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EP3024838A2 - Dérivés de phosphoramidite dans l'hydroformylation de mélanges contenant une oléfine - Google Patents

Dérivés de phosphoramidite dans l'hydroformylation de mélanges contenant une oléfine

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Publication number
EP3024838A2
EP3024838A2 EP14741637.4A EP14741637A EP3024838A2 EP 3024838 A2 EP3024838 A2 EP 3024838A2 EP 14741637 A EP14741637 A EP 14741637A EP 3024838 A2 EP3024838 A2 EP 3024838A2
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European Patent Office
Prior art keywords
substituted
radicals
alkyl
transition metal
unsubstituted
Prior art date
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EP14741637.4A
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German (de)
English (en)
Inventor
Katrin Marie DYBALLA
Robert Franke
Dirk Fridag
Eduard BENETSKIY
Armin BÖRNER
Detlef Selent
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Publication of EP3024838A2 publication Critical patent/EP3024838A2/fr
Withdrawn legal-status Critical Current

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    • 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
    • C07F9/6571—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 and oxygen atoms as the only ring hetero atoms
    • C07F9/657154—Cyclic esteramides of oxyacids of phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/186—Mono- or diamide derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • 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
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • 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
    • C07F9/6571—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 and oxygen atoms as the only ring hetero 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
    • B01J2531/002—Materials
    • B01J2531/004—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
    • 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
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—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
    • B01J2531/845—Cobalt

