JP2011026253A - Method for producing allyl ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new method for producing allyl ether, which has a high reaction efficiency. <P>SOLUTION: The method for producing allyl ether includes a step of reacting a hydroxy group-containing compound with a carboxylic acid allyl ester in the presence of a transition metal catalyst, a complexing agent and a tertiary amine. In the reaction step, preferably the reaction is carried out in the presence of water in the reaction system in a state in which the organic phase and water phase are separated into two phases. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing allyl ether. More specifically, the present invention relates to a method for producing a new allyl ether compound different from a raw material compound by reacting a carboxylic acid allyl ester compound with a hydroxyl group-containing compound in the presence of a catalyst.

  It is known that various types of new allyl compounds can be synthesized by performing a reaction using an allyl compound as a raw material and a transition metal compound as a catalyst.

  The details of the synthesis reaction of allyl compounds are described collectively in the following Non-Patent Document 1, and transition metals derived from allyl group-containing compounds such as allyl chloride, allyl acetate, allyl ether, and propylene. By selecting the π-allyl complex and the type of active hydrogen-containing compound such as carboxylic acid, phenol, alcohol, primary amine, secondary amine, thiol, malonic acid ester, the active hydrogen-containing compound is allylated. Various products can be obtained in a shaped form. In particular, when the active hydrogen-containing compound is an alcohol or a phenol, allyl alkyl ether and allyl phenyl ether are produced, which is one of elementary reactions useful in synthetic chemistry.

  However, in the case of a carboxylate anion as an example of a reaction between a π-allyl complex and an active hydrogen-containing compound (for example, a reaction between propylene and acetic acid), a reaction example with another substrate is generally well known. (In the case of phenolate anion and alcoholate anion derived from phenol or alcohol), the reactivity is low, so it is not widely used.

  For example, as an example of reaction with phenols, as described in Non-Patent Document 2 below, allylphenyl by a palladium catalyst system having a triaryl type monodentate phosphite ligand such as triphenyl phosphite is used. Synthetic examples of ethers are known, but the activity is not sufficient.

  Further, in Patent Document 1 below, an example in which a special multidentate phosphite compound is used to react with an oxygen nucleophile such as phenols or alcohols is known. In addition, the reaction activity is not sufficient.

  Patent Document 2 below discloses that allyl alcohol and a polyhydric phenol are reacted in the presence of a palladium or platinum catalyst and an organic phosphorus compound, but the yield is low and the catalyst efficiency is not sufficient.

  Patent Document 3 below discloses the reaction of phenol, thiophenol, and arylamine with allyl carbonate to form allyl ether in the presence of molybdenum, tungsten or Group VIII metal, and triphenylphosphine. However, it is necessary to use industrially expensive allyl carbonate.

  Non-Patent Document 3 below shows that phenylallyl ether can be obtained by reacting with phenol in the presence of a palladium catalyst and an alumina / KF support at room temperature for 24 hours when allyl acetate is used as a substrate. 84%) is disclosed, but is not sufficient in terms of catalyst activity.

  When allyl carboxylate is used as an allylating agent, especially by-product carboxylic acid is a highly reactive active hydrogen compound, so high conversion using alcohols, phenols and amines as substrates. It was difficult to get a rate. In order to avoid this problem, in Patent Document 4 below, a high conversion rate is obtained by using a large excess of alkali metal carbonate and taking out the produced acetic acid as an acetate out of the system. In such a system, not only is it difficult to recover acetic acid, but it is unavoidable that the alkali metal used is mixed into the product, and this is a problem particularly when used for electrical insulation.

JP 2004-107339 A JP-A-5-306246 U.S. Pat. No. 4,507,492 Japanese National Patent Publication No. 10-511721

"Palladium Reagents and Catalysts-Innovations in Organic Synthesis" published by John Wiley & Sons Organometallics, 1995, 14, p4585. J. et al. Organometallic Chem. , Vol. 326, C23-C24 (1987)

  The problem to be solved by the present invention is to provide a method for producing allyl ether having high reaction efficiency.

