
alkyl, or C(R
3
)(O) wherein R
3
is a C
1
to C
12
alkyl;
each R
4
is independently H, a primary or secondary hydrocarbyl of 1 to 12 carbon atoms or CO
2
R
3
wherein R
3
is a C
1
to C
12
alkyl; and
each R
4
′ is independently H, a primary or secondary hydrocarbyl of 1 to 12 carbon atoms or aryl.
In the above catalyst precursor compositions, the Lewis acid is considered to be a promoter.
The term “hydrocarbyl” is well known in the art and designates a hydrocarbon molecule from which one hydrogen atom has been removed. Such molecules can contain single, double or triple bonds.
The present invention further provides for novel multidentate phosphite ligands selected from one of Formulas I-IX, as defined above and catalyst precursor compositions made therefrom with zero-valent nickel. Preferably, the catalyst precursor compositions also have a Lewis acid present.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Representative ethylenically unsaturated compounds which are useful in the process of this invention are shown in Formulas X or XII, and the corresponding terminal nitrile compounds produced are illustrated by Formulas XI or XII, respectively, wherein like reference characters have same meaning.
wherein
R
5
is H, CN, CO
2
R
3
′, or perfluoroalkyl;
y is an integer of 0 to 12;
x is an integer of 0 to 12 when R
5
is H, CO
2
R
3
′ or perfluoroalkyl;
x is an integer of 1 to 12 when R
5
is CN; and
R
3
′ is aryl or a C
1
to C
12
alkyl.
One of the ligands useful in the catalyst compositions of the present invention is illustrated above by Formula I, as defined above. At least one of R
1
is a primary alkyl, examples of which include methyl, ethyl and n-propyl. In the preferred Formula I ligand, each R
1
is methyl, each R
2
is methyl except R
2
para to oxygen. R
2
para to oxygen is hydrogen and R
2
′ is hydrogen.
The catalyst composition of the invention may be considered a “precursor” composition in that the zero-valent nickel at some point becomes complexed to the multidentate phosphite ligand, and, further in all likelihood, additional reactions occur during hydrocyanation, such as, for example, complexing of the initial catalyst composition to an ethylenically unsaturated compound.
These ligands can be prepared by a variety of methods known in the art, for example, see descriptions in European Patent Application 92109599.8 of Mitsubishi Kasei Corporation and the corresponding U.S. Pat. No. 5,235,113 to Sato et al. The reaction of o-cresol with phosphorus trichloride gives the phosphorochloridite. The reaction of this phosphorochloridite with 3,3′,4,4′,6,6′-hexamethyl-2,2′-biphenol in the presence of triethylamine gives the above-identified preferred ligand of Formula I.
The phosphorochloridite may be prepared by a variety of methods known in the art, for example, see descriptions in
Polymer,
1992, 33, 161;
Inorganic Synthesis,
1966, 8, 68;.U.S. Pat.

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