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WO2000033956A1 - Alkene hydroformylation catalyst - Google Patents

Alkene hydroformylation catalyst Download PDF

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Publication number
WO2000033956A1
WO2000033956A1 PCT/GB1999/004062 GB9904062W WO0033956A1 WO 2000033956 A1 WO2000033956 A1 WO 2000033956A1 GB 9904062 W GB9904062 W GB 9904062W WO 0033956 A1 WO0033956 A1 WO 0033956A1
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group
ligand
complex
catalyst
hydroformylation
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French (fr)
Inventor
David Cole-Hamilton
Douglas Foster
David Gudmunsen
Eric George Hope
Alison Marion Stuart
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University of St Andrews
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University of St Andrews
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Priority claimed from GBGB9826619.0A external-priority patent/GB9826619D0/en
Priority claimed from GBGB9902338.4A external-priority patent/GB9902338D0/en
Application filed by University of St Andrews filed Critical University of St Andrews
Priority to AU15744/00A priority Critical patent/AU1574400A/en
Publication of WO2000033956A1 publication Critical patent/WO2000033956A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/94—Fluorinated solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
    • B01J2540/225—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate comprising perfluoroalkyl groups or moieties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/60—Groups characterized by their function
    • B01J2540/64—Solubility enhancing groups

Definitions

  • the invention concerns an improved process for the hydroformylation of alkenes .
  • Hydroformylation is a major industrial process that involves the reaction of carbon monoxide and hydrogen with an alkene to give an aldehyde.
  • alkenes two products are possible depending upon the regioselectivity of the addition reaction.
  • the two products, linear (n) aldehyde and branched (i) aldehyde are generally obtained as a mixture but it is usually the linear product that is preferred for industrial applications.
  • the two reactions referred to above are both carried out in the homogeneous phase (i.e. the catalyst, substrate and products are all dissolved in a common solvent) and this means that a process is required for the separation of products, solvent and catalyst. Distillation is generally used, but the thermal sensitivity of the rhodium based catalysts means that they cannot be separated from longer chain aldehyde products (>C 4 ) .
  • One way of circumventing this problem is to use a two phase system with the catalyst dissolved in water. Since the substrate and products are immiscible in water, separation can be effected in a simple manner.
  • substrates with chain lengths of greater than 6 have such low solubility in water that the rate of the hydroformylation is too low for the aqueous process to be of commercial interest; and yet, it is just these substrates (C 9 -C 14 aldehydes) that are of interest for the production of soaps and detergents. Consequently the C 9 -C 14 aldehydes are currently manufactured using the older, less selective, more energy intensive cobalt based systems.
  • Desirable properties of such a system are that the reaction rate should be high (comparable to that with Rh/PPh 3 ) , that the rhodium content of the organic phase at the end of the reaction should be negligible and that the n:i ratio should be high, preferably using only a small amount of phosphine relative to rhodium.
  • EP-A-0, 633, 062 describes the use of [Rh(C0 2 ) (acetylacetonate) ] with either P [CH 2 CH 2 (CF 2 ) 5 CF 3 ] 3 or P[OCH 2 CH 2 (CF 2 ) 7 CF 3 ] 3 at a P:Rh ratio of 40:1.
  • the invention concerns new Iigands for use in the fiuorous biphasic hydroformylation of alkenes, which Iigands allow the reaction to occur at rates similar to those obtained using Rh/PPh 3 in organic solvents, which show little leaching of rhodium into the organic phase and which can provide high n:i ratios at low P:Rh loading.
  • the Iigands described herein also promote isomerisation of alkenes and can be used for the hydroformylation of internal alkenes giving significant amounts of n-aldehydes.
  • Iigands of general formula I when complexed to a rhodium centre are especially good at catalysis of alkene hydroformylation in a fiuorous multiphase system of the type described above.