As a result of intensive studies to solve the above-mentioned problems and repeated experiments, the present inventors use carboxylic acid allyl ester, which can be easily obtained industrially by reacting propylene and carboxylic acid, as an allylating agent. It has been found that allyl ether can be efficiently obtained by reacting with a compound having active hydrogen such as phenol and alcohol, and the present invention has been completed.
That is, the present invention is as follows.

[1] The following:
Reacting a compound containing a hydroxyl group with a carboxylic acid allyl ester compound in the presence of a transition metal catalyst, a complexing agent, and a tertiary amine compound;
The manufacturing method of allyl ether containing.
[2] The method for producing allyl ether according to [1], wherein in the reaction step, water is present in the reaction system and the organic phase and the aqueous phase are separated in two phases.

  [3] The concentration of the tertiary amine group of the tertiary amine compound is in the range of 0.1 to 20 molar equivalents based on the hydroxyl group of the compound containing the hydroxyl group. The method for producing allyl ether according to 2].

  [4] The allyl according to [3], wherein the concentration of the tertiary amine group of the tertiary amine compound is in the range of 1 to 10 molar equivalents based on the hydroxyl group of the compound containing the hydroxyl group. A method for producing ether.

  [5] The above [1] to [4], wherein the allyl group concentration of the carboxylic acid allyl ester compound is in the range of 0.8 to 50 molar equivalents based on the hydroxyl group of the compound containing the hydroxyl group. ] The manufacturing method of the allyl ether in any one of.

  [6] The allyl ether according to [5], wherein the allyl group concentration of the carboxylic acid allyl ester compound is in the range of 1 to 5 molar equivalents based on the hydroxyl group of the compound containing the hydroxyl group. Manufacturing method.

  [7] The method for producing allyl ether according to any one of [1] to [6], wherein the transition metal catalyst is a platinum group metal catalyst.

  [8] The method for producing allyl ether according to any one of [1] to [7], wherein the transition metal catalyst is supported on a carrier.

  [9] The method for producing allyl ether according to [8], wherein the transition metal catalyst is a catalyst supporting 0.1 to 20% by mass of palladium with respect to activated carbon.

  [10] The allyl ether according to any one of [1] to [9], wherein the complexing agent is at least one selected from the group consisting of organic monophosphine, organic diphosphine, and organic phosphite. Manufacturing method.

  [11] The method for producing allyl ether according to [10], wherein the complexing agent is at least one selected from the group consisting of triphenylphosphine and triethylphosphite.

  [12] The compound containing a hydroxyl group is bisphenol A, bisphenol F, p, p′-biphenol, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diol, phenol-novolak, The method for producing allyl ether according to any one of [1] to [11], which is at least one selected from the group consisting of cresol-novolak, hydrocarbon-novolak, and trisphenol.

  [13] The method for producing allyl ether according to any one of [1] to [12], wherein the carboxylic acid allyl ester compound is allyl acetate.

  [14] The method for producing allyl ether according to any one of [1] to [12], wherein the carboxylic acid allyl ester compound is a divalent aromatic carboxylic acid diallyl ester.

  According to the method for producing allyl ether of the present invention, industrially available carboxylic acid allyl ester is used, and polyallyl ether which is an industrially important intermediate is obtained without using alkali metal or halogen. Can do.

Hereinafter, the manufacturing method of the allyl ether of this invention is demonstrated in detail.
The method for producing allyl ether of the present invention is characterized by reacting a compound containing a hydroxyl group with a carboxylic acid allyl ester compound in the presence of a transition metal catalyst, a complexing agent, and a tertiary amine compound. In the method for producing allyl ether of the present invention, the reaction is preferably carried out in the state where water is present in the reaction system and the organic phase and the aqueous phase are separated into two phases.

  The carboxylic acid allyl ester compounds used in the present invention are allyl esters of carboxylic acids such as allyl acetate, allyl propionate, allyl benzoate, diallyl phthalate, diallyl isophthalate, and diallyl terephthalate. Among these, allyl acetate, diallyl phthalate, diallyl isophthalate, and diallyl terephthalate are preferable. When diaryl phthalate, diallyl phthalate, diallyl isophthalate, and diallyl terephthalate, which are divalent aromatic carboxylic acid diallyl esters, are used, the resulting dicarboxylic acid becomes solid and the reverse reaction is unlikely to occur, so the reaction rate is high and the side reaction product. Is preferable in that it can be easily recovered by filtration. Moreover, industrially, allyl acetate is most preferable because it can be obtained at a low cost.

