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WO2019088377A1 - Dérivé de phosphoramidite ayant deux structures cycliques, son procédé de production et son utilisation - Google Patents

Dérivé de phosphoramidite ayant deux structures cycliques, son procédé de production et son utilisation Download PDF

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WO2019088377A1
WO2019088377A1 PCT/KR2018/004186 KR2018004186W WO2019088377A1 WO 2019088377 A1 WO2019088377 A1 WO 2019088377A1 KR 2018004186 W KR2018004186 W KR 2018004186W WO 2019088377 A1 WO2019088377 A1 WO 2019088377A1
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alkyl
aryl
formula
cycloalkyl
reaction
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김현우
신태일
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Korea Advanced Institute of Science and Technology KAIST
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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
    • C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C07F9/65842—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring
    • C07F9/65846—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring the phosphorus atom being part of a six-membered ring which may be condensed with another ring system
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0264—Phosphorus acid amides
    • 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
    • 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
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—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
    • C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Definitions

  • the present invention relates to a phosphoramidite derivative having two ring structures, a process for preparing the same, and a use thereof, and more particularly to a process for producing two cyclic phosphoramidite derivatives, a process for producing the same and a process for hydroformylation To a process for the production of aldehydes.
  • Hydroformylation is a reaction developed by Roelen in 1938, in which olefins are used as substrates to produce aldehydes through carbon monoxide, hydrogen, and catalysts.
  • Aldehyde which is a product, is converted into alcohols, amines, carboxylic acids and derivatives through additional chemical reactions, which are widely used in the chemical industry such as polymer materials, detergents, fragrances and drugs.
  • the reaction is mainly carried out using a catalyst coordinated with a ligand to cobalt (Co) and rhodium (Rh) transition metal.
  • the catalyst is oxidized in addition to carbon monoxide and hydrogen in the reaction,
  • the reactant, olefin is converted to an aldehyde through a reaction pathway of migratory insertion and reduction elimination.
  • the aldehyde as the product when the reactant is a mono-substituted olefin, two structural isomers, linear-aldehyde and branched-aldehyde, are obtained depending on the position of the bond between the catalyst and the olefin.
  • the present inventors have made intensive efforts to develop a system capable of selectively producing a tertiary-carbon internal aldehyde by controlling the hydroformylation reaction of a tri-substituted olefin.
  • a phosphoramidite Derivative as a catalyst, it was found that not only the reaction yield was high but also the tertiary-carbon internal aldehyde could be selectively mass-produced, thereby completing the present invention.
  • Another object of the present invention is to provide a method for producing a bicyclic bridgehead phosphoramidite derivative having two ring structures.
  • the present invention provides bicyclic bridgehead phophoramidite derivatives having two ring structures represented by the following formula (1)
  • R 'and R &quot are each independently (C1-20) alkyl or halogen
  • a and b are each independently an integer of 1 to 4, a and b are not 0 at the same time,
  • R is (C3-C20) cycloalkyl fused with hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C7-C20) bicycloalkyl or aromatic ring;
  • the aryl, cycloalkyl, aryl and bicycloalkyl of R are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 1 -C 20) alkoxy, C20) aryl and (C1-C20) alkyl (C6-C20) aryl.
  • the present invention also provides a process for preparing an imine compound represented by the following formula (4): (1) reacting a dihydroxybenzophenone represented by the following formula (2) with a primary amine compound represented by the following formula (3)
  • a bicyclic bridgehead phosphoramidite derivative having two ring structures represented by the following formula (1): < EMI ID 1.0 >
  • R 'and R &quot are each independently (C1-20) alkyl or halogen
  • a and b are each independently an integer of 1 to 4, a and b are not 0 at the same time,
  • R is (C3-C20) cycloalkyl fused with hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) alkoxy, halogen, halo ) Aryl and (C1-C20) alkyl (C6-C20) aryl;
  • R15, R16 and R17 are each independently a di (C1-C20) alkylamino, (C1-C20) alkoxy or halogen.
