WO2006009167A1 - Method for producing ethers - Google Patents

Abstract

Disclosed is a method for producing ethers highly selectively at low catalyst concentration while suppressing lowering of catalyst activity by commercially performing telomerization reaction of conjugated diene compounds. Specifically disclosed is a method for producing ethers by telomerization reaction of conjugated diene compounds in the presence of a palladium compound and a hydroxyl compound represented by the following general formula (I): R1OH (wherein R1 represents an optionally substituted alkyl group or an optionally substituted aryl group) which method is characterized in that the reaction is performed also in the presence of a trialkylphosphine compound represented by the following general formula (II): PR2R3R4 (wherein R2, R3 and R4 independently represent an alkyl group having 1-10 carbon atoms).

Description

 Specification

 Method for producing ethers

 Technical field

 [0001] 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.

 Background art

 [0002] The telomerization reaction of a conjugated genie compound is a reaction in which the conjugated geny compound oligomerizes by incorporating a nucleophilic reactant. For example, a reaction in which two molecules of 1,3-butadiene react with a compound containing active hydrogen such as one molecule of acetic acid to give 1-acetoxy 2,7-octagen. In powerful telomerization reactions, palladium compounds, especially palladium compounds coordinated with phosphine compounds, are known to exhibit excellent activity as catalysts for telomerization reactions! Reference 1).

 On the other hand, a telomerization reaction using a phosphine compound as a ligand is also known (see Patent Document 1 and Patent Document 2).

 [0003] Non-Patent Document 1: Niro Tsuji, “Palladium Reagents and Catalysts”, John Wiley

& Sons), 1995, p. 423-441

 Patent Document 1: Japanese Patent Laid-Open No. 4-504267

 Patent Document 2: Japanese Patent Publication No. 48-43327

 Disclosure of the invention

 Problems to be solved by the invention

[0004] In the method described in 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.

Examples of Patent Document 1 include «radium acetyl cetate and triphenylphosphine ( The telomerization reaction of 1,3-butadiene using a catalyst solution in which the molar ratio = 1: 2) is dissolved in methanol is described. However, the examples of using trialkylphosphine instead of triphenylphosphine do not describe the effect of using trialkylphosphine without any teaching, nor even suggestion. In the examples of Patent Document 2, the telomerization reaction of 1,3-butadiene in the presence of tetrakis (triphenylphosphine) palladium, tributylphosphine and ethylene glycol is described. However, there is a fundamental problem that the target product is hardly obtained.

 Accordingly, 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.

 Means for solving the problem

[0005] According to the present invention, the object is to provide a palladium compound and a general formula (I)

 [Chemical 1] R'OH (I)

(In the formula, R ¹ may have a substituent, or may have an alkyl group or a substituent, and may represent a! / Aryl group.)

 [Hereinafter, this is referred to as hydroxyli compound (I). In the method for producing ethers by telomerization reaction of a conjugated genie compound in the presence of

[Chemical 2] PR ² R ³ R ⁴ (II)

(In the formula, R ² , R ³ and R ⁴ each independently represents an alkyl group having 1 to C0 carbon atoms.) A trialkylphosphine compound represented by the following: Call it. It is achieved by providing a method for producing the ethers, characterized in that the reaction is carried out in the presence of

 The invention's effect

 [0006] According to the present invention, 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. .

BEST MODE FOR CARRYING OUT THE INVENTION [0007] Hereinafter, the present invention will be described in detail.

 [0008] Specific examples of the 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. In addition, conjugated Jenji compounds can be of low purity, for example, 1,3 butadiene. For example, crude butadiene (butenes such as isobutylene, acetylene such as methylacetylene, 1-butyne, etc.) that are commercially available at low cost. 1,2-butadiene containing impurities such as 1,2 butadiene). It is well known to those skilled in the art that strong crude butadiene is obtained as a C4 fraction by thermal decomposition of naphtha. The crude butadiene obtained in this way can be obtained at low cost because the process of isolating 1,3 butadiene is omitted, and if strong crude butadiene is used as a raw material, it is industrially advantageous from the viewpoint of production cost. is there. In the present invention, even when a low-purity conjugate conjugated compound such as strong crude butadiene is used as a raw material, the conversion rate and selectivity can be maintained high.

In the general formula (I), 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. These 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. These 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.