  The allyl group concentration of these carboxylic acid allyl ester compounds is preferably 0.5 to 500 molar equivalents, more preferably 0, based on hydroxyl groups contained in hydroxyl group-containing compounds such as phenol and alcohol-containing compounds. .8 to 50 molar equivalents, more preferably 1 to 5 molar equivalents. If the ratio is greater than 1 molar equivalent, the solvent can also be used. If it exceeds 500 molar equivalents, the reaction rate becomes slow, and the energy cost for recovering and recycling the excess allyl carboxylate is unfavorable. On the other hand, if it is less than 0.5 molar equivalents, the desired product is obtained. This is not preferable because the conversion ratio of is very low and it is necessary to recover the unreacted hydroxyl group-containing compound.

  The compound containing a hydroxyl group used in the present invention contains at least one hydroxyl group per molecule. Further, considering the development to various derivatives thereafter, it is preferable to contain a plurality of hydroxyl groups per molecule. Examples of compounds containing such hydroxyl groups include one of mono-, di- or polyfunctional aliphatic, alicyclic or aromatic hydroxyl group-containing compounds, any combination of such compounds.

  The hydroxyl group-containing compound is preferably an aliphatic, alicyclic or aromatic compound, and among these, an aromatic hydroxyl group-containing compound is preferable, for example, phenol, cresol, catechol, resorcinol, bisphenol A (p, p '-Isopropylidenediphenol), bisphenol F (p, p'-methylenediphenol), bisphenol K (p, p'-diphenolcarbonyl), dihydroxymethylstilbene, dihydroxybiphenyl, tetramethyldihydroxybiphenyl, dihydroxynaphthalene, bis (Hydroxyphenyl) fluorene, methane-type trisphenols, trisphenols, phenol-aldehyde novolak resins, alkyl-substituted phenol-aldehyde novolak resins, Any one or any combination of these Lumpur thereof. Particularly preferred aromatic hydroxyl group-containing compounds include, for example, bisphenol A, bisphenol F, p, p′-biphenol, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diol, 3,3 Examples include ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, phenol-novolak, cresol-novolak, hydrocarbon-novolak, trisphenol, phenol-formaldehyde novolak resin, and cresol-formaldehyde novolak resin.

  As the compound containing an aliphatic hydroxyl group, a compound containing a primary hydroxyl group is preferable. For example, n-propanol, n-butanol, n-hexanol, n-octanol, ethylene glycol, propylene glycol, 1,4- Butanediol, 1,6-hexanediol, 1,8-octanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipetaerythritol, sorbitol, average molecular weight of 106 to 50,000, preferably May be 106 to 5,000, more preferably 106 to 2,500 polyoxyalkylene glycol, polyglycerin, allyl alcohol, methallyl alcohol, benzyl alcohol, and any combination thereof.

  Examples of the alicyclic hydroxyl group-containing compound include cyclopentanol, cyclohexanol, methylcyclohexanol, 5-norbornene-2-methanol, dihydroxycyclohexane, norbornanediol, cyclohexanedimethanol, dicyclopentadienediol, vinylcyclohexene-derived diol, Tricyclodecane dimethanol, any combination thereof.

  The tertiary amine compounds that are reaction accelerators include trimethylamine, N, N-dimethylethylamine, N, N-diethylmethylamine, N-butyldimethylamine, N, N-dimethylisopropylamine, triethylamine, and tri-n-propyl. Amine, tri-n-butylamine, triisobutylamine, tri-n-pentylamine, triisoamylamine, N, N-dimethyl-n-octylamine, tri-n-octylamine, tri- (2-ethylhexyl) amine, And N-ethyldiisopropylamine. Of these, tertiary amines having a boiling point in the range of 50 ° C. to 200 ° C. are preferred from the viewpoint of reaction activity and ease of separation in the purification step. Examples of such amines include N, N-diethylmethylamine, N -Butyldimethylamine, N, N-dimethylisopropylamine, triethylamine, tri-n-propylamine, tri-n-butylamine.

