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WO2002064250A2 - Procede de carbonylation de composes a insaturation ethylenique, composition de diphosphine bidentate utilisee dans ce procede et procedes de preparation de cette composition de diphosphine bidentate - Google Patents

Procede de carbonylation de composes a insaturation ethylenique, composition de diphosphine bidentate utilisee dans ce procede et procedes de preparation de cette composition de diphosphine bidentate Download PDF

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Publication number
WO2002064250A2
WO2002064250A2 PCT/EP2002/001036 EP0201036W WO02064250A2 WO 2002064250 A2 WO2002064250 A2 WO 2002064250A2 EP 0201036 W EP0201036 W EP 0201036W WO 02064250 A2 WO02064250 A2 WO 02064250A2
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Prior art keywords
symmetrical
phosphabicycloalkane
bidentate diphosphine
protonated
bidentate
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PCT/EP2002/001036
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English (en)
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WO2002064250A3 (fr
Inventor
Peter Arnoldy
Cornelius Mark Bolinger
Eit Drent
Michael Rolf Eberhard
Hero Jan Heeres
Adrianus Johannes Van Der Linden
Wilhelmus Petrus Mul
Paul Gerard Pringle
Jacoba Catherina Lucia Johanna Suykerbuyk
Kwoliang David Tau
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Shell Internationale Research Maatschappij B.V.
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Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP02724159A priority Critical patent/EP1358009A2/fr
Priority to JP2002564038A priority patent/JP2004527484A/ja
Priority to AU2002254887A priority patent/AU2002254887A1/en
Priority to CA002436215A priority patent/CA2436215A1/fr
Publication of WO2002064250A2 publication Critical patent/WO2002064250A2/fr
Publication of WO2002064250A3 publication Critical patent/WO2002064250A3/fr

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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
    • B01J31/24—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
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
    • B01J31/248—Bridged ring systems, e.g. 9-phosphabicyclononane
    • 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
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/505—Preparation; Separation; Purification; Stabilisation
    • C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
    • C07F9/5072—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-H
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/505—Preparation; Separation; Purification; Stabilisation
    • C07F9/5095—Separation; Purification; Stabilisation
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • 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
    • B01J2531/828—Platinum

Definitions

  • the present invention relates to a process for the carbonylation of optionally substituted ethylenically unsaturated compounds by reaction with carbon monoxide and a coreactant in the presence of a catalyst system comprising a source of Pt group metal cations and a bidentate diphosphine having the general formula I
  • Q ⁇ and Q 2 represent a phosphabicycloalkyl group, having at least 5 ring atoms; and Z represents a bivalent organic bridging group connecting both phosphorus atoms .
  • the present invention in particular relates to such a reaction in which the coreactant is hydrogen.
  • a commercially important carbonylation reaction using hydrogen as coreactant, is the hydroformylation of olefins, which are reacted with carbon monoxide and hydrogen to form aldehydes and/or alcohols having one carbon atom more than the precursor olefin.
  • the hydroformylation can proceed with varying selectivities to the several possible isomeric aldehydes or alcohols in varying yields, as side reactions occur to a smaller or larger extent.
  • Generally only one isomeric product is preferred.
  • the presence of branched aldehydes or alcohols is undesirable.
  • the selectivity towards one of several possible isomeric products is called regioselectivity.
  • For hydroformylation a regioselectivity towards reaction at the primary carbon atom, resulting in a linear product, is desirable.
  • WO-A-95/05354 describes the carbonylation of ethylenically unsaturated compounds by reaction with carbon monoxide and hydrogen, i.e. hydroformylation, in the presence of a catalyst system comprising a Group VIII metal cation, viz. cationic palladium and platinum, and a bidentate ligand, viz. a diphosphine.
  • a catalyst system comprising a Group VIII metal cation, viz. cationic palladium and platinum, and a bidentate ligand, viz. a diphosphine.
  • 2-bis (1, -cyclooctylene phosphino) ethane i.e. in IUPAC nomenclature
  • 2- PP'bis 9-phosphabicyclo [4.2.
  • the phosphabicyclononyl groups in these ligands are all substituted or non-substituted 1,4-cyclooctylenephosphino groups, i.e. in IUPEC nomenclature 9-phosphabicyclo- [4.2.1] nonyl groups .
  • Such a 9-phosphabicyclo [4.2.1] nonyl group is visualised in Figure A.
  • the 9-phosphabicyclo [4.2.1] nonyl group visualized in Figure A is an example of an asymmetrical phosphabicycloalkyl group.
  • the bridges not containing the phosphorus atom have an unequal number of atoms in the bridge.
  • a symmetrical phosphabicycloalkyl group is understood that the bridges (i.e.
  • hydrocarbyl groups connecting the tertiary carbon atoms) which do not contain the phosphorus atom, have an equal number of atoms.
  • An example of such a symmetrical group is the 9-phosphabicyclo [3.3.1] nonyl group which is visualised in Figure B.
  • WO-A-00/02375 describes a method to prepare a phosphorus-containing ligand by refluxing a phosphabi- cyclononane hydride with 1, 2-dibromoe hane in acetonitrile . After neutralisation with sodium hydroxide a bis- (9-phosphabicyclononyl) ethane can be isolated.
  • the phosphabicyclononane hydride can conveniently be prepared as described by Eisner et al . (Che . Abstr. 1978, vol. 89, 180154X) .
  • non-pre-published WO-A-01/87899 describes the preparation of a bidentate diphosphine ligand by reacting P-cyclo-octyl hydride (e.g. phosphabicyclononane hydride) and butyllithium to generate a lithium cyclo-octyl phosphide and subsequently reacting with an appropriate substituted or non- substituted alkane diol sulphate ester.
  • P-cyclo-octyl hydride can conveniently be prepared as described by Eisner et al . (Chem. Abstr. 1978, vol. 89, 180154x) .
