JP2018184376A - Production method of allyl compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of allyl compounds from allyl alcohol and one, two or more selected from various alcohols, phenols, thiols, and amines in the presence of a transition metal oxide catalyst with a method excellent in environmental harmony in which only water is a by-product.SOLUTION: In a production method of various allyl compounds, allyl alcohol and one, two or more compounds selected from various alcohols, phenols, thiols, and amines are made to react with each other accompanied with dehydration and in a predetermined condition, by using a catalyst comprising titania carrying various transition metal oxides, preferably one, two, or more of molybdenum oxide, tungsten oxide, and rhenium oxide, in particular preferably by using a catalyst carrying molybdenum oxide. In the method, in particular an allyl ether is produced by using allyl alcohol.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an allyl compound. In more detail, allyl ethers are produced by allowing allyl alcohol to act on various alcohols, phenols, thiols, or amines and introducing an allyl group with dehydration by a reaction using a transition metal oxide as a catalyst. , Allyl thioethers, or allyl compounds such as allylamines.

  Synthetic reactions of allyl compounds are known as fundamental reactions in the production of electronic materials, pharmaceuticals and agricultural chemicals. As a method for producing allyl compounds, a method for producing allyl chloride by allowing allyl chloride to act on hydroxyl groups of various organic compounds (Non-patent Document 1) is generally used. However, in the method using allyl chloride, a large amount of chlorinated organic compound is mixed in the target product after the reaction, and a large amount of organic solvent is used for the removal, and it cannot be removed sufficiently, affecting the subsequent process and product purity. There are issues from both energy saving and quality perspectives. Moreover, although the method (patent document 1) which manufactures allyl acetate by making it react with the hydroxyl group of various organic compounds is known, since a lot of wastes, such as an acetic acid, are byproduced after reaction, from a viewpoint of cost or environmental harmony. It is hard to say that it is an excellent method. As for the allyl thioetherification reaction, a reaction using allyl chloride (Non-patent Document 2) is known, but chlorine-based waste is produced as a by-product, and there is a problem of mixing into a product and processing cost. Similarly, in the reaction of allylamine, a method using allyl bromide (Non-patent Document 3) and a method using allyl acetate and a palladium catalyst (Non-patent Document 4) are known, but a large amount of waste is generated. There's a problem.

  On the other hand, the method for producing an allyl compound using allyl alcohol as an allyl source is excellent from the viewpoint of environmental harmony because it can suppress the by-product of waste with high environmental load in addition to low cost. For example, a method for producing allyl ether using a ruthenium complex is known (Non-Patent Document 5). Moreover, the manufacturing method of the allyl ether using a palladium complex and a titanium compound is known (nonpatent literature 6). As for allyl thioether or allylamine, a method in which allyl alcohol is allowed to act on a thiol together with a ruthenium complex, or a method in which allyl alcohol is allowed to act on an amine together with a palladium complex to cause the reaction to proceed (Non-Patent Document 7, 8).

Japanese Patent No. 5511251

Liebigs Ann. Chem. 1851, 77, 37. J.Am.Chem.Soc.2008,130,9642. Chem. A. Eur. J. 2003, 9, 5793. Eur.J.Org.Chem.2017,1078. J. Org. Chem. 1997, 62, 4877. Angew.Chem.Int.Ed.2005,44,1730. Chem. Commun. 2010, 46, 3996. Org. Lett. 2004, 6, 4085. Catal.Commun. 2009, 10, 1394. Green.Chem. 2012, 14, 610. Syn.Commun. 2016,46,1893.

Against the background of the prior art as described above, the present inventor examined a method for producing an allyl compound using allyl alcohol as an allyl source. However, it has been recognized that the following problems exist in the method using the above transition metal complex as a catalyst.
(A) When the transition metal complex is mixed into the product, the quality of the product may be deteriorated, and a post-treatment step for completely removing the transition metal complex is required.
(A) Since the transition metal complex dissolves in the reaction solution and loses its catalytic activity in a single reaction, it is unsuitable for reuse and has a problem in terms of production cost.