  The concentration of the tertiary amine group of the tertiary amine compound is preferably 0.1 to 20 molar equivalents, more preferably 0.5 to 10 molar equivalents, still more preferably based on the hydroxyl group of the compound containing the hydroxyl group. Is in the range of 1 to 10 molar equivalents. If the amount used is too small, the reaction rate will be slow, and if it is too much, the substrate concentration will be low, so the reaction rate will also be slow.

  The method for producing an allyl ether compound of the present invention is carried out in the presence of a transition metal catalyst. Suitable catalysts include, for example, rhodium, ruthenium, rhenium, palladium, iridium, tungsten, molybdenum, chromium, cobalt, platinum, nickel, copper, osmium, iron in the non-oxidized state as free metals or complexes, or salts thereof. For example, it is contained in the oxidized state as carboxylate, halide, oxide, nitrate or sulfate. More preferred catalysts are of the platinum group and contain palladium, platinum, rhodium, ruthenium, iridium or osnium. The most preferred catalyst is a palladium catalyst.

  These transition metal catalysts should be used in the form of a salt such as acetate, chloride, nitrate or sulfate or supported on a support such as carbon, charcoal, activated carbon, silica, alumina, organosol gel, zeolite, clay, etc. Can do. Considering separation from the reaction liquid in particular, the transition metal catalyst is preferably used in a form supported on a carrier. Most preferably, the transition metal catalyst is a catalyst supporting 0.1 to 20% by mass of palladium with respect to the activated carbon.

  The amount of the catalyst used is 1 / 1,000,000 to 1/10, preferably 1 / 10,000 to 1/50, as a metal atom per equivalent of hydroxyl group contained in the compound containing a hydroxyl group, The ratio is more preferably 1 / 5,000 to 1/100.

  When the catalyst is supported and used as a heterogeneous catalyst, the reaction can be carried out, if necessary, in a fixed bed or suspended in a liquid reaction mixture.

  The complexing agent is preferably used to act as a ligand to stabilize and enhance the activity of the metal catalyst. The catalyst complex can be generated in situ by complexing the catalyst with a complexing agent prior to addition to the reaction mixture, or by adding the catalyst and complexing agent separately to the reaction mixture.

  Suitable complexing agents include, for example, organic monophosphine, organic diphosphine, organic phosphite, organic stibine, oxime, organic arsine, diamine, and dicarbonyl compound. Particularly suitable complexing agents include, for example, triphenylphosphine, tri- (o, m, p-) tolylphosphine, tris-p-methoxyphenylphosphine, tricyclohexylphosphine, tributylphosphine, diphenylphosphinostyrene, and the like Examples thereof include polymers, triphenyl phosphite, triethyl phosphite, diphenylmethylphosphine, and diphenylphosphinoethane. More preferred complexing agents include tri- (o, m, p-) tolylphosphine, triphenylphosphine and diphenylphosphinoethane, among which triphenylphosphine and / or triethylphosphite are most preferred. Triethyl phosphite is also preferred because it can be distilled off from the reaction system by distillation. Water-soluble complexing agents such as sulfonated triphenylphosphine can also be used, and this type of ligand has the advantage of being water-soluble and easily washed / separated from the organic product layer.

  The complexing agent is preferably used in an amount of 0.1 to 1000 times mol, more preferably 1 to 100 times mol, and still more preferably 2 to 50 times mol for 1 mol of the transition metal catalyst.

  The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 25 ° C to 150 ° C, and further preferably 50 ° C to 110 ° C. When the reaction temperature is high, particularly in the case of an aromatic hydroxy compound, side reactions such as Claisen rearrangement tend to occur, and when the reaction temperature is low, the reaction rate becomes slow. When the reaction is performed at a temperature higher than the boiling point of the reaction system, the reaction can also be performed in a closed container such as an autoclave.

  As the reaction atmosphere, the reaction can be carried out even in an air atmosphere, but since a transition metal catalyst is used, there is a risk of ignition, so it is desirable to carry out in an inert gas atmosphere such as nitrogen or argon.