  • the method comprises: a) reacting a mixture of both symmetrical and asymmetrical phosphabicyclononane hydride with formaldehyde (CH 2 O) in the presence of hydrochloric acid (HC1) , yielding phosphonium salts; b) reacting these phosphonium salts with sodium hydroxide (NaOH) , yielding a charged symmetrical phosphine and a neutral asymmetrical phosphine; c) extracting the neutral asymmetrical phosphine with pentane, leaving relatively pure, charged symmetrical phosphine in an aqueous solu ion; d) treating the aqueous solution with sodium hydroxide to obtain the neutral symmetrical phosphin .
  • HC1 hydrochloric acid
  • the present invention provides a process for the carbonylation of optionally substituted ethylenically unsaturated compounds by reaction with carbon monoxide and a coreactant in the presence of a catalyst system including: (a) a source of Pt group metal cations, (b) a bidentate diphosphine composition wherein more than 60% w/w of bidentate diphosphine present in the bidentate diphosphine composition has the general formula II i-R-X (II) wherein X ⁇ and X 2 independently represent an optionally substituted symmetrical phosphabicycloalkyl group, having at least 5 ring atoms; and R represents a bivalent organic bridging group, connecting both phosphorus atoms.
  • a catalyst system including: (a) a source of Pt group metal cations, (b) a bidentate diphosphine composition wherein more than 60% w/w of bidentate diphosphine present in the bidentate diphosphine composition has the general formula II
  • R preferably represents a bivalent organic bridging group containing from 1 to 10, preferably from 2 to 6, more preferably from 2 to 4, and most preferably 2 to 3 atoms in the shortest connection between both phosphorus atoms.
  • a bivalent organic bridging group having 2 atoms in this connection is especially preferred.
  • the bridging group R represents an alkylene group, but it can also comprise a carbon chain, interrupted by one or more hetero atoms, such as nitrogen, sulphur, silicon or oxygen atom.
  • the shortest connection between both phosphorus atoms contains 2 or 3 carbon atoms, most preferably 2 carbon atoms.
  • the shortest connection between both phosphorus atoms can be substituted or non-substituted or can form part of a aliphatic or aromatic ring structure.
  • the connection forms part of an optionally substituted saturated or non-saturated aliphatic ring structure, such as for example a substituted or non-substituted cyclopentane, cyclopentene, cyclohexane or cyclohexene.
  • the cycloaliphatic ring can be interrupted by one or more heteroatoms such as nitrogen, sulphur, silicon or oxygen atoms .
  • the aliphatic ring structure can further be substituted with any kind of substituent, including heteroatoms, alkyl groups, cycloalkyl groups and aryl groups . If the connection forms part of an optionally substituted saturated or non-saturated aliphatic ring structure the phosphorus atoms are preferably attached at adjacent positions, for example positions 1 and 2.
  • connection is an ethylene or trimethylene group. Most preferably the connection is a ethylene group.
  • the connection can be a substituted alkylene group with at least one substituent and preferably at least two substituents . If the connection is substituted it is preferably substituted with two to four substituents , more preferably with two to three substituents, and most preferably with two substituents.
  • the substituents can be attached to any part of the connection.
  • the carbon atoms of the connection, which are connected to the phosphorus atoms are substituted.
  • the bidentate diphosphine has two chiral C-atoms and can have the RR, SS, or R,S meso-form. The R,S meso-form is preferred.
  • the substituents can contain carbon atoms and/or hetero atoms.
  • Substituents which can be used include groups containing hetero-atoms such as halides, sulphur, phosphorus, oxygen and nitrogen. Examples of such groups include chloride, bromide, iodide, thiol, and groups of the general formula H-0-, A 1 - ⁇ -, -S-A 1 , -CO-A 1 , -NH 2 , -NHA 1 , -NA ⁇ , -CO-NA ⁇ 2 , -OH, -P0 4 , -N0 2 , -NOH, -CO, -SO 2 , -SOH, in which A 1 and A 2 , independently, represent aliphatic groups, preferably having from 1 to 10 carbon atoms , more preferably having from 1 to 4 carbon atoms , like methyl, ethyl, propyl and isopropyl.
  • the substituents are hydrocarbyl groups.
  • the hydrocarbyl groups themselves can be aromatic, aliphatic or cycloaliphatic.
  • the hydrocarbyl groups can contain carbon atoms and hetero atoms .
  • Hydrocarbyl groups can further include groups containing hetero-atoms such as the ones mentioned hereinabove.
  • the hydrocarbyl groups can be straight-chain or branched, and can contain saturated and/or non-saturated links.
  • Aromatic hydrocarbyl substituent groups can be aryl groups such as phenyl groups and alkyl phenyl groups .
  • Preferred hydrocarbyl substituent groups are alkyl groups, preferably having from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms. Linear, branched or cyclic alkyl groups can be used.
  • Alkyl groups can be methyl, ethyl, propyl, iso-propyl, butyl and iso-butyl . More preferably methyl groups are used.
  • the bivalent bridging group R is an ethylene group which is di-substituted, preferably with two alkyl groups, most preferably with two methyl groups.
  • X 2 independently represent a substituted or non-substituted symmetrical phosphabicycloalkyl group.
  • the bridge containing the phosphorus atom is preferably the shortest one.
  • the other two bridges have an equal length, i.e. contain an equal number of atoms in the bridge.
  • a bridge is meant a connection between both tertiary carbon atoms.
  • symmetrical phosphabicycloalkyl groups with at least 7 ring atoms (of which one is, of course, a phosphorus atom) and preferably with from 7 to 11 ring atoms . More preferably X and X 2 represent a substituted or non-substituted symmetrical phosphabicyclononyl group.