 Specific examples of the hydroxyl compound (I) 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 monomethyl E chill ether.

 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 2, 7 Dimethinore 2, 7- Octadi 1, 1 Benzyloxy 2, 7 Dimethinole 2, 7-octagen, 1-Methoxy 2, 6 Dimethinore 2, 7-octadiene, 1 Ethoxy 2, 6 Dimethinore 2, 7- Octagen, 1 Propoxy 2, 6 Dimethyl 2, 7— Octagen, 1 Butoxy-2,6 Dimethyl-2,7-Octadene, 1 Isopentyloxy 2,6 Dimethyl-2,7-Octadene, 1-Cyclohexyloxy 2,6 Dimethylolene 2,7-Octagen, 1 Phenoxy 2,6 Dimethyl 2, 7-octadiene, 1 benzyloxy 2, 6 dimethinole 2, 7-octagen, 1-methoxy 3, 7 dimethinore 2, 7-octadi 1, 1 ethoxy 3, 7 dimethyl-2, 7-octagen, 1 propoxy 3, 7-dimethyl-2, 7-octagen, 1 butoxy3, 7 dimethyl-2, 7-octagen, 1 isopentyloxy 3, 7 dimethyl-2 7-octadiene, 1-cyclohexyloxy 3, 7 dimethyl-2, 7-octadiene, 1 phenoxy 3, 7 dimethyl-2, 7-octadiene, 1 benzyloxy 3, 7 dimethyl-2, 7-octadiene, 1-methoxy 3, 6 Dimethyl-2,7-octadiene, 1 ethoxy 3,6 Dimethyl-2,7-octadiene, 1 Propoxy 3,6 Dimethyl-2,7-octadiene, 1-butoxy3,6 Dimethinole 2,7-octadiene, 1 Isopentyloxy 3 , 6 Dimethinole 2, 7—octadiene, 1-cyclohexyloxy 3, 6 Dimethinole 2,7 Otatagen, 1 Phenyloxy 3, 6 Dimethyl 2, 7-octadiene, 1 Benzyloxy 3, 6 Dimethinole 2, 7-octadiene, 3-methoxy-2, 7-octadiene, 3-- ethoxy 2, 7-octadiene, 3 propoxy 2, 7-octadiene, 3 butoxy 2 , 7-octadiene, 3 isopentyloxy 2, 7-octadiene, 3 cyclohexenoreoxy 2, 7-octadiene, 3 phenoxy 2, 7-octadiene, 3 pendinoreoxy 2,7-octadiene, 3-methoxy 2,7 dimethinole 2, 7-octadiene, 3 ethoxy 2, 7 dimethylene 2, 7-octagen, 3 propoxy 2, 7 dimethylol 2, 7-octadiene, 3 butoxy 2, 7 dimethyl 2, 7-octadiene, 3— isopentyloxy 2, 7 Dimethinore 2, 7-octagen, 3 Cyclohexenoreoxy-2, 7 Dimethinore 2, 7-octadiene, 3 Enoxy 2, 7 Dimethinore 2, 7— Octagen, 3 Benzyloxy 2, 7 Dimethinore 2, 7—Octagen, 3—Methoxyxy 2, 6 Dimethinore 2, 7—Octadiene, 3 Ethoxy 2, 6 Dimethinore 2, 7—Octagen, 3 Propoxy 2,6 Dimethyl-2,7-octadiene, 3 Butoxy-2,6 Dimethyl-2,7-octadiene, 3 Isopentyloxy 2,6 Dimethyl-2,7-octadiene, 3 Cyclohexyloxy 2,6 Dimethinole 2, 7— Octagen, 3 Phenoxy 2, 6 Dimethyl 2, 7-octagen, 3-Benzyloxy 2, 6 Dimethylolene 2, 7-Octagen, 3-Methoxy-3, 7 Dimethinole 2, 7-Octagen, 3 Ethoxy 3, 7 Dimethyl 2 , 7-octagen, 3 propoxy 3, 7-dimethyl-2, 7-octagen, 3 butoxy-3, 7 dimethyl-2, 7-oct Tajen , 3 Isopentyloxy 3, 7 Dimethyl-2, 7-octadiene, 3 Cyclohexyloxy 3, 7 Dimethyl-2, 7-octadiene, 3 Phenoxy 3, 7 Dimethyl-2, 7-octadiene, 3-Benzyloxy 3, 7 Dimethyl-2 , 7-octadiene, 3-methoxy 3,6 dimethyl 2, 7-octadiene, 3 ethoxy 3, 6 dimethyl 2, 7-octadiene, 3 propoxy 3, 6 dimethyl-2, 7-octadiene, 3 butoxy 3, 6 dimethylene 2, 7-octadiene, 3 isopentyloxy 3,6 dimethylol 2, 7-octagen, 3 cyclohexyloxy 3, 6 dimethylolene 2, 7 otatagene, 3 phenoxy 3, 6 dimethyl 2, 7-octadiene, 3 benzoxy 3 , 6 Dimethyl-2,7-octagen and the like.