  In the method for producing allyl ether of the present invention, the reaction proceeds even if the reaction system is a single layer system not containing water, but it is preferably carried out in a two-phase system containing an aqueous phase and an organic phase. In particular, when the raw material hydroxyl group-containing compound has low solubility in water, acetic acid as a by-product can be extracted into the aqueous layer, so that the effect of the presence of the aqueous phase is great. As an organic phase, raw material phenol, an alcohol-containing compound, a carboxylic acid allyl compound, and a solvent as required are used. Preferably, the mixture is vigorously stirred to bring the aqueous and organic phases into intimate contact with each other. The mass ratio of the water relative organic phase is preferably 9: 1 to 1: 9.

  Examples of the solvent that can be used for viscosity adjustment in the method of the present invention include oxygen-containing hydrocarbons (for example, secondary, tertiary alcohol, ether, glycol, glycol ether, ester, ketone). Examples of other solvents include nitroalkanes, cyanoalkanes, alkyl sulfoxides, amides, aromatic or aliphatic hydrocarbons, and halogenated hydrocarbons, and these may be used alone or in combination.

  Particularly suitable solvents are, for example, toluene, xylene, methylene chloride, 1,2-dichloroethane, acetonitrile, acetone, methyl ethyl ketone, ethyl acetate, dimethylformamide, dimethyl sulfoxide, nitromethane, tetrahydrofuran, isopropanol, t-butanol, t-amyl alcohol. , Grime, and any combination thereof. Among these, more preferable solvents are isopropanol, t-butanol, t-amyl alcohol, acetonitrile, toluene, 1,2-dichloroethane, and these may be used alone or in combination of two or more.

  The solvent is preferably in the range of 0.5 to 100 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 2 to 10 parts by mass, based on the mass of the compound containing a hydroxyl group.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited only to a following example.

Example 1
In a 200 ml eggplant-shaped flask, 10.0 g (43.8 mmol) of bisphenol-A (Mitsui Chemicals), 0.093 g of 50% water-containing 5% -Pd / C-STD type (manufactured by N.E. Chemcat Co., Ltd.) 0.0438mmol), triphenylphosphine (Hokuko Chemical Co., Ltd.) 0.110g (0.438mmol), triethylamine (Wako Pure Chemical Industries, Ltd.) 35.46g (0.35mol), allyl acetate (Showa Denko Co., Ltd.) 9.65 g (96,4 mmol) and 23.7 g of pure water were added, a Dimroth condenser was attached, and the mixture was reacted at 85 ° C. for 4 hours in a nitrogen atmosphere. After the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography under the following conditions using dimethyl adipate as an internal standard. As a result, the conversion rate of bisphenol-A was 94.1%, and bisphenol-A monoallyl ether The yield was 56.4%, and the yield of bisphenol-A diallyl ether was 38.1%. The results are shown in Table 1 below.

Gas scroll device: Agilent Technologies 6850GC
Column: HP-1 (film thickness 0.25μm x inner diameter 320μm x 30m)
Detector: Hydrogen flame ionization detector Inlet temperature: 300 ° C
Column temperature: 60 ° C (3 min hold) → Temperature increase rate 20 ° C / min → 300 ° C (2 min hold)
Detector temperature: 300 ° C
Sample injection volume: 1.0 μL
Split ratio: 30.0: 1

(Comparative Example 1)
The reaction was performed in the same manner as in Example 1 except that triethylamine in Example 1 was not charged. The results are shown in Table 1 below.

(Comparative Example 2)
The reaction was carried out in the same manner as in Example 1 except that water in Example 1 was not charged. The results are shown in Table 1 below.

(Comparative Example 3)
The reaction was performed in the same manner as in Example 1 except that isopropyl alcohol was used instead of water in Example 1. The results are shown in Table 1 below.