  • the present invention provides a catalytic complex comprising a ligand of general formula I:
  • Ph is an optionally substituted phenyl ring; each group L independently represents a alkenyl group or other linker group;
  • each group Z represents a branched or linear fluorocarbon chain of up to 11 carbon atoms, preferably 3 to 9 carbon atoms ;
  • each group Y independently represents a group
  • each group Y may represent a C 1 -C 12 alkyl or aryl, which may optionally be substituted;
  • each a is 0 or 1;
  • each b is 0 or 1;
  • each m is an integer of from 1 to 5
  • said ligand is complexed directly or indirectly via the phosphorous moiety to a rhodium centre, for use in catalysis of hydroformylation of alkenes in a fiuorous multiphase system.
  • fiuorous multiphase system we mean a system including a liquid-liquid biphase where one phase is a fiuorous phase containing a fiuorous solvent (typically a fluorocarbon or a fluorohydrocarbon) .
  • a fiuorous solvent typically a fluorocarbon or a fluorohydrocarbon
  • Suitable solvents include fluorodimethylcyclohexane, perfluoromethylcyclohexane, hexafluorobenzene, pentafluorobenzene and the like.
  • the ligand of general formula I comprises a single fluorocarbon tail linked to a phenyl ring which is otherwise unsubstituted (apart from its connection to group X or to the phosphorous moiety) .
  • Group Z may represent a linear group -(CF 2 ) n - and n is an integer of from 3 to 11. Desirably integer n represents 3, 4, 5, 6, 7, 8 or 9. Generally Iigands where n represents 4, 5, 6 or 7 are most convenient.
  • the fluorocarbon tail (eg. -Z-CF 3 ) is required to adjust the solubility of the ligand in the fiuorous phase.
  • the exact number of fluorinated carbon atoms is not fixed, but may vary according to the reactants, solvents and other reaction conditions. If a single -Z-CF 3 tail is present, it may be located ortho, meta or para relative to the phosphorous linkage.
  • each group Y represents a group - (X) a -Ph- [ (L) b -Z-CF 3 ] m above, where X, Ph, L, b, Z and m are each as defined above.
  • Z represents a linear group -(CF 2 ) n - where n represents 4, 5, 6 or 7.
  • n represents 4, 5, 6 or 7.
  • la represents 1 and q represents 3) .
  • the present invention provides a catalyst for use in the catalysis of hydroformylation of an alkene, said catalyst comprising a ligand of general formula I (where X, Ph, n and m are as defined above) .
  • the ligand of said catalyst is described by general formula la (where n and m are as defined above, but n preferably represents 4, 5, 6 or 7 and m preferably represents 3) .
  • the catalyst described above is used in the hydroformylation of higher alkenes, that is alkenes of C 6 or above.
  • alkenes that is alkenes of C 6 or above.
  • C ⁇ - C 20 alkenes for example C 9 - C 14 ) are of most commercial interest.
  • the catalyst can either be prepared in situ by addition of the phosphorous based ligand (of Formula I above) to a rhodium containing precursor.
  • the catalyst may be provided as a pre-formed complex between the phosphorous ligand and rhodium. In the latter case excess phosphorous ligand may be added.
  • the rhodium catalytic complex may have the formula:
  • L 1 is a ligand of formula I above and d is an integer of 1 to 6;
  • c is an integer of 1 or more, preferably 1 to 6 , most preferably c is 1 or 2;
  • L 2 , L 3 , L 4 and L 5 are each Iigands attached to the rhodium and may be the same or different.
  • L 2 , L 3 , L 4 and L 5 may each independently represent a ligand according to formula 1 above, a halide (Cl, Br, F) , a carboxylate, 3-diketonate, alkoxide, ketone, open chain or cyclic ether, water, alcohol, sulphoxide, sulphalone, amide, a sulphur donor (such as a thiol, thiolate, dialkyl sulphide, heterocycle containing S, dialkylsulphoxide, dithiocarbamate, dithiophosphonate, dithiophosphate, xanthate, dithiocarbonate) ; a nitrogen donor (such as an amine, amide, nitrogen containing heterocycle, imine, nitric oxide) ; a phosphorous donor (such as mono- or di-prim
  • Iigands L 2 , L 3 , L 4 and 5 are each, independently, an integer of from 0 to 6. Any of Iigands L 2 , L 3 , L 4 and 5 may be joined to each other by a suitable bridging group.
  • rhodium containing precursor refers to a catalytic complex as described above to which a phosphorous ligand of formula I is to be added.
