Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2000-12-12
2002-11-26
Shippen, Michael L. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C502S163000, C556S014000, C556S018000, C556S019000, C558S338000, C558S339000, C558S340000
Reexamination Certificate
active
06486359
ABSTRACT:
The present invention relates to a catalyst which comprises at least one complex of a metal of group VIII, which comprises at least one uni-, bi- or multidentate phosphinite ligand in which the phosphorus atom and the oxygen atom of the phosphinite group are part of a 5- to 8-membered heterocycle, and to processes for the hydroformylation and hydrocyanation of compounds which contain at least one ethylenically unsaturated double bond in the present of a catalyst of this type.
Hydroformylation or oxo synthesis is an important industrial process and is used to prepare aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes may, where appropriate, be hydrogenated with hydrogen in the same operation to give the corresponding oxo alcohols. The reaction itself is highly exothermic and generally proceeds under elevated pressure and at elevated temperatures in the presence of catalysts. The catalysts employed are Co, Rh or Ru compounds or complexes which may be modified with amine- or phosphine-containing ligands to influence the activity and/or selectivity. Additional promoters have not to date achieved any importance in practice. The hydroformylation reaction results, because of the possibility of addition of Co to each of the two C atoms in a double bond, in the formation of mixtures of isomeric aldehydes. In addition, when internal olefins are used, isomerization of the double bond from an internal toward a terminal position may occur. In these isomeric mixtures, the n aldehyde is generally favored over the iso aldehyde but, because the n aldehydes have considerably greater industrial importance, one aim is to optimize the hydroformylation catalysts to achieve greater n selectivity.
A review of hydroformylation processes is given in Beller et al., Journal of Molecular Catalysis A, 104 (1995), pages 17-85. None of the references mentioned therein describes hydroformylation catalysts based on bi- or multidentate phosphinite ligands where the phosphinite group is part of a 5- to 8-membered heterocycle.
EP-A 0 599 284 describes cycloolefin polymer molding compositions which are stabilized with an organophosphorus compound against unwanted oxidative, thermal and photochemical damage. Stabilizers which can be employed in this case are, inter alia, phosphinites in which the phosphorus and the oxygen atom in the phosphinite group are part of a 6-membered heterocycle. DE-A 40 21 195 and WO 92/00306 describe a process for preparing these organophosphorus compounds by Grignard synthesis, and the use thereof for stabilizing plastics. Complex compounds of these organophosphorus compounds and their use as ligands in hydroformylation catalysts are not described.
Catalytic hydrocyanation to prepare nitriles from olefins likewise has great industrial importance. This generally involves reacting mono-, di- or polyolefins in the presence of suitable catalysts with hydrogen cyanide to give mono-, di- and polynitriles or mixtures thereof, which are of outstanding importance in particular as amine precursors, e.g. for preparing polyamides.
“Applied Homogeneous Catalysis with Organometalic Compounds”, Volume 1, VCH Weinheim, pp. 465 et seq., gives a general description of heterogeneous and homogeneous catalysis for addition of hydrogen cyanide onto olefins. The catalysts used for this are in particular those based on phosphine, phosphite and phosphonite complexes of nickel and palladium.
The usual catalysts for the hydrocyanation are, in particular, the nickel(0) phosphite catalysts mentioned above.
C. A. Tolman et al. describe in Organometallics 1984, 3, pp. 33 et seq. the catalytic hydrocyanation of olefins in the presence of nickel(0) phosphite complexes paying special attention to the effects of Lewis acids on the addition of hydrogen cyanide.
Advances in Catalysis, Volume 33, 1985, Academic Press Inc., pp. 1 et seq., gives a review-like description of homogeneous nickel-catalyzed hydrocyanation of olefins. The catalysts employed are nickel(0) complexes with phosphine and phosphite ligands.