  • Examples of symmetrical phosphabicycloalkyl groups therefore include substituted or non-substituted 2-phosphabicyclo [1.1.1] pentyl ; 2-phosphabicyclo [2.1.1]- hexyl; 2-phosphabicyclo [3.1.1] heptyl; 3-phospha- bicyclo [3.1.1] heptyl ; 7-phosphabicyclo [2.2.1] heptyl ; 2-phosphabicyclo [2.2.2] octyl; 2-phosphabicyclo [5.1.1]- nonyl; 3-phosphabicyclo [5.1.1] nonyl; 4-phosphabicyclo- [5.1.1] nonyl; 2-phosphabicyclo [3.2.2] nonyl; 3-phospha- bicyclo [3.2.2] nonyl ; 9-phosphabicyclo [3.3.1] nonyl ; 9-phosphabicyclo [3.3.2] decyl; 2-phosphabic
  • 9-phosphabicyclo [3.3.2] decyl are preferred. Particularly preferred are substituted or non-substituted 9-phosphabicyclo [3.3.1] nonyl groups.
  • X- 1 - and X 2 can each represent a different symmetrical phosphabicycloalkyl or can both represent the same phosphabicycloalkyl .
  • both X 1 and X 2 represent the same symmetrical phosphabicycloalkyl, preferably a symmetrical 9-phosphabicyclo [3.3.1] nonyl group.
  • One or both of the phosphabicycloalkyl rings can be substituted with one or more hydrocarbyl groups containing carbon atoms and/or hetero atoms. If a phosphabicycloalkyl ring is substituted, preferably one or both of the bridges not containing the phosphorus atom is substituted, preferably with one or more alkyl groups, preferably having from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms. Linear, branched or cyclic alkyl groups can be used. Preferred alkyl groups include methyl, ethyl, propyl, iso-propyl, butyl and iso- butyl . More preferably methyl groups are used.
  • the substituted phosphabicycloalkyl ring can be mono- or poly-substituted and is preferably di-substituted. Most preferably the phosphabicycloalkyl ring is substituted with two methyl groups .
  • Examples of substituted phosphabicycloalkyl rings include 3,7 dimethyl, 9-phospha- bicyclo [3.3.1] nonyl; 3,7 diethyl, -phosphabicyclo [3.3.1] - nonyl; 2, 6-dimethyl, 9-phosphabicyclo [3.3.1] nonyl .
  • Preferred bidentate diphosphines of formula II include 1,2-P, P'bis (9-phosphabicyclo [3.3.1] nonyl) ethane; 1, 3-P, P'bis (9-phosphabicyclo [3.3.1] nonyl) ropane; 1,2-P, P'bis (9-phosphabicyclo [3.3.1] nonyl) propane; 2 , 3-P, P 'bis (9-phosphabicyclo [3.3.1] nonyl) butane; 2, 3-P, P 'bis (9-phosphabicyclo [3.3.1] nonyl) pentane; 2, 4-P, P'bis (9-phosphabicyclo [3.3.1] nonyl) pent ne; 1,2-P, P'bis (3, 7-dimethyl, 9-phosphabicyclo [3.3.1] - nonyl) ethane; 1, 3-P, P'bis (3 , 7-dimethyl, 9-phosphabicyclo [3.3.1] nonyl) propane
  • Most preferred is 2 , 3-P, P 'bis (9-phosphabicyclo [3.3.1] onyl) butane .
  • Preferably more than 80% w/w and more preferably more than 85% w/w of the bidentate diphosphine present in the bidentate diphosphine composition of component (b) of the catalyst system has the general formula (II) . Even more preferably in the range of from 90% w/w, more preferably of from 95% w/w to 100% w/w of the bidentate diphosphine present in the composition has the general formula (II) . Most preferably in the range of from 99% w/w to 100% w/w of the bidentate diphosphine present in the composition has the general formula (II) .
  • sources of Pt group metal cations of component (a) of the catalyst system are platinum or palladium compounds such as salts of palladium and nitric acid, sulphuric acid or sulphonic acids, salts of platinum or palladium and carboxylic acids with up to 12 carbon atoms, palladium or platinum complexes, e.g. with carbon monoxide or acetylacetonate, or palladium combined with a solid material such as an ion exchanger.
  • Palladium (II) acetate and platinum (II) acetylacetonate are examples of preferred metal sources .
  • the present invention provides a catalyst system including:
  • a bidentate diphosphine composition wherein more than 60% w/w of bidentate diphosphine present in the bidentate diphosphine composition has the general formula (II) ⁇ l_ R _ ⁇ 2 ( U )
  • X 1 and X 2 independently represent an optionally substituted symmetrical phosphabicycloalkyl group, having at least 5 ring atoms; and R represents a bivalent organic bridging group, connecting both phosphorus atoms. Preferences for components (a) and (b) are as described hereinbefore .
  • the catalyst system also includes as an additional component (c) a source of anions.
  • a source of anions As anion source, any compound generating these anions can be used. Acids, or salts thereof, can be used as source of anions, for example any of the acids mentioned above, which can also participate in the salts of the metals of the platinum group.
  • acids are used as anion source having a pKa value of less than 6, more preferably less than 5, measured in aqueous solution at 18 °C.
  • Typical examples of anions which can be used are anions of phosphoric acid, sulphuric acid, sulphonic acids and halogenated carboxylic acids such as trifluoroacetic acid.
  • Sulphonic acids are in particular preferred, for example methanesulphonic acid, trifluoromethanesulphonic acid, tert-butane-sulphonic acid, p-toluenesulphonic acid and 2,4, 6-trimethylbenzene-sulphonic acid.
  • complex anions can be used, such as the anions generated by a combination of a Lewis acid such as BF3 ,
  • a protic acid such as a sulphonic acid, e.g. CF 3 SO3H or CH3SO3H or a hydrohalic acid such as HF of HC1, or a combination of a Lewis acid with an alcohol.
  • a protic acid such as a sulphonic acid, e.g. CF 3 SO3H or CH3SO3H or a hydrohalic acid such as HF of HC1, or a combination of a Lewis acid with an alcohol.
  • a protic acid such as a sulphonic acid, e.g. CF 3 SO3H or CH3SO3H or a hydro
  • the ethylenically unsaturated compound, used as starting material is preferably an alkene having from 2 to 20 carbon atoms per molecule, or a mixture thereof.
  • the alkene can be substituted or non-substituted.
  • Preferred substituents include alkyl and aryl groups as well as groups containing hetero-atoms such as halides, sulphur, phosphorus, oxygen and nitrogen.