  • the rhodium containing precursor may be of formula :
  • the ligand of formula I may displace an existing ligand attached to the rhodium centre.
  • the present invention provides a process for hydroformylation of alkenes in a fiuorous multiphase system, said process comprising the step of adding a catalyst including a ligand of general formula I to the reactants.
  • the present invention provides a process for hydroformylation of alkenes in a fiuorous multiphase system, said process comprising the step of adding a ligand of formula I above and a rhodium precursor (as described above) to produce a catalyst in situ.
  • the ligand is described by general formula la.
  • the process relates to hydroformylation of higher (eg C 6 and above) alkenes, for example C 6 - C 20 alkenes.
  • C 9 - C 14 alkenes are of most commercial interest .
  • the P:Rh ratio is 20:1 or lower, preferably 12:1 or lower, for example 6:1 or even as low as 3:1.
  • the process further includes the step of recovering the catalytic complex by separating the fiuorous phase from the phase containing the reaction products.
  • Examples 1-12 Hydroformylation of Hex-1-ene
  • the solvents, rhodium complex and phosphorous containing compound were introduced in the autoclave under argon. C ⁇ /H 2 (total pressure 13 bar) was introduced and the autoclave heated with stirring to the reaction temperature. Hexene was contained in an injection unit between the autoclave and the mass flow controller. Once the conditions in the autoclave had stabilised, the tap between the injector and the autoclave was opened and gas from the ballast vessel allowed to pass through the mass flow controller to inject the hexene into the autoclave and bring the pressure in the autoclave to 20 bar. Readings of the pressure in the ballast vessel and the autoclave were taken every 5 seconds for approximately 1 hour. A typical reaction profile is shown in Figure 1.

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Abstract

There is provided a catalytic complex comprising a ligand complexed directly or indirectly via a phosphorous moiety to a rhodium centre. The catalytic complex offers improved catalysis of alkene hydroformylation, preferably C9-C14 alkene hydroformylation, in a fluorous multi-phase system. The ligand disclosed is of general formula (I): (where X, Ph, L, Z, Y, a, b and m are as defined in Claim 1). Preferred ligands are of general formula (Ia): -P-{O-Ph-[Z-CF3]m}q (where Ph is an optionally substituted phenyl group; Z is a C1-11 fluorocarbon group; m is 1 to 5 and q is 1 to 3).

Description

ALKENE HYDROFORMYLATION CATALYST
The invention concerns an improved process for the hydroformylation of alkenes .
Hydroformylation is a major industrial process that involves the reaction of carbon monoxide and hydrogen with an alkene to give an aldehyde. For most alkenes, two products are possible depending upon the regioselectivity of the addition reaction. The two products, linear (n) aldehyde and branched (i) aldehyde are generally obtained as a mixture but it is usually the linear product that is preferred for industrial applications.
R
Figure imgf000003_0001
+ R
CHO There are currently two major industrial processes for the hydroformylation of alkenes. One process involves the use of cobalt catalysts, requires high temperatures and pressures and gives low n:i ratios. It is generally used for the production of higher aldehydes and alcohols (chain length > 5) . The second major process involves the use of Rh/triphenylphosphine complexes. This process operates under mild conditions of temperature and pressure and provides high n:i ratios. It is generally used for hydroformylation of ethene and propene, but also for 2-propen-l-ol conversion to butanediol .
The two reactions referred to above are both carried out in the homogeneous phase (i.e. the catalyst, substrate and products are all dissolved in a common solvent) and this means that a process is required for the separation of products, solvent and catalyst. Distillation is generally used, but the thermal sensitivity of the rhodium based catalysts means that they cannot be separated from longer chain aldehyde products (>C4) . One way of circumventing this problem is to use a two phase system with the catalyst dissolved in water. Since the substrate and products are immiscible in water, separation can be effected in a simple manner. However, substrates with chain lengths of greater than 6 have such low solubility in water that the rate of the hydroformylation is too low for the aqueous process to be of commercial interest; and yet, it is just these substrates (C9-C14 aldehydes) that are of interest for the production of soaps and detergents. Consequently the C9-C14 aldehydes are currently manufactured using the older, less selective, more energy intensive cobalt based systems.
