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WO2006009167A1 - Procédé servant à produire des éthers - Google Patents

Procédé servant à produire des éthers Download PDF

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Publication number
WO2006009167A1
WO2006009167A1 PCT/JP2005/013307 JP2005013307W WO2006009167A1 WO 2006009167 A1 WO2006009167 A1 WO 2006009167A1 JP 2005013307 W JP2005013307 W JP 2005013307W WO 2006009167 A1 WO2006009167 A1 WO 2006009167A1
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WO
WIPO (PCT)
Prior art keywords
group
octadiene
palladium
dimethyl
compound
Prior art date
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PCT/JP2005/013307
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English (en)
Japanese (ja)
Inventor
Hiroshige Ishino
Taketoshi Okuno
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Kuraray Co Ltd
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Kuraray Co Ltd
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Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Publication of WO2006009167A1 publication Critical patent/WO2006009167A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds

Definitions

  • the present invention relates to a method for telomerization of a conjugate conjugate compound.
  • Ethers produced by the telomerization method of the present invention are useful as raw materials for various polymers, intermediates for fragrances, and the like.
  • the telomerization reaction of a conjugated genie compound is a reaction in which the conjugated geny compound oligomerizes by incorporating a nucleophilic reactant.
  • palladium compounds, especially palladium compounds coordinated with phosphine compounds are known to exhibit excellent activity as catalysts for telomerization reactions! Reference 1).
  • Non-Patent Document 1 Niro Tsuji, “Palladium Reagents and Catalysts”, John Wiley
  • Patent Document 1 Japanese Patent Laid-Open No. 4-504267
  • Patent Document 2 Japanese Patent Publication No. 48-43327
  • Non-Patent Document 1 the palladium compound coordinated with the phosphine compound is poor in thermal stability. Since the compound decomposes and palladium black precipitates, there is a problem that it is difficult to reuse the palladium compound and the manufacturing cost is increased.
  • tetrakis triphenylphosphine
  • an object of the present invention is to solve the above problems and provide an industrially more advantageous method for producing ethers by a telomerization reaction of a conjugate conjugated compound.
  • the object is to provide a palladium compound and a general formula (I)
  • R 1 may have a substituent, or may have an alkyl group or a substituent, and may represent a! / Aryl group.
  • hydroxyli compound (I) In the method for producing ethers by telomerization reaction of a conjugated genie compound in the presence of
  • R 2 , R 3 and R 4 each independently represents an alkyl group having 1 to C0 carbon atoms.
  • ethers when a telomerization reaction of a conjugated diene compound is industrially carried out, ethers can be produced with high selectivity at a low catalyst concentration with a small decrease in catalytic activity. .
  • conjugate conjugated compound used in the present invention include, for example, 1,3 butadiene, isoprene, piperylene, 2,3 dimethyl-1,3 butadiene, 1,3,7-otatriene, 1, 3 cyclohexagen, 1, 3 cyclooctagen and the like.
  • conjugated Jenji compounds can be of low purity, for example, 1,3 butadiene.
  • crude butadiene butenes such as isobutylene, acetylene such as methylacetylene, 1-butyne, etc.
  • 1,2-butadiene containing impurities such as 1,2 butadiene).
  • the alkyl group represented by R 1 is preferably an alkyl group having 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, Examples include isobutyl group, sbutyl group, tbutyl group, n-pentyl group, n xyl group, n butyl group, n-octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.
  • substituents which may have a substituent include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; aryl groups such as phenyl group, tolyl group and xylyl group An alkoxyl group such as a methoxy group, an ethoxy group or an isopropoxy group; a 2-methoxyethyloxy group, a 2-ethoxyethyloxy group; a hydroxyl group;