On the other hand, in the method using a solid catalyst such as a transition metal oxide without using a transition metal complex as a catalyst, a method using a solid catalyst in which cesium is introduced into a heteropolyacid (Non-patent Document 9), titanium is introduced into montmorillonite. A method using a solid catalyst (Non-Patent Document 10) and a method in which a sulfone group is supported on tungsten oxide (Non-Patent Document 11) are known. These can be said to be excellent in terms of cost since there is no fear of mixing the transition metal into the product and the catalyst can be recovered and reused as a catalyst.
However, these solid catalysts are not suitable for use as a catalyst for producing a large amount of allyl ethers because the preparation process of the catalyst is complicated and there are many variations among catalyst production batches.
The present inventor has recognized that a method for producing allyl compounds efficiently by using allyl alcohol as an allyl source and using an oxide of a transition metal that can be easily recovered and separated as a catalyst is possible.
Further, the present inventor has developed an industrially useful catalytic reaction that can be used in such a production method, and the necessity of a transition metal oxide catalyst that can be produced by a simple and reliable production method. Also recognized.

  The present invention was made based on the background of the inventor's recognition of the above-described prior art and its problems, and a waste agent such as acetic acid or the like which has a risk of mixing a large amount of chlorine such as allyl chloride. By using transition metal oxides as catalysts without using ester reactants such as allyl acetate as a by-product and transition metal complexes that cannot be reused because they dissolve in the reaction solution, allyl compounds can be efficiently The object is to provide a method of manufacturing.

  As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have used a catalyst in which allyl alcohol is used as a raw material and titania supports molybdenum oxide, tungsten oxide, rhenium oxide, or two or more kinds as a catalyst. By using it, it discovered that an allyl group can be introduce | transduced with dehydration in any alcohol or phenols, thiols, and amines, or two or more types, and came to complete this invention.

That is, this application provides the following invention.
<1> Using a catalyst in which an oxide of a transition metal is supported on titania, allyl alcohol is converted into one or more compounds selected from the group consisting of alcohols, phenols, thiols, and amines. A method for producing an allyl compound, wherein an allyl group is introduced by dehydration to produce one or more allyl compounds selected from the group consisting of allyl ethers, allyl thioethers, and allylamines.
<2> The method for producing an allyl compound according to <1>, wherein the transition metal oxide is one or more selected from the group consisting of molybdenum oxide, tungsten oxide, and rhenium oxide.
<3> The method for producing an allyl compound according to <1> or <2>, wherein the oxide of the transition metal is 1 to 20 percent by weight based on titania.
<4> The method for producing an allyl compound according to any one of <1> to <3>, wherein an allyl ether is produced using an alcohol.
<5> Any one of <1> to <4>, wherein the alcohol is selected from the group consisting of an aliphatic alcohol, an aromatic alcohol, an alicyclic alcohol, and an alcohol containing a hetero element. The manufacturing method of allyl compounds as described in a term.
<6> Any one of <1> to <5>, wherein the produced allyl compound includes at least one selected from the group consisting of an aromatic ring, an alkyl group, a cycloalkyl group, and a sulfur atom in the structure. A process for producing the allyl compounds according to claim 1.
In the present specification, “˜” indicating a numerical range is used as a meaning including numerical values described before and after the numerical value as a lower limit value and an upper limit value.

  According to the present invention, a reactant that has a risk of mixing a large amount of chlorine such as allyl chloride, an ester-based reactant such as allyl acetate that is a by-product of waste such as acetic acid, and the reaction solution is dissolved. Allyl compounds can be produced using a transition metal oxide as a catalyst without using a transition metal complex that cannot be used.

  The method for synthesizing allyl compounds of the method of the present invention comprises allyl alcohol as a catalyst, a group consisting of various alcohols, phenols, thiols, and amines in the presence of a catalyst in which a transition metal oxide is supported on titania. It is characterized by acting on one or more compounds selected from the above, dehydrating at an appropriate reaction temperature, and bonding an allyl group to the organic compound. As the transition metal oxide used here, in particular, any of tungsten oxide, molybdenum oxide, rhenium oxide, or a mixture of two or more types is desirable.

Various alcohols, phenols, and thiols used in the production method of the present invention are represented by the following formula (1).

In the formula, X represents an oxygen atom or a sulfur atom, and R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, a benzyl group, a sulfinyl group, or a sulfonyl group. These groups may further have a substituent such as an alkyl group, an aryl group, or a halogen atom.

In the general formula (1), examples of the alkyl group in the case where R ¹ is an alkyl group which may have a substituent include linear or branched alkyl groups having 1 to 15 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an n-octyl group, and the like.

