WO2017135897A1 - Catalyseur pour la carbonylation d'alcènes - Google Patents

Catalyseur pour la carbonylation d'alcènes Download PDF

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Publication number
WO2017135897A1
WO2017135897A1 PCT/SG2017/050050 SG2017050050W WO2017135897A1 WO 2017135897 A1 WO2017135897 A1 WO 2017135897A1 SG 2017050050 W SG2017050050 W SG 2017050050W WO 2017135897 A1 WO2017135897 A1 WO 2017135897A1
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group
acid
alkyl
ester
formula
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PCT/SG2017/050050
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English (en)
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Martin VAN MEURS
James David NOBBS
Choon Heng LOW
Ludger Paul STUBBS
Eite DRENT
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Agency For Science, Technology And Research
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • 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
    • C07F15/006—Palladium compounds
    • 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
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5027—Polyphosphines
    • 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
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • 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
    • B01J2531/824—Palladium
    • 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
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
    • B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings

Definitions

  • the present invention relates to a metal complex and a catalyst composition comprising the metal complex.
  • the present invention also relates to a process for the preparation of a dicarboxylic acid or ester thereof from an alkenoic acid or ester thereof, or a process for the preparation of a carboxylic acid or ester thereof from an alkene or alkenoic acid with high selectivity and activity using said metal complex or catalyst composition.
  • adipic acid from ⁇ -valerolactone has been disclosed in the past.
  • GVL can be derived from the hydrogenation of levulinic acid, one of the so-called bio-based platform molecules which can be readily obtained from acid-catalyzed decomposition of cellulose or C6 sugars.
  • the known process comprises two steps: (a) reactive distillation of GVL to a mixture of pentenoic acid isomers in the presence of an acid catalyst, (b) hydroxycarbonylation of the mixture of pentenoic acid isomers to adipic acid in the presence of a palladium catalyst, precipitation of adipic acid and recycling of the filtrate containing catalyst and unreacted pentenoic acid isomers, as shown in Fig. 1.
  • the carbonylation of pentenoic acid isomer(s) to adipic acid has been reported to proceed with high selectivity in the presence of a palladium catalyst such as those derived from a palladium compound, a sterically bulky diphosphine, and an acid.
  • a palladium catalyst such as those derived from a palladium compound, a sterically bulky diphosphine, and an acid.
  • a particularly effective catalyst system is derived from palladium(II) acetate, l,2-bis[di(i-butyl)phosphinomethyl]benzene (DTBPX), and methanesulfonic acid (MSA).
  • DTBPX l,2-bis[di(i-butyl)phosphinomethyl]benzene
  • MSA methanesulfonic acid
  • R is C 1 10 alkyl or R is an optionally substituted phenyl of formula II:
  • R 6 and R 7 may each independently represent hydrogen, a C MO alkyl, nitro, halogen, -O- C MO alkyl, a halogenated C MO alkyl, carboxylic acid or ester, amide, amino, ammonium, -S0 3 H or an optionally substituted -S0 2 -; n is 1 or 2;
  • L is a ligand
  • R 2 and R 3 are either the same or different and independently represent a C 4 12 tertiary alkyl or, together with the P atom to which they are attached, form a phosphorous-containing ring having formula (III);
  • R 4 and R 5 are either the same or different and independently represent a C 4 12 tertiary alkyl or, together with the P atom to which they are attached, form a phosphorous-containing ring having formula (III):
  • R 8 , R 9 , R 10 , R n , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 each independently represent hydrogen or an optionally substituted Q to C u alkyl, provided that the metal complex does not have the following structure:
  • the metal complex may be capable of producing a dicarboxylic acid or ester thereof from an alkenoic acid or ester thereof, or producing a carboxylic acid or ester thereof from an alkene or alkenoic acid with high selectivity and activity.
  • a catalyst composition comprising the metal complex as defined above.
  • the catalyst composition may further comprise an activating acid XH.
  • the activating acid may be capable of increasing the selectivity and activity of the metal complex as defined above.
  • high acid strength i.e. low pKa
  • the catalyst composition may be more active in carboxylic acid and ester solvents rather than in ethers, without compromising the selectivity.
  • the R 1 may be an optionally substituted phenyl of formula II.
  • introduction of substituents on the phenyl ring may result in the catalyst composition having improved selectivity without compromising the activity.
  • electron withdrawing substituents may provide the best improvement in selectivity.
  • the combination of the catalyst composition comprising metal complex as defined above and a strongly acidic co-catalyst gives comparative activity and improved selectivity for the hydroxycarbonylation of alkenoic acids isomers such as pentenoic acid isomers in a polar medium comprising pentenoic acid isomers and water.
  • the catalyst composition may also advantageously give improved selectivity and activity in the hydroxy/alkoxycarbonylation of a wider range of substrates such as ethylene, butadiene, and unsaturated fatty acid esters.
  • the catalyst composition may provide a cost and time efficient method of producing dicarboxylic acids such as adipic acid from renewable feedstock.
  • a method for preparing a catalyst composition as defined above comprising the step of combining a group 10 metal compound, and a bidentate diphosphine.
  • method may further comprise the step of adding an activating acid XH.
  • the method may enable the facile formation of the catalyst composition. Further advantageously, the formation of the catalyst may be done in situ.
  • a process for preparing a dicarboxylic acid or an ester thereof comprising the step of (2) contacting an alkenoic acid or an ester thereof with a catalyst composition as defined above in the presence of carbon monoxide.
  • the process may facilitate the conversion of alkenoic acid or an ester thereof to a dicarboxylic acid or an ester thereof with high yield and selectivity.
  • the method may enable a conversion yield of greater than 40% and a selectivity greater than 96%.
  • a process for the production of a carboxylic acid or ester thereof comprising the step of contacting an alkene or alkenoic acid with a catalyst composition as defined above in the presence of carbon monoxide.
  • the process may facilitate the conversion of alkene or alkenoic acid to a carboxylic acid or an ester thereof with high yield and selectivity.
  • the method may enable a conversion yield of greater than 80% and a selectivity greater than 95%.
  • Nylon 6-6 In another aspect, there is provided a method of preparing Nylon 6-6 comprising the step of copolymerising adipic acid prepared in accordance with the process as defined above with hexamethylenediamine, to form Nylon 6-6.
  • the disclosed method may facilitate increased rate in production of Nylon 6-6 using bio-based starting materials.
  • solvent' is to be defined herein as any substance, which upon addition to a composition increases the solubility of parts of the composition, without participating in the reaction process as a reactive partner or part of the catalyst system, i.e. there are no reaction products containing parts of the solvent.
  • the group may be a terminal group or a bridging group. This is intended to signify that the use of the term is intended to encompass the situation where the group is a linker between two other portions of the molecule as well as where it is a terminal moiety.
  • alkyl As an example, some publications would use the term “alkylene” for a bridging group and hence in these other publications there is a distinction between the terms “alkyl” (terminal group) and “alkylene” (bridging group). In the present application no such distinction is made and most groups may be either a bridging group or a terminal group.
  • examples of acyl include acetyl and benzoyl.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the carbonyl carbon.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
  • Alkenoic acid as a group or part of a group donates an aliphatic carbon group containing at least one carbon-carbon double bond and a carboxylic acid, wherein the aliphatic carbon group may be straight or branched preferably having 2-20 carbon atoms, more preferably 2-12 carbon atoms, more preferably 2-10 carbon atoms, most preferably 2-6 carbon atoms, in the normal chain.
  • the group may contain a plurality of double bonds in the normal chain and the orientation about each is independently E or Z.
  • alkenoic acid groups include, but are not limited to, acrylic acid, trans-2-butenoic acid, cis-2-butenoic acid, 3-butenoic acid, 4- pentenoic acid, trans-3-pentenoic acid, cis-3-pentenoic acid, trans-2-pentenoic acid and cis-2- pentenoic acid.
  • the group may be a terminal group or a bridging group.
  • Alkenyl as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be straight or branched preferably having 2-12 carbon atoms, more preferably 2-10 carbon atoms, most preferably 2-6 carbon atoms, in the normal chain.
  • the group may contain a plurality of double bonds in the normal chain and the orientation about each is independently E or Z.
  • Exemplary alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and nonenyl.
  • the group may be a terminal group or a bridging group.
