WO2006090832A1 - Bisphosphite, procede de production d’un compose aldehyde utilisant du bisphosphite et compose de metal du groupe viii au groupe x - Google Patents

Bisphosphite, procede de production d’un compose aldehyde utilisant du bisphosphite et compose de metal du groupe viii au groupe x Download PDF

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WO2006090832A1
WO2006090832A1 PCT/JP2006/303405 JP2006303405W WO2006090832A1 WO 2006090832 A1 WO2006090832 A1 WO 2006090832A1 JP 2006303405 W JP2006303405 W JP 2006303405W WO 2006090832 A1 WO2006090832 A1 WO 2006090832A1
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group
substituent
bisphosphite
reaction
atom
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PCT/JP2006/303405
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Japanese (ja)
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Takashi Sugioka
Jin Tokuyasu
Hideharu Iwasaki
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Kuraray Co., Ltd.
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Priority to JP2007504808A priority Critical patent/JP4964760B2/ja
Publication of WO2006090832A1 publication Critical patent/WO2006090832A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—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
    • 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
    • C07F9/6571—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
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus 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 novel bisphosphite.
  • the present invention also relates to a composition containing the bisphosphite and a Group 8-10 metal compound. Furthermore, the present invention relates to a method for producing an aldehyde compound using the bisphosphite and a Group 8-10 metal compound. Aldehyde compounds obtained by powerful manufacturing methods are useful as intermediates for medicines and agrochemicals and as raw materials for various chemical products.
  • a method for producing an aldehyde compound by reacting an olefinic compound with carbon monoxide and hydrogen in the presence of a Group 8 to 10 metal compound or a Group 8 to 10 metal compound and a phosphorus compound is known as “hydroformylation”. It is called “reaction” or “oxo reaction”, and it is widely known that it is industrially extremely valuable as a method for producing aldehyde compounds.
  • a rhodium compound or a rhodium compound and a phosphorus compound are generally used industrially as catalysts.
  • phosphine such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (p-tolyl) phosphine (for example, see Patent Document 1);
  • Monophosphites such as ruphosphite, tri-n-butylphosphite, tris (2-tert-butyl-4-methylphenol) phosphite (see, for example, Non-Patent Documents 1 and 2); bis [3,3 ', 5, 5, -tetra-t-butyl (1,1, -biphenyl) -2,2,1gyl] 1,2 ethenolebisphosphite, bis [3,3
  • the bisphosphites such as bisphosphite (see, for example, Non-Patent Document 3, Non-Patent Document 4, Patent Document 2, and Patent Document 3) are known. Acupuncture reactions have been developed.
  • Patent Document 1 Japanese Patent Laid-Open No. 8-10624
  • Patent Document 2 JP-A-6-184036
  • Patent Document 3 International Publication No. 04Z035595 Pamphlet
  • Non-Patent Document 1 The Journal of Organic Chemistry, 1969, No. 34, No. 2, p. 327-330
  • Non-Patent Document 2 Journal of the Chemical Society, Chemical Communications, 1991, p. 1096-1097
  • Non-Patent Document 3 Organometallics, 1996, Vol. 15, p. 835-847
  • Non-Patent Document 4 Helvetica Chimica Acta, 2001, 84th, p. 3269-3280
  • the amount of the Group 8-10 metal compound used in the reaction system is small [for example, ⁇ Group 10 metal atom concentration 50ppm (mass ratio) or less] or recovering Group 8 ⁇ 10 metal compound 'Hydroformyl reaction while reusing is preferable from the viewpoint of reducing production cost of aldehyde compound .
  • the present inventors use the bisphosphite described in Patent Document 2 to reduce the concentration of the rhodium compound in the reaction system under the condition of 3 MPa '120 ° C [rhodium atom concentration 5 p pm (mass ratio)].
  • the isomerization rate the ratio of the carbon-carbon double bond isomerization of the olefinic compound
  • the target compound was selected. It was confirmed that the problem of a decrease in rate occurred (see Comparative Example 1 in the present specification).
  • the phosphorus compound used in the conventional hydroformylation reaction has room for further improvement, and even if the concentration of the Group 8-10 metal compound is reduced, the productivity is not lowered and the isomerism is reduced.
  • a bisphosphite that can control the cocoon rate is desired.
  • an object of the present invention is to provide a bisphosphite that has solved the above problems, a composition containing the bisphosphite and a Group 8-10 metal compound, and the bisphosphite and a Group 8-10 metal.