Examples of the cycloalkyl group in the case where R ¹ is an optionally substituted cycloalkyl group include a monocyclic, polycyclic or condensed cyclic cycloalkyl group having 3 to 10 carbon atoms, and more Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

As the aryl group in the case where R ¹ is an aryl group which may have a substituent, for example, the monocyclic, polycyclic or condensed ring aromatic hydrocarbon having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. More specifically, examples thereof include a phenyl group, a tolyl group, a xylyl group, an anisyl group, a nitrophenyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group.

The benzyl group in the case where R ¹ is an optionally substituted benzyl group is, for example, a monocyclic, polycyclic or condensed cyclic aromatic hydrocarbon having 7 to 20 carbon atoms, preferably 7 to 14 carbon atoms. More specifically, examples include benzyl group, 1-phenylethyl group, 1-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.

Specific examples of the sulfinyl group in the case where R ¹ is a sulfinyl group which may have a substituent include a methylsulfinyl group and a phenylsulfinyl group.

Specific examples of the sulfonyl group in the case where R ¹ is a sulfonyl group which may have a substituent include a methylsulfonyl group and a phenylsulfonyl group.

  In the present invention, various alcohols, phenols, and thiols represented by the general formula (1) can be used, and preferably ethanol, butanol, octanol, cyclohexanol, It is desirable to use benzyl alcohol, octanethiol, dodecanethiol, phenol or 2-phenylthioethanol.

Various amines used in the production method of the present invention are represented by the following formula (2).

In the formula, R ² and R ³ are independently the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a benzyl group, a sulfinyl group, or a sulfonyl group. These groups may be further substituted with a substituent such as an alkyl group, an aryl group, or a halogen atom.

In the general formula (2), examples of the alkyl group in the case where R ² and R ³ may have a substituent include a linear or branched alkyl group having 1 to 15 carbon atoms. It is done. Specific examples include a methyl group, an ethyl group, a propyl group, an n-octyl group, and the like.

Examples of the cycloalkyl group in the case where R ² and R ³ are optionally substituted cycloalkyl groups include monocyclic, polycyclic or condensed cyclic cycloalkyl groups having 3 to 10 carbon atoms. More specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like can be given.

Examples of the aryl group in the case where R ² and R ³ are optionally substituted aryl groups include monocyclic, polycyclic, and condensed cyclic aromatics having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. More specifically, for example, phenyl group, tolyl group, xylyl group, anisyl group, nitrophenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group, biphenyl group and the like can be mentioned. It is done.

Examples of the benzyl group in the case where R ² and R ³ are optionally substituted benzyl groups include, for example, monocyclic, polycyclic or condensed cyclic aromatics having 7 to 20 carbon atoms, preferably 7 to 14 carbon atoms. More specifically, for example, benzyl group, 1-phenylethyl group, 1-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like can be mentioned.

Specific examples of the sulfinyl group in the case where R ² and R ³ may have a substituent include a methylsulfinyl group and a phenylsulfinyl group.

Specific examples of the sulfonyl group in the case where R ² and R ³ are optionally substituted sulfonyl groups include a methylsulfonyl group and a phenylsulfonyl group.

A residue obtained by removing a hydrogen atom from each of R ² and R ³ may be bonded to each other to form a ring, and a residue obtained by removing a hydrogen atom from each of R ² and R ³ is divalent. They may be bonded to each other via atoms to form a ring. Examples of the divalent atom in this case include an oxygen atom, a nitrogen atom, and a sulfur atom.

  In the present invention, various amines represented by the general formula (2) can be used, but preferably diethylamine, phenylethylamine, benzylethylamine, dibenzylamine, or aniline is used. It is desirable.

  The titania used in the present invention may be in any state of only anatase type, only rutile type, or a mixture of anatase type and rutile type, and the specific surface area may be 50 square meters or more per gram. desirable. As the transition metal oxide to be supported, any transition metal oxide may be used as long as it can be supported, but tungsten oxide, molybdenum oxide, or rhenium oxide is preferably used. Those carrying 1 to 20% by weight are used, more preferably those carrying 5 to 15% by weight. These may be used alone or in combination of two or more. The amount used is selected from the range of 1 to 200 mg, preferably 50 to 100 mg, per 1 mmol of the substrate.

  In the production method of the present invention, it proceeds sufficiently in air, but the yield may be improved in the presence of an inert gas such as nitrogen or argon.