  • substituents include chloride, bromide, iodide and hydroxy, alkoxy, carboxy, a ino, amido, nitro, cyano, thiol or thioalkoxy groups.
  • substituents include chloride, bromide, iodide and hydroxy, alkoxy, carboxy, a ino, amido, nitro, cyano, thiol or thioalkoxy groups.
  • ethylenically unsaturated compounds include ethene, propene, 1-butene, 2-butene, isobutene, pentenes, hexenes, octenes and dodecenes, 1,5-cyclo- octadiene, cyclododecene, methyl pen enoates and pentene nitriles .
  • these ethylenically unsaturated compounds can be converted by reaction with carbon monoxide and a coreactant with a high regioselectivity towards the linear product.
  • the ethylenically unsaturated starting material and the formed product can act as reaction diluent.
  • the carbonylation reaction can be carried out in the additional presence of a solvent.
  • saturated hydrocarbons e.g.
  • paraffins and isoalkanes are recommended and furthermore alcohols, the saturated hydrocarbons and alcohols preferably having from 4 to 10 carbon atoms per molecule, such as butanol, ethylhexanol-1, nonanol-1, or in general terms the alcohols formed as carbonylation product; ethers such as 2, 5, 8-trioxanonane (diglyme) , diethylether and anisole, and ketones, such as methylbutylketone .
  • Solvents comprising or substantially consisting of sulphones are also preferred.
  • Sulphones are in particular preferred, for example dialkylsulphones such as dimethylsulphone and diethylsulphone and cyclic sulphones, such as sulfolane (tetrahydrothiophene-2, 2-dioxide) , sulfolane, 2-methyl- sulfolane and 2-methyl-4-ethylsulfolane.
  • the quantity in which the catalyst system is used is not critical and can vary within wide limits. Usually amounts in the range of 10 ⁇ 8 to 10 -1 , preferably in the range of 10 "7 to 10 ⁇ 2 mole atom of platinum group metal per mole of ethylenically unsaturated compound are used.
  • the amounts of the participants in the catalyst system are conveniently selected such that per mole atom of platinum group metal from 0.5 to 10, preferably from 1 to 6 moles of bidentate diphosphine are used, from 0.5 to 15, preferably from 1 to 8 moles of anion source or a complex anion source.
  • catalyst promoter comprising a source of halide anions
  • the conversion reaction proceeds at high rate, even at moderate temperatures, with very little formation of saturated hydrocarbons .
  • the coreactant can be molecular hydrogen, or more generally a hydride source.
  • the carbon monoxide and hydrogen can be supplied in equimolar or non-equimolar ratios, e.g. in a ratio within the range of 5:1 to 1:5, preferably 3:1 to 1:3. More preferably they are supplied in a ratio within the range of 2:1 to 1:2.
  • the carbonylation can be carried out at moderate reaction conditions. Hence temperatures in the range of 50 to 200 °C are recommended, preferred temperatures being in the range of 70 to 160 °C. Reaction pressures in the range of 500 to 10000 kPa (5 to 100 bar) are preferred; lower or higher pressures can be selected, but are not considered particularly advantageous. Moreover, higher pressures require special equipment provisions.
  • the claimed catalyst system can also be useful in conversion reactions other than hydroformylation.
  • the coreactant can be represented by NuH, wherein Nu represents the remnant nucleophilic moiety of the coreactant after removal of a hydrogen atom. The nature of the coreactant largely determines the type of product formed.
  • the coreactant can be a nucleophilic compound having a mobile hydrogen atom, such as an alcohol, an acid, an amine or water.
  • a mobile hydrogen atom such as an alcohol, an acid, an amine or water.
  • bidentate diphosphine compositions which can be used in the process according to the present invention are novel.
  • the present invention also provides a bidentate diphosphine composition wherein more than 60% w/w of bidentate diphosphine present has the general formula II X -R-X 2 (II) wherein X 1 and X 2 independently represent an optionally substituted symmetrical phosphabicycloalkyl group, having at least 5 ring atoms; and R represents a bivalent organic bridging group, connecting both phosphorus atoms, with the proviso that the bidentate diphosphine is not 1,3-PP'bis (9-phosphabicyclo [3.3.1] nonyl)propane .
  • more than 80% w/w and more preferably more than 85% w/w of the bidentate diphosphine present in the bidentate diphosphine composition has the general formula (II) .
  • Even more preferably in the range of from 90% w/w, more preferably of from 95% w/w, to 100% w/w of the bidentate diphosphine present in the composition has the general formula (II) .
  • Most preferably in the range of from 99% w/w to 100% w/w of the bidentate diphosphine present in the composition has the general formula (II) .
  • Preferences for the bidentate diphosphine itself are as described above for the process .
  • Bidentate diphosphine compositions wherein a bidentate diphosphine is present having the general formula II are known in the art.
  • US-A-3527818 describes in example I a mixture of octamethylene ??' -bis (9-phosphabicyclo [4.3. l]nonane) , octamethylene-PP' -bis (9-phosphabicyclo [3.3.1] nonane) and octamethylene-P- (9-phosphabicyclo [4.2.1] nonane) P' (9-phosphabicyclo [3.3.1] nonane) .
  • To obtain a bidentate diphosphine composition which can be used in the process of the present invention however, such compositions/ mixtures need to be purified to obtain a higher percentage of bidentate diphosphine having the general formula (II) .
  • a purified bidentate diphosphine composition that is a bidentate diphosphine composition wherein the percentage of bidentate diphosphine having the general formula (II) is as specified above, can be established by one or more of the following 3 ways:
  • oxygen during all processes is avoided as much as possible in order to avoid the formation of oxides of the phosphabicycloalkanes and/or bidentate diphosphines .
  • Most preferably processes are conducted under essentially oxygen-free conditions.
  • compounds used such as for example solvents and solutions, are deoxygenated before use.
  • the process is preferably conducted in an oxygen-free environment, for example by applying an atmosphere of nitrogen during all manipulations.