  • alkenyloxy refers to an alkenyl-O- group in which alkenyl is as defined herein.
  • Preferred alkenyloxy groups are Q-Ce alkenyloxy groups.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
  • Alkyl as a group or part of a group refers to a straight or branched aliphatic hydrocarbon group, preferably a Q-Q2 alkyl, more preferably a C C w alkyl, most preferably C C 6 unless otherwise noted.
  • suitable straight and branched C C 6 alkyl substituents include methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, t-butyl, hexyl, and the like.
  • the group may be a terminal group or a bridging group.
  • Alkylamino includes both mono-alkylamino and dialkylamino, unless specified.
  • Mono- alkylamino means a Alkyl-NH- group, in which alkyl is as defined herein.
  • Dialkylamino means a (alkyl) 2 N- group, in which each alkyl may be the same or different and are each as defined herein for alkyl.
  • the alkyl group is preferably a C C 6 alkyl group.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the carbonyl carbon.
  • Alkyloxy refers to an alkyl-O- group in which alkyl is as defined herein.
  • the alkyloxy is a Q-Ceaikyloxy. Examples include, but are not limited to, methoxy and ethoxy.
  • the group may be a terminal group or a bridging group.
  • Alkyloxyalkyl refers to an alkyloxy-alkyl- group in which the alkyloxy and alkyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
  • Alkyloxyary refers to an alkyloxy-aryl- group in which the alkyloxy and aryl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the aryl group.
  • the alkyl group is preferably a Ci-Ce alkyl group. Examples include, but are not limited to, methoxycarbonyl and ethoxycarbonyl.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the carbonyl carbon.
  • Alkyloxy cycloalkyl refers to an alkyloxy-cycloalkyl- group in which the alkyloxy and cycloalkyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the cycloalkyl group.
  • Alkyloxyheteroaryl refers to an alkyloxy-heteroaryl- group in which the alkyloxy and heteroaryl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroaryl group.
  • Alkyloxyheterocycloalkyl refers to an alkyloxy-heterocycloalkyl- group in which the alkyloxy and heterocycloalkyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heterocycloalkyl group.
  • the alkyl group is preferably a C C 6 alkyl group.
  • Exemplary alkylsulfinyl groups include, but not limited to, methylsulfinyl and ethylsulfinyl.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
  • the alkyl group is preferably a Q-Ce alkyl group. Examples include, but not limited to methylsulfonyl and ethylsulfonyl.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
  • Alkynyl as a group or part of a group means an aliphatic hydrocarbon group containing a carbon-carbon triple bond and which may be straight or branched preferably having from 2-12 carbon atoms, more preferably 2-10 carbon atoms, more preferably 2-6 carbon atoms in the normal chain.
  • Exemplary structures include, but are not limited to, ethynyl and propynyl.
  • the group may be a terminal group or a bridging group.
  • Alkynyloxy refers to an alkynyl-O- group in which alkynyl is as defined herein. Preferred alkynyloxy groups are C C 6 alkynyloxy groups.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
  • Amino refers to groups of the form -NR a R b wherein R a and R b are individually selected from the group including but not limited to hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, and optionally substituted aryl groups.
  • Aminoalkyl means an NH 2 -alkyl- group in which the alkyl group is as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
  • Aryl as a group or part of a group denotes (i) an optionally substituted monocyclic, or fused polycyclic, aromatic carbocycle (ring structure having ring atoms that are all carbon) preferably having from 5 to 12 atoms per ring.
  • aryl groups include phenyl, naphthyl, and the like; (ii) an optionally substituted partially saturated bicyclic aromatic carbocyclic moiety in which a phenyl and a C5 7 cycloalkyl or C5 7 cycloalkenyl group are fused together to form a cyclic structure, such as tetrahydronaphthyl, indenyl or indanyl.
  • the group may be a terminal group or a bridging group.
  • an aryl group is a Ce-Qs aryl group.
  • Arylalkenyl means an aryl-alkenyl- group in which the aryl and alkenyl are as defined herein.
  • Exemplary arylalkenyl groups include phenylallyl.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkenyl group.
  • “Arylalkyl” means an aryl-alkyl- group in which the aryl and alkyl moieties are as defined herein.
  • Preferred arylalkyl groups contain a C 1 5 alkyl moiety.
  • Exemplary arylalkyl groups include benzyl, phenethyl, 1 -naphthalenemethyl and 2-naphthalenemethyl.
  • the group may be a terminal group or a bridging group.
  • Arylalkyloxy refers to an aryl-alkyl-O- group in which the alkyl and aryl are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
  • Arylamino includes both mono-arylamino and di-arylamino unless specified.
  • Mono-arylamino means a group of formula arylNH-, in which aryl is as defined herein.
  • di-arylamino means a group of formula (aryl) 2 N- where each aryl may be the same or different and are each as defined herein for aryl.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
  • Arylheteroalkyl means an aryl-heteroalkyl- group in which the aryl and heteroalkyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroalkyl group.
  • Aryloxy refers to an aryl-O- group in which the aryl is as defined herein.
  • the aryloxy is a Ce-Qsaryloxy, more preferably a Ce-Qoaryloxy.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
  • a “bond” is a linkage between atoms in a compound or molecule.
  • the bond may be a single bond, a double bond, or a triple bond.
  • Cycloalkenyl means a non-aromatic monocyclic or multicyclic ring system containing at least one carbon-carbon double bond and preferably having from 5-10 carbon atoms per ring.
  • Exemplary monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl or cycloheptenyl.
  • the cycloalkenyl group may be substituted by one or more substituent groups.
  • a cycloalkenyl group typically is a C3-Q2 alkenyl group. The group may be a terminal group or a bridging group.
  • Cycloalkyl refers to a saturated monocyclic or fused or spiro polycyclic, carbocycle preferably containing from 3 to 9 carbons per ring, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, unless otherwise specified. It includes monocyclic systems such as cyclopropyl and cyclohexyl, bicyclic systems such as decalin, and polycyclic systems such as adamantane.
  • a cycloalkyl group typically is a C 3 -C 12 alkyl group. The group may be a terminal group or a bridging group.
  • Cycloalkylalkyl means a cycloalkyl-alkyl- group in which the cycloalkyl and alkyl moieties are as defined herein.
  • Exemplary monocycloaikylaikyl groups include cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl and cycloheptylmethyl.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
  • Cycloalkylalkenyl means a cycloalkyl-alkenyl- group in which the cycloalkyl and alkenyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkenyl group.
  • Cycloalkylheteroalkyl means a cycloalkyl-heteroalkyl- group in which the cycloalkyl and heteroalkyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroalkyl group.
  • Cycloalkyloxy refers to a cycloalkyl-O- group in which cycloalkyl is as defined herein.
  • the cycloalkyloxy is a Ci-Cecycloalkyloxy. Examples include, but are not limited to, cyclopropanoxy and cyclobutanoxy.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
  • Cycloalkenyloxy refers to a cycloalkenyl-O- group in which the cycloalkenyl is as defined herein. Preferably the cycloalkenyloxy is a Q-Cecycloaikenyloxy.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
  • Cycloamino refers to a saturated monocyclic, bicyclic, or polycyclic ring containing at least one nitrogen in at least one ring. Each ring is preferably from 3 to 10 membered, more preferably 4 to 7 membered.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
  • Haloalkyl refers to an alkyl group as defined herein in which one or more of the hydrogen atoms has been replaced with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • a haloalkyl group typically has the formula C n H (2n+ i m) X m wherein each X is independently selected from the group consisting of F, CI, Br and I .
  • n is typically from 1 to 10, more preferably from 1 to 6, most preferably 1 to 3.
  • m is typically 1 to 6, more preferably 1 to 3.
  • Examples of haloalkyl include fluoromethyl, difluoromethyl and trifluoromethyl.
  • Haloalkenyl refers to an alkenyl group as defined herein in which one or more of the hydrogen atoms has been replaced with a halogen atom independently selected from the group consisting of F, CI, Br and I.
  • Haloalkynyl refers to an alkynyl group as defined herein in which one or more of the hydrogen atoms has been replaced with a halogen atom independently selected from the group consisting of F, CI, Br and I.
  • Heteroalkyl refers to a straight- or branched-chain alkyl group preferably having from 2 to 12 carbons, more preferably 2 to 6 carbons in the chain, one or more of which has been replaced by a heteroatom selected from S, O, P and N.
