WO1997002232A1 - PROCEDE D'HYDROGENATION D'IMINES EN PRESENCE DE CATALYSEURS IMMOBILISES Ir-DIPHOSPHINE - Google Patents

PROCEDE D'HYDROGENATION D'IMINES EN PRESENCE DE CATALYSEURS IMMOBILISES Ir-DIPHOSPHINE Download PDF

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WO1997002232A1
WO1997002232A1 PCT/EP1996/002729 EP9602729W WO9702232A1 WO 1997002232 A1 WO1997002232 A1 WO 1997002232A1 EP 9602729 W EP9602729 W EP 9602729W WO 9702232 A1 WO9702232 A1 WO 9702232A1
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process according
alkyl
group
phenyl
acid
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Benoît PUGIN
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Novartis Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/36—Nitrogen atoms
    • 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
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • 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
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • 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
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
    • 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
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • 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
    • B01J2531/827—Iridium
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for the hydrogenation of imines with hydrogen at increased pressure in the presence of iridium-diphosphine catalysts immobilized on a support material and of a halide.
  • the reaction mixture must necessarily comprise an inorganic or organic acid.
  • heterogeneous catalysts have also been proposed for enantioselective hydrogenation of multiple bonds.
  • EP-A-0496699 and EP-A-0496700 propose dioxolane- and pyrrolidine- phosphines containing silane groups and iridium complexes thereof, which are fixed to an inorganic support material, for example silicates.
  • an inorganic support material for example silicates.
  • the catalyst activity can be increased considerably if the reaction mixture additionally comprises an acid, in addition to a halide.
  • the catalysts can easily be separated off and reused without substantial loss in activity, which renders their use in large-scale industrial processes particularly advantageous and economical.
  • the invention relates to a process for the hydrogenation of imines with hydrogen under increased pressure in the presence of iridium catalysts and with or without an inert solvent, wherein the reaction mixture comprises iridium catalysts immobilized on a support material, an ammonium chloride, bromide or iodide or a metal chloride, bromide or iodide which is soluble in the reaction mixture, and in addition an acid.
  • the imines can contain further chiral C atoms.
  • the free bonds in the above formulae can be saturated with H or organic radicals having 1 to 22 C atoms or organic heteroradicals having 1 to 20 C atoms and at least one heteroatom from the group consisting of O, S, N and P.
  • the organic radicals can be substituted, for example, by F, Cl, Br, C ⁇ -C 4 haloalkyl, where halo is preferably F or CI.-CN, -NO 2) -CO 2 H, -CONH 2 , -SO3H, -PO 3 H 2) or C ⁇ -C ⁇ 2 alkyl esters or amides, or phenyl esters or benzyl esters of the groups -CO 2 H, -SO 3 H or -PO 3 H 2 .
  • Aldimine and ketimine groups are particularly reactive, so that selective hydrogenation of groups
  • Aldimine and ketimine groups are also understood as meaning hydrazone groups
  • the process according to the invention is particularly suitable for hydrogenation of aldimines, ketimines and hydrazones to form corresponding amines or hydrazines.
  • the ketimines are preferably N-substituted.
  • chiral iridium catalysts are used and enantiomerically pure, chiral or prochiral ketimines are hydrogenated.
  • the optical yields are, for example, more than 30 %, preferably more than 50 %, and yields of about 80 % or more can be achieved.
  • the imines are preferably those of the formula I
  • R 3 is preferably a substituent, and in which R 3 is linear or branched cycloalkyl having 3 to 8 ring C atoms; heterocycloalkyl which is bonded via a C atom and has 3 to 8 ring atoms and 1 or 2 heteroatoms from the group consisting of O, S and NR 6 ; CrCiearalkyl bonded via an alkyl-C or d-C ⁇ 2 alkyl substituted by the cycloalkyl or heterocycloalkyl or heteroaryl mentioned; or in which R 3 is C 6 -Ci 2 aryl or C -Cn heteroaryl which is bonded via a ring C atom and has 1 or 2 heteroatoms in the ring; where R3 is unsubstituted or substituted by -CN, -NO 2 , F, Cl, C ⁇ -C ⁇ 2 alkyl, C ⁇ -C ⁇ 2 alkoxy, C ⁇ -C 6 haloalkyl, -OH, C 6 -
  • FU and R 5 independently of one another are H, d-C ⁇ alkyl, phenyl or benzyl, or l ⁇ and R 5 together are tetra- or pentamethylene or 3-oxapentylene;
  • R 6 independently is defined as R ;
  • Ri and R 2 independently of one another are a hydrogen atom, d-C ⁇ alkyl or cycloalkyl having 3-8 ring C atoms which are unsubstituted or substituted by -OH, d-C ⁇ alkoxy, phenoxy, benzyloxy, secondary amino having 2 to 24 C atoms, -CONR R 5 or -COOF ; C 6 -C ⁇ 2 aryl or CrCiearalkyl which are unsubstituted or substituted as R 3 , or -CONFUR 5 or -COOR 4 , in which R 4 and R 5 are as defined above; or R 3 is as defined above and
  • the radicals Ri, R 2 and R 3 can contain one or more chirality centres.
  • Ri, R 2 and R 3 can be substituted in any positions by identical or different radicals, for example by 1 to 5, preferably 1 to 3, substituents.
  • Suitable substituents for R as well as R 2 and R 3 are: C1-C 12 -, preferably Ci-Ce- and in particular C ⁇ -C 4 alkyl, -alkoxy or -alkylthio, for example methyl, ethyl, propyl, n-, i- and t-butyl, the isomers of pentyl, hexyl, octyl, nonyl, decyl, undecyl and dodecyl, and corresponding alkoxy- and alkylthio radicals;
  • R 4 and R 5 are as defined; examples are methyl, ethyl, n- and i-propyl, butyl, corresponding alkoxy- and alkylthio radicals, F, Cl, Br, dimethyl-, methylethyl-, or diethylcarbamoyl and methoxy-, ethoxy-, phenoxy- and benzyloxycarbonyl;
  • halogen preferably F and Cl
  • Secondary amino having 2 to 24, preferably 2 to 12, and in particular 2 to 6, C atoms, where the secondary amino preferably contains 2 alkyl groups, for example dimethyl-, methylethyl-, diethyl-, methylpropyl, -methyl-n-butyl-, di-n-propyl-, di-n-butyl- and di-n- hexylamino;
  • FU and R 5 independently of one another are C ⁇ -C ⁇ 2 -, preferably C ⁇ -C 6 -, and in particular
  • C ⁇ -C 4 alkyl, or R 4 and R 5 together are tetra- or pentamethylene or 3-oxapentylene, where the alkyl can be linear or branched, for example dimethyl-, methylethyl-, diethyl-, methyl-n- propyl-, ethyl-n-propyl-, di-n-propyl-, methyl-n-butyl-, ethyl-n-butyl-, n-propyl-n-butyl- and di- n-butylcarbamoyl;
  • l ⁇ is C ⁇ -C 12 -, preferably C ⁇ -C 6 alkyl, which can be linear or branched, for example methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
  • Ri, R 2 and R 3 can contain, in particular, functional groups, for example keto groups, -CN, -N0 2 , carbon double bonds, N-O-, aromatic halogen groups and amide groups.
  • Heteroaryl Ri and R2 is preferably a 5- or 6-membered ring having 1 or 2 identical or different heteroatoms, in particular O, S or N, which preferably contains 4 or 5 C atoms and can be fused with benzene.
  • heteroaromatics from which Ri can be derived are furan, pyrrole, thiophene, pyridine, pyrimidine, indole and quinoline.
  • Alkyl R and R2 substituted by heteroaryl is preferably derived from a 5- or 6-membered ring having 1 or 2 identical or different heteroatoms, in particular O, S or N, which preferably contains 4 or 5 C atoms and can be fused with benzene.