  In the production method of the present invention, the reaction proceeds efficiently without using an organic solvent, but all common organic solvents can be used as the solvent, more preferably benzene, toluene, benzonitrile, xylene. Etc. can be used. These may be used alone or in combination of two or more. The amount used is selected from the range of 0.1 to 1000 times, preferably 1 to 100 times the weight ratio to the substrate.

  The reaction conditions for the process of the present invention are not particularly limited, but the reaction is usually carried out in the range of 10 to 200 ° C, preferably 120 to 150 ° C.

  The reaction time in the production method of the present invention depends on the amount of catalyst used, the reaction temperature, and the like, and cannot be generally defined, but is usually in the range of 1 to 20 hours, preferably in the range of 2 to 6 hours. Is called.

  The allyl compounds obtained by the method of the present invention are, for example, allyl ethyl ether, allyl butyl ether, allyl octyl ether, allyl cyclohexyl ether, allyl benzyl ether, allyl (2-phenylthioethyl) ether, allyl octyl sulfide, allyl dibenzylamine. And diallylphenylamine.

  In a general embodiment of the present invention, a catalyst and allyl alcohol are mixed in a reactor, and one or more of various alcohols, phenols, thiols, and amines are mixed therein and mixed. The reaction is carried out at a temperature of After completion of the reaction, the obtained allyl compounds can be taken out by ordinary methods such as distillation, chromatographic separation, recrystallization and sublimation.

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

Example 1 Preparation of Catalyst 1 In a flask, 2.0 g of titania (for example, “AEROXIDE TiO ₂ P25” (manufactured by Nippon Aerosil Co., Ltd., distributed by the Catalytic Society Reference Catalysis Group)) was added. A product obtained by dissolving 24.5 mg (manufactured by Mitsui Pure) in 1.0 ml of pure water was added. After stirring and kneading, the mixture was dried in an oven at 110 ° C. for 24 hours and then calcined at 500 ° C. for 3 hours to obtain 2.0 g of titania carrying 1 wt% molybdenum oxide (calculated as MoO ₃ ).

Preparation of Example Catalyst 2 The result was the same as Example Catalyst 1 except that 122.5 mg of hexaammonium hexamolybdate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used. As a result, 5 wt% molybdenum oxide (calculated as MoO ₃₎ 2.0 g of titania carrying) was obtained.

Example catalyst 3 was prepared in the same manner as Example catalyst 1 except that hexaammonium hexamolybdate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 245.3 mg. As a result, 10 wt% molybdenum oxide (calculated as MoO ₃₎ 2.1 g of titania carrying) was obtained.

Preparation of Example Catalyst 4 Preparation of Example Catalyst 1 was carried out in the same manner as Example Catalyst 1 except that hexaammonium hexamolybdate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 490.6 mg. As a result, 20 wt% molybdenum oxide (calculated as MoO ₃₎ 2.1 g of titania carrying) was obtained.

Example 5 Preparation of catalyst 5 Instead of 24.5 mg of hexamolybdenum hexamolybdate tetrahydrate, 225 mg of ammonium tungstate parapentahydrate (manufactured by Wako Pure Chemical Industries) and 300 mg of citric acid (manufactured by Wako Pure Chemical Industries) of 1. As a result of preparing in the same manner as Example Catalyst 1 except that it was dissolved in 0 ml of pure water, 2.0 g of titania carrying 10 wt% tungsten oxide (calculated as WO ₃ ) was obtained.

Preparation of Example Catalyst 6 Same as Example Catalyst 1 except that 286 mg of perrhenic acid solution (manufactured by Sigma-Aldrich) was dissolved in 1.0 ml of pure water instead of 24.5 mg of hexamolybdate hexamolybdate tetrahydrate. As a result, 2.0 g of titania carrying 10 wt% rhenium oxide (calculated as ReO ₃ ) was obtained.

Example 1
In a pressure-resistant glass flask (25 ml of ace glass manufactured by Osaka Chemical Co., Ltd.) capable of being sealed, 100 mg of 10 wt% molybdenum oxide-supporting titania (Example Catalyst 3) and 232.3 mg (4.0 mmol) of allyl alcohol were added. 130.2 mg (1.0 mmol) manufactured by Wako Pure Chemical Industries, Ltd. was added. Stir at 140 ° C. for 5 hours. Thereafter, 40.0 mg (0.259 mmol) of biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as an internal standard, and gas chromatographic measurement was performed. The conversion of octanol was 95%, and the yield of allyl octyl ether was The selectivity was 84% and the selectivity was 88%.