(Example 2)
In a 200 ml eggplant-shaped flask, 10.0 g (43.8 mmol) of bisphenol-A (Mitsui Chemicals), 0.093 g of 50% water-containing 5% -Pd / C-STD type (manufactured by N.E. Chemcat Co., Ltd.) 0.0438mmol), triphenylphosphine (Hokuko Chemical Co., Ltd.) 0.110g (0.438mmol), triethylamine (Wako Pure Chemical Industries, Ltd.) 17.75g (0.175mol), allyl acetate (Showa Denko Co., Ltd.) 9.65 g (96,4 mmol) and 23.7 g of pure water were added, a Dimroth condenser was attached, and the mixture was reacted at 85 ° C. for 4 hours in a nitrogen atmosphere. After the reaction, analysis was performed in the same manner as in Example 1. The results are shown in Table 2 below.

(Examples 3 to 6)
The reaction was conducted in the same manner as in Example 2 except that instead of allyl acetate in Example 2, the dicarboxylic acid diallyl compound shown in Table 2 below was charged in an equimolar amount as an allyl ester. The results are shown in Table 2 below.

(Examples 7 to 9)
The reaction was conducted in the same manner as in Example 2 except that the compounds shown in Table 3 below were charged instead of triphenylphosphine in Example 2. The results are shown in Table 3 below.

(Examples 10 to 12)
The reaction was conducted in the same manner as in Example 1 except that 23.7 g of pure water in Example 1 was charged with the solvent and concentration shown in Table 4 below. The results are shown in Table 4 below.

溶媒濃度単位：質量％
トルエン−純水＝トルエン：純水を１：１の質量比で仕込んだ（実施例１２では、総溶媒濃度が46%なので、トルエンと純粋は23%ずつであった）。

Solvent concentration unit: mass%
Toluene-pure water = toluene: pure water was charged at a mass ratio of 1: 1 (in Example 12, the total solvent concentration was 46%, so toluene and pure were 23% each).

(Example 13)
The reaction was conducted in the same manner as in Example 1 except that dimethyl-n-octylamine was used instead of triethylamine in Example 1. The results are shown in Table 5 below.

(Examples 14 to 15)
The reaction was conducted in the same manner as in Example 2 except that the diphenol compound shown in Table 6 was used instead of bisphenol-A in Example 2. The results are shown in Table 6 below.

(Example 16)
In a 200 ml eggplant-shaped flask, 10.0 g of cresol novolac resin CRG-951 (manufactured by Showa Polymer Co., Ltd.), 50% water-containing 5% -Pd / C-STD type (manufactured by N.E. Chemcat Co., Ltd.) 0.180 g ( 0.0424mmol), triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 0.222g (0.847mmol), triethylamine (made by Wako Pure Chemical Industries, Ltd.) 17.15g (0.169mol), allyl acetate (made by Showa Denko Co., Ltd.) 9.33 g (93.2 mmol) and 15.8 g of pure water were added and reacted in a nitrogen atmosphere at 85 ° C. for 4 hours. After the reaction, a part was sampled, diluted with ethyl acetate, washed with pure water until the washing solution became neutral, and then ethyl acetate was distilled off, and the hydroxyl value was determined according to JIS K0070 to determine the hydroxyl equivalent (hydroxyl equivalent = 56100 / hydroxyl value) was calculated. The hydroxyl equivalent increased from 118 to 1753 of the raw material and was allyl etherified.

(Example 17)
In a 200 ml eggplant-shaped flask, 10.0 g of methane type trisphenols NCR-231 (made by Showa High Polymer Co., Ltd.), 50% water content 5% -Pd / C-STD type (made by N.E. Chemcat Co., Ltd.) 0.201 g (0.0472 mmol), triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd.) 0.247 g (0.943 mmol), triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 19.1 g (0.189 mol), allyl acetate (manufactured by Showa Denko KK) ) 10.4 g (0.104 mol) and 17.1 g of pure water were added and reacted at 85 ° C. for 4 hours in a nitrogen atmosphere. After the reaction, a part was sampled, diluted with ethyl acetate, washed with pure water until the washing solution became neutral, ethyl acetate was distilled off, and the hydroxyl equivalent was measured in the same manner as in Example 16. The hydroxyl equivalent was increased from 106 to 1305 of the raw material and allyl etherified.