  • the starting compound is purified to the extent that the resulting phosphabicycloalkane composition comprises more than 60% w/w, preferably more than 80% w/w, more preferably at least 90% w/w and even more preferably in the range of 95 to 100% w/w of symmetrical phosphabicycloalkan .
  • the resulting composition is essentially 100% w/w pure, that is it comprises in the range of from 99% w/w, most preferably of from 99.5% w/w to 100% w/w of symmetrical phosphabicycloalkane .
  • the present invention therefore also provides a process for the separation of symmetrical phosphabicycloalkane from a composition containing symmetrical and asymmetrical phosphabicycloalkanes comprising the following steps : a) adding means to protonate a phosphabicycloalkane to a composition containing symmetrical phosphabicycloalkane (SPBA) and asymmetrical phosphabicycloalkane (APBA) , yielding a composition comprising protonated symmetrical phosphabicycloalkane (SPBA+) and non-protonated asymmetrical phosphabicycloalkane (APBA) ; b) separating protonated symmetrical phosphabicycloalkane (SPBA+) and non-protonated asymmetrical phospha- bicycloalkane (APBA) , yielding separated protonated symmetrical phosphabicycloalkane (SPBA
  • protonate a phosphabicycloalkane is meant that a phosphabicycloalkane accepts a proton, i.e. a positively charged hydrogen atom (H+) .
  • Preferred means to protonate a phosphabicycloalkane include a wide range of acids, such as hydrohalic acids, e.g. hydrogen chloride, hydrogen bromide, hydrogen iodide and hydrogen fluoride; halogen oxo acids, e.g. hypobromous acid, chlorous acid, hypochlorous acid, perchloric acid and periodic acid; mineral acids, e.g.
  • sulphuric acids nitric acids and phosphoric acids
  • organic acids such as acetylacetonic acids, sulphonic acids, carboxylic acids and halogenated carboxylic acids e.g. trichloroacetic acid and trifluoroacetic acid
  • complex acids such as HBF 4 , HSnCl3,- and mixtures of those acids .
  • inorganic acids such as the hydrohalic acids, halogen oxo acids and mineral acids mentioned. More preferred are hydrohalic acids of which
  • HCl, HI, and HBr are most preferred.
  • Preferred means to de-protonate the separated protonated symmetrical phosphabicycloalkane (SPBA+) in step c) include a wide range of bases, such as ammonia and primary, secondary and tertiary amines; carbonates and hydrogencarbonates, such as for example Na 2 C03,
  • alkali metal hydroxides such as potassium hydroxide and sodium hydroxide.
  • the separation in step b) is achieved by making use of a difference in solubility of SPBA+ and APBA.
  • a composition containing SPBA and APBA is solved in a solvent which does not dissolve SPBA+ .
  • Means to protonate a phosphabicycloalkane such as for example a hydrohalogenic acid, can be added to the dissolved phosphabicycloalkanes as a gas, as a (dissolved) liquid or a solid, whichever is most suitable.
  • a HCl gas or a 1 M aqueous solution of HCl can be added to a diethylether solution of phosha- bicycloalkanes .
  • the SPBA+ can subsequently be separated as a precipitated solid or as a solution in a second liquid phase.
  • the precipitate can, however, be thick and sticky and difficult to handle in isolation and purification.
  • the separation in step b) is therefore achieved by phase separation.
  • An especially preferred process for the separation of symmetrical phospha- bicycloalkane from a composition containing symmetrical and asymmetrical phosphabicycloalkanes accordingly comprises : i] dissolving a composition containing SPBA and APBA in a suitable non-water miscible solvent, which does not dissolve SPBA+, yielding a non-aqueous phosphabicycloalkane (PBA) solution; ii] combining the non-aqueous PBA solution with an aqueous solution of a suitable acid, yielding an aqueous phase containing protonated SPBA+ and a non-aqueous phase containing non-protonated APBA; iii] separating the aqueous phase containing protonated SPBA+ and the non-aqueous phase containing non-protonated APBA, yielding an aqueous solution containing protonated SPBA+ and a
  • an extra step vi] is added to the process comprising removing the solvent from the non-aqueous solution containing non-protonated APBA, yielding separated APBA.
  • a non-water miscible solvent is meant a hydrophobic solvent . Such a solvent can be mixed with water but upon standing two phases will eventually separate .
  • a wide range of non-water miscible solvents are available in which SPBA and APBA can be solved and which do not dissolve SPBA+ .
  • the solvent is an aprotic solvent .
  • Solvents which can be used include saturated and unsaturated hydrocarbons, e.g. paraffins and linear, branched and cyclic alkanes, alkenes and alkynes, such as hexane, hexene, pentene and pentane, aromatics such as toluene and benzene; ethers, such as for example dimethylether anisole (methyl phenyl ether), 2,5,8- trioxanonane (diglyme) , diethylether, tetrahydrofuran, diphenylether, diisopropylether and the dimethylether of di-ethyleneglycol; esters, such as for example methylacetate, dimethyladipate, butyrolactone, propionates and pentenoates; ketones, such as methylbutylketone and diethylketone; and sulphones, for example dialkylsulphones such as dimethyl
  • aprotic solvents having a dielectric constant that is below a value of 50, more preferably in the range of 1 to 8, at 298.15 °K and 100 kPa (1 bar).
  • the dielectric constant for a given solvent is used in its normal meaning of representing the ratio of the capacity of a condenser with that substance as dielectric to the capacity of the same condenser with a vacuum for dielectric. Values for the dielectric constants of common organic liquids can be found in general reference books, such as the Handbook of
  • the dielectric constant of anisole is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoe
  • solvents are saturated alkanes and aromatics, such as hexane, pentane or toluene and ethers.
  • Ethers are especially preferred because the use of ethers in this separation process results in a quick and efficient phase-separation.
  • ethers which can be used include dimethylether, methylethylether, anisole, diethylether and diphenylether.
  • Another especially preferred solvent is toluene, since toluene is less volatile and less flamable than some of the other solvents and therefore easy to handle.