 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. For example, palladium formate, palladium acetate, palladium chloride, palladium bromide, carbonate Palladium, palladium sulfate, palladium nitrate, sodium chloropalladate, potassium chloropalladate, palladium acetylethylacetonate, bis (benzo-tolyl) palladium dichloride, bis (t-butylisocyanide) palladium dichloride, bis (dibenzylideneacetone) Examples thereof include palladium, tris (dibenzylideneacetone) dipalladium, and bis (1,5-cyclooctagen) palladium. Among these, from the viewpoint of availability and economy, it is preferable to use palladium acetate or palladium acetyl cetate. 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.

In the general formula (一般), 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.

[0014] Specific examples of the trialkylphosphine (Π) 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.

 [0015] 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)

[Chemical 3] M (OR ⁵ ) (III)

(In the formula, 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.)

 A compound of formula (IV)

 [0016] [Chemical 4]

R ⁷

,, _R8 . (IV)

R, R ⁹

[0017] (wherein 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)

 [0018] [Chemical 5]

NO 013 ^0R (V)

[Wherein, 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. ) And the like.

[0020] the general formula (III), in (IV) and ^{(V), 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. Examples of the aryl group include a phenol group and a naphthyl group. Examples of such a substituent that may have a substituent include aryl groups such as a phenol group, a tolyl group, and a xylyl group.

 Specific examples of 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, calcium phenoxide, calcium benzyl O, dimethylsulfoxide and the like.

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. -Um hydroxide, benzyltrimethylammonium hydroxide, tetramethylammonium methoxide, tetramethylammonium methoxide, tetramethylammonium n-propoxide, tetramethylammonium methoxide, tetraethylammonium methoxide, tetraethylammonium methoxide, tetraethylammonium -Um _n —propoxide, te Traetylammo-umphenoxide, tetra- _n -propylammomethoxide, tetra- _n -propylammomethoxide, triisopropylammomethoxide, trisopropylammomethoxide, tetra- _n- butylammomethoxide, tetra- _n- butylammooxide , Tetra-n-butylammonium phenoxide, benzyltrimethylammonium methoxide, benzyltrimethylammonium methoxide, benzyltrimethylammonium phenoxide, and the like.

 Specific examples of 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-mumethoxide, Rafue - Ruhosuho - Umumetokishido, Tetorafue - Ruhosuho - Umuetokishido, Tet Rafue - Ruhosuho - Umufuenokishido the like.

 [0024] When a basic substance is used, 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.

[0025] The present invention can be carried out in the presence or absence of a solvent. Examples of powerful solvents 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.

[0026] 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.

[0027] The embodiment of the present invention is not particularly limited, and can be carried out either continuously or batchwise. For example, when carried out continuously, 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. On the other hand, in the case of a batch method, a palladium compound, a trialkylphosphine (Π), 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.

 [0028] After completion of the reaction, there is no particular limitation on the method for separating and purifying ethers from the obtained reaction mixture, and a normal method for separating and purifying organic compounds can be used. For example, after distilling off unreacted raw materials and the solvent used as necessary, the residual strength of the catalyst components (palladium compounds, trialkyls, etc.) by thin film evaporation, decantation, extraction, adsorption, etc. High purity ethers can be obtained by separating phosphine (ホ ス フ ィ ン)) and purifying the obtained residue by distillation, recrystallization or column chromatography. The mixed solution containing the separated catalyst component can be reused in the ether production method of the present invention.

 Example

[0029] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Gas chromatography in each example and comparative example The graphic analysis was performed according to the following procedure.