  • exemplary heteroalkyls include alkyl ethers, secondary and tertiary alkyl amines, amides, alkyl sulfides, and the like.
  • heteroalkyl also include hydroxyCi-Cealkyl, Ci-CealkyloxyCi-Cealkyl, aminoCi-Cealkyl, Q- CealkylaminoCi-Cealkyl, and di(Ci-C 6 alkyl)aminoCi-C 6 alkyl.
  • the group may be a terminal group or a bridging group.
  • Heteroalkyloxy refers to an heteroalkyl-O- group in which heteroalkyl is as defined herein.
  • the heteroalkyloxy is a Q-Ceheteroaikyloxy.
  • the group may be a terminal group or a bridging group.
  • Heteroaryl either alone or part of a group refers to groups containing an aromatic ring (preferably a 5 or 6 membered aromatic ring) having one or more heteroatoms as ring atoms in the aromatic ring with the remainder of the ring atoms being carbon atoms. Suitable heteroatoms include nitrogen, oxygen and sulphur.
  • heteroaryl examples include thiophene, benzothiophene, benzofuran, benzimidazole, benzoxazole, benzothiazole, benzisothiazole, naphtho[2,3-b]thiophene, furan, isoindolizine, xantholene, phenoxatine, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, tetrazole, indole, isoindole, lH-indazole, purine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, cinnoline, carbazole, phenanthridine, acridine, phenazine, thiazole, isothiazole, phenothiazine, oxazole, isooxazole, furazane, phen
  • Heteroarylalkyl means a heteroaryl-alkyl group in which the heteroaryl and alkyl moieties are as defined herein. Preferred heteroarylalkyl groups contain a lower alkyl moiety. Exemplary heteroarylalkyl groups include pyridylmethyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
  • Heteroarylalkenyl means a heteroaryl-alkenyl- group in which the heteroaryl and alkenyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkenyl group.
  • Heteroarylheteroalkyl means a heteroaryl-heteroalkyl- group in which the heteroaryl and heteroalkyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroalkyl group.
  • Heteroarylamino refers to groups containing an aromatic ring (preferably 5 or 6 membered aromatic ring) having at least one nitrogen and at least another heteroatom as ring atoms in the aromatic ring, preferably from 1 to 3 heteroatoms in at least one ring. Suitable heteroatoms include nitrogen, oxygen and sulphur.
  • Arylamino and aryl is as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
  • Heteroaryloxy refers to a heteroaryl-O- group in which the heteroaryl is as defined herein.
  • the heteroaryloxy is a Q-Qgheteroaryloxy.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
  • Heterocyclic refers to saturated, partially unsaturated or fully unsaturated monocyclic, bicyclic or polycyclic ring system containing at least one heteroatom selected from the group consisting of nitrogen, sulfur and oxygen as a ring atom.
  • heterocyclic moieties include heterocycloalkyl, heterocycloalkenyl and heteroaryl.
  • Heterocycloalkenyl refers to a heterocycloalkyl as defined herein but containing at least one double bond.
  • a heterocycloalkenyl group typically is a C 2 -Cn heterocycloalkenyl group.
  • the group may be a terminal group or a bridging group.
  • Heterocycloalkyl refers to a saturated monocyclic, bicyclic, or polycyclic ring containing at least one heteroatom selected from nitrogen, sulfur, oxygen, preferably from 1 to 3 heteroatoms in at least one ring. Each ring is preferably from 3 to 10 membered, more preferably 4 to 7 membered.
  • heterocycloalkyl substituents include pyrrolidyl, tetrahydrofuryl, tetrahydrothiofuranyl, piperidyl, piperazyl, tetrahydropyranyl, morphilino, 1,3- diazapane, 1 ,4-diazapane, 1 ,4-oxazepane, and 1,4-oxathiapane.
  • a heterocycloalkyl group typically is a C 2 -C 12 heterocycloalkyl group. The group may be a terminal group or a bridging group.
  • Heterocycloalkylalkyl refers to a heterocycloalkyl-alkyl- group in which the heterocycloalkyl and alkyl moieties are as defined herein.
  • exemplary heterocycloalkylalkyl groups include (2- tetrahydrofuryl)methyl, (2-tetrahydrothiofuranyl) methyl.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkyl group.
  • Heterocycloalkylalkenyl refers to a heterocycloalkyl-alkenyl- group in which the heterocycloalkyl and alkenyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the alkenyl group.
  • Heterocycloalkylheteroalkyl means a heterocycloalkyl-heteroalkyl- group in which the heterocycloalkyl and heteroalkyl moieties are as defined herein.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the heteroalkyl group.
  • Heterocycloalkyloxy refers to a heterocycloalkyl -O- group in which the heterocycloalkyl is as defined herein.
  • the heterocycloalkyloxy is a Ci-Ceheterocycloaikyloxy.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
  • Heterocycloalkenyloxy refers to a heterocycloalkenyl-O- group in which heterocycloalkenyl is as defined herein.
  • the Heterocycloalkenyloxy is a C C 6 Heterocycloalkenyloxy.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the oxygen atom.
  • Heterocycloamino refers to a saturated monocyclic, bicyclic, or polycyclic ring containing at least one nitrogen and at least another heteroatom selected from nitrogen, sulfur, oxygen, preferably from 1 to 3 heteroatoms in at least one ring.
  • Each ring is preferably from 3 to 10 membered, more preferably 4 to 7 membered.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
  • Hydroalkyl refers to an alkyl group as defined herein in which one or more of the hydrogen atoms has been replaced with an OH group.
  • a hydroxyalkyl group typically has the formula C n H (2n+ i-x ) (OH) x
  • n is typically from 1 to 10, more preferably from 1 to 6, most preferably from 1 to 3.
  • x is typically from 1 to 6, more preferably from 1 to 4.
  • “Lower alkyl” as a group means unless otherwise specified, an aliphatic hydrocarbon group which may be straight or branched having 1 to 6 carbon atoms in the chain, more preferably 1 to 4 carbons such as methyl, ethyl, propyl (n-propyl or isopropyl) or butyl (n-butyl, isobutyl or tertiary-butyl).
  • the group may be a terminal group or a bridging group.
  • “Subject” refers to a human or an animal.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the sulfur atom.
  • the group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom.
  • Some of the compounds of the disclosed embodiments may exist as single stereoisomers, racemates, and/or mixtures of enantiomers and /or diastereomers. All such single stereoisomers, racemates and mixtures thereof, are intended to be within the scope of the subject matter described and claimed.
  • each formula includes compounds having the indicated structure, including the hydrated as well as the non-hydrated forms.
  • compounds of the invention may contain more than one asymmetric carbon atom.
  • the use of a solid line to depict bonds to asymmetric carbon atoms is meant to indicate that all possible stereoisomers are meant to be included.
  • the use of a solid line to depict bonds to one or more asymmetric carbon atoms in a compound of the invention and the use of a solid or dotted wedge to depict bonds to other asymmetric carbon atoms in the same compound is meant to indicate that a mixture of diastereomers is present.
  • optionally substituted means the group to which this term refers may be unsubstituted, or may be substituted with one or more groups independently selected from alkyl, alkenyl, alkynyl, thioalkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkylalkenyl, heterocycloalkyl, cycloalkylheteroalkyl, cycloalkyloxy, cycloalkenyloxy, cycloamino, halo, carboxyl, haloalkyl, haloalkynyl, alkynyloxy, heteroalkyl, heteroalkyloxy, hydroxyl, hydroxyalkyl, alkoxy, thioalkoxy, alkenyloxy, haloalkoxy, haloalkenyl, haloalkynyl, haloalkenyloxy, nitro, amino, nitroalkyl, cycloal
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • range format may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range. Certain embodiments may also be described broadly and generically herein.
