Organic compounds -- part of the class 532-570 series – Organic compounds – Nitriles
Reexamination Certificate
2000-11-30
2003-02-18
McKane, Joseph K. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitriles
C502S213000, C558S339000, C558S340000, C558S156000
Reexamination Certificate
active
06521778
ABSTRACT:
The present invention relates to a catalyst which comprises a complex of a metal of subgroup VIII, which comprises at least one bidentate phosphonite ligand, a process for the preparation of mixtures of monoolefinic C
5
-mononitriles and a process for the preparation of adipodinitrile by catalytic hydrocyanation in the presence of such a catalyst.
For the industrial production of polyamides, there is a considerable demand worldwide for &agr;,&ohgr;-alkylenediamines, which serve as an important starting material. &agr;,&ohgr;-alkylenediamines, such as hexamethylenediamine, are obtained virtually exclusively by hydrogenating the corresponding dinitriles. Virtually all industrial routes for the production of hexamethylenediamine are therefore essentially variants of the production of adipodinitrile, of which about 1.0 million metric tons are produced annually worldwide.
K. Weissermel, H.-J. Arpe, Industrielle Organische Chemie, 4th edition, VCH Weinheim, page 266 et seq., describe four basically different routes for the preparation of adipodinitrile, including the direct hydrocyanation of 1,3-butadiene with hydrogen cyanide. In the last-mentioned process, monoaddition in a first stage gives a mixture of isomeric pentenenitriles, which is isomerized in a second stage to give predominantly 3- and 4-pentenenitrile. Adipodinitrile is then formed in a third stage by an anti-Markownikow hydrogen cyanide addition reaction with 4-pentenenitrile.
“Applied Homogeneous Catalysis with Organometalic Compounds”, Vol. 1, VCH Weinheim, page 465 et seq., describes in general the addition reaction of hydrogen cyanide with olefins under heterogeneous and homogeneous catalysis. In particular, catalysts based on phosphine, phosphite and phosphinite complexes of nickel and of palladium are used. For the preparation of adipodinitrile by hydrocyanation of butadiene, predominantly nickel(0) phosphite catalysts are used, in the presence or absence of a Lewis acid as a promoter.
J. Chem. Soc., Chem. Commun., 1991, page 1292, describes chiral aryl diphosphites as ligands for hydrocyanation catalysts. In these ligands, the phosphite group is bonded via two of its oxygen atoms to the 3- and 3′-positions of a 2,2′-binaphthyl unit, with which it thus forms a 7-membered heterocycle. In addition, two of these heterocycles may likewise be linked via a 2,2′-binaphthyl unit to form a bidentate chelate ligand. In J. Chem. Soc., Chem. Commun., 1991, page 803 et seq., analogous chelate diphosphite complexes of nickel(0) and platinum(0) are described for this purpose, a 2,2′-biphenyl unit being used instead of a 2,2′-binaphthyl unit as the bridging group.
U.S. Pat. No. 5,449,807 describes a process for the gas-phase hydrocyanation of diolefins in the presence of a supported nickel catalyst based on at least one bidentate phosphite ligand, the two phosphite groups being bridged by an unsubstituted or substituted 2,2′-biphenyl group. U.S. Pat. No. 5,440,067 describes a process for the gas-phase isomerization of 2-alkyl-3-monoalkenenitriles to give linear 3- and/or 4-monoalkenenitriles in the presence of the catalysts described in U.S. Pat. No. 5,449,807.
WO 95/14659 describes a process for the hydrocyanation of monoolefins, in which catalysts based on zero-valent nickel and bidentate phosphite ligands may be used. In these ligands, the phosphite groups together with two of their oxygen atoms are part of an aryl-fused 7-membered heterocycle. Pairs of these phosphite groups are then bridged by aryl-fused alkylene groups via the oxygen atoms which are not part of the heterocycle.
U.S. Pat. No. 5,512,695 likewise describes a process for the hydrocyanation of monoolefins in the presence of a nickel catalyst which comprises a bidentate phosphite ligand.
