Multidentate phosphite ligands, catalytic compositions...

Details Multidentate phosphite ligands, catalytic compositions... Multidentate phosphite ligands, catalytic compositions...

2000-08-30

2002-04-30

Higel, Floyd D. (Department: 1626)

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

Organic compounds

Nitriles

C558S338000

Reexamination Certificate

active

06380421

ABSTRACT:

FIELD OF THE INVENTION
The invention relates to certain multidentate phosphite ligands, the catalyst compositions made therefrom and a catalytic hydrocyanation process which employs such multidentate phosphite ligands. In particular, the ligands have phenyl containing substituents attached to the ortho position of the terminal phenol group and/or attached to the ortho position of the backbone.
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 ethylenically 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 nitrites as well as a liquid phase process for the isomerization of those nitrites to 3- and/or 4-monoalkene linear nitriles 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 nitriles 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 4-monoalkene linear nitrites.
The use of multidentate phosphate ligands having binaphthalene and/or biphenyl bridging groups for hydroformylation reactions is disclosed in U.S. Pat. Nos. 5,235,113, 5,874,641, 5,710,344 and published PCT Application WO 97/33854
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 a commercially important reaction such hydrocyanation or isomerazation. 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, monoethylenicaly 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 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 II or III, in which all like reference characters have the same meaning, except as further explicitly limited.
wherein
R
1
is independently C
1
to C
18
primary or secondary alkyl;
R
2
is independently aryl or substituted aryl;
R
3
is independently aryl or substituted aryl;
R
4
is independently C
1
to C
18
primary alkyl;
R
5
is hydrogen;
R
6
is independently aryl or substituted aryl;
R
7
is independently C
1
to C
18
primary or secondary alkyl;
R
8
is independently C
1
to C
18
primary or secondary alkyl; and
R
9
is independently C
1
to C
18
primary or secondary alkyl;
wherein other positions on the aromatic rings may also be substituted with alkyl, ether or ester groups, or combinations of two or more thereof.
The invention also provides for a multidentate phosphite ligand having the structure represented by the following Formula I, II or III in which all like reference characters have the same meaning, except as further explicitly limited.
wherein
R
1
is independently C
1
to C
18
primary or secondary alkyl;
R
2
is independently aryl or substituted aryl;
R
3
is independently aryl or substituted aryl;
R
4
is independently C
1
to C
18
primary alkyl;
R
5
is hydrogen;
R
6
is independently aryl or substituted aryl;
R
7
is independently C
1
to C
18
primary or secondary alkyl;
R
8
is independently C
1
to C
18
primary or secondary alkyl; and
R
9
is independently C
1
to C
18
primary or secondary alkyl;
wherein other positions on the aromatic rings may also be substituted with alkyl, ether or ester groups, or combinations of two or more thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention provides for certain multidentate phosphite ligands, improved catalyst systems employing such ligands, and the use of such multidentate phosphite ligands in hydrocyanation reactions.
The catalyst compositions useful in the invention preferably are comprised of a multidentate phosphite ligand of formula I, II and III and a transition metal.
wherein
R
1
is independently C
1
to C
18
primary alkyl;
R
2
is independently aryl or substituted aryl;
R
3
is independently aryl or substituted aryl;
R
4
is independently C
1
to C
18
primary alkyl;
R
5
is hydrogen;
R
6
is independently aryl or substituted aryl;
R
7
is independently C
1
to C
18
primary or secondary alkyl;
R
8
is independently C
1
to C
18
primary or secondary alkyl; and
R
9
is independently C
1
to C
18
primary or secondary alkyl;
wherein other positions on the aromatic rings may also be substituted with alkyl, ether or ester groups, or combinations of two or more thereof.
The divalent bridging compounds used in the ligands described in formulae I, II, and III may be prepared by a variety of methods known in the art. For example, 3,3′,5,5′-tetramethyl-2,2′-biphenol can be prepared according to
J. Org. Chem.,
1963, 28, 1063 and 3,3′,5,5′,6,6′-Hexamethyl-2,2′-b

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