  • R 1 is Ci ioalkyl or R 1 is an optionally substituted phenyl of formula II:
  • R 6 and R 7 may each independently represent hydrogen, a C MO alkyl, nitro, halogen, -O- C MO alkyl, a halogenated C 1 10 alkyl, carboxylic acid or ester, amide, amino, ammonium, -S0 3 H or an optionally substituted -S0 2 -; n is 1 or 2;
  • L is a ligand
  • R 2 and R 3 are either the same or different and independently represent a C 4 _i 2 tertiary alkyl or, together with the P atom to which they are attached, form a phosphorous-containing ring having formula (III);
  • R and R" are either the same or different and independently represent a C 4 _i 2 tertiary alkyl or, together with the P atom to which they are attached, form a phosphorous-containing ring having formula (III):
  • R 8 , R 9 , R 10 , R n , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 each independently represent hydrogen or an optionally substituted Q to C 12 alkyl, provided that the metal complex does not have the following structure:
  • the alkyl may be a Q to C 12 alkyl, C 4 to C 12 alkyl, Q to C 10 alkyl, or selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, teri-butyl, pentyl, isopentyl, teri-pentyl, hexyl and isohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
  • R 8 , R 9 , R 14 and R 15 may each independently be Q to C 10 alkyl.
  • R 8 , R 9 , R 14 and R 15 may each independently be methyl or R 8 , R 9 , R 14 and R 15 may all be methyl.
  • M may be nickel, palladium or platinum. M may be palladium. M may be palladium (II) or palladium (0).
  • the metal complex does not have the following structure, where L is a ligand:
  • the metal complex may not comprise l,2-bis[di(i-butyl)phosphinomethyl]benzene (DTBPX).
  • DTBPX l,2-bis[di(i-butyl)phosphinomethyl]benzene
  • Ph may be a phenyl group.
  • L may independently be a neutral ligand, monoanionic ligand or dianionic ligand.
  • n 2 and L is independently a neutral ligand
  • the two ligands may be connected to form a single bidentate ligand.
  • L may independently be selected from the group consisting of hydride, methyl, allyl, 1- methylallyl, acetate, trifluoroacetate, triflate, methanesulfonate, ,para-toluenesulfonate, propylsulfonate, camphorsulfonate, benzenesulfonate, phosphate, chloride, bromide, iodide, sulfate, carbonate, acetonitrile, 1,4-benzoquinone, pyridine, carbon monoxide, triphenylphosphine and dibenzilideneacetone, alkyl, carboxylate, sulfonate, carboxylic acid, ester, ketone, alkene, diene, nitrile, amine, phosphine, ether, alcohol, imine.
  • L may independently be a deprotonated acid XH.
  • the acid XH may have a pKa of less than about 5, less than about 4.5, less than about 4, less than about 3.5, less than about 3, less than about 2.5, less than about 2, less than about 1.5 or less than about 1, when measured in water at 18°C.
  • the acid XH may be selected from the group consisting of sulfonic acids, sulfuric acids, phosphorous acids and carboxylic acids.
  • the acid XH may be selected from the group consisting of methanesulfonic acid, para-toluenesulfonic acid, triflic acid, propylsulfonic acid, camphorsulfonic acid, benzenesulfonic acid, phosphoric acid, sulfuric acid, trifluoroacetic acid, and acetic acid.
  • M may be palladium (II), n may be 2 and each L may independently be a monoanionic ligand.
  • M may be palladium (II)
  • n may be 1 and L may be a dianionic ligand.
  • M may be palladium (II), n may be 2, L may independently be a neutral ligand and the metal complex may have non-coordinating counter anions.
  • M may be palladium (0), n may be 1 or 2, and L may independently be a neutral ligand.
  • catalyst composition wherein the catalyst composition may comprise the metal complex as defined above.
  • the catalyst composition may further comprise an activating acid XH.
  • the composition may be substantially free of oxygen.
  • composition may further comprise a solvent.
  • solvent may depend on the selected catalyst and/or the selected substrate to be catalysed.
  • the solvent may be such that the product of the catalytic reaction can be separated from the unreacted reactants by reducing the temperature of the reaction.
  • the solvent may be any substance which is not a reactant, catalyst component, a product or a precursor of the reactant.
  • composition may be substantially free of an organic solvent or may be substantially free of a water-immiscible solvent.
  • the composition may comprise a biphasic system or may be substantially an emulsion.
  • the activating acid XH may have a pKa of less than about 5, less than about 4.5, less than about 4, less than about 3.5, less than about 3, less than about 2.5, less than about 2, less than about 1.5 or less than about 1, when measured in water at 18°C.
  • the activating acid XH may be selected from the group consisting of sulfonic acids, sulphuric acids, phosphorous acids and carboxylic acids.
  • the activating acid XH may be selected from the group consisting of methanesulfonic acid, para-toluenesulfonic acid, triflic acid, propylsulfonic acid, camphorsulfonic acid, phosphoric acid, sulfuric acid, trifluoroacetic acid, trifluoromethylsulfonic acid and acetic acid.
  • the activating acid XH in the catalyst composition may be methane sulfonic acid.
  • the activating acid XH may be present in at least two molar equivalents relative to the metal.
  • the activating acid XH may be present in at least about 2 molar excess, at least about 4 molar excess, at least about 6 molar excess, at least about 8 molar excess, at least about 10 molar excess, at least about 12 molar excess, at least about 14 molar excess, at least about 16 molar excess, at least about 17 molar excess or at least about 20 molar excess relative to the metal.
  • composition may be used to convert an alkene to a carboxylic acid or an ester thereof.
  • the metal complex, the temperature and pressure of the composition may be such that the conversion of alkene to carboxylic acid or ester thereof is greater than about 95% in yield.
  • a method for preparing a catalyst composition as defined above the method may comprise the step of combining a group 10 metal compound and a bidentate diphosphine.
  • the method may further comprise the step of adding an activating acid XH.
  • the metal may be nickel, palladium or platinum.
  • the metal may be palladium.
  • the palladium compound may be selected from the group consisting of palladium carboxylate, palladium(O) compound, palladium acetate, tris(dibenzylideneacetone)dipalladium(0) and palladium acetylacetonate.
  • the bidentate diphosphine may have the formula (IV):
  • R 1 is C 1 10 alkyl or R 1 is an optionally substituted phenyl of formula II:
  • R 6 and R 7 may each independently represent hydrogen, a C M0 alkyl, nitro, halogen, -O-alkyl, a halogenated C M0 alkyl, carboxylic acid or ester, amide, amino, ammonium, -S0 3 H or an optionally substituted -S0 2 -;
  • R 2 and R 3 are either the same or different and independently represent a C 4 12 tertiary alkyl or, together with the P atom to which they are attached, form a phosphorous-containing ring having formula (III);
  • R 4 and R 5 are either the same or different and independently represent a C 4 _i 2 tertiary alkyl or, together with the P atom to which they are attached, form a phosphorous-containing ring having formula (III):
  • R 8 , R 9 , R 10 , R n , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 each independently represent hydrogen or an optionally substituted Q to C 2 alkyl, provided that the bidentate diphosphine does not have the following structure:
  • the alkyl may be a Q to C 2 alkyl, C 4 to C 2 alkyl, Q to Ci 0 alkyl, or selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, teri-butyl, pentyl, isopentyl, teri-pentyl, hexyl and isohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
  • R 8 , R 9 , R 14 and R 15 may each independently be Q to C 10 alkyl.
  • R 8 , R 9 , R 14 and R 15 may each independently be methyl or R 8 , R 9 , R 14 and R 15 may all be methyl.
  • the bidentate diphosphine does not comprise l,2-bis[di(i-butyl)phosphinomethyl] benzene (DTBPX) having the following structure:
  • the bidentate diphosphine may be selected from the group consisting of the following:
  • Ph may be a phenyl group.
  • the compression in the C-P-C angle in the phosphorinone ring relative to the corresponding angle in DTBPX also causes a decrease in the ⁇ -donating character of the P lone pair and a concomitant increase in the ⁇ -accepting character of the phosphorus, overall reducing the basicity of the phosphorous atom.
  • the activating acid XH may have a pKa of less than about 5, less than about 4.5, less than about 4, less than about 3.5, less than about 3, less than about 2.5, less than about 2, less than about 1.5 or less than about 1, when measured in water at 18°C.
  • the activating acid XH may be selected from the group consisting of sulfonic acids, sulphuric acids, phosphorous acids and carboxylic acids.
  • the activating acid XH may be selected from the group consisting of methanesulfonic acid, para-toluene sulfonic acid, triflic acid, propylsulfonic acid, camphorsulfonic acid, phosphoric acid, sulfuric acid, trifluoroacetic acid, trifluoromethylsulfonic acid and acetic acid.