  • heteroaromatics are furan, pyrrole, thiophene, pyridine, pyrimidine, indole and quinoline.
  • Heterocycloalkyl Ri and R 2 or alkyl R and R 2 substituted by heterocycloalkyl preferably contains 4 to 6 ring atoms and 1 or 2 identical or different heteroatoms from the group consisting of O, S and NR 6 . It can be fused with benzene. It can be derived, for example, from pyrrolidine, tetrahydrofuran, tetrahydrothiophene, indane, pyrazolidine, oxazolidine, piperidine, piperazine or morpholine.
  • Alkyl RL R 2 and R 3 are preferably unsubstituted or substituted C ⁇ -C 6 -, in particular CrC alkyl, which can be linear or branched.
  • Examples are methyl, ethyl, i- and n-propyl, i-, n- and t-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
  • Unsubstituted or substituted cycloalkyl R , R 2 and R 3 preferably contain 3 to 6, in particular 5 or 6, ring C atoms. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Aryl Ri, R 2 and R 3 are preferably unsubstituted or substituted naphthyl and, in particular, phenyl.
  • Aralkyl R 1f R 2 , and R 3 are preferably unsubstituted or substituted phenylalkyi having 1-10, preferably 1 to 6, and in particular 1 to 4, C atoms in the alkylene, where the alkylene can be linear or branched.
  • Examples are, in particular, benzyl, as well as 1-phenyleth-1-yl, 2-phenyleth-1 -yl, 1-phenylprop-1-yl, 1-phenylprop-2-yl, 1-phenylprop-3-yl, 2-phenylprop-1 -yl, 2-phenylprop-2-yl and 1 -phenylbut-4-yl.
  • FU and R 5 are preferably Ci-Ce-, in particular C ⁇ -C 4 alkyl, or R 4 and R 5 together are tetramethylene, pentamethylene or 3-oxapentylene. Examples of alkyl have been mentioned above.
  • alkylene examples include: ethylene, 1 ,2- or 1 ,3-propylene, 1 ,2-, 1 ,3- or 1 ,4-butylene, 1 ,5-pentylene and 1 ,6-hexylene.
  • fused alkylene are:
  • FU and R 5 independently of one another are preferably H, C ⁇ -C alkyl, phenyl or benzyl.
  • R 6 is preferably H or C ⁇ -C alkyl.
  • Another preferred group is that of prochiral imines in which, in formula I, Ri, R 2 and R 3 differ from one another and are not hydrogen.
  • R 3 is 2,6-di-C ⁇ -C 4 alkylphen-1-yl and in particular 2,6-dimethylphen-1-yl or 2-methyl-6- ethylphen-1-yl,
  • Ri is C ⁇ -C 4 alkyl, and in particular ethyl or methyl, and
  • R 2 is C ⁇ -C alkyl, C ⁇ -C 4 alkoxymethyl or CrC 4 alkoxyethyl, and in particular methoxymethyl.
  • I mines of the formula I are known or they can be prepared by known processes from aldehydes or ketones and primary amines.
  • the iridium catalysts are preferably homogeneous or inhomogeneous catalysts which are soluble, swellable or essentially insoluble in the reaction medium.
  • the term catalyst also includes catalyst precursors which are converted into an active catalyst species at the start of a hydrogenation.
  • the catalysts preferably have the formulae III, Ilia, lllb, Ilio and llld,
  • X is two olefin ligands or one diene ligand
  • Y is a ditertiary diphosphine, (a) the phosphine groups of which are bonded to different
  • An " is the anion of an oxygen acid or complex acid, and + is an alkali metal cation or quaternary ammonium, and
  • R a and R b independently of one another are H, C ⁇ -C 8 alkyl, CrC 4 fluoroalkyl, phenyl or benzyl or phenyl or benzyl which is substituted by 1 to 3 d-C 4 alkyl or C ⁇ -C 4 alkoxy.
  • R b is preferably
  • R a is preferably d-C 4 alkyl and particularly preferably methyl.
  • the diphosphine Y preferably contains at least one chiral C atom, and the diphosphine is particularly preferably an optically pure stereoisomer (enantiomer or diastereomer), or a diastereomer pair, since optical inductions are achieved in asymmetric hydrogenations with catalysts which contain these ligands.
  • Olefin ligands X can be branched or preferably linear C 2 -C ⁇ 2 alkylene, in particular C 2 -C 6 alkylene. Some examples are dodecylene, decylene, octylene, 1-, 2- or 3-hexene, 1-, 2- or 3-pentene, 1 - or 2-butene, propene and ethene. Diene ligands X can be open-chain or cyclic dienes having 4 to 12, preferably 5 to 8 C atoms, the diene groups preferably being separated by one or two saturated C atoms.
  • Some examples are butadiene, pentadiene, hexadiene, heptadiene, octadiene, decadiene, dodecadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene and bridged cyclodienes, such as norbornadiene and bicyclo-[2.2.2]octadiene. Hexadiene, cyclooctadiene and norbornadiene are preferred.
  • the diphosphine Y is bonded via a silyl group to an inorganic support material T which is chosen from the group consisting of silicates, semimetal or metal oxides, glasses or mixtures thereof.
  • the solid support material T is preferably a powder having average particle diameters of 10 nm to 2000 ⁇ m, preferably 10 nm to 1000 ⁇ m, and particularly preferably 10 nm to 500 ⁇ m.
  • the support can be either compact or porous particles.
  • Porous particles preferably have high internal surface areas (determined by the BET method), for example 1 to 1200 m 2 , preferably 30 to 600 m 2 .
  • oxides and silicates are SiO 2 , TiO 2 , Zr0 2 , MgO, NiO, WO 3 , AI 2 O 3 , La 2 0 3 , silica gels, clays and zeolites.
  • Preferred support materials are silica gels, aluminium oxide, titanium oxide or glass and mixtures thereof.
  • An example of glasses as the support material is "controlled pore glass", which is commercially obtainable.
  • a preferred group of diphosphines fixed to an inorganic support material is formed by the ferrocenyldiphosphines of the formula IVa
  • R 7 is C ⁇ -C 8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C ⁇ -C alkyl or C ⁇ -C 4 alkoxy;
  • R 8 and R 9 independently of one another are d-C ⁇ alkyl, C 5 -C ⁇ 2 cycloalkyl, phenyl,
  • C 5 -Ci2cycloalkyl which is substituted by C ⁇ -C 4 alkyl or d-C 4 alkoxy, or phenyl which is mono- or polysubstituted by one to three d-dalkyl, d-C 4 alkoxy, -SiR ⁇ 0 RnR ⁇ 2 , halogen, -SO 3 Me,
  • Rn and R ⁇ 2 independently of one another are d-C ⁇ 2 alkyl or phenyl;
  • R ⁇ 3 and R M are H, C ⁇ -C ⁇ 2 alkyl or phenyl or
  • R ⁇ 3 and R 4 together are tetramethylene, pentamethylene or 3-oxa-1 ,5-pentylene;
  • R ⁇ s is H or d-dalkyl
  • R ⁇ e and R 17 are identical or different and are d-C ⁇ 2 alkyl, C 5 -C ⁇ 2 cycloalkyl, phenyl,
  • R ⁇ 8 are identical or different radicals and independently of one another are C ⁇ -C ⁇ 2 alkyl, Cs-dcycloalkyl, benzyl or phenyl, or together are C 5 -d 2 alkylene and R 19 is C -C ⁇ 2 alkylene or phenylene, Me is H or an alkali metal,
  • X " is the anion of a monobasic acid
  • A is NH or N(d-d 2 alkyl)
  • Ra is d-dalkyl or O-C ⁇ -C ⁇ 2 alkyl
  • R 2 ⁇ is C ⁇ -C ⁇ 2 alkyl
  • T is the inorganic support material defined above and if n is 0, r is 1 , 2 or 3, if n is 1 , r is 1 or 2 and if n is 2, r is 1.