  • a phosphabicycloalkane composition is conveniently supplied as a toluene solution.
  • concentrations of the reactants can be varied over a wide range, but is preferably kept high so as to reduce the amounts of solvent to be used.
  • Phosphabicycloalkanes are preferably dissolved in the non-water miscible solvent to give a concentration in the range of 0.01 to 10 molar, more preferably in the range from 0.1 to 5 molar .
  • Preferred acids in step ii] are as described above for means to protonate a phosphabicycloalkane.
  • concentrations in the range from 2 to 20 molar are used, and more preferably concentrations in the range from 5 to 15 molar are used. Most preferred are concentrations in the range from 5 to 10 molar.
  • the aqueous solution of suitable acid in step ii] can be added as such to the non-aqueous PBA solution or can be prepared in si tu by first adding water and subsequently adding acid in a more concentrated form.
  • a ratio of aqueous solution to non- aqueous solution in step ii] is used in the range from 1:10 to 10:1 v/v, more preferably in the range from 1:2 to 2:1 v/v.
  • the system is preferably shaken or stirred, such to establish close contact between the acid and the phosphabicycloalkanes, whereafter the two phases are allowed to separate .
  • the two phases are separated in step iii] .
  • the aqueous solution containing protonated SPBA+ is extracted one or more, preferably in the range from 1 to 50, times with a non-water miscible solvent as described for step i] to remove residues of non-protonated phosphabicycloalkanes and protonated APBA+ .
  • non-aqueous solution containing non- protonated APBA is preferably extracted one or more, preferably in the range from 1 to 50, times with a aqueous solution of a suitable acid to remove residues of protonated SPBA+ .
  • aqueous solution containing protonated SPBA+ is combined in step iv] with a non-water miscible solvent as described for step i] and an aqueous solution of a suitable base, yielding a non-aqueous solution containing non-protonated SPBA;
  • Preferred bases are as described above for means to de-protonate the protonated symmetrical phosphabicycloalkane.
  • concentrations in the range from 2 to 20 molar are used, and more preferably concentrations in the range from 5 to 15 molar are used.
  • residues of water are removed from the non-aqueous solutions yielded in steps iii] and/or iv] in a way known to one skilled in the art.
  • residues of water can be removed by washing with bases such as hydroxides and carbonates, such as Na 2 C0 3 ,
  • a non-aqueous solution can be dried over a drying agent such as for example K 2 S ⁇ 4, a 2 S ⁇ 4 and MgS ⁇ 4-
  • Removal of the non-aqueous solvents in steps v] and vi] can be established in any way known to one skilled in the art to remove such solvents .
  • Further purification can be be established by sublimation of the isomers.
  • pressures in the range from 0.0033 to 0.33 kPa (0.025 to 2.5 mm Hg) , more preferably in the range from 0.027 to 0.27 kPa (0.2 to 2 mm Hg) are used.
  • the temperatures can vary widely.
  • a temperature in the range of 40 °C and higher is used, more preferably a temperature in the range from 40 °C to 90 °C is used.
  • a preferred method for the preparation of some bidentate diphosphine ligands comprises refluxing a phosphabicycloalkane hydride, viz. 9-phosphabicyclononane hydride, with a , ⁇ -dihaloalkane, such as 1,2- dibromoethane or 1, 3-diiodopropane in a suitable solvent. After neutralisation with a suitable basic compound the bidentate diphosphine can be isolated.
  • a similar preparation process can be used to prepare a bidentate diphosphine composition wherein more than 60% w/w of bidentate diphosphine present has the general formula II Xi-R-X 2 (II) wherein X 1 and X 2 independently represent an optionally substituted symmetrical phosphabicycloalkyl group, having at least 5 ring atoms; and R represents a bivalent organic bridging group, connecting both phosphorus atoms.
  • the present invention therefore also relates to a process for the preparation of bidentate diphosphines having general formula (II) comprising: Al) heating a composition of phosphabicycloalkane hydrides with a ⁇ , ⁇ -dihaloalkane in a suitable solvent, in a molar ratio of phosphabicycloalkane to ⁇ , ⁇ -dihalo- alkane of more than 2, yielding a charged bidentate diphosphine dihydride;
  • the ⁇ , ⁇ -dihaloalkane is a , ⁇ -dibromo- alkane, ⁇ , ⁇ -dichloroalkane or , ⁇ -diiodoalkane.
  • the molar ratio of phosphabicycloalkane to ⁇ , ⁇ -dihaloalkane is preferably more than 3, more preferably more than 4 and most preferably in the range more than 4 to 20.
  • the solvent used in step Al) can be any solvent found suitable for the process .
  • Preferred solvents include saturated hydrocarbons, e.g. paraffins and linear, branched and cyclic alkanes, such as hexane and pentane, aromatics such as toluene and benzene; nitriles such as for example acetonitrile and alkanols such as for example ethanol, methanol and isopropanol and mixtures of two or more of those.
  • Especially preferred solvents are acetonitrile, hexane, ethanol and toluene, and mixtures of two or more of those.
  • the basic compound in step A2) is ammonia or a primary, secondary and tertiary amine or a hydroxide such as Ba(OH) , Na(OH) or K(OH) . More preferred are alkali metal hydroxides, such as potassium hydroxide and sodium hydroxide .
  • the present invention therefore also relates to a process for the preparation of bidentate diphosphines having general formula (II)
  • X -R-X 2 (II) wherein X ⁇ and X 2 independently represent an optionally substituted symmetrical phosphabicycloalkyl group, having at least 5 ring atoms; and R represents a bivalent organic bridging group, connecting both phosphorus atoms, comprising: Bl) heating a composition of phosphabicycloalkane hydrides with a ⁇ , ⁇ -dihaloalkane in an alkanol, yielding a charged bidentate diphosphine dihydride; B2) neutralisation of the charged bidentate diphosphine dihydride with a suitable basic compound, yielding a bidentate diphosphine composition wherein more than 60% w/w of bidentate diphosphine present has the general formula II.