WO 96/11182 describes a process for hydrocyanation in the presence of a nickel catalyst based on a bidentate or polydentate phosphite ligand in which the phosphite groups are not part of a heterocycle. The groups used for bridging the phosphite groups correspond to those described in WO 95/14659.
U.S. Pat. No. 5,523,453 describes a process for hydrocyanation in the presence of a nickel catalyst based on a bidentate ligand which comprises at least one phosphinite group and a further phosphorus-containing group which is selected from phosphinites and phosphites. The two phosphorus-containing groups of these bidentate ligands are in turn bridged via aryl-fused groups. WO 97/23446 describes a process for the hydrocyanation of diolefins and for the isomerization of 2-alkyl-3-monoalkenenitriles in the presence of catalysts which correspond to those described in U.S. Pat. No. 5,523,453.
WO 96/22968 likewise describes a process for the hydrocyanation of diolefinic compounds and for the isomerization of the resulting, nonconjugated 2-alkyl-3-monoalkenenitriles, a nickel(0) catalyst based on a polydentate phosphite ligand being used in the presence of a Lewis acid as promoter. The phosphite groups of these polydentate ligands are once again components of aryl-fused heterocycles and may be bridged via aryl-fused groups.
None of the abovementioned publications describes hydrocyanation catalysts based on phosphonite ligands. In particular, no catalysts based on bidentate chelate phosphonites are described.
U.S. Pat. No. 3,766,237 describes a process for the hydrocyanation of ethylenically unsaturated compounds which may have further functional groups, such as nitriles, in the presence of a nickel catalyst. These nickel catalysts carry four ligands of the formula M(X,Y,Z), where X, Y and Z, independently of one another, are each a radical R or OR and R is selected from alkyl and aryl groups of up to 18 carbon atoms. However, only phosphines and phosphites are mentioned explicitly and are used in the examples for the hydrocyanation. On the other hand, it is not disclosed that phosphonites can be used as ligands for nickel(0) hydrocyanation catalysts. In particular, no bidentate chelate phosphonite ligands are described.
It is an object of the present invention to provide novel catalysts based on a metal of subgroup VIII. They should preferably have good selectivity and good catalytic activity in the hydrocyanation of 1,3-butadiene and 1,3-butadiene-containing hydrocarbon mixtures. Preferably, they should also be suitable for the catalytic isomerization of monoalkenenitriles and for the addition reaction of the second molecule of hydrogen cyanide with said monoalkenenitriles, for example for the preparation of adipodinitrile.
We have surprisingly found that this object is achieved by catalysts based on a metal of subgroup VIII which comprise at least one bidentate phosphonite ligand.
The present invention therefore relates to a catalyst comprising a complex of a metal of subgroup VIII, having a bidentate phosphonite ligand of the formula I
where
A is a C
2
- to C
7
-alkylene bridge which may have 1, 2 or 3 double bonds and/or 1, 2 or 3 substituents which are selected from alkyl, cycloalkyl and aryl, it being possible for the aryl substituent additionally to carry 1, 2 or 3 substituents which are selected from alkyl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl and cyano, and/or the C
2
- to C
7
-alkylene bridge may be interrupted by 1, 2 or 3 non-neighboring, unsubstituted or substituted heteroatoms, and/or the C
2
- to C
7
-alkylene bridge may be fused with one, two or three aryl and/or hetaryl groups, it being possible for the fused aryl and hetaryl groups each to carry 1, 2 or 3 substituents which are selected from alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, alkoxycarbonyl and NE
1
E
2
, where E
1
and E
2
are identical or different and are each alkyl, cycloalkyl or aryl,
R
1
and R
1′
, independently of one another, are each alkyl, cycloalkyl, aryl or hetaryl, each of which may carry 1, 2 or 3 substituents which are selected from alkyl, cycloalkyl and aryl,
R
2
and R
2′
, independently of one another, are each alkyl, cycloalkyl, aryl or hetaryl, it being possible
Fischer Jakob
Keitel Dagmar Pascale
Siegel Wolfgang
Siggel Lorenz
Anderson Rebecca
BASF - Aktiengesellschaft
Keil & Weinkauf
McKane Joseph K.
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