  • diphosphines fixed to an inorganic support material is formed by compounds having the structure of the formula IVb or IVc
  • radicals R 22 are identical or different radicals, m and n independently of one another are 0 or 1 , the radicals R 22 independently of one another are C ⁇ -C ⁇ 2 alkyl, C 5 -C ⁇ 2 cycloalkyl, phenyl,
  • -R 23 -U- is a bond or -(C x H 2)( -O) y -, or U is -O- and
  • R 23 is C ⁇ -C 6 alkylene, x is an integer from 2 to 6 and y is a number from 2 to 6,
  • R 2 is C 2 -C ⁇ 8 alkylene, phenylene or benzylene,
  • R 25 is hydrogen, linear or branched C ⁇ -C ⁇ 2 alkyl, phenyl or benzyl, r is 0,1 or 2 and
  • R 2 ⁇ and T are as defined in claim 21.
  • the compounds of the formula IVa, IVb and IVc are idealized as regards the bonding site to the solid support material and represent the most probable number of bonds to the solid support material which occur. Specifically, the following cases may as a rule occur in distribution:
  • R 2i and T are as defined above, including the preferences, and R 2 ⁇ is preferably d-C 4 alkyl.
  • the compounds of the formula IVb and IVc are known and their preparation is described in EP-A-0 496 699, EP-A-0 496 700 and in Heterogeneous Catalysis and Fine Chemicals III, Stud. Surf. Sci. and Cat., 78 (1993) 107-1 14.
  • the diphosphines of the formula IVa can be reacted by a reaction procedure analogous to that described in EP-A-0 496 699, by reacting compounds of the formula Villa
  • the reaction advantageously being carried out under an inert gas, for example argon, and at a temperature of 40 to 180°C.
  • the solid material is initially introduced into a reaction vessel, a solution of the compound of the formula Villa is added and the mixture is stirred at elevated temperature, for example 50 to 110°C.
  • Suitable solvents have been mentioned above, and particularly preferred solvents are toluene and xylene.
  • the product can be either decanted off or centrifuged off or filtered. The residue can be purified by washing with alkanol and then dried under a high vacuum.
  • the compounds of the formula Villa can be prepared by a procedure in which, in a first step,
  • Vllld CISi(R ⁇ 8 ) 2 -(Ri9)-CI (Vllld) to give compounds of the formula Vllle (Vllle);
  • Vlllk 16 or compounds of the formula Vlllg are first reacted with K phthalimide and then with hydrazine to give compounds of the formula Vlllm
  • An example of an amine complexing agent for Li is N,N,N,N-tetramethylethylenediamine.
  • Vlllb, Vlllc, Vllld, Vlllf, Vlllh and Vllln are known and in some cases are commercially obtainable. They can otherwise be prepared by the processes described in the literature.
  • reaction steps b), c) and d) are processes analogous to those described, for example, in EP-A-612 758 for b) and in EP-A-496699 for d).
  • Step c) is known to the expert from the usual textbooks of organic chemistry.
  • the mixture of compounds of the formula Vlllc and Vllld is preferably present in reaction step a) in a molar ratio of 1 :10 to 10:1, particularly preferably 1 :1 to 10:1.
  • Reaction step a) is preferably carried out at a temperature of -40°C to +70°C, and the mixture of the compounds of the formula Vlllc and Vllld is particularly preferably added at a temperature of 0°C to -40°C, especially preferably at a temperature of 0°C to -15°C.
  • the compound of the formula Vllld in reaction step a) is particularly preferably 1-(dimethylchlorosilyl)-3-chloropropane.
  • Reaction step b) is described, for example, in EP-A-612 758.
  • the reaction temperature in step b) can be, for example, 20 to 150°C, preferably 40 to 100°C.
  • Suitable solvents are polar protic and aprotic solvents, which can be used by themselves or as a mixture of two or more solvents. Some examples of solvents are alkanols, such as methanol and ethanol, and carboxylic acids, such as formic acid and acetic acid.
  • the compounds of the formula Villa, Vlllg, Vlllk and Vlllm are obtained as racemates, pure enantiomers or mixtures of enantiomers. Racemates and mixtures of enantiomers can be separated into the stereoisomers by means of known methods, chromatographic methods in general being preferred.
  • the compounds are isolated and purified by methods known per se, for example distillation, extraction, crystallization and/or chromatographic methods.
  • hydrazine is employed as hydrazine hydrate in reaction step c).
  • Organic polymeric support materials can also be used without problems in the present process.
  • the nature of the fixing of the diphosphine component to the polymer can be achieved in various ways here. An overview of polymer-bonded diphosphines and metal complexes thereof is given, for example, by J.K. Stille in Reactive Polymers, 10 (1989) 165- 174 and by Selke et al. in J. Mol. Catal., 56 (1989) 315-328.
  • polymeric support materials in which the diphosphine component is on a copolymerizable unit, which is then copolymerized together with other monomers so that the diphosphine or its metal complex is bonded directly in the polymer chain, have been disclosed.
  • K. Achiwa describes, in J. Chem. Japan. Soc, Chemistry Letters, pages 905 to 908 (1978) polystyrene copolymers, benzene radicals of which contain pyrrolidine-diphosphine-N- carbonyl groups complexed with rhodium.
  • Another possibility comprises preparing a functionalized polymer in a first step, either by copolymerization or by subsequent functionalization of a previously formed polymer, and building up a diphosphine ligand on the functionalized site in a second step. Examples of this procedure are described, inter alia, by Stille et al. in J. Amer. Chem. Soc. 100 (1978) 268-272 and by Kagan et al. in J. Amer. Chem. Soc. 95 (1973) 8295-8299 .
  • Another possibility is to start from polymers having known properties and to modify these with catalytically active compounds such that the polymer properties are changed only slightly and no inclusions or other changes may occur to the catalytically active part of the compounds.
  • the catalyst can be optimally adapted to the reaction medium during the hydrogenation step by the choice of polymer, and then separated off completely, which is of importance in particular for hydrogenations carried out on a large industrial scale. Purification of the hydrogenated end product is also facilitated considerably in this way.
  • the diphosphine Y is preferably bonded to a partly crosslinked swellable or a highly crosslinked polymeric or a linear support material which is soluble in organic solvents.
  • diphosphines bonded to organic polymers is obtained if the diphosphine Y is bonded to the support material in the manner of a copolymer.
  • Another group of polymer-bonded diphosphine ligands which is also preferred is obtained by bonding the diphosphine with a functional group to a functional group of the polymer either directly or by a bridge group.
  • the functional groups in the diphosphine and in the polymer are preferably chosen independently of one another from the group consisting of -OH, -NH 2 , -NH(C ⁇ -C ⁇ 2 alkyl), -NCO, -COOH, -COO(d-C ⁇ 2 alkyl), -COhalogen and a glycidyl group.
  • the bridge group preferably contains 2 to 30 carbon atoms, which are linked directly to one another or interrupted by heteroatoms, and a functional group which can react with the functional groups of the polymer and of the diphosphine is present on both ends.
  • Th e functional groups on both ends of the bridge group are particularly preferably identical and are chosen from the group consisting of -OH, -NH 2 , -NH(C ⁇ -C ⁇ 2 alkyl), -NCO, -COOH, -COO(C ⁇ -C ⁇ 2 alkyl), -COhalogen and a glycidyl group.
  • An especially preferred group of polymer-bonded diphosphines is obtained by starting from polymeric base structures containing hydroxyl or primary or secondary amine functional groups, some or all of the functional groups of which are bonded to a diisocyanate which provides distance from the polymer chain, to form a urethane or urea bridge, the second isocyanate group thereof being bonded to a diphosphine Y which likewise contains a hydroxyl or primary or secondary amine group.
  • the diphosphine Y is preferably an aliphatic, cycloaliphatic, heterocycloaliphatic, aromatic or heteroaromatic 1 ,2-, 1 ,3-, 1 ,4- or 1 ,5-tertiary diphosphine Y.