(Example 18)
Tokyo Rika Machine's personal organic synthesizer (Chem Station) Using PPS-5511, phenol 1.00g (10.6mmol), 5% -Pd / C STD type (manufactured by NP Chemcat Co., Ltd.) 0.0226g (0.0106mmol) ), Triphenylphosphine (Hokuko Chemical Co., Ltd.) 0.0279 g (0.106 mmol), triethylamine (Wako Pure Chemical Industries, Ltd.) 2.150 g (21.3 mmol), allyl acetate (Showa Denko Co., Ltd.) 1.170 g ( 11.7 mmol) and 0.486 g of pure water were added, a Dimroth condenser was attached, and a heating apparatus was set at 105 ° C. in a nitrogen atmosphere for 4 hours. After the reaction, a part of the reaction solution was sampled and analyzed by gas chromatography under the same conditions as in Example 1 using dimethyl adipate as the internal standard. As a result, the phenol conversion was 42.3% and the yield of phenylallyl ether was obtained. The rate was 41.9% and the selectivity was 99.1%.

(Example 19)
A similar reaction was performed except that the organophosphorus compound (triethyl phosphite (manufactured by Johoku Chemical Industry Co., Ltd.)) shown in Table 7 was used instead of the triphenylphosphine of Example 18. The results are shown in Table 7 below.

(Example 20)
The same reaction as in Example 19 was performed except that pure water was not used. The conversion rate of phenol was 45.3%, the yield of allylphenyl ether was 43.0%, and the selectivity was 94.9%.

(Example 21)
A similar reaction was carried out except that benzyl alcohol was used instead of the phenol of Example 18. The results are shown in Table 7 below.

Claims (14)

below:
Reacting a compound containing a hydroxyl group with a carboxylic acid allyl ester compound in the presence of a transition metal catalyst, a complexing agent, and a tertiary amine compound;
The manufacturing method of allyl ether containing.   The method for producing allyl ether according to claim 1, wherein, in the reaction step, water is present in the reaction system and the organic phase and the aqueous phase are reacted in a two-phase separated state.   The allyl group according to claim 1 or 2, wherein the concentration of the tertiary amine group of the tertiary amine compound is in the range of 0.1 to 20 molar equivalents based on the hydroxyl group of the compound containing the hydroxyl group. A method for producing ether.   The method for producing an allyl ether according to claim 3, wherein the concentration of the tertiary amine group of the tertiary amine compound is in the range of 1 to 10 molar equivalents based on the hydroxyl group of the compound containing the hydroxyl group. .   The concentration of the allyl group of the carboxylic acid allyl ester compound is in the range of 0.8 to 50 molar equivalents based on the hydroxyl group of the compound containing the hydroxyl group. A method for producing allyl ether according to 1.   The method for producing allyl ether according to claim 5, wherein the allyl group concentration of the carboxylic acid allyl ester compound is in the range of 1 to 5 molar equivalents based on the hydroxyl group of the compound containing the hydroxyl group.   The method for producing allyl ether according to any one of claims 1 to 6, wherein the transition metal catalyst is a platinum group metal catalyst.   The method for producing allyl ether according to any one of claims 1 to 7, wherein the transition metal catalyst is supported on a carrier.   The method for producing allyl ether according to claim 8, wherein the transition metal catalyst is a catalyst supporting 0.1 to 20% by mass of palladium with respect to activated carbon.   The method for producing allyl ether according to any one of claims 1 to 9, wherein the complexing agent is at least one selected from the group consisting of organic monophosphine, organic diphosphine, and organic phosphite.   The method for producing allyl ether according to claim 10, wherein the complexing agent is at least one selected from the group consisting of triphenylphosphine and triethylphosphite.   The compound containing the hydroxyl group is bisphenol A, bisphenol F, p, p′-biphenol, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diol, phenol-novolak, cresol-novolak The method for producing allyl ether according to any one of claims 1 to 11, which is at least one selected from the group consisting of, hydrocarbon-novolak and trisphenol.   The method for producing allyl ether according to any one of claims 1 to 12, wherein the carboxylic acid allyl ester compound is allyl acetate.   The method for producing allyl ether according to any one of claims 1 to 12, wherein the carboxylic acid allyl ester compound is a divalent aromatic carboxylic acid diallyl ester.