Hydrocyanation of diolefins and isomerization of...

Details Hydrocyanation of diolefins and isomerization of... Hydrocyanation of diolefins and isomerization of...

1999-08-12

2001-01-09

McKane, Joseph K. (Department: 1626)

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

Catalyst or precursor therefor

Organic compound containing

Reexamination Certificate

active

06171997

ABSTRACT:

FIELD OF THE INVENTION
This invention generally relates to an improved liquid phase process useful in the hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitriles and to a liquid phase process of isomerization of said nitriles to, among other things, 3- and/or 4-monoalkene linear nitriles. The improvement resides in conducting the processes in the presence of zero-valent nickel and a multidentate phosphite ligand.
BACKGROUND OF THE INVENTION
Catalytic hydrocyanation systems, particularly pertaining to the hydrocyanation of olefins, are known in the art. For example, liquid phase systems useful for the hydrocyanation of butadiene to form pentenenitriles (PN) are known in the art. For example, Drinkard, U.S. Pat. No. 3,496,215, discloses the hydrocyanation of butadiene using nickel catalysts with monodentate phosphite ligands. As used in this patent, and as will be used herein, the term “pentenenitrile” is intended to mean cyanobutene. Likewise, “butenenitrile” means cyanopropene. Bidentate phosphite ligands complexed to zero-valent nickel and platinum are known to be useful in the liquid phase hydrocyanation of butadiene, as described by Baker et al.,
J. Chem. Soc., Chem. Commun.,
1991, 803-804.
The pentenenitriles so formed are subjected to further hydrocyanation and/or isomerization to form adiponitrile (ADN), a commercially important material in the manufacture of nylon. For example, Drinkard, U.S. Pat. No. 3,536,748, discloses the liquid phase isomerization of 2-methyl-3-butenenitrile in the presence of a zero valent nickel complex and Chia, U.S. Pat. No. 3,676,481, discloses an improvement additionally utilizing tri(hydrocarbyl)boron promoters.
The hydrocyanation of activated olefins such as 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-pentenenitrile normally require 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.
Certain multidentate phosphite ligands useful in the present invention for the hydrocyanation of diolefins have been used for the hydrocyanation of monoolefins. Commonly assigned, WO 95/14659 and U.S. Pat. No. 5,512,696, disclose bidentate phosphite ligands preferably used in combination with a Lewis acid promotor to hydrocyanate monoolefins.
The present invention provides for an improved process for the hydrocyanation of diolefinic compounds, such as butadiene, and isomerization of nonconjugated acyclic nitriles without the need for Lewis acid promoters utilizing zero-valent nickel and a multidentate phosphite ligand wherein there is at least one 1-naphthol terminus present. 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 an improved process for the liquid phase hydrocyanation of diolefinic compounds and isomerization of the resulting nonconjugated acyclic nitriles comprising, reacting an acyclic aliphatic diolefinic compound, preferably butadiene, with a source of HCN, wherein the improvement comprises conducting the hydrocyanation and/or isomerization in the presence of a catalyst precursor composition comprising zero-valent nickel and at least one multidentate phosphite ligand selected from the group consisting of compounds represented by Formulas I, II, III, IV, V, VI, VII, VIII, IX and X, as set forth below:
wherein
each R
1
is independently a H, halogen, primary, secondary, or tertiary 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 a C
1
to C
12
alkyl, or aryl;
each R
2
and R
2′
are independently a H, halogen, primary, secondary or tertiary 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 a C
1
to C
12
alkyl, or aryl; when R
2′
is not hydrogen, R
2′
cannot be ortho to the oxygen;
each R
5′
is independently a H, halogen, primary, secondary or tertiary 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 a C
1
to C
12
alkyl, or aryl;
each R
9
is independently H, halogen, primary, secondary or tertiary 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 a C
1
to C
12
alkyl, or aryl; and
each X is independently O or CH(R
4′
), wherein R
4′
is H, aryl, or a C
1
to C
12
alkyl.
The present invention provides an improved process for the liquid phase hydrocyanation of diolefinic compounds, reacting an acyclic aliphatic diolefinic compound, preferably butadiene, with a source of HCN, wherein the improvement comprises conducting the hydrocyanation in the presence of a catalyst precursor composition comprising zero-valent nickel and at least one multidentate phosphite ligand selected from the group consisting of compounds represented by Formulas I, II, III, IV, V, VI, VII, VIII, IX and X, as set forth below:
wherein
each R
1
is independently a H, halogen, primary, secondary, or tertiary 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 a C
1
to C
12
alkyl, or aryl;
each R
2
and R
2′
are independently a H, halogen, primary, secondary or tertiary 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 a C
1
to C
12
alkyl, or aryl; when R
2′
is not hydrogen, R
2′
cannot be ortho to the oxygen;
each R
5′
is independently a H, halogen, primary, secondary or tertiary 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 a C
1
to C
12
alkyl, or aryl;
each R
9
is independently H, halogen, primary, secondary or tertiary 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 a C
1
to C
12
alkyl, or aryl; and
each X is independently O or CH(R
4′
), wherein R
4′
is H, aryl, or a C
1
to C
12
alkyl.
As used herein, the terms “secondary” and “tertiary” refer to the carbon atom bonded to an aromatic ring.
The reactions are most conveniently performed continuously from hydrocyanation of the starting diolefin to the final 3- and/or 4-monoalkene linear nitriles. However, the processes can be conducted stepwise, i.e., the nonconjugated acyclic nitriles resulting from the hydrocyanation can be isolated per se, prior to isomerization. Furthermore, nonconjugated acyclic nitriles prepared by any method can be used as starting materials for the isomerization in accordance with this invention.
The invention also provides for certain multidentate phosphite ligands and catalyst precursor compositions made therefrom useful in these processes. In particular, these include the ligands of Formulas I-IV and VI-X.
Catalyst precursor compositions consisting of zero-valent nickel and at least one multidentate phosphite ligand according to Formula I-X are also covered.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The catalyst precursor compositions useful in the processes of the invention are comprised of a multidentate phosphite ligand and zero-valent nickel.
The catalyst composition is referred to as a “precursor” only to indicate in all likelihood, during the hydrocyanation reaction the structure of the active catalyst composition may in fact be complexed to an olefin.
These ligands may be prepared by a variety of methods known in the art, for example, see descriptions in WO 93,03839, U.S. Pat. No. 4,769,498; U.S. Pat. No. 4,688,651,
J. Amer. Chem. Soc.,
1993, 115, 2066. The reaction of di-(1-naphthyl)phosphorochloridite with 1,

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