  • the mobility and accessibility of the ligand can be adjusted by the choice of the nature and length of the diisoocyanate. Diphosphines bonded in this way lead to valuable catalysts for hydrogenations, in particular for enantioselective hydrogenations.
  • tertiary phosphine group designates a phosphorus atom bonded to 3 carbon atoms, as is defined, for example, in H. Beyer, Lehrbuch der organischen Chemie [Text book of organic chemistry], S. Hirzel Verlag für, 1968 edition, on page 138.
  • the polymers can be polymers of olefinically unsaturated monomers, for example polyolefins, polyacrylates, polyisoprenes, polybutadiene, polystyrene, polyphenylene, polyvinyl chloride, polyvinylidene chloride or polyallyl compounds. They can be polyaddition compounds, for example polyurethanes or polyethers. Polycondensed products are polyesters or polyamides.
  • the polymers are essentially non-crosslinked ( thermoplastics ), they can be polymers which are soluble in organic solvents. Partly crosslinked polymers are usually only swellable in organic solvents, and highly crosslinked polymers can be insoluble and advantageously porous materials.
  • Crosslinked polymers thermosetting resins
  • thermosetting resins can be phenol-aldehyde resins, for example in the form of commercially obtainable Bakelites®, urea- or melamine-formaldehyde resins, crosslinked polyurethanes or crosslinked epoxy resins.
  • Di- or triamines are particularly suitable crosslinking components for epoxy resins.
  • Crosslinked polymers based on triglycidyl isocyanurate are also possible.
  • unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and also vinyl compounds as crosslinking agents.
  • Crosslinkable acrylic resins which are derived from substituted acrylic acid esters, for example from epoxy acrylates, urethane-acrylates or polyester-acrylates, are also possible.
  • Another group is formed by alkyd resins, polyester resins and acrylate resins, which are crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.
  • Preferred crosslinked systems are those of olefinically unsaturated monomers. Examples are polyacrylates, polyolefins or polystyrene.
  • the crosslinking component is also olefinically unsaturated.
  • An example is polystyrene crosslinked with divinylbenzene.
  • the polymers to be used according to the invention are known per se, in some cases are commercially obtainable, or they can be prepared by known polymerization processes or by subsequent modification of polymers.
  • linear polymers which are soluble in organic solvents are given below.
  • the monomers which form the polymer are preferably chosen from the group consisting of styrene, p-methylstyrene, and ⁇ -methylstyrene, at least one of which contains a hydroxyl group or a primary or secondary amine group bonded as a functional group.
  • comonomers which form copolymers with styrene derivatives may be present, for example styrene, p-methylstyrene or ⁇ -methylstyrene, butadiene, maleic anhydride, acrylates or methacrylates and ethylene, propylene or butylene.
  • the polymers are also graft copolymers of styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene/styrene or polybutadiene acrylonitrile copolymers, or styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene te ⁇ o
  • the comonomers of dienes or acrylic derivatives for example butadiene, acrylonitrile, alkyl methacrylate, butadiene/alkyl acrylate and methacrylate, maleic anhydride and acrylonitrile/methyl acrylate, which form random or block copolymers are preferred.
  • Another preferred group of polymers is formed by monomers which are derived from ⁇ , ⁇ -unsaturated acids or esters or amides thereof, structural elements of which contain a hydroxyl group or a primary or secondary amine group bonded as a functional group.
  • the monomers from the group consisting of acrylates and d-C 4 alkyl esters thereof, methacrylates and C ⁇ -C alkyl esters thereof, acrylamide and acrylonitrile, structural elements of which contain a hydroxyl group or a primary or secondary amine group bonded as a functional group in the ester or amide group are particularly preferred.
  • copolymers which are derived from olefinically unsaturated monomers and which form random polymers or block copolymers
  • Suitable comonomers are acrylates and C ⁇ -C 4 alkyl esters thereof, methacrylates and d-C 4 alkyl esters thereof, acrylamide and acrylonitrile, as well as butadiene, vinyl chloride or vinyl fluoride.
  • Another group of preferred polymers is formed by monomers which contain vinyl alcohol as a homopolymer or vinyl alcohol as a copolymer with vinyl acetate, stearate, benzoate, or maleate, vinylbutyral, allyl phthalate or allylmelamine.
  • Preferred polymers are also formed from phenol and a C ⁇ -C aldehyde, particularly preferably from phenol and formaldehyde.
  • the polymers are known as phenol- formaldehyde resins, in particular as novolaks, and are commercially obtainable.
  • Another preferred group of polymers is derived from bisglycidyl ethers and diols. These are hydroxyl-functional polyethers which are prepared, for example, from bisglycidyl ethers and bisphenol A.
  • the polyepoxides can be built up from diepoxide comonomers having preferably 6 to 40, and particularly preferably 8 to 30, C atoms, and diols, as comonomers, having preferably 2 to 200, and particularly preferably 2 to 50, C atoms.
  • a preferred group derived therefrom is formed from monomers which build up a polymer from cyclic C 3 -C 6 ethers or C 2 -C 6 alkylene glycols with bisglycidyl ethers.
  • the bisglycidyl ethers can be aromatic, aliphatic or cycloaliphatic.
  • Partial cellulose acetates, propionates or butyrates, partial cellulose ethers, starch, chitin and chitosan are particulariy preferred.
  • polymers are derived from polymers with reducible groups, for example nitrile groups, ketone groups, carboxylic acid esters and carboxylic acid amides.
  • Polymers which are insoluble in the reaction medium and are functionalized with hydroxyl or amine groups on the surface by a chemical or physical process can also be used.
  • partially unsaturated polymers can be provided with hydroxyl groups on the surface by oxidation, for example with hydrogen peroxide.
  • plasma treatment in, for example, an oxygen atmosphere or nitrogen or ammonia atmosphere.
  • the polymers are preferably in the form of a powder.
  • support materials polystyrene which is subsequently functionalized with hydroxyl, amino or hydroxymethyl groups by known methods is particularly preferred.
  • Another particularly preferred group of compounds are those having structural repeating units of the formula VI
  • R 7 , Rs , R9, R16, R17 , R18 and R19 are as defined above;
  • Q is a bridge group formed from a diisocyanate
  • PM is the radical of a polymer-forming monomer which contains, directly or in a side chain, a hydroxyl group or a primary or secondary amine group bonded as a functional group, which is bonded to the diphosphine via a bridge group Q formed by a diisocyanate.
  • diphosphine with a hydroxyl or primary or secondary amine functional group is a compound of the formula Vila or Vllb
  • B is -NR 27 - or -0-;
  • R 27 is hydrogen or linear or branched C ⁇ -C 6 alkyl
  • R 22 , R 2 3, R 2 5, m and n are as defined above.
  • the diisocyanate which forms the bridge group Q is preferably chosen from the group consisting of 1 ,6-bis[isocyanato]hexane, 5-isocyanato-3-(isocyanatomethyl)-1 ,1 ,3- trimethylcyclohexane, 1 ,3-bis[5-isocyanato-1 ,3,3-trimethylphenyl]-2,4-dioxo-1 ,3-diazetidine, 3,6-Bis[9-isocyanatononyl]-4,5-di-(1 -heptenyl)cyclohexene, bis[4-isocyanatocyclohexyl] methane, trans-1 ,4-bis[isocyanato]cyclohexane, 1 ,3-bis[isocyanatomethyl]benzene, 1 ,3-bis[1-isocyanato-1-methylethyl]benzene, 1 ,4-bis[2-is
  • the monomer containing a hydroxyl or primary or secondary amine functional group preferably participates in the build-up of the polymer in an amount of 5 to 100 mol per cent, particularly preferably 10 to 100 mol per cent.