  • the present invention also provides a process for preparing an aldehyde by hydroformylation reaction using a tri-substituted olefin as a reaction substrate and a phosphoramidite derivative having the two-ring structure as a catalyst.
  • FIG. 1 shows the production yields of a phosphoramidite derivative having two ring structures synthesized in an embodiment of the present invention and a known ligand with respect to a tri-substituted olefin reactant.
  • Figure 2 shows the crystal structure of a synthesized tBu briFose (3,5-MeOPh) ligand in one embodiment of the present invention.
  • FIG. 3 is a table summarizing the results of hydroformylation reaction using various trisubstituted olefins as a reaction material using tBu brioose (3,5-MeOPh) ligand synthesized in one embodiment of the present invention.
  • alkyl &quot refers to a monovalent straight or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms.
  • alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Butyl, pentyl, hexyl, octyl, dodecyl, and the like.
  • alkoxy &quot means an -O-alkyl radical, where 'alkyl' is as defined above.
  • alkoxy radicals include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.
  • " cycloalkyl " as used in the present invention means a monovalent alicyclic alkyl radical consisting of one ring, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclo Nonyl, cyclodecyl, and the like.
  • " aryl " refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, with a single or fused ring containing, suitably, 4 to 7, preferably 5 or 6 ring atoms in each ring A ring system, and a form in which a plurality of aryls are connected by a single bond.
  • Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.
  • bicycloalkyl &quot refers to a saturated or partially unsaturated fused two bicyclic or bridged multicyclic ring radical, examples of bicycloalkyl being bicyclo [2.2 3] heptyl, bicyclo [3.3.1] octyl, bicyclo [3.3.1] heptyl, bicyclo [2.2.2] octyl, bicyclo [3.1.1] heptyl, bicyclo [3.2.1] But are not limited to.
  • &quot means a fluorine, chlorine, bromine or iodine atom.
  • " haloalkyl " as used herein refers to an alkyl radical substituted with a halogen atom as defined above, examples of haloalkyl include fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoro Ethyl, bromopropyl, and the like.
  • alkylaryl &quot as defined in the present invention means an aryl radical substituted with an alkyl radical as defined above.
  • alkylaryl radicals include, but are not limited to, tolyl, xylyl, mesityl, and the like.
  • cycloalkyl fused with an aromatic ring means that an aromatic hydrocarbon ring is fused to two adjacent carbon atoms of a cycloalkyl radical as defined above.
  • " tertiary-carbon internal aldehyde " as used in the present invention means an aldehyde prepared via a hydroformylation reaction without isomerization of tri-substituted olefins.
  • an upper panel aldehyde rather than an aldehyde of the lower panel produced via isomerization in Scheme 1 below.
  • the present inventors have modified the structure of the biphospholys ligand developed in the existing patent (Korean Patent No. 10-1574071) to synthesize a new structure of the biphos ligand through stereoscopic and electronic control. That is, the ortho- and para-positions of 2,2'-dihydroxybenzophenone, which is the basic skeleton for synthesizing the bifurc, are substituted with tert-butyl or chlorine instead of hydrogen at the para- , 2'-dihydroxybenzophenone, and synthesized the modified tBu and Cl brios through modified basic frameworks.
  • R 'and R &quot are each independently (C1-20) alkyl or halogen
  • a and b are each independently an integer of 1 to 4, a and b are not 0 at the same time,
  • R is (C3-C20) cycloalkyl fused with hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C7-C20) bicycloalkyl or aromatic ring;
  • the aryl, cycloalkyl, aryl and bicycloalkyl of R are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 1 -C 20) alkoxy, C20) aryl and (C1-C20) alkyl (C6-C20) aryl.
  • R may be selected from the following structures:
  • R3 to R7 are each independently hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, halogen, halo (C1-C20) alkyl or (C6-C20) aryl;
  • n is an integer of 1 to 5;
  • the phosphoramidite derivative having two ring structures of Formula 1 may be selected from the following structures, but is not limited thereto:
  • R 'and R &quot are each independently (C1-20) alkyl or halogen
  • a and b are each independently an integer of 1 to 4, a and b are not 0 at the same time,
  • R is (C3-C20) cycloalkyl fused with hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C1-C20) alkoxy, halogen, halo ) Aryl and (C1-C20) alkyl (C6-C20) aryl;
  • R15, R16 and R17 are each independently a di (C1-C20) alkylamino, (C1-C20) alkoxy or halogen.