  • the object is to provide a method for producing an aldehyde compound using the compound.
  • the present inventors have studied various bisphosphites, and as a result of intensive studies, bisphosphites having a specific structure, which will be described later, are the 8th to 1st. It has been found that even when the concentration of the group 0 metal compound is reduced, it has a high effect of suppressing the isomerization rate and a high hydroformyl soot reaction activity, thus completing the present invention.
  • the specific bisphosphite described in detail in the present invention is formally included in the bisphosphite of the general formula (I) described in Patent Document 3 (when W is the formula ( ⁇ )).
  • the present invention provides:
  • A represents an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, an arylene group which may have a substituent, Z—Z,-(wherein Z and Z ′ may be the same or different and each represents an arylene group which may have a substituent) or a group represented by the formula ZQZ ′ (
  • Z and Z ′ are as defined above, Q represents an oxygen atom or an alkylene group which may have a substituent, and a group represented by In any case, at least one carbon atom may be substituted with an oxygen atom.
  • RR 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 and R 12 are good Guso respectively hydrogen atom be the same or different, halogen
  • Bisphosphite (I)) bisphosphite (I))
  • a method for producing an aldehyde compound comprising reacting an olefinic compound with carbon monoxide and hydrogen in the presence of bisphosphite (I) and a Group 8-10 metal compound, and
  • composition ( ⁇ ) (3) a composition containing bisphosphite (I) and a Group 8-10 metal compound (hereinafter abbreviated as composition ( ⁇ )),
  • novel bisphosphite (I) of the present invention can be used in a hydroformylation reaction of an olefinic compound, for example, as a catalyst component, even if the concentration of the Group 8-10 metal compound is small.
  • the isomeric ratio can be suppressed even under high temperature conditions (eg, 3 MPa '100 ° C).
  • the alkylene groups each independently represented by A and Q include, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, Nonamethylene group, decamethylene group, following formula
  • Examples of the cycloalkylene group represented by A include cyclopropylene group, 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene. Group, 1,4-cyclohexylene group, etc. It is done.
  • Examples of arylene groups independently represented by A, Z and Z ′ include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthylene group, for example. 1, 8-naphthylene group and the like.
  • Specific examples of the group represented by the formula —Z—Z′— include, for example, the following formula
  • the group represented by Any of these groups which may have a substituent includes, for example, a methyl group, an ethyl group, an n propyl group, an isopropyl group, an n butyl group, an isobutyl group, an s butyl group, a t —Butyl group, n-pentyl group and the like, preferably alkyl groups having 1 to 5 carbon atoms; difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 1 fluoropropyl group
  • a fluorine-containing alkyl group having 1 to 3 carbon atoms a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an an a
  • At least one carbon atom may be substituted with an oxygen atom.
  • Examples of the alkyl group that R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represent include, for example, methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group and the like.
  • the alkyl group which may have a substituent is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methoxy group, an ethoxy group, a propoxy group or an isopropoxy group.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
  • Group, butoxy group, isobutoxy group, s butoxy group, t butoxy group such as butoxy group and the like.
  • Examples of the aryl group which R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represent include phenyl Group, naphthyl group and the like.
  • the aryl group may have a substituent, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an sbutyl group, or a tbutyl group.
  • Alkyl groups such as cyclohexyl group; difluoromethyl group, trifluoromethyl group, 1,1 difluoroethyl group, 2,2-difluoroethyl group, 1 fluoroalkyl group such as fluoropropyl group; methoxy group, ethoxy group, propoxy group , Alkoxyl groups such as isopropoxy group, butoxy group, isobutoxy group, s-butoxy group and t-butoxy group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently represented.
  • the alkoxyl group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n -butoxy group, an isobutoxy group, an s -butoxy group, and a t-butoxy group.
  • fluorine atom, chlorine atom, bromine atom, iodine atom and the like can be mentioned.
  • A is as defined above, and M 1 and M 2 represent a hydrogen atom or an alkali metal.
  • diol (III) Diol compounds or diol derivatives (hereinafter collectively referred to as diol (III)) represented by the following general formula (IV)
  • RR 2 , R 3 , R 4 , R 5 and R 6 are as defined above, and X represents a chlorine atom, a bromine atom or an iodine atom.