  • the aryl group represented by R 1 is preferably an aryl group having 614 carbon atoms, such as a phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group, and the like.
  • substituents which may have a substituent include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, Alkyl groups such as isobutyl group, sbutyl group, tbutyl group, pentyl group, hexyl group, heptyl group and octyl group; alkoxyl groups such as methoxy group, ethoxy group and isopropoxy group; hydroxyl Groups and the like.
  • halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom
  • hydroxyl compound (I) examples include, for example, methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1 propanol, 1-butanol, 2-butanol, pentano-nore, isopentino-leanol Nore, cyclopentanol, hexanol, 2-hexanol, cyclohexanol, heptanol, octanol, 2-octanol, 3-octanol, benzyl alcohol, phenethyl alcohol, phenol, ethylene glycol, diethylene glycol, propylene glycol , Ethylene glycol monomethino ethenore, ethylene glycol monomethino ethenore, diethylene glycol monomethino methinore ethenore, diethylene glycol monomethino techinore, propylene group Konoremo Bruno methyl ether, propylene glycol
  • the amount of the hydroxyl compound (I) to be used is preferably in the range of 0.1 to 10 times mol, more preferably in the range of 0.5 to 5 times mol, with respect to the conjugation compound.
  • Examples of the ethers obtained in the present invention include 1-methoxy 2,7-octadiene, 1 ethoxy-2,7-octadiene, 1 propoxy 2,7-octadiene, 1 butoxy-2,7-octadiene, 1 isopentyl mouth Xy 2,7-octadiene, 1-cyclohexyloxy 2,7-octagen, 1 phenoxy 2,7-octagen, 1 benzyloxy 2,7-octagen, 1-methoxy 2,7 dimethinole 2, 7-octadiene, 1 Ethoxy-2,7 Dimethinole 2,7-octadiene, 1 Propoxy 2,7 Dimethylo 2,7-Octagene, 1 Butoxy 2,7 Dimethyl-2,7-Octagene, 1 Isopentyloxy 2,7 Dimethinole 2,7-Octagen, 1-Cyclohexenoreoxy-2, 7 Dimethinole 2, 7-octagen, 1 Phenoxy
  • the palladium compound used in the present invention is not particularly limited as long as it does not have a phosphine compound having an aryl group such as triphenylphosphine.
  • a phosphine compound having an aryl group such as triphenylphosphine.
  • the amount of the palladium compound used is preferably in the range of 0.1 ppm to 100 ppm and more preferably in the range of 10 ppm to 50 ppm with respect to the conjugated diene compound in terms of palladium atoms.
  • R 2 , R 3 and R 4 each independently represent an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n propyl group, an isopropyl group N-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nor group, n-decyl group, cyclopentyl Group, cyclohexyl group, cyclooctyl group and the like.
  • trialkylphosphine ( ⁇ ) used in the present invention include, for example, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, triisobutylphosphine, tri-n-hexyl. Phosphine, tri-n-octylphosphine, trisi And chlorohexylphosphine. These may be used alone or in combination of two or more.
  • the amount of the trialkylphosphine used is preferably in the range of 0.1 to 100 times mol of the palladium atom in the palladium compound, more preferably in the range of 1 to 20 times mol.
  • the method for producing an ether of the present invention can also be carried out in the presence of a basic substance.
  • Powerful basic substances include general formula (III)
  • M represents an alkali metal or an alkaline earth metal
  • R 5 has a hydrogen atom or a substituent, may have an alkyl group or a substituent, or may have an aryl group.
  • N represents 1 when M represents an alkali metal, and 2 when M represents an alkaline earth metal.
  • R 6 , R 7 , R 8 , R 9 and R 1C may each independently have a hydrogen atom or a substituent, and have an alkyl group or a substituent, Of course, it represents the Aryl group.
  • a compound represented by the general formula (V) may each independently have a hydrogen atom or a substituent, and have an alkyl group or a substituent, Of course, it represents the Aryl group.
  • R L R 12 , R 13 , R and R 15 each independently have a hydrogen atom or a substituent.
  • V may have an alkyl group or a substituent, and may represent an aryl group.
  • R 5 R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 1 4 and
  • Examples of the alkyl group independently represented by R 15 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sbutyl group, tbutyl group, pentyl group, hexyl group, heptyl group, An octyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like can be mentioned.