  • the polymer is preferably charged with between 5 and 100 mol-% of tertiary diphosphine groups, based on the hydroxyl or primary or secondary amine group available.
  • the monomers which form the polymer are preferably chosen from the group consisting of styrene, p-methylstyrene and ⁇ -methylstyrene, at least one of which contains a hydroxyl group or a primary or secondary amine group bonded as a functional group.
  • comonomers of dienes or acrylic derivatives for example butadiene, acrylonitrile, alkyl methacrylate, butadiene/alkyl acrylate and methacrylate, maleic anhydride and acrylonitrile/methyl acrylate, which form random or block copolymers, are preferably also present.
  • the monomers which form the polymer are particularly preferably chosen from the group consisting of ⁇ , ⁇ -unsaturated acids and esters or amides thereof, at least one of which contains a hydroxyl group or a primary or secondary amine group bonded as a functional group.
  • the monomers which form the polymer are especially preferably chosen from the group consisting of acrylates and d-dalkyl esters thereof, methacrylates and d-dalkyl esters thereof, acrylamide and acrylonitrile, at least one of which contains a hydroxyl group or a primary or secondary amine group bonded as a functional group.
  • polystyrene resin e.g., polystyrene resin
  • polystyrene resin e.g., polystyrene resin
  • vinyl alcohol as a homopolymer or vinyl alcohol as a copolymer with vinyl acetate, stearate, benzoate or maleate, vinylbutyral, allyl phthalate or allylmelamine.
  • polystyrene resin polystyrene resin
  • polyepoxides are formed from cyclic C 3 -C 6 ethers or C 2 -C 6 alkylene glycols and bisglycidyl ethers.
  • Polysaccharides are also particularly suitable.
  • polystyrene or polyacrylate is particularly preferred.
  • the particle size of the crosslinked polymers is preferably 10 ⁇ m to 2000 ⁇ m.
  • the specific surface area of the porous highly crosslinked polymers is preferably 5 to 1000 m 2 .
  • the polymer-bonded diphosphines can be copolymerized, for example, by the processes described in the prior art mentioned above.
  • diphosphines are bonded via a bridge group Q to a polymer which is soluble, swellable or insoluble in organic solvents, they can be prepared by a procedure in which the polymers having structural repeating units of at least one monomer MM, which contains, directly or in a side chain, a hydroxyl group or a primary or secondary amine group bonded as a functional group,
  • A) in a first step are reacted completely or partly with a diisocyanate which forms a bridge group Q in an inert organic solvent, and in a second step the product is reacted completely or partly with an aliphatic, cycloaliphatic, heterocycloaliphatic, aromatic or heteroaromatic ditertiary diphosphine, the phosphine groups of which are bonded to a carbon chain in the 1 ,2,-, 1 ,3-, 1 ,4- or 1 ,5-position relative to one another, and which contains a hydroxyl group or a primary or secondary amine group; or
  • the polymer can subsequently be modified further in its properties in a controlled manner in this way.
  • crosslinked polymers are prepared, 0.01 to 10 mol per cent of the total isocyanate groups present are preferably croslinked.
  • the process is preferably carried out in a polar or non-polar aprotic solvent, and the solvent is particularly preferably a halogenated hydrocarbon, an ester, a ketone, an acid amide, ether, dimethylsulfoxide, an aromatic compound or an alkane.
  • the solvent is particularly preferably a halogenated hydrocarbon, an ester, a ketone, an acid amide, ether, dimethylsulfoxide, an aromatic compound or an alkane.
  • reaction of the hydroxyl group or the primary or secondary amine group is carried out by known processes, preferably in a temperature range from 10°C to 100°C.
  • Subsequent introduction of, for example, a hydroxyl group into highly crosslinked polystyrene can be carried out by known processes. Chloromethylation is first carried out as described in Mol. Catal. 51 (1989), 13-27, and hydrolysis is then carried out by the method described by J. M. Frechet et al. in Polymer, 20 (1979) 675-680. The subsequent modification can also be carried out in bulk, for example by plasma processes. Chemical processes in solution or in emulsion are also possible.
  • insoluble polymers are ground beforehand by known processes and adjusted to the desired particle size.
  • R 7 is preferably methyl or ethyl.
  • R 8 and R 9 are preferably identical and are phenyl, i-propyl or t-butyl are likewise suitable.
  • Substituted phenyl R 8 , R 9 , R 16 and R ⁇ 7 in the compounds of the formula IVa are preferably 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4-i-propyl-, 2- or 4-t-butyl-, 2-methoxy-, 3-methoxy-, 4-methoxy-, 2- or 4-ethoxy-, 4-trimethylsilyl-, 2- or 4-fluoro-, 2,4-difluoro-, 2- or 4-chloro-, 2,4-dichloro-, 2,4-dimethyl-, 3,5-dimethyl-, 2-methoxy-4-methyl-, 3,5-dimethyl- 4-methoxy-, 3,5-dimethyl-4-(dimethylamino)-, 2- or 4-amino-, 2- or 4-methylamino-, 2- or 4-(dimethylamino)-, 2- or 4-SO 3 H- f 2- or 4-SO 3 Na-, 2- or 4-f NH 3 CI
  • R 8 and R 9 in the compounds of the formula IVa are identical radicals and are cyclohexyl or phenyl.
  • R ⁇ 6 and R ⁇ 7 in the compounds of the formula IVa are identical and are cyclohexyl, phenyl, t-butyl, 2- or 4-methylphen-1-yl, 2- or 4-methoxyphen- 1-yl, 2- or 4-(dimethylamino)phen-1-yl, 3,5-dimethyl-4-(dimethylamino)phen-1-yl or 3,5-dimethyl-4-methoxyphen-1-yl.
  • the radicals R 22 are preferably identical or different and are phenyl, 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4-i-propyl-, 2- or 4-t-butyl-, 2-methoxy-, 3-methoxy-, 4-methoxy-, 2- or 4-ethoxy-, 4-trimethylsilyl-, 2- or 4-fluoro-, 2,4-difluoro-, 2- or 4-chloro-, 2,4-dichloro-, 2,4-dimethyl-, 3,5-dimethyl-, 2-methoxy- 4-methyl-, 3,5-dimethyl-4-methoxy-, 3,5-dimethyl-4-(dimethylamino)-, 2- or 4-amino-, 2- or 4-methylamino-, 2- or 4-(dimethylamino)-, 2- or 4-SO 3 H-, 2- or 4-SO 3 Na-, 2- or 4-rNH 3 CI , 2,4,6-trimethyl
  • the radicals R 22 are particularly preferably identical radicals and are phenyl, cyclohexyl, t-butyl, 2- or 4-methylphen-1-yl, 2- or 4- methoxyphen-1-yl, 2- or 4-(dimethylamino)phen-1-yl, 3,5-dimethyl-4-(dimethylamino)phen- 1-yl or 3,5-dimethyl-4-methoxyphen-1-yl, 4-trifluoromethylphenyl or 3,5-di(trifluoromethyl).
  • the R 22 are particularly preferably phenyl, and m+n in formula IVb is 0, 1 or 2.
  • Preferred iridium catalysts are shown in the formulae III, Ilia, lllb, lllc and llld.
  • An " in formula Ilia can be derived from inorganic or organic oxygen acids. Examples of such acids are H 2 SO 4 , HCIO 4 , HCIO 3 , HBrO 4 , HIO 4 , HNO 3 , H 3 PO 3 , H 3 PO 4 , CF 3 SO 3 H, C 6 H 5 SO 3 H, CH 3 COOH, CF 3 COOH and CCI 3 COOH.
  • Complex acids from which An " can be derived are, for example, the halogen complex acids of the elements B, P, As, Sb and Bi.
  • Preferred examples of An " in formula Ilia are CIO “ , CF 3 S0 3 " , BF 4 “ , B(phenyl) 4 “ , PF 6 “ , SbCI 6 “ , AsF 6 “ and SbF 6 " .