There is thus a requirement for a more selective, less energy intensive process for the formation of aldehydes which is also suitable for higher aldehydes.
Recently, a new approach to the problem of separating rhodium-based catalysts from reaction product has been suggested. This approach suggests the use a two phase system in which one of the phases is fluorinated and the other phase is organic. These phases are immiscible at room temperature but, by careful choice of the two solvents, can be made miscible at the reaction temperature. If the catalyst is designed to be soluble only in the fiuorous phase, the reaction can be carried out in the monophasic higher temperature regime. Cooling effects phase separation such that the catalysts remain in the fiuorous phase and the products are in the organic phase. Separation of the two phases can then be carried out and the fiuorous phase containing the catalyst recycled.
Desirable properties of such a system are that the reaction rate should be high (comparable to that with Rh/PPh3) , that the rhodium content of the organic phase at the end of the reaction should be negligible and that the n:i ratio should be high, preferably using only a small amount of phosphine relative to rhodium.
Horvath et al . describe the use of P (CH2CH2C6F13) 3 and [Rh(CO)2 (acetylacetonate) ] as catalyst precursors (see J. Am. Chem. Soc . 120: pages 3133-3143, 1998) . Good reaction rates and low solubilities of the rhodium complex in the organic phase were obtained but, even with a P:Rh ratio as high as 102:1, the maximum n:i ratio was merely 7.84. An advantage of the system of the invention described below is that high rates and selectivity can be obtained using much less phosphorous compound. EP-A-0, 633, 062 describes the use of [Rh(C02) (acetylacetonate) ] with either P [CH2CH2 (CF2) 5CF3] 3 or P[OCH2CH2 (CF2)7CF3]3 at a P:Rh ratio of 40:1.
The invention concerns new Iigands for use in the fiuorous biphasic hydroformylation of alkenes, which Iigands allow the reaction to occur at rates similar to those obtained using Rh/PPh3 in organic solvents, which show little leaching of rhodium into the organic phase and which can provide high n:i ratios at low P:Rh loading. The Iigands described herein also promote isomerisation of alkenes and can be used for the hydroformylation of internal alkenes giving significant amounts of n-aldehydes.
We have found that Iigands of general formula I when complexed to a rhodium centre are especially good at catalysis of alkene hydroformylation in a fiuorous multiphase system of the type described above.
Thus, the present invention provides a catalytic complex comprising a ligand of general formula I:
-P-(X)a-Ph- [(L)b-Z-CF3]m I I (Y)2
(where
X is 0, S, C=0, N-R or C (R) 2 (where each group R independently represents H, a C^ alkyl group or an aryl group) ;
Ph is an optionally substituted phenyl ring; each group L independently represents a
Figure imgf000007_0001
alkenyl group or other linker group;
each group Z represents a branched or linear fluorocarbon chain of up to 11 carbon atoms, preferably 3 to 9 carbon atoms ;
each group Y independently represents a group
-(X)a-Ph-[(L)b-Z-CF3]m
(where each of the groups X, Ph, Z and L, and each of the integers a, b and m are independently as defined above) or each group Y may represent a C1-C12 alkyl or aryl, which may optionally be substituted;
each a is 0 or 1;
each b is 0 or 1; and
each m is an integer of from 1 to 5,
wherein said ligand is complexed directly or indirectly via the phosphorous moiety to a rhodium centre, for use in catalysis of hydroformylation of alkenes in a fiuorous multiphase system.
By "fiuorous multiphase system" we mean a system including a liquid-liquid biphase where one phase is a fiuorous phase containing a fiuorous solvent (typically a fluorocarbon or a fluorohydrocarbon) . Suitable solvents include fluorodimethylcyclohexane, perfluoromethylcyclohexane, hexafluorobenzene, pentafluorobenzene and the like.
In one embodiment the ligand of general formula I comprises a single fluorocarbon tail linked to a phenyl ring which is otherwise unsubstituted (apart from its connection to group X or to the phosphorous moiety) .