  • aryl group examples include a phenol group and a naphthyl group.
  • substituents examples include aryl groups such as a phenol group, a tolyl group, and a xylyl group.
  • the compound represented by the general formula (III) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkaline earth metal hydroxides such as magnesium hydroxide and barium hydroxide; lithium methoxide, sodium methoxide, sodium isopropoxide, sodium s butoxide, sodium phenoxide, sodium benzyloxide, potassium methoxide, potassium Ethoxide, potassium isopropoxide, potassium s butoxide, potassium tert butoxide, potassium phenoxide, potassium benzyloxide, magnesium methoxide, magnesium ethoxide, magnesium isopropoxide, magnesium s butoxide, magnesium t -Butoxy , Mag Neshi ⁇ Muhu Enoki Sid, magnesium benzyl O, dimethylsulfoxide, calcium methoxide, Karushiu Muetokishido, calcium isopropoxide, calcium s-butoxide, calcium t-Bed Tokishido
  • Specific examples of the compound represented by the general formula (IV) include, for example, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetra n-propyl ammonium hydroxide, tetraisopropyl ammonium hydroxide, tetra n-butyl ammonium.
  • the compound represented by the general formula (V) include, for example, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetra-n-propylphosphonium hydroxide, tetraisopropylphosphonium hydroxide, tetra-n —Butylphospho-um hydroxide, benzyltrimethinorephospho-muumoxide, tetraphenol-norephospho dihydroxide, tetramethylphospho-mumethoxide, tetraethylphospho-mumethoxide, tetra-n-propylphospho-ummethoxide, triisopropylphospho-ummethoxide, tetra-n —Butylphosphonium methoxide, tetra-n-butylphosphonium ethoxide, tetra-n-butylphosphonium phenoxide, benzyltrimethylphospho-
  • the amount of the strong basic substance used is preferably in the range of 0.1 to: LOOOOO times moles with respect to the palladium atom in the palladium compound. It is more preferable to be in the range of ⁇ 10,000 times mole.
  • the present invention can be carried out in the presence or absence of a solvent.
  • a solvent examples include hydrocarbons such as butane, isobutane, butene, isobutene, pentane, hexane, cyclohexane, benzene, toluene, and xylene; halogens such as dichloromethane, 1,2-dichloroethane, and chloroform.
  • Hydrocarbons Tetrahydrofuran, dipentyl ether, dihexyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and other ethers; formamide, acetoamide, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone And amides.
  • a solvent may be used individually by 1 type and may use 2 or more types together. When the reaction is carried out in the presence of a solvent, the amount of the solvent used is not particularly limited. The range is 0.01 to 10 times the mass of the phenoxy compound.
  • the reaction temperature is preferably in the range of 0 to 150 ° C, more preferably in the range of 20 to 110 ° C. If it is less than 0 ° C, the reaction time tends to be extremely slow, and if it exceeds 150 ° C, by-products tend to increase.
  • the reaction pressure is usually in the range of 0.1-3 MPa.
  • the reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
  • the embodiment of the present invention is not particularly limited, and can be carried out either continuously or batchwise.
  • a palladium compound, a trialkylphosphine (11), a hydroxyl compound (I) and, if necessary, a solvent and Z or a basic substance are mixed, and the resulting mixed solution is subjected to a nitrogen atmosphere.
  • the reaction mixture is continuously or intermittently added to the mixture of the conjugate genide compound and the hydroxyl compound (I) at a predetermined temperature and a predetermined pressure, and is allowed to react for a predetermined time, and then the resulting reaction mixture is continuously added. It can be carried out by extracting regularly or intermittently.
  • a palladium compound, a trialkylphosphine ( ⁇ ), a hydroxyl compound (I) and, if necessary, a solvent and Z or a basic substance are mixed, and the resulting mixture is mixed with a conjugate It can be carried out by injecting a compound and reacting at a predetermined temperature and a predetermined pressure for a predetermined time.
  • catalyst solution A was prepared by dissolving 4.5 g (14.3 mmol) of palladium acetylacetonate and 3.4 g (28.6 mmol) of triethylphosphine in 18 L of methanol.