  • Preferred alkanols in step Bl) are methanol, ethanol and isopropanol. Most preferred is ethanol.
  • Preferences for ⁇ , ⁇ -dihaloalkane, the molar ratio of phosphabicycloalkane to ⁇ , ⁇ -dihaloalkane, and the basic compound in step B2) are as described hereinabove for the steps Al) and A2) .
  • III Purification of a composition of bidentate diphosphines .
  • a further method for the preparation of a bidentate diphosphine composition wherein more than 60% w/w of the bidentate diphosphine present has the general formula (II) comprises purification of a bidentate diphosphine composition wherein 60% w/w or less of the bidentate diphosphine present has the general formula (II) .
  • a bidentate diphosphine with general formula (II) can be separated from a composition comprising a mixture of bidentate diphosphine with two symmetrical phosphabicycloalkyl groups (s,s BDP), bidentate diphosphine with two asymmetrical phosphabicycloalkyl groups (a, a BDP) and bidentate diphosphine with a symmetrical and an asymmetrical phosphabicycloalkyl group (a,s BDP), by exploiting a difference found in solubility.
  • the present invention therefore also provides a process for separation of a bidentate diphosphine with two symmetrical phosphabicycloalkyl groups (s,s BDP) from a mixture of bidentate diphosphines with two symmetrical phosphabicycloalkyl groups (s,s BDP), bidentate diphosphines with two asymmetrical phosphabicycloalkyl groups (a, a BDP) and bidentate diphosphines with a symmetrical and a symmetrical phosphabicycloalkyl group (a,s BDP), comprising selective extraction and/or recrystallisation of the mixture in a suitable solvent.
  • s,s BDP symmetrical phosphabicycloalkyl groups
  • selective is meant that isomers of a bidentate diphosphine with two phosphabicycloalkyl groups are extracted and/or recrystallised to a different extent.
  • the selective extraction and/or recrystallisation is carried out such that it yields a liquor containing a, a BDP and a,s BDP and a solid or suspension containing s,s BDP.
  • An advantage of the selective extraction and/or recrystallisation process is that the process is easy to perform. In addition, the process does not involve the handling of toxic, volatile phosphabicycloalkanes for purification but the more easily handled bidentate diphosphine itself. Furthermore the process enables the preparation of bidentate diphosphine compositions with very high percentages of bidentate diphosphine having general formula (II) by repeated recrystallisation steps.
  • a bidentate diphosphine composition is prepared wherein more than 80% w/w, more preferably more than 90% w/w, and even more preferably in the range of from 95 to 100% w/w of bidentate diphosphine present is s,s BDP. More preferably a bidentate diphosphine composition is prepared wherein in the range of from
  • 99% w/w, most preferably of from 99.5% w/w to 100% w/w of bidentate diphosphine present is s,s BDP.
  • Preferred solvents for recrystallisation include organic solvents such as saturated and unsaturated hydrocarbons, e.g. paraffins and linear, branched and cyclic alkanes and alkenes, such as hexane and pentane, cyclohexane, hexene, aromatics such as toluene and benzene; alkanols such as methanol, phenol, ethanol, propanol, isopropanol, butanol, iso-butanol; ethers, such as for example dimethylether anisole (methyl phenyl ether), 2 , 5, 8-trioxanonane (diglyme) , diethylether, tetrahydrofuran, diphenylether, diisopropylether and the dimethylether of di-ethyleneglycol; esters, such as for example methylacetate, dimethyladipate, butyrolactone, propionates and pentenoates ;
  • Preferred solvents are alkanols and ketones, preferably those comprising from 1 to 15 carbon atoms, and mixtures thereof with water.
  • More preferred solvents are alkanols, preferably those comprising from 1 to 10 carbon atoms and mixtures thereof with water. Most preferred are methanol, ethanol and isopropanol and mixtures thereof with water.
  • Alkanols and mixtures of alkanols with water have the additional advantage that any bidentate diphosphine oxides present dissolve readily and can be easily separated from the s,s BDP, which dissolves to a much lesser extent.
  • the amount of solvent used depends on whether a selective extraction or recrystallisation or a combination of those is carried out. Extraction can be economically more attractive because less solvent can be used and/or less energy is required for heating.
  • extraction preferably a, a BPA and a,s BPA are extracted from the bidentate diphosphine compositions by repeated washings with a suitable solvent .
  • the temperature of the solvent depends on the solvent used, the amount of solvent used, and on the extent to which one wishes to dissolve (parts of) the bidentate diphosphine composition. Low temperatures and low amounts of solvent are economically more attractive.
  • Selective extraction and/or recrystallisation can be carried out by refluxing the composition of bidentate diphosphine in the solvent.
  • the reflux temperature depends on the solvent used.
  • solvents are used resulting in a reflux temperature in range of 5 to 200 °C, more preferably in the range of 15 to 150 °C.
  • the pressure during refluxing is in the range from 100 to 500 kPa (1 to 5 bar) .
  • Higher pressures have the advantage that a larger part of the bidentate diphosphine can be dissolved.
  • Atmospheric pressures are economically more advantageous.
  • the bidentate diphosphine is refluxed in a suitable solvent for 0.01 to 10 hours, more preferably in the range from 0.01 to 5 hours.
  • Extraction can be performed intermittently or continuously.
  • the bidentate diphosphine composition is preferably extracted in the range from 1 to 20 times, as much as is sufficient to obtain the desired extraction of unwanted isomers. If possible, a small number of extractions, i.e. in the range from 1 to 5 times, is preferred for economical reasons.
  • Preferably continuous extraction can be performed with a Soxhlet configuration.
  • Example 1 The experiment was carried out in a 250 ml magnetically stirred Hastelloy C autoclave (Hastelloy is a trademark) .
  • the autoclave was charged with 10 ml of propene, 40 ml anisole and 10 ml sulfolane, 0.25 mmol of platinum(II) acetylacetonate, 0.3 mmol of 1, 2-PP'bis (9- phosphabicyclo [3.3.1] nonyl) ethane with a purity of > 99%, 0.3 mmol SnCl 2 and 0.3 mmol HCl.