  • Halogenated phosphite (IV) halogenated phosphite
  • V general formula
  • the halophyllated phosphite (V) may have the same structure as the halogenated phosphite (IV). ))
  • M 1 and Z or M 2 in the diol (III) are hydrogen atoms, they are further reacted simultaneously or sequentially in the presence of a basic substance (hereinafter, (Referred to as “bisphosphite production reaction A”).
  • bisphosphite production reaction A See, for example, Organometallics, 1996, Vol. 15, p. 83 5-847].
  • this method will be described.
  • the diol ( ⁇ ), which is a raw material of bisphosphite (I), has, for example, the following formula:
  • the dioli compound represented by [0033] can be produced by, for example, a method of purifying a diol contained as a by-product in a distillation residue when a catechol derivative is synthesized by hydrolyzing a 2-loganol phenol derivative (for example, JP-A-50-111030). Also, the following formula
  • diol ( ⁇ ) include, for example, the following formula:
  • Examples of the alkali metal represented by M 1 and M 2 include a lithium atom and a sodium atom.
  • the diol ( ⁇ ) in which M 1 and M 2 are alkali metals There are no particular restrictions on the production method of the diol ( ⁇ ) in which M 1 and M 2 are alkali metals.
  • a diol ( ⁇ ) in which M 1 and M 2 are hydrogen atoms and a solvent such as hexane or tetrahydrofuran. Metal hydrides such as sodium hydride and potassium hydride, or alkyllithium such as methyllithium and n-butyllithium at 80 ° C to 25 ° C and normal pressure.
  • a method of acting in the range of 1.8 to 4 moles can be mentioned.
  • halogenated phosphite (IV) and the halogen phosphite (V), which are also raw materials of bisphosphite (I), are represented by, for example, the general formula ⁇ (wherein X is as defined above). is there. )
  • a reaction temperature of 100 to 100 ° C. in the presence of a basic substance and a solvent, if necessary, in an inert gas atmosphere such as nitrogen or argon. It can be produced by reacting at a reaction pressure of 0.05 to 3 MPa [see, for example, Journal of Chemical Society, 1953, p. 1920-1926].
  • raw material manufacturing 1 a powerful raw material manufacturing method (hereinafter referred to as “raw material manufacturing 1”) will be described.
  • phosphorus trihalide compounds include phosphorus trichloride, phosphorus tribromide, and phosphorus triiodide.
  • saligenin salicylic alcohol
  • 4- 6-dimethyl 2-hydroxymethylphenol 4, 6-di-tert-butyl 2-hydroxymethyl phenol
  • 4, 6-dimethyl 2- (a-Hydroxyethyl) phenol 4, 6-dimethyl 2- (a-Hydroxy-1- ⁇ -methylethyl) phenol
  • 4,6-dimethyl-2- (a-Hydroxy-1- ⁇ -phenyl) phenol 2, 2-— (j8, ⁇ -dimethyl mono- ⁇ -hydroxypropyl) phenol and the like.
  • the amount of orthohydroxymethylphenol used is preferably in the range of 0.1 to 1 mole per mole of phosphorus trihalide compound.
  • basic substances used as necessary include, for example, trimethylamine, triethylamine, tri- ⁇ -butylamine, tri- ⁇ -octylamine, jetylisopropylamine, ⁇ , ⁇ -dimethylaniline, pyridine, Nitrogen-containing compounds such as picoline, collidine, lutidine, quinoline and the like can be mentioned. These may be used alone or in combination of two or more. When such a basic substance is used, the amount used is preferably in the range of 2 to 10 moles per mole of orthohydroxymethylphenols.
  • the solvent used as necessary is, for example, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, and cyclohexane.
  • Examples of the method for producing the raw material 1 include a method in which a basic substance and a phosphorus trihalide compound are charged into a reactor, and orthohydroxymethylphenols are added at a predetermined temperature and stirred.
  • the halogenated phosphite (IV) and the halogenated phosphite (V) obtained in this way remove the by-produced salt by filtration from the reaction mixture, and remove the solvent from the filtrate.
  • the crude product obtained is distilled off and used as it is in bisphosphite production reaction A. If necessary, it is further purified by distillation or the like to obtain a highly purified halogenated phosphite (IV) or halogenated phosphite ( V) can also be used in the reaction A for producing bisphosphite.