Group Z may represent a linear group -(CF2)n- and n is an integer of from 3 to 11. Desirably integer n represents 3, 4, 5, 6, 7, 8 or 9. Generally Iigands where n represents 4, 5, 6 or 7 are most convenient.
The fluorocarbon tail (eg. -Z-CF3) is required to adjust the solubility of the ligand in the fiuorous phase. Thus, the exact number of fluorinated carbon atoms is not fixed, but may vary according to the reactants, solvents and other reaction conditions. If a single -Z-CF3 tail is present, it may be located ortho, meta or para relative to the phosphorous linkage.
In one preferred embodiment each group Y represents a group - (X) a-Ph- [ (L) b-Z-CF3] m above, where X, Ph, L, b, Z and m are each as defined above.
One preferred embodiment of the ligand of the present invention is shown below in general formula la.
-P-{0-Ph- [Z-CF3]m}q la
(where q represents 1, 2 or 3 , and Ph, Z and m are each as defined above for general formula I) . Preferably Z represents a linear group -(CF2)n- where n represents 4, 5, 6 or 7. Preferably in formula la m represents 1 and q represents 3) .
A protocol suitable for preparation of the Iigands of general formulae I and la is described in Bhattacharyya et al . , J. Chem. Soc . , Perkin Trans. 1, pages 3609-3612 (1997). Whilst Battacharyya et al . suggest that the Iigands synthesised may be of use in a fiuorous biphasic reaction, there is no suggestion that the ability of these Iigands would be suitable for catalysis of alkene hydroformylation, nor that the catalysis of that reaction would provide the improved results - especially with regard to higher alkenes - now reported.
In a further aspect the present invention provides a catalyst for use in the catalysis of hydroformylation of an alkene, said catalyst comprising a ligand of general formula I (where X, Ph, n and m are as defined above) .
In a preferred embodiment the ligand of said catalyst is described by general formula la (where n and m are as defined above, but n preferably represents 4, 5, 6 or 7 and m preferably represents 3) .
Desirably the catalyst described above is used in the hydroformylation of higher alkenes, that is alkenes of C6 or above. Generally Cβ - C20 alkenes (for example C9 - C14) are of most commercial interest.
The catalyst can either be prepared in situ by addition of the phosphorous based ligand (of Formula I above) to a rhodium containing precursor. Alternatively, the catalyst may be provided as a pre-formed complex between the phosphorous ligand and rhodium. In the latter case excess phosphorous ligand may be added. The rhodium catalytic complex may have the formula:
L^Rh^L^gL5,.
where L1 is a ligand of formula I above and d is an integer of 1 to 6;
c is an integer of 1 or more, preferably 1 to 6 , most preferably c is 1 or 2;
L2, L3, L4 and L5 are each Iigands attached to the rhodium and may be the same or different. L2, L3, L4 and L5 may each independently represent a ligand according to formula 1 above, a halide (Cl, Br, F) , a carboxylate, 3-diketonate, alkoxide, ketone, open chain or cyclic ether, water, alcohol, sulphoxide, sulphalone, amide, a sulphur donor (such as a thiol, thiolate, dialkyl sulphide, heterocycle containing S, dialkylsulphoxide, dithiocarbamate, dithiophosphonate, dithiophosphate, xanthate, dithiocarbonate) ; a nitrogen donor (such as an amine, amide, nitrogen containing heterocycle, imine, nitric oxide) ; a phosphorous donor (such as mono- or di-primary, secondary or tertiary phosphine, phosphite, phosphinite, phosphonite, phosphole or heterocycle containing phosphorous, phosphide, phosphoalkene, phosphoalkyene) ; arsenic donor (such as mono- or di-tertiary arsine or heterocycle containing arsenic) ; an antimony donor (such as stibine) ; a carbon donor (such as carbon monoxide, carbon dioxide, diene, triene or polyene, an alkyl or aryl goup, a carbene) ; a silicon donor (such as silyl or silylene group) ; and
e, f, g and h are each, independently, an integer of from 0 to 6. Any of Iigands L2, L3, L4 and 5 may be joined to each other by a suitable bridging group.