  • the activating acid XH in the catalyst composition may be methane sulfonic acid.
  • the activating acid XH may be present in at least two molar equivalents relative to the metal.
  • the activating acid XH may be present in at least about 2 molar equivalents, at least about 4 molar equivalents, at least about 6 molar equivalents, at least about 8 molar equivalents, at least about 10 molar equivalents, at least about 12 molar equivalents, at least about 14 molar equivalents, at least about 16 molar equivalents, at least about 18 molar equivalents or at least about 20 molar equivalents relative to the metal.
  • the catalyst composition may be prepared in situ. If the catalyst composition is prepared in situ, the composition may comprise a group 10 metal and a bidentate disphosphine.
  • the composition may comprise a group 10 metal, a bidentate diphosphine and an activating acid XH. If the catalyst composition is prepared in situ, the composition may comprise a metal complex as defined above and a co-catalyst.
  • the group 10 metal may be nickel, palladium or platinum.
  • the group 10 metal may be palladium.
  • the group 10 metal may be palladium (II) or palladium (0).
  • the catalyst composition may be formed in situ by mixing any palladium (0) compound, for example palladium tetrakis(triphenylphosphine), with a bidentate diphosphine ligand, as defined above, together with an activating acid HX.
  • a cationic palladium (II) complex may then be formed by protonation of palladium (0), to first form L 2 Pd(II) H(X), optionally followed by an additional equivalent of acid HX to generate L 2 Pd(II)X 2 .
  • the co-catalyst may be acid XH. Since the anion X- of acid XH is typically a weakly/non-coordinating ligand, the structure of the metal complexes in the catalyst composition prepared in situ may not have the anion X- of acid XH each occupying a coordination site on the metal. If the acid is multi-dentate, one anion X- of acid XH may occupy two coordination sites on the metal (e.g. two oxygens on a sulfonate), while the other anion may be present as a non-coordinating counter-anion. Furthermore, other ligands such as carbon monoxide, methanol solvent molecules and substrate molecules which may also be present in the reaction may occupy a coordinating site on the metal.
  • the catalyst composition may be pre -formed.
  • the catalyst composition may comprise a metal complex as defined above. If the catalyst composition is pre-formed, the catalyst composition may comprise a metal complex having the following structure:
  • Me may be a -CH 3 group.
  • OAc may be an acetate group, dba may be dibenzylideneacetone.
  • the two anionic ligands in the divalent palladium complexes may each occupy one coordination site on palladium, or one anionic ligand may occupy two coordination sites on palladium (e.g. two oxygens on a sulfonate), while the other anion is present as a non-coordinating counter- anion.
  • the pre -formed catalyst composition comprises acetate or trifluoroacetate ligands
  • the composition may inherently have very low activity, but the activity may increase by orders of magnitude by the addition of a co-catalyst such as sulfonic acid.
  • a co-catalyst such as sulfonic acid.
  • the alkenoic acid that may be present as a reaction substrate may also function as the acidic co-catalyst, for example with the Pd(0)dba complex.
  • the group 10 metal in the catalyst composition or M in the metal complex is palladium(II) (i.e. divalent)
  • an excess of acid HX may be optionally present.
  • the group 10 metal in the catalyst composition or M in the metal complex is palladium(O) (i.e. metallic Pd)
  • the activating acid HX may be essential to form an active catalyst composition.
  • the catalytically active form of the group 10 metal in the catalyst composition or M in the metal complex may be a palladium (II) hydride capable of inserting an alkene, but palladium (0) may also be present as an intermediate or dormant species in the catalytic carbonylation cycle.
  • a process for preparing a dicarboxylic acid or an ester thereof may comprise the step of (2) contacting an alkenoic acid or an ester thereof with a catalyst composition as defined above in the presence of carbon monoxide.
  • the contacting step (2) may be carried out substantially in the absence of oxygen.
  • the contacting step (2) may be carried out under a carbon monoxide atmosphere.
  • the carbon monoxide may be in the form of carbon monoxide gas, or may be generated in situ using carbon monoxide surrogates that decompose to form carbon monoxide.
  • the carbon monoxide surrogate may be formates such as N-formylsaccharin, formic acid or alkyl formates.
  • the contacting step (2) may be performed in the presence or absence of a solvent.
  • the contacting step (2) may be carried out at a temperature of between about 50°C and about 150°C, or about 80°C and about 120°C.
  • the contacting step (2) may be carried out at a pressure of between about 100 kPa (1 bar) and about 15000 kPa (150 bar), about 300 kPa (3 bar) and about 8000 kPa (80 bar) or about 500 kPa (5 bar) and about 6000 kPa (60 bar).
  • the process may further comprise, before the contacting step (2), a process for preparing the alkenoic acid or ester thereof, comprising the step of either (la) heating a lactone in the presence of an acidic catalyst system and water or an alcohol to produce an alkenoic acid or ester thereof; or (lb) reacting a diene with carbon monoxide and the metal complex in the presence of water or an alcohol to produce an alkenoic acid or ester thereof.
  • Step (la) may comprise reactive distillation, thereby providing a distillate comprising the alkenoic acid or ester thereof.
  • Step (la) may be carried out at a temperature at or above the normal boiling point of the lactone.
  • Step (la) may be carried out at a temperature of between about 150°C to about 370°C, about 200°C to about 350°C, or about 250°C to about 300°C.
  • Step (la) may be carried out at a pressure of between about 50 kPa (0.5 bar) to about 3000 kPa (30 bar). Step (la) may be carried out at a pressure of about 100 kPa (1 bar).
  • the acidic catalyst system may comprise an acidic catalyst or a heterogeneous solid catalyst.
  • the acidic catalyst system may comprise alumina, silica, zeolite, clay or any mixture thereof.
  • the acidic catalyst system may, for example, comprise a mixture of alumina and silica.
  • the acidic catalyst system may, for example, comprise a mixture of zeolite and clay.
  • the clay may be montmorillonite or kaolinite.
  • the zeolite may be selected from the group consisting of analcime, chabazite, clinoptilite, heulandite, natrolite, phillipsite and stilbite.
  • the alkenoic acid or ester thereof produced in step (la) may comprise a plurality of isomers.
  • Step (lb) may be carried out as an alternative method for the production of alkenoic acid or ester thereof.
  • the reaction may be a hydroxycarbonylation reaction or an alkoxycarbonylation reaction.
  • the diene may be a C 3 _i 0 alkene.
  • the alkene may comprise two double bonds.
  • the alkene may be selected from the group consisting of allene, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, and decadiene.
  • the diene may be bio-based.
  • the process may further comprise a step (3) of separating part or substantially all the unreacted lactone from the alkenoic acid or ester thereof and recycling part or substantially all of the separated unreacted lactone by carrying out heating step (la) as defined above on the part or substantially all of the separated unreacted lactone.
  • the process may further comprise the steps of: (4) separating part or substantially all of the unreacted alkenoic acid or ester from the dicarboxylic acid or ester thereof and recycling part or substantially all of the separated unreacted alkenoic acid or ester thereof by carrying out contacting step (2) as defined above on the part or substantially all of the separated unreacted alkenoic acid or ester thereof.
  • the lactone used in step (la) may be ⁇ -valerolactone and the alkenoic acid may be pentenoic acid.
  • the pentenoic acid may comprise one or more, or optionally all, of 2- pentenoic acid, 3-pentenoic acid and 4-pentenoic acid.
  • the double bond in 2-pentenoic acid and 3-pentenoic acid may be in the trans or in the cis configuration.
  • the dicarboxylic acid may be adipic acid, methylglutaric acid, ethylsuccinic acid or propylmalonic acid.
  • the lactone used in step (la) may be ⁇ -valerolactone
  • the alkenoic acid ester may be alkyl pentenoate.
  • the alkyl pentenoate may comprise one or more, or optionally all, of alkyl 2-pentenoate, alkyl 3 -pentenoate and alkyl 4-pentenoate.
  • the double bond in alkyl 2-pentenoate and alkyl 3 -pentenoate may be in the trans or in the cis configuration.
  • the dicarboxylic acid ester may be dialkyl adipate.