  • the basic substances used when M 1 and Z or M 2 in the diol ( ⁇ ) are hydrogen atoms include, for example, trimethylamine, triethylamine, Tri-n-butylamine, tri-n-octylamine, jetylisopropylamine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminoline, pyridine, picoline, collidine, lutidine, quinoline, etc.
  • Nitrogen-containing compounds of: carbonates or bicarbonates such as lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and the like.
  • the amount used is preferably in the range of 1 to: LOO mol per mol of diol (III), and from the viewpoint of economy and removal efficiency, A range of 1 to 10 moles is more preferred.
  • the amounts of halogenated phosphite (IV) and halogenated phosphite (V) used are 0.4 to 0.4 1. 2 times mole It is preferable that it is the range of these.
  • the total amount of diol ( ⁇ ) is preferably in the range of 0.8 to 2.4 mol with respect to 1 mol. .
  • the solvent examples include saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane and cyclohexane; benzene, toluene, ethylbenzene, propylene benzene, o xylene, m-xylene, p-xylene, o Aromatic hydrocarbons such as ethyl ether, m-ethyl toluene, p ethyl toluene; dimethyl ether, ethyl ethyl ethere, jetino vinyl ether, dipropino vinyl ether, butino vinyl alcohol, t-butyl methyl ether, dibutyl ether And ethers.
  • the inert gas include nitrogen and argon.
  • the reaction temperature is usually in the range of 100 to 100 ° C
  • the reaction pressure is usually in the range of 0.05 to 3
  • the method for reacting diol (III), halogenated phosphite (IV) and halogenated phosphite (V) is not particularly limited.
  • diol (III) is used, and M 1 and M 2 are hydrogen atoms.
  • a method of adding to halogenated phosphite (IV) and neurogenic phosphite (V), and halogenated phosphite (IV) and halogenated phosphate (V) examples thereof include a method of adding to diol (III) simultaneously or sequentially in the presence of a substance.
  • reaction 1 The method for producing aldehyde compounds (hereinafter referred to as “Reaction 1”) will be described in detail.
  • olefinic compound used in Reaction 1 ethylene, propylene 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 nonene, butadiene, 1,7-octagen, cyclooctagen, dicyclopentagen, cyclopentene, cyclohexene , 1-methylcyclohexene, cyclooctene, limonene, 2 pentene-1 ol, 2-methyl-2-propene-1 ol, 3-methyl-3-butene 1 ol, 7 otaten 1 ol, 2, 7-octagen 1-ol, butyl acetate, acetic acid Aryl, methyl acrylate, ethyl acrylate, allylic acrylate, methyl methacrylate, vinyl methyl ether, aryl ether, 5-hexene amide, acrylonitrile, 7
  • rhodium compounds for example, rhodium compounds, cobalt compounds, ruthenium compounds, iron compounds and the like can be mentioned.
  • rhodium compounds include Rh (acac) (CO), RhCl (CO) (PPh), RhCl (PPh), RhBr (CO) (PPh), Rh (CO),
  • Rh (CO).
  • cobalt compounds include HCo (CO) and HCo (HCo).
  • Examples include Ru (CO) (PPh), RuCl (PPh), RuCl (PPh), Ru (CO), etc.
  • iron compounds include Fe (CO), Fe (CO) PPh, Fe (CO) (PP
  • the amount of group 8-10 metal compound used is preferably in the range of 1-50 ppm (mass ratio) in terms of the concentration of group 8-10 metal atoms in the reaction mixture. : More preferably in the range of LOppm (mass ratio). 8th: If the concentration of the L0 group metal compound is less than 10 ppm relative to the reaction mixture, the reaction rate tends to be extremely slow, and if it exceeds 50 ppm, the cost of the catalyst increases, and the aldehyde compound concentration increases. It does not meet the objective of carrying out the reaction while reducing manufacturing costs.
  • one bisphosphite (I) may be used alone, or two or more may be used in combination.
  • the amount of strong bisphosphite (I) used is the 8th: gold in the L0 group metal compound
  • the range of 2 to L in terms of phosphorus atoms is preferably in the range of 2 to L000 mol, more preferably in the range of 5 to 500 mol, with respect to 1 mol of the genus atom. More preferably, it is in the molar range. If the amount of bisphosphite (I) used is less than 2 moles relative to 1 mole of metal atoms in the Group 8-10 metal compound, the stability of the catalyst will be impaired. The speed tends to be very small.