Definitions

  • Hydroformylation is one of the quantitatively most important homogeneous catalysis on an industrial scale.
  • the aldehydes produced therewith are important intermediate or end products in the chemical industry (Rhodium Catalyzed Hydroformylation, PWNM van Leeuwen, C. Claver, ed., Klüver Academic Publishers: Dordrecht Netherlands, 2000. R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675). Of particular importance is the hydroformylation with Rh catalysts.
  • Phosphoramidites i. Compounds that possess one or more P-N bonds instead of P-O have rarely been used as ligands in hydroformylation.
  • Van Leeuwen and co-workers (A. van Rooy, D. Burgers, PCJ Kamer, PWNM van Leeuwen, Recl. Trav. Chim. Pays-Bas 1996, 115, 492) first studied monodentate phosphoramidites in hydroformylation. Overall, only moderate catalytic properties were observed at the high to extremely high ligand / rhodium ratios of up to 1000: 1. At the lowest ligand / rhodium or P / Rh ratio of 10: 1, a high isomerization activity and the formation of internal Olefins found that are not hydroformylated. Only increasing the P / Rh ratio increased the TOF to a moderate 910 h "1 and increased the selectivity.
  • phosphoramidites are more likely to react with nucleophiles than phosphites. This property is e.g. widely used for the synthesis of phosphites from phosphoramidites (e-EROS Encyclopedia of Reagents for Organic Synthesis, doi: 10.1002 / 047084289X.rn00312; R. Hülst, NK de Vries, BL Feringa, Tetrahedron: Asymmetry 1994, 5, 699-708) , but at the same time it is particularly questioning its suitability as a long-term stable ligand for catalysis.
  • P-substituents For the stabilization of hydrolysis-prone phosphorus compounds, the use of suitable P-substituents may contribute.
  • the only hitherto described method in the context of phosphoramidite ligands is the use of N-pyrrolyl radicals on the phosphorus (WO 02/083695).
  • Substituents on the heterocycle such as e.g. 2-ethylpyrrolyl (WO 03018192, DE 102005061642) or indolyl (WO 03/018192) further improve the hydrolytic stability.
  • hydrolytic degradation of phosphoramidite ligands can also be slowed by the addition of amines to the hydroformylation reaction, as taught in EP 167791 1, US 2006/0224000 and US 8,110,709.
  • the use of hydrolysis-stable pyrrolylphosphines or the addition of basic stabilizers narrows the scope of the hydroformylation reaction strongly to these embodiments.
  • the object of the present invention is to provide hydrolysis-stable ligands for catalytically active compositions for the chemical synthesis of organic compounds, in particular hydroformylation, hydrocyanation and the hydrogenation of unsaturated compounds.
  • hydrolysis-stable ligands for catalytically active compositions for the chemical synthesis of organic compounds, in particular hydroformylation, hydrocyanation and the hydrogenation of unsaturated compounds.
  • An object of the present invention are phosphoramidites of the formula (I), wherein Q is a bivalent substituted or unsubstituted aromatic radical; wherein R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals;
  • R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N.
  • Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals.
  • R 1 is selected from C 1 -C 5 -alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from C 1 -C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N.
  • R 1 is selected from C 1 -C 5 -alkyl, C 4 -C 6 -cycloalkyl or phenyl radicals
  • R 2 is selected from C 1 -C 5 -alkyl, C 4 -C 6 -cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N.
  • the compounds of the formula (I) are selected from:
  • transition metal-containing compounds of the formula Me (acac) (CO) L with Me transition metal, wherein L is selected from: wherein Q is a divalent substituted or unsubstituted aromatic radical;
  • R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N.
  • Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -Biphenylresten.ln a variant of this Ausry- R 1 form is selected from d- - C 5 -alkyl, substituted or unsubstituted
  • R 2 is selected from C 1 -C 5 -alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or
  • R 1 and R 2 form a heterocyclic structure via alkylene groups with N.
  • R 1 is selected from C 1 -C 5 -alkyl
  • R 2 is selected from C 1 -C 5 -alkyl-, C 4 -C 6-
  • R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N.
  • the compounds of the formula (I) are selected from:
  • salts such as halides, carboxylates - e.g. Acetates - or commercially available complex compounds, such.
  • Q is a divalent substituted or unsubstituted aromatic radical
  • R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N.
  • Q is a divalent substituted or unsubstituted aromatic radical
  • R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N.
  • solvents are understood to mean, in addition to substances which do not inhibit product formation-externally added to the reaction mixture or submitted to it-also mixtures of compounds which are formed in situ from secondary or subsequent reactions of the products; For example, so-called high boilers that arise from the aldol condensation, the acetalization of the primary product aldehydes as well as the esterification and lead to the corresponding aldol products, formates, acetals and ethers.
  • Solvents initially introduced into the reaction mixture can be aromatics, such as, for example, toluene-rich aromatic mixtures or alkanes or mixtures of alkanes.
  • high boilers are understood as meaning those substances or else mixtures of substances which boil aldehydes at a higher temperature than the primary product and have higher molar masses than the primary product aldehydes.
  • the structural element Q - in the transition metal-containing compounds as well as the free ligand - is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 '-Binaphthyl- or ortho- Phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals.
  • R 1 is selected from C 1 -C 5 -alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from C 1 to C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N ,
  • R 1 is selected from C 1 -C 5 -alkyl, C 4 -C -cycloalkyl or phenyl radicals
  • R 2 is selected from C 1 -C 5 alkyl, C 4 -C 8 cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic via N-alkylene groups Structure.
  • transition metal-containing compounds of the formula Me (acac) (CO) L with Me transition metal, where L is selected from:
  • the free ligands are selected under:
  • the unsaturated compounds which are hydroformylated in the process of the invention include hydrocarbon mixtures obtained in petrochemical processing plants. These include, for example, so-called C 4 - Thomaste. Typical compositions of C 4 cuts from which most of the polyunsaturated hydrocarbons have been removed and which can be used in the process according to the invention are listed in the following Table 1 (see DE 10 2008 002188). Table 1 :