  • M + in formula lllb as an alkali metal cation can be, for example, the Li, Na, K, Rb or Cs cations.
  • M + as quatemary ammonium can be quaternary ammonium which contains a total of 4 to 40, preferably 4 to 24, C atoms.
  • M + can have the formulae phenylN + (C ⁇ -C 6 alkyl) 3 , benzylN + (C ⁇ -C 6 alkyl) 3 or (C ⁇ -C 6 alkyl) 4 N + .
  • M + in formula lllb is preferably Li + , Na + or K + or (d-C 6 alkyl) 4 N + .
  • Z in formula III is preferably Br or Cl, and particularly preferably Cl.
  • Z in formula lllb is preferably Br or I, and Z in the formulae lllc and llld is preferably I.
  • the preparation of the catalysts is known per se and is described, for example, in US-A-4 994 615, US-A-5 011 995, US-A-5 112 999 and EP-A-0 564 406.
  • the catalysts of the formula III can be prepared, for example, by reaction of a diiridium complex of the formula [lrXZ] 2 with a diphosphine Y.
  • the iridium catalysts can be added to the reaction mixture as isolated compounds.
  • the molar ratio of imine to iridium catalyst can be, for example, 5,000,000 to 10, in particular 2,000,000 to 20, more preferably 1 ,000,000 to 20, and particularly preferably 500,000 to 100.
  • the process is preferably carried out at a temperature from -20 to 100°C, in particular 0 to 80°C, and particularly preferably 10 to 70°C, and preferably under a hydrogen pressure from 2 x 10 5 to 150 x 10 5 Pa (2 to 150 bar), in particular 10 6 to 10 7 Pa (10 to 100 bar).
  • the chlorides, bromides and iodides used are preferably employed in concentrations of 0.01 to 500 mmol/l, in particular 0,01 to 50 mmol/l, based on the volume of the reaction mixture.
  • the process according to the invention comprises additionally using an ammonium or metal chloride, bromide or iodide.
  • the chlorides, bromides and iodides are preferably employed in amounts of 0.01 to 200, in particular 0.05 to 100 equivalents, and in particular 0.5 to 50 equivalents, based on the iridium catalyst.
  • the iodides are preferred.
  • Ammonium is preferably tetraalkylammonium having 1 to 6 C atoms in the alkyl groups, and sodium, lithium or potassium is preferred as the metal. Tetrabutylammonium iodide and sodium iodide are particulariy preferred.
  • Suitable solvents which can be employed by themselves or as a mixture of solvents, are: aliphatic and aromatic hydrocarbons, for example pentane, hexane, cyclohexane, methylcyclohexane, benzene, toluene and xylene; ethers, for example diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons, for example methylene chloride, chloroform, 1 ,1 ,2,2-tetrachloroethane and chlorobenzene; esters and lactones, for example ethyl acetate, butyrolactone and valerolactone; acid amides and lactams, for example dimethylformamide, dimethylacetamide and N- methylpyrrolidone; ketones, for example acetone, dibutyl ketone,
  • the process according to the invention furthermore comprises additionally using an acid.
  • Such acids can be inorganic or, preferably, organic acids.
  • the acid is preferably employed in at least the same molar amount as the iridium catalyst (same catalytic amounts), and can also be used in excess. The excess can even comprise the use of the acid as the solvent.
  • 0.001 to 50, in particular 0.005 to 50 % by weight of acid, based on the amine, is preferably employed. In some cases, it may be advantageous to use anhydrous acids.
  • inorganic acids are H 2 SO , highly concentrated sulfuric acid (oleum), H 3 PO 4 , orthophosphoric acid, HF, HCl, HBr, HI, HCI0 4 , HBF 4 , HPF 6 , HAsF 6> HSbCI 6 , HSbF 6 and HB(phenyl) 4 .
  • H 2 SO 4 is particularly preferred.
  • the molar ratio of imine to hydrogen iodide is preferably 500,000 to 500, and particularly preferably 10,000 to 1000.
  • Hydrogen iodide can be added here in gaseous form or as an aqueous solution or in the form of any solution. In some cases, it is advantageous to work under anhydrous conditions.
  • organic acids are aliphatic or aromatic non-halogenated or halogenated (fluorinated or chlorinated) carboxylic acids, sulfonic acids and phosphorus(V) acids (for example phosphonic acids and phosphonous acids) having preferably 1 to 20, particularly preferably 1 to 12, and especially preferably 1 to 6, C atoms.
  • Examples are formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, phenylacetic acid, cyclohexanecarboxylic acid, chloro- or fluoroacetic acid, dichloro- or difluoroacetic acid, trichloro- or trifluoroacetic acid, chlorobenzoic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, chlorobenzenesulfonic acid, trifluoromethanesulfonic acid, methylphosphonic acid and phenylphosphonic acid.
  • Preferred acids are acetic acid, propionic acid, trifluoroacetic acid, methanesulfonic acid and chloroacetic acid.
  • the solid inorganic or organic support material can also be pretreated with an acid such that this acid is liberated again to a sufficient extent during the hydrogenation.
  • Porous inorganic or organic support materials which bond the acid, for example adsorptively, and liberate it again under the hydrogenation conditions are particularly suitable for such pretreatment.
  • Solid acids are to be understood as meaning, for example:
  • Zeolites such as zeolite A, ZSM-5, ZSM-11 , L, X, Y, mordenite or TiSi, and large-pored zeolites such as MCM-41 , AIPO, SAPO or VAPO;
  • Phyllosilicates such as montmorillonite, hectorite, vermiculite or kaolinite
  • metal oxide systems in gel form such as SiO 2 , AI 2 O 3 , TiO 2 , ZrO or combinations thereof
  • acid ion exchanger resins for example Amberlyst® or Nafion®.
  • the process according to the invention can be carried out by first preparing the catalyst, for example by dissolving (lrdieneCI) 2 in a solvent or an acid or both, adding a diphosphine and then an alkali metal halide or ammonium halide and stirring the mixture.
  • (lrdieneCI) 2 can also be employed as a solid.
  • the solution of the imines is added to this catalyst solution (or vice versa) and, in an autoclave, hydrogen is forced in and the inert gas advantageously used is thus removed. It is advantageous to ensure a short standing time of the catalyst solution and to carry out the hydrogenation of the imines as far as possible directly after preparation of the catalyst solution.
  • the reaction mixture is heated, if appropriate, and hydrogenated.
  • the mixture is cooled, if appropriate, and the autoclave is let down.
  • the reaction mixture can be forced out of the autoclave with nitrogen and the hydrogenated organic compound can be isolated and purified in a manner known per se, for example by precipitation, extraction or distillation.
  • the catalyst After the hydrogenation, the catalyst can as a rule easily be separated off by filtration and re-used several times.
  • aldimines and ketimines these can also be formed in situ before or during the hydrogenation.
  • a procedure is followed in which an amine and an aldehyde or a ketone are mixed, the mixture is added to the catalyst solution and the aldimine or ketimine formed in situ is hydrogenated.
  • an amine, a ketone or an aldehyde it is also possible for an amine, a ketone or an aldehyde to be initially introduced into the reaction vessel together with the catalyst and for the ketone or the aldehyde or the amine to be added, either in one portion or by metering.
  • the hydrogenation can be carried out continuously or discontinuously, i.e. batchwise, in various types of reactor. Those reactors which allow comparatively favourable thorough mixing and good removal of heat, for example loop reactors, are preferred. This type of reactor has proved particularly suitable if small amounts of catalyst are used.
  • the molar ratio of imine to iridium catalyst is preferably from 500,000 to 100.
  • the reaction temperature is preferably -20 to 100°C and the hydrogen pressure is preferably 2 x 10 5 pascal to 150 x 10 5 pascal.
  • An aldimine or ketimine which is formed in situ before or during the hydrogenation is preferably hydrogenated.