  • composition (II) When a composition containing bisphosphite (I) and a Group 8-10 metal compound, that is, composition (II) is used in Reaction 1, there is no particular limitation on the method for preparing composition (ii).
  • a bisphosphite (I) and a Group 8-10 metal compound are mixed in the presence of a solvent described later as necessary to produce a composition (II), and the reaction (1) is carried out.
  • the bisphosphite (I) and Groups 8 to 10 can be added to the mixed solution prepared to be used, or to the mixed solution containing the olefinic compound and, if necessary, the solvent. It is also possible to add a metal compound at the same time to obtain a composition ( ⁇ ) in the reaction system!
  • composition (ii) containing the bisphosphite (I) and the Group 8-10 metal compound obtained by the above method has an olefinic combination even if the amount of the Group 8-10 metal compound used is small.
  • the productivity is not lowered and the isomerization rate can be suppressed.
  • This composition ( ⁇ ⁇ ) is used not only as a catalyst for the reaction 1 (hydroformylation reaction) described here, but also as a catalyst for hydrogenation reaction of unsaturated bonds, carbon-carbon bond formation reaction, etc. Can also be used.
  • a phosphorus compound may be used together with the bisphosphite (I).
  • phosphorus compounds include triisopropylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tribenzylphosphine, triphenylphosphine, tris (p-methoxyphenyl) phosphine, and tris (p-N, N-dimethylaminophenol) phosphine, tris (p-fluorophenyl) phosphine, tris (p-phlorophenyl) phosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine , Tris (pentafluorophenyl) phosphine, bis (pentafluorophenyl) phenylphosphine, diphenyl (pentafluorophenyl) pho
  • the isomeric ratio does not increase in Reaction 1.
  • the range is 5 mol or less per 1 mol of bisphosphite (1).
  • the range of 0.5 to 3 mol is more preferable.
  • Reaction 1 is performed in the presence or absence of a solvent.
  • powerful solvents include saturated aliphatic hydrocarbons such as bentane, hexane, heptane, octane, nonane, decane, and cyclohexane; benzene, toluene, ethylbenzene, propylbenzene, o-xylene, m-xylene, p Aromatic hydrocarbons such as xylene, o ethynyl nolene, m-ethitil nolene, p ethyl toluene; alcohols such as isopropyl alcohol, isobutyl alcohol, isopentyl alcohol, neopentyl alcohol; dimethyl etherol, ethino reme chinole ethenore, Jetinoreethenore, Dipropinoleetenore, Butinoremethinoreatenore, To
  • the reaction temperature is usually preferably in the range of 40 to 150 ° C, and more preferably in the range of 50 to 130 ° C. From the viewpoint of maintaining high activity with a small amount of catalyst, 80 More preferably, it is in the range of ⁇ 130 ° C.
  • the reaction pressure is preferably in the range of 0.0 l to 10 MPa (gauge pressure), and more preferably in the range of 0.5 to 5 MPa (gauge pressure).
  • Reaction 1 can be carried out continuously or batchwise using a stirring reaction tank, a circulation reaction tank, a bubble column reaction tank, or the like.
  • the method for carrying out Reaction 1 is not particularly limited.
  • an olefinic compound is charged in the presence of a mixed gas of carbon monoxide and hydrogen and stirred at a predetermined temperature, and bisphosphite (I) and It can be carried out by supplying a mixed solution of the Group 8-10 metal compound and the solvent (composition (ii)).
  • the purification method can be carried out by a known method without any particular limitation. For example, by distilling low boiling components such as solvents from the reaction mixture under reduced pressure, the residue is further purified by distillation, High purity aldehyde can be obtained. Prior to distillation separation, the composition (s) may be separated in advance by subjecting the residue to a method such as evaporation, extraction or adsorption. The separated composition ( ⁇ ) can be used again for the hydroformylation reaction (Reaction 1).
  • a method such as evaporation, extraction or adsorption.
  • Example 1 the reaction and reaction were carried out in the same manner as in Example 1, except that 4.14 g (27.2 mmol) of 4,6 di-tert-butyl-2-hydroxymethylphenol was used instead of 3.38 g (27.2 mmol) of saligenin.
  • the following bisphosphite (hereinafter referred to as bisphosphite (I) 7) 4.88g [yield 68% based on 2,2, -methylenebis (4,6 dimethylphenol)] It was. 1 H-NMR data of the obtained bisphosphite (I) 7 are shown.