  • the phosphorus compound of formula (6) may more preferably be a hexaalkylphosphorus triamide of the following formula (7), a phosphite of the formula (8) or a phosphorus trihalide of the formula (9).
  • R21, R22 and R23 are each independently (C1-C20) alkyl and X is halogen.
  • the primary amine compound of Formula 3 may be selected from the following structures:
  • R3 to R7 are each independently hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, halogen, halo (C1-C20) alkyl or (C6-C20) aryl;
  • n is an integer of 1 to 5;
  • a commercially available 2,2'-dihydroxybenzophenone of formula (2) is reacted with a primary amine compound of formula (3) to produce an imine compound of formula (4).
  • the internal hydrogen bonding of the 2,2'-dihydroxybenzophenone of Compound 2 significantly promotes the formation of the imine compound of Formula 4, and the resulting imine compound of Formula 4 reacts with the axial compounds and the chiral metal complex chiral-at-metal complexes. < / RTI >
  • the primary amine compound of Formula 3 is used in an excessive amount relative to the 2,2'-dihydroxybenzophenone of Formula 2, preferably 2,2'-dihydroxybenzophenone of Formula 2 1.1 to 100 equivalents based on 1 equivalent of phenone.
  • the reaction temperature for preparing the imine compound of Formula 4 according to one embodiment of the present invention may be controlled according to the type of the primary amine compound of Formula 3, and preferably from room temperature to 250 ° C.
  • the reaction proceeded at room temperature.
  • aniline it was necessary to raise the temperature.
  • a microwave is also irradiated to improve the yield.
  • the imine compound of Chemical Formula 4 may be produced in an organic solvent or neat, and it is not necessary to limit the organic solvent as long as it can dissolve the reaction material.
  • the neat means that the dihydroxybenzophenone of Formula 2 and the primary amine compound of Formula 3 are mixed without using an organic solvent to carry out the imination reaction.
  • the solvent for the above reaction examples include methanol, ethanol, isopropanol, butanol, acetone, ethyl acetate, acetonitrile, isopropyl ether, methyl ethyl ketone, methylene chloride, dichlorobenzene, chlorobenzene, dichloroethane, tetrahydrofuran,
  • the inert solvent is preferably an inert solvent selected from the group consisting of benzene, xylene, mesitylene, dimethylformamide, dimethylsulfoxide and the like in consideration of the solubility and ease of removal of the reactants.
  • the resulting imine compound of formula (4) can be used in the next reaction without purification and without purification, or may be subjected to purification if necessary.
  • the resulting imine compound of formula (4) is reduced using a reducing agent to prepare a secondary amine compound of formula (5).
  • a reducing agent in accordance with one embodiment of the present invention may be a metal hydride, preferably NaBH 4, NaBH (OAc) 3 , NaBH 2 (OAc) 2, NaBH3OAc, NaBH 3 CN, KBH 4, KBH (OAc) , LiAlH 4 , B 2 H 6 and DIBAL-H (Diisobutylaluminium hydride), and more preferably NaBH 4 or LiAlH 4 can be used.
  • a metal hydride preferably NaBH 4, NaBH (OAc) 3 , NaBH 2 (OAc) 2, NaBH3OAc, NaBH 3 CN, KBH 4, KBH (OAc) , LiAlH 4 , B 2 H 6 and DIBAL-H (Diisobutylaluminium hydride), and more preferably NaBH 4 or LiAlH 4 can be used.
  • the amount of the reducing agent according to one embodiment of the present invention is not limited, but the same or an excess amount is used for the imine compound of the formula (4), preferably 1 to 100 equivalents based on 1 equivalent of the imine compound of the formula (4).
  • the reaction temperature for preparing the secondary amine compound of Formula 5 according to an embodiment of the present invention is from room temperature to 250 ° C.