  • HCC 4 typical of a C 4 mixture obtained from the C 4 cut of a high-severity steam after the hydrogenation of the 1,3-butadiene without additional moderation of the catalyst.
  • HCC 4 / SHP composition HCC 4 in which residues of 1, 3-butadiene in one
  • CC 4 / SHP composition of a C 4 cut in which residues of 1,3-butadiene were further reduced in a selective hydrogenation process / SHP.
  • the unsaturated compound or its mixture is selected from:
  • Hydrocarbon mixtures from catalytically operated splitting plants such as e.g. FCC cracking plants;
  • Hydrocarbon mixtures from oligomerization processes in homogeneous phase and heterogeneous phases such as the OCTOL, DIMERSOL, Fischer-Tropsch, Polygas, CatPoly, InAlk, Polynaphtha, Selectopol, MOGD, COD, EMOGAS, NExOCTANE or SHOP process;
  • Hydrocarbon mixtures comprising polyunsaturated compounds.
  • the mixture comprises unsaturated compounds having 2 to 30 carbon atoms.
  • the mixture comprises unsaturated compounds having 2 to 8 carbon atoms.
  • the mixture has polyunsaturated hydrocarbons.
  • the mixture comprises butadienes.
  • n-octenes, 1-octene and Cs-containing olefin mixtures are hydroformylated as olefin-containing mixtures.
  • phosphoramidites of the formulas (I) are prepared in a first process step:
  • Q is a divalent substituted or unsubstituted aromatic radical
  • R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or Aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N;
  • Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals;
  • R 1 is selected from C 1 to C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from the group consisting of - C 5 - alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
  • R 1 is selected from C 1 -C 5 -alkyl, C 4 -C -hydroxyalkyl or phenyl radicals
  • R 2 is selected from C 1 -C 5 alkyl, C 4 -C 6 cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form heterocyclic via alkylene groups with N Structure;
  • R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N;
  • Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals;
  • R 1 is selected from C 1 to C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from the group consisting of - C 5 - alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
  • R 1 is selected from C 1 -C 5 -alkyl, C 4 -C 6 -cycloalkyl or phenyl radicals
  • R 2 is selected from C 1 -C 5 alkyl, C 4 -C 6 cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
  • Q is a divalent substituted or unsubstituted aromatic radical
  • R 1 is selected from alkyl, substituted or unsubstituted Cydoalkyl- or aryl radicals
  • R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N;
  • Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals;
  • R 1 is selected from C 1 to C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
  • R 2 is selected from the group consisting of - C 5 - alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
  • R 1 is selected from C 1 -C 5 -alkyl, C 4 -C 6 -cycloalkyl or phenyl radicals
  • R 2 is selected from C 1 -C 5 alkyl, C 4 -C 6 cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
  • the unsaturated compounds are added to form a multi-phase reaction mixture
  • the reaction mixture is separated into aldehydes, alcohols, high boilers, ligands, degradation products of the catalytically active composition.
  • the addition of the unsaturated compounds takes place together with that of the precursor of the transition metal and of the ligands; This is preferably when the unsaturated compounds are present at room temperature and atmospheric pressure corresponding to 1013 hPa in a liquid state.
  • decomposition products are understood to mean substances which originate from the decomposition of the composition catalytically active in the hydroformylation. They are disclosed, for example, in US 5364950, US 5763677, as well as in Catalyst Separation, Recovery and Recycling, edited by DJ Cole-Hamilton, RP Tooze, 2006, NL, pages 25-26, and in rhodium-catalyzed hydroformylation, ed. by PWNM van Leeuwen et C. Claver, Kluwer Academic Publishers 2006, AA Dordrecht, NL, page 206-21.
  • the final subject of the present invention is a multiphase reaction mixture containing: - unsaturated compounds
  • transition metal Me is selected from ruthenium, cobalt, rhodium, iridium, in particular rhodium;
  • unsaturated compounds are selected from:
  • Hydrocarbon mixtures from catalytically operated splitting plants such as e.g. FCC cracking plants;
  • Hydrocarbon mixtures from oligomerization processes in homogeneous phase and heterogeneous phases such as the OCTOL, DIMERSOL, Fischer-Tropsch, Polygas, CatPoly, InAlk, Polynaphtha, Selectopol, MOGD, COD, EMOGAS, NExOCTANE or SHOP process;
  • Hydrocarbon mixtures comprising polyunsaturated compounds; wherein the solvent is added externally and does not interfere with the hydroformylation reaction, in particular if the solvent is formed in-situ from the primary products.
  • Nuclear resonance spectra were recorded on Bruker Avance 300 and Bruker Avance 400, gas chromatographic analysis on Agilent GC 7890A, elemental analysis on Leco TruSpec CHNS and Varian ICP-OES 715, and ESI-TOF mass spectrometry on Thermo Electron Finnigan MAT 95 XP and Agilent 6890 N / 5973 devices.
  • the hydroformylation was carried out in a 200 ml autoclave equipped with pressure maintenance, gas flow measurement, gassing stirrer and pressure pipette as the reaction zone.
  • the toluene used as the solvent was treated with sodium ketyl and distilled under argon.
  • the mixture of the n-octenes used as substrate was refluxed for several hours over sodium and distilled under argon.
  • the transition metal was used as a precursor in the form of
  • reaction was conducted at constant pressure. After the reaction time, the autoclave was cooled to room temperature, expanded with stirring and purged with argon. Each 1 ml of the reaction mixtures was taken immediately after switching off the stirrer, diluted with 5 ml of pentane and analyzed by gas chromatography.
  • the relative activities are determined by the ratio of k 1-order to k0, i. the k value at time 0 of the reaction (reaction start) determines and describes the relative decrease in activity during the experimental period.
  • the k-values of the I order are obtained from a plot of (-ln (1-gain)) versus time.
  • the hydroformylation series of Tables 1 and 2 disclose that the phosphoramidites (1 a) to (1 d) according to the invention have at least comparable results in terms of catalytic activity - measured as k 0 bs. [min "1] -.. and having the yield and selectivity of n-ligands for comparison Alkanox ® 240 according to CAS Reg No. [93347- 72-9], [31570-04-4], sometimes even in these individual features superior to the comparison ligand are.
  • the ligands (1 a) and (1d) according to the invention thus fulfill the stated object due to their particular hydrolytic stability, as already explained above.