A reference to a "rhodium containing precursor" refers to a catalytic complex as described above to which a phosphorous ligand of formula I is to be added. The rhodium containing precursor may be of formula :
RhcL2 e 3 fL4 gL5 h
where c, e, f, and h are as defined above, but e+f+g+h=l or more; and L2, L3, L4 and L5 are as defined above .
Optionally, the ligand of formula I may displace an existing ligand attached to the rhodium centre.
In a further aspect the present invention provides a process for hydroformylation of alkenes in a fiuorous multiphase system, said process comprising the step of adding a catalyst including a ligand of general formula I to the reactants.
In an alternative embodiment the present invention provides a process for hydroformylation of alkenes in a fiuorous multiphase system, said process comprising the step of adding a ligand of formula I above and a rhodium precursor (as described above) to produce a catalyst in situ.
Desirably the ligand is described by general formula la.
Optionally, the process relates to hydroformylation of higher (eg C6 and above) alkenes, for example C6 - C20 alkenes. C9 - C14 alkenes are of most commercial interest .
In one embodiment the P:Rh ratio is 20:1 or lower, preferably 12:1 or lower, for example 6:1 or even as low as 3:1.
Optionally the process further includes the step of recovering the catalytic complex by separating the fiuorous phase from the phase containing the reaction products.
The present invention will now be described further with reference to the following, non-limiting, examples. (Examples 1 to 5 inclusive are comparative Examples.)
Examples
All reactions were carried out in a mechanically stirred Hastelloy C autoclave fitted with a ballast vessel from which gas was metered into the reaction autoclave via a mass-flow controller so as to maintain a constant pressure within the reaction autoclave. The rate of reaction was measured by monitoring the rate of pressure drop within the ballast vessel.
Examples 1-12: Hydroformylation of Hex-1-ene The solvents, rhodium complex and phosphorous containing compound were introduced in the autoclave under argon. Cθ/H2 (total pressure 13 bar) was introduced and the autoclave heated with stirring to the reaction temperature. Hexene was contained in an injection unit between the autoclave and the mass flow controller. Once the conditions in the autoclave had stabilised, the tap between the injector and the autoclave was opened and gas from the ballast vessel allowed to pass through the mass flow controller to inject the hexene into the autoclave and bring the pressure in the autoclave to 20 bar. Readings of the pressure in the ballast vessel and the autoclave were taken every 5 seconds for approximately 1 hour. A typical reaction profile is shown in Figure 1.
From the results in Table 1 it is clear that P(OC6H4-4-C6F13)3 and P (OC6H4-3-C6F13) 3 have considerable benefits over other Iigands studied with high reaction rates and good n:i ratio at a P:Rh ration of 3:1. Visual inspection of the resulting two phase mixture showed that the top (organic) phase was colourless whilst the lower (fiuorous) phase was yellow in colour. Analytical data on the rhodium content of the organic phase is currently being obtained.
The results, collected in Table 1, were obtained under the following conditions (unless otherwise stated) : [Rh(acac) (CO)2_ (0.01 mol dm"3), phosphine (0.03 mol dm"3) , hex-1-ene (1 cm3) in a mixture of toluene (2 cm3) and PP3 (2 cm3), 70'C, 20 bar, 1 hour.
t
Figure imgf000014_0002
lisom=isomerised hexenes, 2EtP=2-ethylpentanal, 2MeH=2-methylhexanal, H=heptanal, TOF=turnover frequency (moles of hex-1-ene consumed per mol of rhodium per second); n:i=ratio of straight to total branched aldehydes. a In toluene (4 cm3) ; b Zero order throughout most of the reaction; c [Rh(acac) (CO)2] (0.001 mol dm"3), P (OC6H4-4-C6F13) 3 (0.003 mol dm"3); d
Figure imgf000014_0001
Conditions (unless otherwise stated): [Rh(acac) (CO) 2] (0.01 mol dm"3), phosphine (0.03 mol dm"3), hex-1-ene (1 cm3) in a mixture of toluene (2 cm3) and PP3 (2 cm3), 70 °C, 20 bar, 1 hour.
Examples 13-16 : Hydroformylation of Nonenes
The procedure of Examples 1-12 was followed, using either 1-nonene or 2-nonene as substrate.