  • the process may comprise the steps of:
  • step (la) is carried out with or without water and the heating of the ⁇ -valerolactone in step (la) comprises reactive distillation, thereby providing a distillate comprising the pentenoic acid, and step (2), reacting pentenoic acid to adipic acid using a catalyst composition as defined above, wherein the palladium catalyst is prepared by combining palladium acetate, l,2-bis[(2,2,6,6-tetramethylphosphinan-4-on)methyl]benzene, and methanesulfonic acid.
  • the process may comprise the steps of:
  • step (la) is carried out with or without water and the heating of the y-valerolactone in step (la) comprises reactive distillation, thereby providing a distillate comprising the methyl pentenoate, and step (2), reacting methyl pentenoate to dimethyl adipate using a catalyst composition as defined above, wherein the palladium catalyst is prepared by combining palladium acetate, l,2-bis[(2,2,6,6-tetramethylphosphinan-4-on)methyl]benzene, and methanesulfonic acid.
  • An alternative route to producing bio-based adipic acid may involve hydroxycarbonylation of bio-based butadiene to firstly 3-pentenoic acid and subsequent hydroxycarbonylation of the 3- pentenoic acid to adipic acid in the presence of a palladium catalyst.
  • the reaction may therefore be applied not only to GVL-derived pentenoic acid isomers but also to compounds such as butadiene, ethylene and unsaturated fatty acids/esters.
  • the process may facilitate the conversion of alkenoic acid or an ester thereof to a dicarboxylic acid or an ester thereof with high yield and selectivity.
  • the method may enable a conversion yield of greater than 40% and a selectivity greater than 96%.
  • the adipic acid product when the substrates pentenoic acids and water are used as the medium, the adipic acid product is a solid at reaction temperature and therefore has limited solubility. In theory, a much higher yield than 40% may be achieved if GVL or a carboxylic acid is used as a solvent (for example at >50% by volume). In such cases, the pentenoic acid conversion may be much higher, in principle, quantitative (>99%).
  • the solid adipic acid may be easily separated from the reaction mixture by filtration, while the liquid phase, comprising among others unconverted pentenoic acids and catalyst, can be recycled to result in both an increased catalyst turnover number and a much higher overall pentenoic acids conversion.
  • the process may comprise the step of contacting an alkene or alkenoic acid with a catalyst composition as defined above in the presence of carbon monoxide.
  • the contacting step may be carried out substantially in the absence of oxygen.
  • the contacting step may be carried out under a carbon monoxide atmosphere.
  • the carbon monoxide may be in the form of carbon monoxide gas, or may be generated in situ using carbon monoxide surrogates that decompose to form carbon monoxide.
  • the carbon monoxide surrogate may be formats such as N-formylsaccharin.
  • the contacting step may be carried out at a temperature of between about 50°C to about 150°C, or about 80°C to about 120°C.
  • the contacting step may be carried out at a pressure of between about 100 kPa (1 bar) to about 15000 kPa (150 bar), about 300 kPa (3 bar) to about 8000 kPa (80 bar) or about 500 kPa (5 bar) to about 6000 kPa (60 bar).
  • the reaction may be a hydroxycarbonylation reaction or an alkoxycarbonylation reaction.
  • the alkene may be a C 2 - 2 o alkene comprising one or more double bonds, with the alkene positioned in a terminal or internal position.
  • the alkene may be selected from the group consisting of ethylene, propylene, butene, butadiene, pentene, pentadiene, hexene, hexadiene, heptene, heptadiene, octene, octadiene, nonene, nonadiene, decene and decadiene, methylpentenoate, 1 -hexene, 3-hexene, 3-pentenenitrile, methyl butenoate, unsaturated fatty acids or esters thereof, and monounsaturated fatty acids or esters thereof and polyunsaturated fatty acids or esters thereof.
  • the fatty acid or ester thereof may be an odd-chain fatty acid or an ester thereof.
  • An odd chain fatty acid may contain an odd number of carbon atoms in the structure.
  • the alkene or diene may be bio-based.
  • the alkene or diene may be produced by alkene metathesis of monounsaturated fatty acids or esters thereof, or polyunsaturated fatty acids or esters thereof.
  • the alkene may be 1-decene produced by alkene cross-metathesis of oleic acid or an ester thereof with ethylene.
  • the alkene may be 9-octadecene produced by self-metathesis of the 1-decene described above or produced by self-metathesis of oleic acid or an ester thereof.
  • the alkene may be an internal alkene, an isomeric mixture of alkenes of the same chain length, or a mixture of internal alkenes of different chain length.
  • An internal alkene is where the double bond is positioned in an internal position of the aliphatic chain, in contrast to being a terminal alkene.
  • the product of the process may be saturated or unsaturated carboxylic acids or carboxylic esters.
  • the product of the process may be odd-chain saturated or unsaturated carboxylic acids or carboxylic esters.
  • the carboxylic acid may be a fatty acid.
  • the carboxylic acid may be an odd-chain fatty acid.
  • the process may further comprise water as a co-reagent. If water is used as the co-reagent, then the process would be referred to as a hydroxycarbonylation reaction and the reaction product may comprise a carboxylic acid.
  • the process may further comprise alcohol as a co-reagent. If alcohol is used as a co-reagent, the process would be referred to as an alkoxycarbonylation reaction and the reaction product may comprise an alkyl ester, the alkyl being the alkyl moiety of the alcohol co-reagent.
  • the alcohol co-reagent may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, pentanol and hexanol.
  • the alkene may be an alkyl alkenoate.
  • the alkyl alkenoate may be produced by a ring-opening reaction of a lactone.
  • the process may facilitate the conversion of alkene or diene to a carboxylic acid or an ester thereof with high yield and selectivity.
  • the method may enable a conversion yield of greater than 80% and a selectivity greater than 95%.
  • typically methanol was present in large excess as the solvent and the methyl ester product was generally a liquid as well. Quantitative conversion may also be possible for this reaction, depending on the substrate:catalyst ratio and reaction time.
  • a method of preparing Nylon 6-6 the method may comprise the step of copolymerising adipic acid prepared in accordance with the process as defined above with hexamethylenediamine, to form Nylon 6-6.
  • FIG. 1 is a schematic diagram showing a prior art process of converting GVL to adipic acid.
  • Fig.2 is a schematic diagram showing a prior art process of converting GVL to adipic acid.
  • FIG. 2 is a schematic diagram showing some conversions of alkenoic acids to dicarboxylic acids using a catalyst.
  • FIG. 3 is a schematic diagram showing the possible pathways for making a metal complex with the diphosphines and possible activation pathways leading to an active catalyst composition.
  • FIG. 2 is a schematic diagram showing some conversions of alkenoic acids to dicarboxylic acids using a catalyst.
  • a mixture of 4-pentenoic acid, trans-3- pentenoic acid, cis-3- pentenoic acid, trans-2- pentenoic acid and cis-2- pentenoic acid can be converted to dicarboxylic acids such as adipic acid, methylglutaric acid, ethylsuccinic acid and propylmalonic acid.
  • FIG. 3 is a schematic diagram showing possible pathways for making a metal complex with the diphosphines and possible activation pathways leading to an active catalyst composition.
  • the palladium complex may have an oxidation state of 0 or 2, and the type of ligand may depend accordingly.
  • the ligand may be monoanionic, dianionic, neutral, monodentate or bidentate, and the resulting catalyst composition may have a weakly coordinating anion coordinated to the metal or present as a non-coordinating counterion.
  • the oxidation of palladium(O) to palladium(II) as well as the reduction of palladium(II) to palladium(O) are both indicated.
  • the position of the reaction may depend on the reaction conditions such as whether the environment is oxidising or reducing, and the strength of the acid present.
  • Air- or moisture-sensitive reactions were carried out under an atmosphere of purified argon, and compounds were stored in a nitrogen or argon filled glove box.
  • Solvents were dried using a Glass Contour solvent purification system where the solvents were passed through oxy- and moisture traps under an atmosphere of purified argon. CO gas was purified by passing through oxy- and moisture traps.
  • NMR spectra were recorded on a Bruker 400 MHz Spectrometer. The chemical shifts were referenced to residual protio impurities in the NMR solvent used; 13 C chemical shifts were referenced to the 13 C chemical shift of the NMR solvent used; whereas 31 P chemical shifts were referenced against a H 3 P0 4 external standard.