 [Gas chromatography analysis]

 Equipment: GC— 14B (manufactured by Shimadzu Corporation)

 Column used: DB—WAX (10m) (manufactured by Agilent Technologies)

 Analysis conditions: injection temp. 220 ° C, detection temp. 250 ° C, temperature rising condition: hold at 40 ° C for 8 minutes → temperature rise at 15 ° C, minutes → hold at 240 ° C for 30 minutes

[0030] <Reference Example 1>

 (Preparation of catalyst solution A)

 In a nitrogen atmosphere, 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.

 (Preparation of catalyst solution B)

 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.

 (Preparation of catalyst solution C)

 Under a nitrogen atmosphere, 4.5 g (14.3 mmol) of palladium acetylylacetonate and 5.8 g (28.6 mmol) of tributyl phosphate were dissolved in 18 L of methanol to prepare catalyst solution C.

 (Preparation of catalyst solution D)

 In 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)

 Under a nitrogen atmosphere, 18 g (59 mmol) of palladium acetylylacetonate and 3 lg (118 mmol) of triphenylphosphine were dissolved in 18 L of methanol to prepare catalyst solution E.

<Example 1>

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). A part of the reaction mixture after the reaction for 2 hours and 4 hours from this point was extracted (the sampling valve in the middle of the reactor and the distilling site force in the lower part of the reactor were also extracted), and gas chromatography analysis was performed. It was. The results are shown in Table 1.

 <Example 2>

 In 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 3>

 In 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.

 [0034] <Comparative Example 1>

 In 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.

 [0035] <Comparative Example 2>

 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)]. After 12 hours the reactor was full (initial composition: palladium 67.3 mmol / L, 1,3 butadiene 4.6 mol / L) o Reaction mixture after 2 hours, 4 hours and 6 hours of reaction from this point Part of the liquid is withdrawn (the sampling valve at the middle of the reactor and the distillation site at the bottom of the reactor are withdrawn, and the reaction mixture that has been distilled off at the bottom of the reactor is further separated in another reactor for another 2 hours. A part of the reaction mixture was extracted after reaction, and gas chromatography was analyzed. The results are shown in Table 1.

[0036] From Examples 1 to 3, 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 (Π) in the present invention unexpectedly increased the conversion rate and produced 1-methoxy-2,7-octadiene. Keep selectivity high Succeeded in doing.

[table 1]

Reaction time ¾ Conversion Selectivity (%)

 (Time) (%) MODE 1 1 MOD E-3 〇τ VCH

2 7 5. 9 92. 1 4. 2 2. 2 0. 9 Example 1

 4 98. 3 92. 2 4. 3 2. 1 0. 6

2 67. 3 92. 3 3. 3 2. 3 1. 0 Example 2

 4 9 5. 9 92. 0 3. 9 2. 2 0. 6

2 7 6. 1 9 1. 3 4. 3 2. 3 0. 4 Example 3

 4 98. 0 92. 0 4. 0 2. 4 0. 6

2 1 1. 9 90. 3 5. 0 3. 4 0. 7 Comparative Example 1

 4 29. 2 90. 2 4. 9 3. 5 0. 8

2 40. 7 90. 3 5. 0 3. 7 0. 9 Comparative example 2 4 7 6. 3 90. 1 4. 9 3 5 5 0.8

 6 7 8. 2 90. 1 5. 1 3. 4 0. 7

MODE—1: 1—Methoxy 1, 2, 7—Octagen

 MOD E—3: 3-chome methoxy 1,7—talenta

 OT: 1, 3, 7—Oketatriene

VCH: Vinylcyclohexene

Industrial applicability

 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.

Claims

Claims Palladium compounds and general formula (I)

[Chemical 1] R'OH (I)

(In the formula, R ¹ may have a substituent, or may have an alkyl group or a substituent, and may represent a! / Aryl group.)

In the process for producing ethers by telomerization reaction of a conjugate conjugate compound in the presence of a hydroxyl compound represented by the general formula (II)

[Chemical 2] PR ² R ³ R ⁴ (II)

(Wherein R ² , R ³ and R ⁴ each independently represents an alkyl group having 1 to C carbon atoms: L0.) In the presence of a trialkylphosphine compound represented by A method for producing the ethers as described above.