The results, collected in Table 2, were obtained under the following conditions (unless otherwise stated) : [Rh(acac) (CO)2] (0.01 mol dm"3), P (OC6H4-4-C6F13) 3 (0.03 mol dm"3) , nonene (1 cm3) in a mixture of toluene (2 cm3) and PP3 (2 cm3), 70*C, 20 bar, 1 hour.
TABLE 2. Hydroformylation of Nonenes
Figure imgf000016_0003
2PrH=2 propylhexanal, 2EtO=2-ethyloctanal, 3MeN=2-methylnonanal, D=decanal
Figure imgf000016_0001
a 1-nonene as substrate;
0x> b 2 -nonene as substrate;
otherwise stated): [Rh(acac) (CO) 2] (0.01 mol dm"3 P(C6H4-4-C3F13)3 (0.03 mol dm" 1 -nonene (1 f toluene (2 cm3) and PP3 (2 cm3), 70*C, 20 bar, 1 hour.
Figure imgf000016_0002

Claims

1. A catalytic complex comprising a ligand of general formula I :
-P-(X)a-Ph-[(L)b-Z-CF3]m I I (Y)2
(where
X is O, S, C=0, N-R or C (R) 2 (where each group R independently represents H, a Cx_s alkyl group or an aryl group) ;
Ph is an optionally substituted phenyl ring;
each group L independently represents a C _6 alkenyl group or other linker group;
each group Z represents a branched or linear fluorocarbon chain of up to 11 carbon atoms;
each group Y independently represents a group
-(X)a-Ph-[(L)b-Z-CF3]m
(where each of the groups X, Ph, Z and L, and each of the integers a, b and m are independently as defined above) or each group Y may represent a C1-C12 alkyl or aryl, which may optionally be substituted;
each a is 0 or 1;
each b is 0 or 1; and
each m is an integer of from 1 to 5, wherein said ligand is complexed directly or indirectly via the phosphorous moiety to a rhodium centre.
2. A complex as claimed in Claim 1 wherein in said ligand group Z represents a branched or linear fluorocarbon chain having 3 to 9 carbon atoms .
3. A complex as claimed in either one of Claims 1 and 2 wherein in said ligand group Ph is substituted by hydrogen only apart from its connection to group X or to the phosphorous moiety and its connection to a single fluorocarbon tail .
4. A complex as claimed in any one of Claims 1 to 3 wherein in said ligand group Z represents a linear group -(CF2)n-, where n is an integer of from 3 to 11.
5. A complex as claimed in Claim 4 wherein in said ligand n represents 4, 5, 6 or 7.
6. A complex as claimed in any one of Claims 1 to 5 wherein in said ligand each group Y represents a group - (X)a-Ph- [ (L)6-Z-CF3]ra-, where X, Ph, L, b, Z and m are each as defined in Claim 1.
7. A complex as claimed in any one of Claims 1 to 6 wherein said ligand is of general formula la,
-P-{0-Ph-[Z-CF3]m}q la
(where q represents 1, 2 or 3, and Ph, Z and m are each as defined in Claim 1) .
8. A complex as claimed in Claim 7 wherein in said ligand Z represents a linear group -(CF2)n- where n is 4, 5, 6 or 7.
9. A complex as claimed in either one of Claims 7 and 8 wherein in said ligand m is 1 and q is 3.
10. A complex as claimed in any one of Claims 1 to 9 wherein Iigands which are not of formula I are also attached to the rhodium centre.
11. Use of the complex as claimed in any one of Claims 1 to 10 in the catalysis of alkene hydroformylation in a fiuorous multiphase system.
12. The use as claimed in Claim 11 wherein the fiuorous multiphase system comprises a fiuorous solvent selected from fluorodimethylcyclohexane, perfluoromethylcyclohexane, hexafluorobenzene and pentafluorobenzene.
13. The use as claimed in either one of Claims 11 and 12 wherein said alkene has six or more carbon atoms.
14. The use as claimed in Claim 13 wherein said alkene has from nine to fourteen carbon atoms.
15. A process for the hydroformylation of alkenes in a fiuorous multi-phase system, said process comprising the step of adding a catalyst to the reactants, wherein said catalyst is a complex as claimed in any one of Claims 1 to 10.