  • the autoclave was pressurised with carbon monoxide and hydrogen to a partial pressure of 3000 kPa (30 bar) of each. Subsequently, the reactor was sealed and the contents were heated to 115 °C and maintained at that temperature for 1.5 hours. After cooling, a sample was taken from the contents of the reactor and analysed by Gas Liquid Chromatography. The selectivity towards the linear product n-butyraldehyde was 98.6%.
  • the experiment was carried out in a 250 ml magnetically stirred Hastelloy C autoclave.
  • the autoclave was charged with 10 ml of propene, 40 ml anisole and 10 ml sulfolane, 0.25 mmol of platinum (II) acetylacetonate, 0.3 mmol of 1, 3-PP'bis (9-phosphabicyclo [3.3.1] nonyl) - propane with a purity of > 99%, 0.3 mmol SnCl and 0.3 mmol HCl .
  • the autoclave was pressurised with carbon monoxide and hydrogen to a partial pressure of 3000 kPa (30 bar) of each.
  • the example was carried out in a 250 ml magnetically stirred Hastelloy C autoclave.
  • the autoclave was charged with 10 ml of propene, 40 ml anisole and 10 ml sulfolane, 0.25 mmol of platinum (II) acetylacetonate, 0.3 mmol of meso (R,S) 2, 3-PP' bis (9-phosphabicyclo [3.3.1] nonyl) butane with a purity of > 99% by weight, 0.3 mmol SnCl and 0.3 mmol HCl .
  • the autoclave was pressurised with carbon monoxide and hydrogen to a partial pressure of 3000 kPa (30 bar) of each.
  • Example 4 (separation of phosphabicyclononanes) A mixture of symmetrical and asymmetrical phosphabicyclononanes (33.9 g, 239 mmol, 153 mmol symmetrical: 86 mmol asymmetrical isomer) was dissolved in diethyl ether (240 ml) .
  • BPE-S 1, 2-PP'bis (phosphabicyclo [3.3.1] onyl) ethane.
  • BPE-A mixture of 1,2-PP' -bis (9-phosphabicyclo- [4.2.l]nonane) ethane, and 1-P- (9-phosphabicyclo- [4.2.1] nonane) 2-P' (9-phosphabicyclo [3.3.1] nonane) ethane .
  • BPE-0 mixture of oxides of 1, 2-PP'bis (phosphabicyclo- nonyl) ethane
  • Example 8 Soxhlet extraction with methanol .
  • Example 11 Extraction of BPE material using 200 ml portions methanol/water (90/10 v / v ) :
  • Example 12 Extraction of BPE material with isopropanol/water (98/2 v / v )
  • Example 13 Repetitive extraction of BPE material with methanol/water (95/5 v / v )

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Abstract

L'invention concerne un procédé de carbonylation de composés à insaturation éthylénique, éventuellement substitués, consistant à mettre en réaction du monoxyde de carbone et un coréactant en présence d'un système catalyseur. Le système catalyseur comprend (a) une source de cations métalliques du groupe du Pt, (b) une composition de diphosphine bidentate. Plus de 60 % en poids du diphosphine bidentate présent dans la composition de diphosphine bidentate est représenté par la formule générale (II) X1-R-X2 dans laquelle X1 et X2 représentent, de manière indépendante, un groupe phosphabicycloalkyle symétrique, éventuellement substitué, constitué d'au moins 5 atomes cycliques, et R représente un groupe de pontage organique divalent, reliant les deux atomes de phosphore. L'invention concerne aussi une composition de diphosphine bidentate dans laquelle plus de 60 % en poids de diphosphine bidentate est représenté par la formule générale (II) ) X1-R-X2 dans laquelle X1 et X2 représentent, de manière indépendante, un groupe phosphabicycloalkyle symétrique, éventuellement substitué, constitué d'au moins 5 atomes cycliques, et R représente un groupe de pontage organique divalent, reliant les deux atomes de phosphore, sous réserve que le diphosphine bidentate ne soit pas du 1,3-PP'bis(9-phosphabicyclo[3.3.1]nonyl)propane. Elle concerne enfin des procédés de préparation d'un telle composition de diphosphine bidentate.
PCT/EP2002/001036 2001-01-31 2002-01-31 Procede de carbonylation de composes a insaturation ethylenique, composition de diphosphine bidentate utilisee dans ce procede et procedes de preparation de cette composition de diphosphine bidentate WO2002064250A2 (fr)

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JP2002564038A JP2004527484A (ja) 2001-01-31 2002-01-31 エチレン性不飽和化合物のカルボニル化方法、その方法において使用される二座ジホスフィン組成物、およびその二座ジホスフィン組成物の調製方法
AU2002254887A AU2002254887A1 (en) 2001-01-31 2002-01-31 Process for the carbonylation of ethylenically unsaturated compounds, bidentate diphosphine composition used in this process and processes for preparation of this bidentate diphosphine composition
CA002436215A CA2436215A1 (fr) 2001-01-31 2002-01-31 Procede de carbonylation de composes a insaturation ethylenique, composition de diphosphine bidentate utilisee dans ce procede et procedes de preparation de cette composition de diphosphine bidentate

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WO2004028689A2 (fr) 2002-09-26 2004-04-08 Shell Internationale Research Maatschappij B.V. Procede d'hydroformylation d'un compose ethyleniquement insature
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CN100363319C (zh) * 2002-09-26 2008-01-23 国际壳牌研究有限公司 利用双齿二膦组合物使烯属不饱和化合物加氢甲酰化的方法
US7414155B2 (en) 2002-09-26 2008-08-19 Shell Oil Company Process for the hydroformylation of an ethylenically unsaturated compound

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AU2002254887A1 (en) 2002-08-28
JP2004527484A (ja) 2004-09-09
ZA200305228B (en) 2004-05-13
WO2002064250A3 (fr) 2003-01-30
EP1358009A2 (fr) 2003-11-05
CA2436215A1 (fr) 2002-08-22

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