  • Chlorotrimethylsilane (10.3 mL, 81.5 mmol) was added dropwise to LiAlH 4 (3.09 g, 81.5 mmol) suspended in THF (150 mL) at -78°C. After complete addition, the reaction was allowed to warm to room temperature and stirred. After 2 hours the reaction was cooled to -50°C and a solution of tetrabutyl(l ,2-phenylenebis(methylene))bis(phosphonate) (10.0 g, 20.4 mmol) in THF (100 mL) was added dropwise, after which the reaction was allowed to warm to room temperature and stirred an additional 2 hours.
  • L1AIH 4 (2.0M in THF, 6.75 mL, 13.52 mmol) was diluted with THF (25 mL) and cooled to -10 °C.
  • BPX (1.03 g, 2.3 mmol) in THF (8 mL) was added dropwise. The mixture was allowed to warm to room temperature and stirred for 16 hours. After this time (20% NaOH, 2 mL) was added cautiously to the mixture. The mixture was filtered and the solvent removed in vacuo. The product was a mixture of diastereomers.
  • Quantitative deprotection was achieved by warming the protected phosphine (0.38 g, 0.78 mmol) in pyrrolidine at 50°C overnight followed by removal of the volatiles in vacuo and eluting the residue with CH 2 C1 2 through a silica plug under argon.
  • the diphosphine was obtained quantitatively via a similar deprotection to 4-CF 3 -DTBPX.
  • BPX (0.93 g, 2.09 mmol) and Pd(dba) 2 (1.21 g, 2.09 mmol) were suspended in CH 2 C1 2 (15 mL) and stirred at room temperature for 8 hours.
  • HC1 2.0M in diethyl ether, 2.1 mL, 4.19 mmol
  • the volatile s were then removed in vacuo and the residue washed with CH 2 C1 2 (2 x 20 mL), the combined washings were reduced in volume and Et 2 0 added to induce precipitation.
  • the precipitate was collected via filtration and washed with Et 2 0 (3 x 10 mL) to yield a yellow powder (1.04 g, 80%).
  • Example 4 Preparation of Pentenoic Acid Isomers
  • a mixture of pentenoic acid isomers was prepared via catalytic distillation of gamma- valerolactone.
  • a continuous reactive distillation was set up consisting of a 1 litre round bottom flask with heating mantle and agitation, a 1.5 metre tall insulated distillation column (internal diameter 24 mm), a top condenser with reflux controller and a dual piston pump.
  • the column was packed with stainless steel Raschig rings.
  • the flask was initially loaded with 500 mL gamma-valerolactone and 5wt% (25 g) silica-alumina catalyst (grade 135). The mixture was then heated to a bottom temperature of around 220°C.
  • Example 5 Hydroxycarbonylation of Pentenoic Acids to Adipic Acid With BPX Derivatives (Sample No. 1 to 7)
  • a stainless steel 300 ml Parr reactor was charged with degassed distillate from Example 4 (65 mL) and the amount of degassed water specified in Table 1 under a stream of argon gas.
  • a preformed catalyst solution consisting of palladium(II) acetate (55 ⁇ ), l ,2-bis[(2,2,6,6- tetramethylphosphinan-4-onyl)methyl]benzene (BPX, ⁇ ⁇ ⁇ ) or l,2-bis[(2,2,6,6- tetramethylphosphinan-4-ol)methyl]benzene (BPX-OH, 110 umol) and methanesulfonic acid (1.5 mmol) in degassed pentenoic acids distillate (15 mL) was then injected into the reactor.
  • a stainless steel 300 ml Parr reactor was charged with degassed distillate from Example 4 (65 mL) and degassed water (10 ml) under a stream of argon gas.
  • a preformed catalyst solution consisting of palladium(II) acetate (55 ⁇ ), l,2-bis[di(i-butyl)phosphinomethyl] benzene (DTBPX or BPPr, 110 ⁇ ) and methanesulfonic acid (0 or 1.5 mmol) in degassed pentenoic acids distillate (15 mL) was then injected into the reactor.
  • the Parr reactor was then purged with CO gas and pressurised to 40 bar CO.
  • the reaction mixture was stirred at 1000 rpm and heated to 115°C.
  • Example 6 Analysis of Hydroxycarbonylation of Pentenoic Acids to Adipic Acid With BPX Derivatives
  • a DTBPX/Pd/MSA catalyst used diglyme as a reaction diluent and as a solvent for catalyst preparation, typically composing -75% of the medium.
  • the DTBPX/Pd/MSA produced adipic acid with a good activity (TOF 100 - 200 IT 1 ) and selectivity (96 - 98%).
  • TOF 100 - 200 IT 1 good activity
  • selectivity 96 - 98%).
  • the use of a medium consisting of only the 2 substrates i.e. pentenoic acid isomers and water was investigated because this would eliminate issues with diglyme recycle and would make better use of the reactor space.
  • the new catalyst system of the present disclosure based on ligand BPX does not follow the same trend as the benchmark catalyst.
  • a catalyst with low activity is formed (Sample No. 5 and 6).
  • MSA the catalyst is both highly active and selective for the hydroxycarbonylation of pentenoic acid isomers (Sample No. 1-4).
  • Example 7 Carbonylation of Pentenoic Acids to Adipic Acid with DTBPX in Different Solvents (Sample No. 11 to 17)
  • a catalyst solution was prepared by dissolving palladium(II) acetate (35 ⁇ ), l,2-bis[di(i- butyl)phosphinomethyl] benzene (DTBPX, 70 ⁇ ) in 3.0 ml of degassed solvent as specified in Table 2, followed by the addition of 0.35 mmol of MSA co-catalyst.
  • This solution degassed water (0.5 mL, 27.7 mmol), pentenoic acids distillate (1.5 ml) and an additional 4 ml of the solvent were then injected into a stainless steel 12 ml autoclave under a stream of argon gas.
  • the reactor was purged with CO gas and pressurised to 50 bar CO.
  • the reaction mixture was stirred magnetically at 2000 rpm at a temperature of 105°C for 3 hours. After this time the reactor was cooled and the product mixture was analysed by GC (Table 2Table ).
  • a catalyst solution was prepared by dissolving palladium(II) acetate (20 umol) and 1,2- bis[(2,2,6,6-tetramethylphosphinan-4-onyl)methyl]benzene (BPX, 40 ⁇ ) in 8.5 ml of degassed pentenoic acids distillate from Example 4 followed by the addition of 0.2 mmol of co- catalyst as specified in Table 3.
  • This solution and degassed water (0.5 mL, 27.7 mmol) were then injected into a stainless steel 12 ml autoclave under a stream of argon gas.
  • the reactor was purged with CO gas and pressurised to 50 bar CO.
  • the reaction mixture was stirred magnetically at 2000 rpm at a temperature of 115°C for 12 hours. After this time the reactor was cooled and the product mixture was analysed by GC (Table 3). Table 3. Hydroxycarbonylation of pentenoic acids to adipic acid by varying the co-catalyst
  • Example 9 Carbonylation of Pentenoic Acids to Adipic Acid with BPX in Different Solvents (Sample No. 28 to 32)
  • a catalyst solution was prepared by dissolving palladium(II) acetate (20 umol), l,2-bis[(2,2,6,6- tetramethylphosphinan-4-onyl)methyl]benzene (BPX, 40 ⁇ ) in 3.0 ml of degassed pentenoic acids distillate from Example 4 followed by the addition of 0.2 mmol of MSA co-catalyst.
  • This solution degassed water (0.5 mL, 27.7 mmol) and 5.5 ml of a co-solvent as specified in Table 4 were then injected into a stainless steel 12 ml autoclave under a stream of argon gas.
  • the reactor was purged with CO gas and pressurised to 50 bar CO.
  • the reaction mixture was stirred magnetically at 2000 rpm at a temperature of 115°C for 12 hours. After this time the reactor was cooled and the product mixture was analysed by GC (Table 4).
  • Example 10 Analysis of BPX/PdVMSA Catalyst
  • the combination of the BPX ligand with a palladium source and strongly acidic co-catalyst outperforms the benchmark DTBPX catalyst in activity and selectivity for the hydroxycarbonylation of pentenoic acid isomers in a polar medium comprising pentenoic acid isomers and water.