  • the process according to the invention gives the corresponding amines at high chemical conversions in short reaction times, surprisingly excellent optical yields (ee) of 70 % or more being achieved even at higher temperatures of above 50°C, and even at high molar ratios of imine to catalyst.
  • the hydrogenated organic compounds which can be prepared according to the invention are biologically active substances or intermediates for the preparation of such substances, in particular in the field of preparation of pharmaceuticals and agrochemicals.
  • o,o-dialkylarylketamine derivatives in particular those having alkyl and or alkoxyalkyl groups, act as fungicides, in particular as herbicides.
  • the derivatives can be amine salts, acid amides, for example of chloroacetic acid, tertiary amines and ammonium salts (cf., for example, EP-A-0 077755 and EP-A-0 115470).
  • TMEDA N,N,N,N-tetramethylethylenediamine
  • a solution comprising a mixture of 7.4 ml of chlorodiphenylphosphine (40 mmol) and 22.9 ml of 3-chloropropyl-dimethylchlorosilane (140 mmol) is then added dropwise at about -20°C. The reaction mixture is then stirred overnight at room temperature.
  • the compound of the formula 2 with the (S)-(R) configuration is prepared in the same manner starting from (S)-N,N-dimethyl-1-ferrocenylethylamine.
  • Example A2 Synthesis of the compounds of the formula 3a: All the following syntheses were carried out starting from the compound of the formula 2 in the (R)-(S) configuration and give the corresponding (R)-(S) ligands.
  • Example A2a Synthesis of m)-1-ri'- ⁇ "-dimethylsilyl-3"-chloroDropylHS)- 2-diphenylphosphino-ferrocenyl)ethyldi-3.5-xyl-1-ylphosphine 3a: 1.12 g (4.6 mmol) of bis(3,5-xylyl)phosphine in 5 ml of acetic acid are added to 2.66 g (4.6 mmol) of the compound prepared in Example A1 in 10 ml of acetic acid, and the mixture is stirred in an oil bath at 95°C for 90 minutes.
  • Example A3a 492 mg of potassium phthalimide and 130 mg of hexadecyltributyl- phosphonium bromide (catalyst) are added to a solution of 1.64 g (2.1 mmol) of the compound of the formula 3a from Example A2a in 2 ml of DMF and the mixture is stirred at
  • Example A5 Synthesis of the li ⁇ ands of the formula 7a and 8a immobilized on inorganic supports:
  • Example A5a 0.65 ml (2.46 mmol) of 1-triethoxysilyl-3-isocyanatopropane is added dropwise to a solution of 1.48 g (1.97 mmol) of the compound of the formula 5a from
  • Example A3a in 20 ml of methylene chloride and the mixture is stirred overnight at room temperature. The solvent is then stripped off under reduced pressure and the crude product is purified by chromatography (mobile phase: hexane/ethyl acetate). 1.45 g of an orange viscous foam of the compound of the formula 7a are obtained (yield 74 %).
  • Example A5d 0.1 ml (0.37 mmol) of 1-triethoxysilyl-3-isocyanatopropane is added dropwise to a solution of 251 mg (0.31 mmol) of the compound of the formula 6a from Example A4 in
  • Example B Li ⁇ ands immobilized on silica gel or controlled pore glass: Immobilization: The support material is in each case dried at 130°C for 3 hours under a high vacuum before use and then placed under argon. A solution of the immobilizable ligand from Example A5 in toluene is then added and the mixture is stirred at 85-90°C for 20 hours. After the mixture has been allowed to cool and settle, the supernatant solution is drawn off with a syringe. The mixture is then washed 6 times with MeOH (in each case 7 ml per g of support) and finally dried at 40-50°C under a high vacuum. The result is shown in Table 1.
  • TDI 2,4-tolylene diisocyanate
  • the excess TDI is then removed by filtering off the solution and washing 5 times with 30 ml of methylene chloride.
  • the support which has been reacted with TDI is then stirred into 30 ml of methylene chloride, and a solution of 94 mg (0.125 mmol) of the compound of the formula 5a from Example A3a in 2 ml of methylene chloride is added dropwise. The mixture is stirred overnight.
  • 10 ml of ethyl alcohol with 30 microlitres of triethylamine as a catalyst are added and the mixture is stirred at 40°C for 8 hours.
  • the yellow-orange support is then filtered off and washed 5 times with 20 ml of methylene chloride each time. Finally, it is dried under a high vacuum.
  • the 50 ml steel autoclave is equipped with a magnetic stirrer (1500 rpm) and flow breaker.
  • the inert gas in the autoclave is displaced by hydrogen in 4 cycles each time (10 bar, normal pressure) before the hydrogenation.
  • the desired hydrogen pressure is then established in the autoclave and the hydrogenation is started by switching on the stirrer.
  • Example D1 A solution of 0.64 mg of [lr(COD)CI] 2 (0.0019 mmol of Ir) in 1 ml of THF is added in one portion to 53 mg of ligand 201 in the (R),(S) configuration, (Si-Xyliphos 1 ) and the mixture is stirred slowly, the yellow solution decolorizing. The catalyst is then allowed to settle, the supernatant THF is drawn off with a syringe and the catalyst is dried under a high vacuum.
  • Example D2 A solution of 1.65 mg of [lr(COD)CI] 2 (0.0049 mmol of Ir) in 2 ml of THF is added in one portion to 128 mg of ligand 202 in the (R),(S) configuration (Si-Xyliphos 2) and the mixture is stirred slowly, the yellow solution decolorizing. The catalyst is then allowed to settle, the supematant THF is drawn off with a syringe and the catalyst is dried under a high vacuum.
  • Example D3 A solution of 0.27 mg of [lr(COD)CI] 2 (0.00082 mmol of Ir) in 1 ml of THF is added in one portion to 40 mg of ligand 202 in the (R).(S) configuration (Si-Xyliphos 2) and the mixture is stirred slowly, the yellow solution decolorizing. The catalyst is then allowed to settle, the supernatant THF is drawn off with a syringe and the catalyst is dried under a high vacuum.
  • Example D4 A solution of 0.64 mg of [lr(COD)CI] 2 (0.0019 mmol of Ir) in 2 ml of THF is added in one portion to 143 mg of ligand 203 in the (R),(S) configuration (Si-Xyliphos 3) and the mixture is stirred slowly, the yellow solution decolorizing. The catalyst is then allowed to settle, the supematent THF is drawn off with a syringe and the catalyst is dried under a high vacuum.
  • Example D5 A solution of 1.65 mg of [lr(COD)CI] 2 (0.0049 mmol of Ir) in 2 ml of THF is added in one portion to 206 mg of ligand 204 in the (R),(S) configuration (Si-Xyliphos 4) and the mixture is stirred slowly, the yellow solution decolorizing. The catalyst is then allowed to settle, the supernatant THF is drawn off with a syringe and the catalyst is dried under a high vacuum.
  • Example D6 A solution of 1.65 mg of [lr(COD)CI] 2 (0.0094 mmol of Ir) in 5 ml of THF is added in one portion to 900 mg of ligand 205 in the (R),(S) configuration (CPG-Xyliphos) and the mixture is stirred slowly, the yellow solution decolorizing. The catalyst is then allowed to settle, the supernatant THF is drawn off with a syringe and the catalyst is dried under a high vacuum.
  • Example D7 A solution of 1.65 mg of [lr(COD)CI] 2 (0.0049 mmol of Ir) in 5 ml of toluene is added in one portion to 60 mg of ligand 206 in the (R),(S) configuration (PS-Xyliphos) and the mixture is stirred slowly, the yellow solution decolorizing.