  • a catalyst solution B was prepared by dissolving 4.5 g (14.3 mmol) of palladium acetylylacetonate and 6.8 g (57.2 mmol) of triethylphosphine in 18 L of methanol under a nitrogen atmosphere.
  • catalyst solution D was prepared by dissolving 4.5 g (14.3 mmol) of palladium acetylylacetonate and 7.5 g (28.6 mmol) of triphenylphosphine in 18 L of methanol. (Preparation of catalyst solution E)
  • a total volume 3L plug flow type reactor with a sampling valve in the middle of the heating equipment and reactor, methanol at 237g (7.4mol) / hour, 1,3-butadiene in nitrogen atmosphere at 2MPa and 100 ° C 200 g (3.70 mol) / hour and catalyst solution A were simultaneously fed at 11.25 g / hour [abundance ratio of 1,3-butadiene and palladium atoms at the time of supply: 270000 to 1 (molar ratio)].
  • the reactor was filled 12 hours after the start of feeding (initial composition: Radium 17mmolZL, 1,3 Butadiene 4.6molZL).
  • Example 1 the reaction and analysis were performed in the same manner as in Example 1 except that catalyst solution B was used instead of catalyst solution A. The results are shown in Table 1.
  • Example 1 the reaction and analysis were performed in the same manner as in Example 1 except that the catalyst solution C was used instead of the catalyst solution A. The results are shown in Table 1.
  • Example 1 the reaction and analysis were performed in the same manner as in Example 1 except that catalyst solution D was used instead of catalyst solution A. The results are shown in Table 1.
  • a 3 L plug flow type reactor with a sampling valve in the heating equipment and the middle stage of the reactor was charged with 237 g (7.4 mol) / hr of methanol and 1,3 butadiene at 2 MPa and 100 ° C in a nitrogen atmosphere.
  • 200 g (3.70 mol) / hour and catalyst solution E were simultaneously fed at 11.25 g / hour [abundance ratio of 1,3 butadiene and palladium atoms at the time of supply: 68000 to 1 (molar ratio)].
  • the method for producing ethers according to the present invention can provide a high conversion rate and a high selectivity for 1-methoxy 2,7-octagene. Furthermore, from Example 1 and Comparative Examples 1 and 2, the use of trialkylphosphine ( ⁇ ) in the present invention unexpectedly increased the conversion rate and produced 1-methoxy-2,7-octadiene. Keep selectivity high Succeeded in doing.
  • Ethers produced by the telomerization method provided by the present invention can be widely used as raw materials for various polymers, intermediates for fragrances, and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Il est exposé un procédé servant à produire des éthers de façon extrêmement sélective à une faible concentration en catalyseur tout en supprimant la baisse d'activité du catalyseur, en effectuant à l'échelle industrielle une réaction de télomérisation de composés diènes conjugués. Il est plus précisément exposé un procédé servant à produire des éthers par une réaction de télomérisation de composés diènes conjugués en présence d'un composé du palladium et d'un composé hydroxylé représenté par la formule générale (I) suivante : R1OH (R1 représentant un groupe alkyle facultativement substitué ou un groupe aryle facultativement substitué), lequel procédé est caractérisé en ce qu'on effectue la réaction également en présence d'un composé de type trialkylphosphine représenté par la formule générale (II) suivante : PR2R3R4 (R2, R3 et R4 représentant indépendamment un groupe alkyle ayant 1-10 atomes de carbone).
PCT/JP2005/013307 2004-07-22 2005-07-20 Procédé servant à produire des éthers Ceased WO2006009167A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-213927 2004-07-22
JP2004213927 2004-07-22

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WO2006009167A1 true WO2006009167A1 (fr) 2006-01-26

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS507590B1 (fr) * 1968-09-18 1975-03-27
JP2001039914A (ja) * 1999-07-27 2001-02-13 Kao Corp グリセリルエーテルの製法
JP2001072636A (ja) * 1999-09-03 2001-03-21 Kao Corp ポリオールアルキルエーテルの製法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS507590B1 (fr) * 1968-09-18 1975-03-27
JP2001039914A (ja) * 1999-07-27 2001-02-13 Kao Corp グリセリルエーテルの製法
JP2001072636A (ja) * 1999-09-03 2001-03-21 Kao Corp ポリオールアルキルエーテルの製法

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