  • the preparation of the secondary amine compound of Formula 5 according to an embodiment of the present invention may be carried out in an organic solvent, and the organic solvent is not limited as long as it can dissolve the reaction material.
  • the solvent of the reaction may be selected from the group consisting of methanol, ethanol, isopropanol, acetone, ethyl acetate, acetonitrile, isopropyl ether, methyl ethyl ketone, methylene chloride, dichlorobenzene, chlorobenzene, dichloroethane, tetrahydrofuran, Xylene. It is more preferable to use an inert solvent selected from the group consisting of methanol, ethanol or a mixed solvent thereof in view of the solubility and ease of removal of the reactants.
  • the phosphorus compound of Formula 6 according to an embodiment of the present invention is used in an excess amount relative to the secondary amine compound of Formula 5, preferably 1 to 20 equivalents based on 1 equivalent of the secondary amine compound of Formula 5.
  • the reaction temperature for preparing the phosphoramidite having the triply structure of Formula 1 according to an embodiment of the present invention is -78 to 100 ° C.
  • the preparation of phosphoramidite having a tripod structure according to an embodiment of the present invention can be carried out in an organic solvent.
  • the organic solvent is not limited as long as it can dissolve the reactant.
  • the solvent of the reaction may be selected from the group consisting of methanol, ethanol, isopropanol, acetone, ethyl acetate, acetonitrile, isopropyl ether, methyl ethyl ketone, methylene chloride, dichlorobenzene, chlorobenzene, dichloroethane, tetrahydrofuran, Xylene, and the like.
  • the starting material is completely consumed through TLC or the like, and the reaction is completed.
  • the solvent can be distilled off under reduced pressure if necessary, and the desired product can be separated and purified through a conventional method such as column chromatography.
  • the present invention relates to a process for the hydroformylation of an olefinic compound comprising a bicyclic bridgehead phophoramidite derivative having two ring structures represented by the following formula (1) and a rhodium or palladium transition metal catalyst ≪ / RTI >
  • R 'and R &quot are each independently (C1-20) alkyl or halogen
  • a and b are each independently an integer of 1 to 4, a and b are not 0 at the same time,
  • R is (C3-C20) cycloalkyl fused with hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C7-C20) bicycloalkyl or aromatic ring;
  • the aryl, cycloalkyl, aryl and bicycloalkyl of R are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 1 -C 20) alkoxy, C20) aryl and (C1-C20) alkyl (C6-C20) aryl.
  • the transition metal catalyst is a hydro-port one is available without a back-transition metal which can be limited using the milhwa reaction, preferably Rh (C 2 H 4) 2 (acac), Pd (dba) 3 , and Rh (CO 2 ) (acac), but the present invention is not limited thereto.
  • the present invention also relates to a process for the hydroformylation of olefinic compounds, characterized in that an aldehyde is produced by reacting an olefinic compound with a synthesis gas of carbon monoxide and hydrogen in the presence of the catalyst composition.
  • the olefin-based compound may be a tri-substituted olefin.
  • R 10 and R 11 are each independently hydrogen, (C 1 -C 20) alkyl, fluorine, chlorine, bromine, trifluoromethyl or (C 6 -C 20) phenyl group having 0-5 substituents, , The substituent is nitro, fluorine, chlorine, bromine, methyl, ethyl, propyl, or butyl group.
  • the aldehyde can be used without limitation as long as it is produced from the hydroformylation reaction of the tri-substituted olefin, but is preferably a tert-carbon internal aldehyde.
  • 1-Methylcyclohexene was used as a tri-substituted olefin substrate, and the bryophos (L9 to L12 in FIG. 3) developed in Korean Patent No. 10-1574071 and the tBu briocose (L13 to L19 in FIG. 3), Clbrifor (L20 to L23 in FIG. 3) prepared in Examples 8 to 11, and commercially available ligands (L1 to L8 in FIG. 3) were subjected to a hydroformylation reaction Respectively.