  • Example D8 A solution of 0.64 mg of [lr(COD)CI] 2 (0.0019 mmol of Ir) in 8 ml of THF is added in one portion to 25 mg of ligand 206 in the (R),(S) configuration (PS-Xyliphos) and the mixture is stirred slowly, the yellow solution decolorizing. 10 mg of tetrabutylammonium iodide, 2 ml of acetic acid and, finally, 19.5 g (95 mmol) of N-(2'- methyl-6'-ethylphen-1'-yl)-N-(1-methoxymethyl)ethylimine are introduced into a second flask, and the solution is placed under inert gas and added to the catalyst.
  • reaction mixture is then forced with a steel capillary under a countercurrent of inert gas into a 50 ml steel autoclave and hydrogenation is subsequently carried out under a hydrogen pressure of 80 bar at 25°C. After 41 hours, the hydrogen is let down and the catalyst is filtered off. The conversion is 95 % and the optical yield is 77.8 % of (S).
  • Example D9 A solution of 1.65 mg of [lr(COD)CI] 2 (0.0049 mmol of Ir) in 2 ml of THF is added in one go to 130 mg of ligand 202 in the (R),(S) configuration (Si-Xyliphos 2) and the mixture is stirred slowly, the yellow solution decolorizing. The catalyst is then allowed to settle, the supernatant THF is drawn off with a syringe and the catalyst is dried under a high vacuum.
  • Example D10 A solution of 1.65 mg of [lr(COD)CI] 2 (0.0049 mmol of Ir) in 4 ml of THF is added in one go to 60 mg of ligand 206 in the (R),(S) configuration (PS-Xyliphos) and the mixture is stirred slowly, the yellow solution decolorizing.
  • Example D11 A solution of 3.3 mg of [lr(COD)CI] 2 (0.0097 mmol of Ir) in 2 ml of THF is added in one portion to 128 mg of ligand 207 in the (R),(S) configuration (Si-PPM) and the mixture is stirred slowly, the yellow solution decolorizing. The catalyst is then allowed to settle, the supernatant THF is drawn off with a syringe and the catalyst is dried under a high vacuum.

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Abstract

Cette invention concerne un procédé d'hydrogénation d'imines avec de l'hydrogène dans des conditions de pression plus forte en présence de catalyseurs à iridium-diphosphine immobilisés sur une matière de support et un halogène. Le mélange réactionnel doit nécessairement comprendre un acide inorganique ou organique. On peut considérablement accroître l'activité du catalyseur dans ces conditions, ce procédé permettant également de réduire ou d'éliminer totalement la désactivation des catalyseurs. On a également découvert, de manière fortuite, que l'énantiosélectivité est élevée dans les conditions choisies et qu'on peut atteindre des puissances optiques élevées pouvant aller jusqu'à 80 % environ, même à des températures de réaction relativement élevées. Un autre avantage considérable de ces catalyseurs réside dans le fait qu'on peut facilement les séparer et les enlever pour les réutiliser sans perte substantielle de leur activité, ceci permettant de les utiliser d'une manière particulièrement avantageuse et économique dans des procédés réalisés à échelle industrielle.
PCT/EP1996/002729 1995-07-06 1996-06-24 PROCEDE D'HYDROGENATION D'IMINES EN PRESENCE DE CATALYSEURS IMMOBILISES Ir-DIPHOSPHINE WO1997002232A1 (fr)

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AU64149/96A AU6414996A (en) 1995-07-06 1996-06-24 Process for the hydrogenation of imines in the presence of imobilized ir-diphosphine catalysts

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CH197595 1995-07-06
CH1975/95 1995-07-06

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998001457A1 (fr) * 1996-07-10 1998-01-15 Novartis Ag Ferrocenyldiphosphines fonctionnalisees, procede pour leur preparation et leur utilisation
US6015919A (en) * 1995-04-11 2000-01-18 Novartis Ag Dihalogenated ferrocenes and processes for the preparation thereof
FR2790477A1 (fr) * 1999-03-01 2000-09-08 Rhodia Chimie Sa Polymere lineaire optiquement actif utilisable comme ligand dans la preparation de complexes metalliques destines a la catalyse asymetrique
US6133464A (en) * 1996-10-07 2000-10-17 Novartis Ag Chiral ferrocenyls
WO2001004131A1 (fr) * 1999-07-14 2001-01-18 Solvias Ag Ligands de diphosphine pour complexes metalliques
US9358532B2 (en) 2011-02-28 2016-06-07 Dalian Heterogeneous Catalyst Co. Ltd. Catalyst for asymmetric hydrogenation of imine, synthesis method and application thereof
WO2023171694A1 (fr) * 2022-03-08 2023-09-14 国立大学法人東京大学 Catalyseur hétérogène de type coeur-coquille et procédé de fabrication d'un composé optiquement actif l'utilisant

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0496699A1 (fr) * 1991-01-25 1992-07-29 Ciba-Geigy Ag Disphosphines contenant des groupes silane, diphosphines immobilisées et leur utilisation comme catalyseurs d'hydrogenation
EP0496700A1 (fr) * 1991-01-25 1992-07-29 Ciba-Geigy Ag Diphosphines contenant des groupes silane, diphosphines immobilisées et leur utilisation comme catalyseurs d'hydrogenation
EP0605363A1 (fr) * 1992-12-29 1994-07-06 Ciba-Geigy Ag Procédé pour la préparation de 2-alkyl-5-méthyl-N-(1'-méthoxy-2'-propyl)-aniline et ses chloracetanilides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0496699A1 (fr) * 1991-01-25 1992-07-29 Ciba-Geigy Ag Disphosphines contenant des groupes silane, diphosphines immobilisées et leur utilisation comme catalyseurs d'hydrogenation
EP0496700A1 (fr) * 1991-01-25 1992-07-29 Ciba-Geigy Ag Diphosphines contenant des groupes silane, diphosphines immobilisées et leur utilisation comme catalyseurs d'hydrogenation
EP0605363A1 (fr) * 1992-12-29 1994-07-06 Ciba-Geigy Ag Procédé pour la préparation de 2-alkyl-5-méthyl-N-(1'-méthoxy-2'-propyl)-aniline et ses chloracetanilides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6015919A (en) * 1995-04-11 2000-01-18 Novartis Ag Dihalogenated ferrocenes and processes for the preparation thereof
WO1998001457A1 (fr) * 1996-07-10 1998-01-15 Novartis Ag Ferrocenyldiphosphines fonctionnalisees, procede pour leur preparation et leur utilisation
US6169192B1 (en) 1996-07-10 2001-01-02 Novartis Ag Functionalized ferrocenyldiphosphines, a process for their preparation and their use
US6133464A (en) * 1996-10-07 2000-10-17 Novartis Ag Chiral ferrocenyls
FR2790477A1 (fr) * 1999-03-01 2000-09-08 Rhodia Chimie Sa Polymere lineaire optiquement actif utilisable comme ligand dans la preparation de complexes metalliques destines a la catalyse asymetrique
WO2000052081A1 (fr) * 1999-03-01 2000-09-08 Rhodia Chimie Polymere lineaire optiquement actif utilisable comme ligand dans la preparation de complexes metalliques destines a la catalyse asymetrique
US6646106B1 (en) 1999-03-01 2003-11-11 Rhodia Chimie Optically active linear polymer used as ligand in the preparation of metallic complexes designed for asymmetric catalysis
WO2001004131A1 (fr) * 1999-07-14 2001-01-18 Solvias Ag Ligands de diphosphine pour complexes metalliques
US9358532B2 (en) 2011-02-28 2016-06-07 Dalian Heterogeneous Catalyst Co. Ltd. Catalyst for asymmetric hydrogenation of imine, synthesis method and application thereof
WO2023171694A1 (fr) * 2022-03-08 2023-09-14 国立大学法人東京大学 Catalyseur hétérogène de type coeur-coquille et procédé de fabrication d'un composé optiquement actif l'utilisant

Also Published As

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ZA965728B (en) 1997-01-06
AR002687A1 (es) 1998-03-25
HRP960295A2 (en) 1997-08-31
IL118788A0 (en) 1996-10-31

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