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Abstract

La présente invention a pour objet : a) des phosphoramidite de formule (I); b) des composés contenant un métal de transition, de formule Me(acac)(CO)L, dans laquelle L est choisi dans la formule (I); c) des compositions catalytiquement actives dans l'hydroformylation, qui présentent les composés mentionnés aux points a) et b); d) des procédés d'hydroformylation de composés insaturés au moyen de la composition catalytiquement active mentionnée au point c); et e) un mélange réactionnel à plusieurs phases contenant des composés insaturés, un mélange gazeux qui présente du monoxyde de carbone, de l'hydrogène, des aldéhydes et la composition catalytiquement active décrite au point c).
EP14741637.4A 2013-07-23 2014-07-22 Dérivés de phosphoramidite dans l'hydroformylation de mélanges contenant une oléfine Withdrawn EP3024838A2 (fr)

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DE102013214378.8A DE102013214378A1 (de) 2013-07-23 2013-07-23 Phosphoramiditderivate in der Hydroformylierung von olefinhaltigen Gemischen
PCT/EP2014/065722 WO2015011139A2 (fr) 2013-07-23 2014-07-22 Dérivés de phosphoramidite dans l'hydroformylation de mélanges contenant une oléfine

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CN114685564B (zh) * 2020-12-27 2023-09-22 西北大学 新型亚磷酰胺配体及其合成方法和应用

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SG11201600386UA (en) 2016-02-26
DE102013214378A1 (de) 2015-01-29
US20170014816A1 (en) 2017-01-19
WO2015011139A4 (fr) 2015-05-07
WO2015011139A2 (fr) 2015-01-29
WO2015011139A3 (fr) 2015-03-19

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