  • Rh (CO) 2 (acac) (0.01 mmol, 1 mol%) and ligand (0.02 mmol, 2 mol%) were taken in a glove box filled with argon gas and the ligand was coordinated with a transition metal through a stirrer in a toluene solvent (1.0 mmol), the autoclave reactor was closed, and a carbon monoxide / hydrogen mixed gas and an autoclave reactor were connected to the autoclave reactor. And purging was repeated three times using a mixed gas of carbon monoxide and hydrogen (5 bar). After the pressure was applied to the mixed gas of carbon monoxide / hydrogen (20 bar), the mixture was placed in a stirrer set at 100 oC and the reaction was carried out for 12 hours. The remaining gas mixture was removed using a gas valve of the reaction vessel, The vessel was opened and the reaction mixture was transferred to a glass vial (20 mL) and the reaction results were analyzed using NMR and GC-MS analysis equipment.
  • the ligands L1 to L7 of the commercially available phosphorescent ligands exhibited low reactivity and low tertiary-carbon internal aldehyde selectivity, mainly 70% or less, and 65% of the L8 ligand TDTBPP It was confirmed that the selectivity of the internal aldehyde exhibited low selectivity of 65% or less even though it showed moderate reactivity at conversion.
  • (2a-2d) showed good reactivity and tert-carbon internal aldehyde selectivity without modification of the functional groups in the substrates having aliphatic and alcohol and acetate series functional groups in the linear tri-substituted olefinic reactants.
  • the selectivity of low internal aldehyde was shown by the catalytic reaction of 1 mol%, but high selectivity was obtained by increasing the amount of rhodium and ligand used as the catalyst.
  • reaction products of the substrates were purified and separated to obtain spectroscopic data.
  • decomposition of aldehydes into alcohols through additional reduction reaction is confirmed.
  • the products which are not easily evaporated are separated and analyzed by aldehyde.
  • the phosphoramidite derivative having two ring structures according to the present invention is a strong ⁇ -acceptor ligand which increases the ⁇ -bonding force due to the change in the angle between the metal d-orbital and the ⁇ * -orientation of the PN bond , It has an effect of remarkably increasing the activity of the reaction when applied to a chemical reaction using a transition metal having a low oxidation state as a catalyst.
  • the phosphoramidite having two ring structures of the present invention is a geometrically bound phosphorus ligand, and is useful for increasing the selectivity and production yield of the tert-carbon internal aldehyde in a hydroformylation reaction using a tri-substituted olefin as a reactant .

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un dérivé de phosphoramidite ayant deux structures cycliques, son procédé de production et son utilisation et, plus particulièrement, l'invention concerne un dérivé de phosphoramidite bicyclique, un procédé de production de celui-ci, et un procédé de production d'aldéhyde par hydroformylation d'oléfine tri-substituée à l'aide de celui-ci. La présente invention a mise au point un système de catalyseur approprié pour une réaction d'hydroformylation d'oléfine tri-substituée qui n'était pas auparavant capable d'obtenir une réactivité et une sélectivité en aldéhyde interne, par modification des propriétés électroniques stériques, ce qui permet au ligand de briphos selon l'invention d'atteindre une bonne réactivité et une sélectivité en aldéhyde interne de carbone tertiaire. Dans le cas du tBubriphos selon la présente invention, des réactions sont traitées dans des conditions de réaction modérées telles qu'une pression relativement faible et un temps de réaction court par comparaison avec des réactions d'hydroformylation d'oléfines tri-substituées classiques, et les deux composés cycliques ainsi que les composés linéaires présentent, non seulement une bonne réactivité et une sélectivité en aldéhyde interne, mais également une résistance à une réaction d'hydrogénation qui conduit à un problème dans la réaction d'hydroformylation. En outre, le tBubriphos fourni une résistance sans changements des groupes fonctionnels présents dans un réactif, ce qui le rend utile dans des réactions d'hydroformylation d'oléfines tri-substituées.
PCT/KR2018/004186 2017-11-03 2018-04-10 Dérivé de phosphoramidite ayant deux structures cycliques, son procédé de production et son utilisation Ceased WO2019088377A1 (fr)

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* Cited by examiner, † Cited by third party
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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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