16. The process as claimed -in Claim 15 wherein said ligand is as defined in any one of Claims 7 to 9.
17. The process as claimed in either of Claims 15 and 16 for the hydroformylation of alkenes having six or more carbon atoms.
18. The process as claimed in Claim 17 for the hydroformylation of C9-C14 alkenes.
19. The process as claimed in any one of Claims 15 to 18 wherein said catalyst has a P:Rh ratio of 20:1 or lower.
20. The process as claimed in Claim 19 wherein said catalyst has a P:Rh ratio of 12:1 or lower.
21. The process as claimed in any one of Claims 15 to 20 which further includes the step of recovering the catalyst by separating the fiuorous phase from the phase containing the reaction products.
22. A process for the hydroformylation of alkenes in a fiuorous multi-phase system, said process comprising the step of adding a rhodium containing precursor and a ligand to the reactants to produce a catalytic complex as claimed in any one of Claims 1 to 10 in situ.
23. The process as claimed in Claim 22 wherein said ligand is as defined in any one of Claims 7 to 9.
24. The process as claimed in either of Claims 22 and 23 for the hydroformylation of alkenes having six or more carbon atoms.
25. The process as claimed in Claim 24 for the hydroformylation of C9-C14 alkenes.
26. The process as claimed in any one of Claims 22 to 25 wherein said catalyst has a P:Rh ratio of 20:1 or lower.
27. The process as claimed in Claim 26 wherein said catalyst has a P:Rh ratio of 12:1 or lower.
28. The process as claimed in any one of Claims 22 to 27 which further includes the step of recovering the catalyst by separating the fiuorous phase from the phase containing the reaction products.
PCT/GB1999/004062 1998-12-04 1999-12-03 Alkene hydroformylation catalyst Ceased WO2000033956A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495497B1 (en) * 2001-09-26 2002-12-17 International Flavors & Fragrances Inc. Use of 4-ethyloctanal in perfume compositions
US6495186B1 (en) * 2001-09-26 2002-12-17 International Flavors & Fragrances Inc. Use of 4-ethyloctanal in perfume and flavor compositions
US7404943B2 (en) 2001-05-30 2008-07-29 The Regents Of The University Of California Methods for solubilizing and recovering fluorinated compounds
US10625249B2 (en) 2016-04-14 2020-04-21 Technische Universität Berlin Catalyst for the hydroformylation of olefins, and use thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0633062A1 (en) * 1993-07-08 1995-01-11 Exxon Research And Engineering Company Fluorous multiphase catalyst or reagent systems, and processes using them
DE19702025A1 (en) * 1997-01-23 1998-07-30 Studiengesellschaft Kohle Mbh Use of perfluoroalkyl-substituted phosphorus compounds as ligands for homogeneous catalysis in supercritical carbon dioxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0633062A1 (en) * 1993-07-08 1995-01-11 Exxon Research And Engineering Company Fluorous multiphase catalyst or reagent systems, and processes using them
DE19702025A1 (en) * 1997-01-23 1998-07-30 Studiengesellschaft Kohle Mbh Use of perfluoroalkyl-substituted phosphorus compounds as ligands for homogeneous catalysis in supercritical carbon dioxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
P. BHATTACHARYYA ET AL.: "Phosphorus(III) ligands with fluorous ponytails", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1., 1997, CHEMICAL SOCIETY. LETCHWORTH., GB, pages 3609 - 3612, XP002131617, ISSN: 0300-922X *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7404943B2 (en) 2001-05-30 2008-07-29 The Regents Of The University Of California Methods for solubilizing and recovering fluorinated compounds
US6495497B1 (en) * 2001-09-26 2002-12-17 International Flavors & Fragrances Inc. Use of 4-ethyloctanal in perfume compositions
US6495186B1 (en) * 2001-09-26 2002-12-17 International Flavors & Fragrances Inc. Use of 4-ethyloctanal in perfume and flavor compositions
US10625249B2 (en) 2016-04-14 2020-04-21 Technische Universität Berlin Catalyst for the hydroformylation of olefins, and use thereof

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