J. Chem. Soc., Chem. Commun., 1991, p. 1292, describes chiral aryl diphosphites as ligands for hydrocyanation catalysts. The phosphite group in these ligands is bonded by 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. It is additionally possible for two of these heterocycles likewise to be linked via a 2,2′-binaphthyl unit to a bidentate chelating ligand.
J. Chem. Soc., Chem. Commun., 1991, pp. 803 et seq., describes chelate diphosphite complexes of nickel(0) and platinum(0) analogous thereto, employing a 2,2′-biphenyl unit in place of a 2,2′-binaphthyl unit.
WO 95/28228 describes a process for the hydrocyanation of aliphatic monoolefins which may additionally have an unconjugated nitrile group or an unconjugated or conjugated ester group. The nickel(0) catalysts employed in this case likewise comprise bidentate phosphite ligands in which the phosphite groups are parts of aryl-fused heterocycles.
WO 95/29153 describes a process for the hydrocyanation of monoolefins employing catalysts based on zero-valent nickel and unidentate phosphite ligands. The phosphite group in these ligands is once again, together with two of its oxygen atoms, part of an aryl-fused 7-membered heterocycle. The third oxygen atom of the phosphite group carries a t-butyl-substituted phenyl radical which may have further substituents.
WO 96/11182 describes a process for the hydrocyanation of aliphatic, monoethylenically unsaturated compounds in which the ethylenic double bond is not conjugated with another unsaturated group or in which the ethylenic double bond is conjugated with an ester group. In this case, a nickel(0) catalyst based on a multidentate phosphite ligand is employed in the presence of a Lewis acid as promoter. The phosphite groups in these multidentate ligands are in turn constituents of aryl-fused heterocycles and may be linked together via aryl-fused groups.
WO 96/22968 describes a process for the hydrocyanation of diolefinic compounds and for the isomerization of the resulting unconjugated 2-alkyl-3-monoalkenonitriles by reacting an acyclic aliphatic diolefin with a source of hydrogen cyanide. The reaction in this case takes place in the liquid phase. The hydrocyanation catalysts employed are analogous to those described in WO 96/11182.
U.S. Pat. No. 5,512,695 has a disclosure content corresponding to that of WO 95/28228.
Apart from the hydrocyanation catalysts based on uni-, bi- and multidentate phosphite ligands described above, catalysts based on phosphinite ligands are also known. J. Am. Chem. Soc., 1994, 116, pp. 9869 et seq. and U.S. Pat. No. 5,484,902 describe catalysts for the enantioselective hydrocyanation of aromatic vinyl compounds based on a chiral, non-racemic, bidentate chelating phosphinite ligand. The ligand preferably employed in this case is a phenyl 2,3-bis-O-(3,5-bis(trifluoromethyl)phenyl)phosphino-4,6-O-benzylidene-&bgr;-D-glucopyranoside.
U.S. Pat. No. 5,523,453 describes a process for the hydrocyanation of monoolefins which may additionally have a cyano group in the presence of a Lewis acid as promoter and of a nickel(0) catalyst. These catalysts have ligands based on chelating phosphinites where two aryl-substituted phosphinite groups are linked together via their oxygen atom and an aryl-fused alkylene bridge.
None of the abovementioned references describes hydrocyanation catalysts based on phosphinite ligands in which the phosphinite group is part of a 5- to 8-membered heterocycle.
U.S. Pat. No. 3,766,237 describes a process for the hydrocyanation of ethylenically unsaturated compounds which may have other functional groups, e.g. nitriles, in the presence of a nickel catalyst. These nickel catalysts have four ligands of the general formula M(X,Y,Z) where X, Y and Z are, independently of one another, a radical R or OR, and R is selected from alkyl and aryl groups having up to 18 carbon atoms. However, only phosphines and phosphites are explicitly mentioned therein and employe
Fischer Jakob
Maas Heiko
Paciello Rocco
Röper Michael
BASF - Aktiengesellschaft
Keil & Weinkauf
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