  • the catalyst system can also be applied to the hydroxy/alkoxycarbonylation of a wider range of substrates, including but not limited to methylpentenoates, 1 -hexene, 3- hexene, 3-pentenitrile, butadiene, unsaturated fatty acids/esters, 3-butenoic acid, and methyl but-3-enoate.
  • Example 11 Methoxycarbonylation of Methyl Pent-2-enoate (Sample No. 33 to 35)
  • a catalyst solution was prepared by dissolving palladium(II) acetate (20 ⁇ ), diphosphine specified in Table 5 (BPX, 40 umol) in 6.0 ml of degassed methanol followed by the addition of 0.2 mmol of MSA co-catalyst. This solution and 3.0 ml of 2-methyl pentenoate were then injected into a stainless steel 12 ml autoclave under a stream of argon gas. The reactor was purged with CO gas and pressurised to 50 bar CO. The reaction mixture was stirred magnetically at 2000 rpm at a temperature of 105°C for 12 hours. After this time the reactor was cooled and the product mixture was analysed by GC (Table 5). DTBPX (Sample 33) is included as a control.
  • Example 12 Carbonylation of Other Substrates
  • the catalyst system can also be applied to the hydroxy/alkoxycarbonylation of a wider range of substrates as shown below.
  • a catalyst solution was prepared by dissolving palladium(II) acetate (10 ⁇ ), and BPX (180 ⁇ ) in 10.0 ml of degassed methanol followed by the addition of 2.0 mmol of MSA co- catalyst. A portion of this solution (5.0 mL: 5 umol Pd) was injected into a stainless steel 300 ml autoclave followed by methanol (100 mL) under a stream of argon gas. The reactor was then flushed and pressurised with 8 bar of ethylene and then an additional 8 bar of CO. The reaction mixture was stirred at 1000 rpm at a temperature of 80°C for 0.5 hours. After this time the reactor was cooled, anisole (0.4309 g) (GC internal standard) was added and the product mixture was analysed by GC. The TOF was 2500 h 1 and the selectivity to methyl propanoate was 99%.
  • a catalyst solution was prepared by dissolving palladium(II) acetate (80 umol), l,2-bis[(2,2,6,6- tetramethylphosphinan-4-onyl)methyl]benzene (BPX, 160 ⁇ ) in 24.0 ml of degassed methanol followed by the addition of 0.1 ml of MSA co-catalyst. A portion of this solution (6.0 ml: 20 ⁇ Pd) and 1-hexene (3.0 mL) were then injected into a stainless steel 12 ml autoclave under a stream of argon gas. The reactor was purged with CO gas and pressurised to 50 bar CO.
  • a catalyst solution was prepared by dissolving palladium(II) acetate (80 umol), l,2-bis[(2,2,6,6- tetramethylphosphinan-4-onyl)methyl]benzene (BPX, 160 ⁇ ) in 22.0 ml of degassed diglyme followed by the addition of 0.1 ml of MSA co-catalyst. A portion of this solution (5.5 ml: 20 ⁇ Pd), degassed water (0.5 mL, 27.7 mmol) and 3-pentenenitrile (3.0 mL) were then injected into a stainless steel 12 ml autoclave under a stream of argon gas. The reactor was purged with CO gas and pressurised to 50 bar CO.
  • a stainless steel 300 ml Parr reactor was charged with degassed distillate from Example 4 (65 mL) and the amount of degassed water specified in Table 6 under a stream of argon gas.
  • a preformed catalyst solution consisting of palladium(II) acetate (55 umol), bidentate phosphine specified in Table 6 and methanesulfonic acid (1.5 mmol) in degassed pentenoic acids distillate (15 mL) was then injected into the reactor.
  • the Parr reactor was then purged with CO gas and pressurised to 40 bar CO. The reaction mixture was stirred at 1000 rpm and heated to 105°C.
  • Example 14 Hydroxycarbonylation of Pentenoic Acids to Adipic Acid with Functionalized DTBPX Without Methane Sulfonic Acid Co-Catalyst (Sample No. 46 to 48)
  • a stainless steel 300 ml Parr reactor was charged with degassed distillate from Example 4 (65 mL) and degassed water (10 ml) under a stream of argon gas.
  • a preformed catalyst solution consisting of palladium(II) acetate (55 umol) and bidentate phosphine specified in Table 6 in degassed pentenoic acids distillate (15 mL) was then injected into the reactor.
  • the Parr reactor was then purged with CO gas and pressurised to 40 bar CO.
  • the reaction mixture was stirred at 1000 rpm and heated to 115°C. After 17 hours the reaction was terminated by the cessation of the stirring, followed by cooling the reactor to room temperature and then venting the excess CO gas.
  • the functionalized DTBPX having electron withdrawing groups perform better with higher selectivity relative to unfunctionalized DTBPX both in the presence of methane sulfonic acid (samples 41 to 43) and absence of methane sulfonic acid (samples 47 to 48).
  • the metal complex and composition thereof disclosed in the present application have useful applications in preparing a dicarboxylic acid or ester thereof from an alkenoic acid or ester thereof, or in preparing a carboxylic acid or ester thereof from an alkene or diene with high selectivity and activity.
  • the catalyst and composition thereof may also be useful in preparing Nylon 6-6 from adipic acid prepared using the metal complex and composition thereof disclosed in the present application.
  • the catalyst and composition thereof may also be useful in preparing long chain aliphatic polyesters or poly amides from long chain aliphatic alpha -omega-dicarboxylic acids or esters prepared using the metal complex and composition thereof disclosed in the present application.
  • the catalyst and composition thereof may also be useful in preparing odd chain fatty acids or esters from even internal or terminal alkenes.

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Abstract

La présente invention concerne un complexe métallique de Formule (I) et une composition de catalyseur pour la carbonylation d'alcènes comprenant le complexe métallique, le métal étant un élément du groupe 10 tel que le palladium, le platine ou le nickel, et le complexe comprenant un ligand de phosphine bidentate. La présente invention concerne également un procédé pour la préparation d'un acide dicarboxylique ou d'un ester de ce dernier à partir d'un acide alcénoïque ou d'un ester de ce dernier, ou un procédé pour la préparation d'un acide carboxylique ou d'un ester de ce dernier à partir d'un alcène ou acide alcénoïque ayant une grande sélectivité et activité en utilisant ledit complexe métallique ou ladite composition de catalyseur. La présente invention concerne également un procédé de préparation de Nylon 6-6 comprenant l'étape de copolymérisation d'acide adipique avec l'hexaméthylènediamine.
PCT/SG2017/050050 2016-02-02 2017-02-02 Catalyseur pour la carbonylation d'alcènes WO2017135897A1 (fr)

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WO2019153203A1 (fr) * 2018-02-08 2019-08-15 凯特立斯（深圳）科技有限公司 Synthèse et application d'un ligand oxaspirocyclodiphosphine
CN110128471A (zh) * 2018-02-08 2019-08-16 凯特立斯（深圳）科技有限公司 氧杂螺环双膦配体的合成与应用
CN114308129A (zh) * 2021-11-24 2022-04-12 中国科学院兰州化学物理研究所 用于烯烃烷氧羰基化的催化剂组合物及其制备方法与应用
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WO2019153203A1 (fr) * 2018-02-08 2019-08-15 凯特立斯（深圳）科技有限公司 Synthèse et application d'un ligand oxaspirocyclodiphosphine
CN110128471A (zh) * 2018-02-08 2019-08-16 凯特立斯（深圳）科技有限公司 氧杂螺环双膦配体的合成与应用
CN110128471B (zh) * 2018-02-08 2021-01-15 凯特立斯（深圳）科技有限公司 氧杂螺环双膦配体的合成与应用
CN109503659A (zh) * 2019-01-03 2019-03-22 凯特立斯（深圳）科技有限公司 氧杂螺环双膦配体及其在α,β-不饱和羧酸不对称氢化中的应用
CN109503659B (zh) * 2019-01-03 2021-06-18 凯特立斯（深圳）科技有限公司 氧杂螺环双膦配体及其在α,β-不饱和羧酸不对称氢化中的应用
WO2022132048A1 (fr) * 2020-12-15 2022-06-23 Agency For Science, Technology And Research Composés phosphorés et leurs procédés
CN114308129A (zh) * 2021-11-24 2022-04-12 中国科学院兰州化学物理研究所 用于烯烃烷氧羰基化的催化剂组合物及其制备方法与应用

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