  • a 300 ml three-necked flask equipped with a thermometer and a dropping funnel was charged with 10.3 g (75 mmol) of phosphorus trichloride and 100 ml of toluene, and 11.87 g (150 mmol) of pyridine was substituted with nitrogen in the system. After cooling the system to -70 ° C, a solution of 11. 6 g (50 mmol) of 4, 6 di-tert-butyl-2 hydroxymethylphenol in 50 ml of toluene was added. It was dripped so that it might be kept below.
  • Example 8 instead of 4, 4, 6, 6, 6, monotetra-tert-butyl 2, 2, monobiphenol 10. 27 g (25 mmol), 6, 6, di-tert-butyl-4, 4, The reaction and isolation / purification operations were performed in the same manner as in Example 8 except that 8.96 g (25 mmol) of dimethoxy-2,2-biphenol was used, and the following bisphosphite (hereinafter referred to as bisphosphite (I)) was used. (Referred to as —10) 16.19 g (6,6, -di-tert-butyl-4,4, -dimethoxy-2,2, -biphenol based yield 73%) was obtained. 1 H-NMR data of the obtained bisphosphite (I) 10 are shown.
  • catalyst solution A In a 100 ml electromagnetic stirring autoclave with gas inlet and sampling port, catalyst solution A2.5 ml (Rh (acac) (CO) 0.
  • TOF Turn Over The frequency
  • Example 11 the reaction and analysis were performed in the same manner as in Example 11 except that 47.5 ml of 1 otaten was replaced with 47.5 ml of 7-otatenal.
  • Rhodium metal atom concentration 5. Oppm (mass Ratio)]
  • 7-Otatenal conversion rate is 99%
  • Example 11 47.5 ml of 1 otaten was replaced with 47.5 ml of 7-otatenal, and “bisphosphite (I) 8” was replaced by

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Abstract

L’invention concerne un nouveau bisphosphite représenté par la formule générale (I) : (I) dans laquelle A représente un groupe alkylène qui peut avoir un substituant, un groupe cycloalkylène qui peut avoir un substituant, un groupe arylène qui peut avoir un substituant, un groupe représenté par la formule : -Z-Z'- (dans laquelle Z et Z' représentent indépendamment un groupe arylène qui peut avoir un substituant) ou un groupe représenté par la formule : -Z-Q-Z'- (dans laquelle Z et Z' sont tels que définis ci-dessus et Q représente un atome d’oxygène ou un groupe alkylène qui peut avoir un substituant), où au moins un atome de carbone du groupe alkylène ou du groupe cycloalkylène peut être substitué par un atome d’oxygène ; et R1 à R12 représentent indépendamment un atome d’hydrogène, un atome d’halogène, un groupe alkyle qui peut avoir un substituant, un groupe aryle qui peut avoir un substituant ou un groupe alcoxyle.
PCT/JP2006/303405 2005-02-25 2006-02-24 Bisphosphite, procede de production d’un compose aldehyde utilisant du bisphosphite et compose de metal du groupe viii au groupe x WO2006090832A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014189525A (ja) * 2013-03-27 2014-10-06 Kuraray Co Ltd 直鎖状ジアルデヒドの製造方法
CN108129515A (zh) * 2017-12-05 2018-06-08 中海油天津化工研究设计院有限公司 一种双亚磷酸酯的合成方法
EP4180439A1 (fr) * 2021-11-15 2023-05-17 Evonik Operations GmbH Procédé de réduction de la teneur en chlore des organobisphosphites par fritte de gaz de protection

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JP2005500384A (ja) * 2001-08-16 2005-01-06 オクセノ　オレフィンヒェミー　ゲゼルシャフト　ミット　ベシュレンクテル　ハフツング 新規ホスファイト化合物及びその金属錯体

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DE10031493A1 (de) * 2000-06-28 2002-01-10 Oxeno Olefinchemie Gmbh Neue Bisphosphitverbindungen und deren Metallkomplexe

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014189525A (ja) * 2013-03-27 2014-10-06 Kuraray Co Ltd 直鎖状ジアルデヒドの製造方法
CN108129515A (zh) * 2017-12-05 2018-06-08 中海油天津化工研究设计院有限公司 一种双亚磷酸酯的合成方法
EP4180439A1 (fr) * 2021-11-15 2023-05-17 Evonik Operations GmbH Procédé de réduction de la teneur en chlore des organobisphosphites par fritte de gaz de protection

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