The conversion rate, yield, and selectivity were calculated by the following calculation formula based on the results analyzed by gas chromatography.
Conversion rate (%) = (1-Mole number of remaining raw material / Mole number of used raw material) × 100
Yield (%) = (number of moles of target compound / number of moles of starting material used) × 100
Selectivity (%) = yield (%) / conversion (%) × 100

Comparative Example 1
The reaction was carried out under the same conditions as in Example 1 except that 10% by weight of molybdenum oxide-supporting titania (Example Catalyst 3) was not added. As a result, the yield of allyl octyl ether was 0%.

Example 2
The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 150 ° C. instead of 140 ° C. As a result, the conversion of octanol was 92%, and the yield of allyl octyl ether was 75%.

Example 3
The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 130 ° C. instead of 140 ° C. As a result, the conversion of octanol was 83%, and the yield of allyl octyl ether was 75%.

Example 4
The reaction was carried out under the same conditions as in Example 1 except that 1 wt% molybdenum oxide-supporting titania (Example Catalyst 1) was used instead of 10 wt% molybdenum oxide-supported titania (Example Catalyst 3). As a result, the conversion of octanol was 19%, and the yield of allyl octyl ether was 5%.

Example 5
The reaction was carried out under the same conditions as in Example 1 except that 5% by weight molybdenum oxide-supporting titania (Example Catalyst 2) was used instead of 10% by weight of molybdenum oxide-supporting titania (Example Catalyst 3). As a result, the conversion of octanol was 91%, and the yield of allyl octyl ether was 78%.

Example 6
The reaction was carried out under the same conditions as in Example 1 except that 20 wt% molybdenum oxide-supporting titania (Example catalyst 4) was used instead of 10 wt% molybdenum oxide-supporting titania (Example catalyst 3). As a result, the conversion of octanol was 90%, and the yield of allyl octyl ether was 79%.

Example 7
The reaction was carried out under the same conditions as in Example 1 except that 10% by weight of tungsten oxide supported titania (Example Catalyst 5) was used instead of 10% by weight of molybdenum oxide supported titania (Example Catalyst 3). As a result, the conversion of octanol was 68%, and the yield of allyl octyl ether was 41%.

Example 8
The reaction was carried out under the same conditions as in Example 1 except that 10% by weight of rhenium oxide supported titania (Example Catalyst 6) was used instead of 10% by weight of molybdenum oxide supported titania (Example Catalyst 3). As a result, the conversion of octanol was 37%, and the yield of allyl octyl ether was 19%.

Comparative Example 2
The reaction was carried out under the same conditions as in Example 1 except that 10% by weight of molybdenum oxide-supported titania (Example Catalyst 3) was used and 10% by weight of vanadium oxide-supported titania (Comparative Catalyst 1) prepared from a vanadium complex was used. It was. As a result, the yield of allyl octyl ether was 0%, and octanone was obtained instead with a yield of 20%.

Comparative Example 3
The reaction was carried out under the same conditions as in Example 1 except that 10% by weight of molybdenum oxide-supported titania (Example Catalyst 3) was used instead of 10% by weight of copper oxide-supported titania (Comparative Catalyst 2) prepared from a copper complex. It was. As a result, the yield of allyl octyl ether was 0%, and octanone was obtained instead with a yield of 15%.

Comparative Example 4
The reaction was carried out under the same conditions as in Example 1, except that 10% by weight of ruthenium oxide-supported titania (comparative catalyst 3) prepared from a ruthenium complex was used instead of 10% by weight of molybdenum oxide-supported titania (Example catalyst 3). It was. As a result, the reaction hardly proceeded and the yield of allyl octyl ether was 0%.

Comparative Example 5
A 10% by weight molybdenum oxide-supported alumina (comparative catalyst 4) using alumina as a support was prepared in the same manner as Example Catalyst 3 except that alumina was used instead of titania as the support. The reaction was carried out under the same conditions as in Example 1 except that 10% by weight molybdenum oxide-supported alumina (comparative catalyst 4) using alumina as a support was used instead of 10% by weight molybdenum oxide-supported titania (Example catalyst 3). went. As a result, the reaction hardly proceeded and the yield of allyl octyl ether was 0%.

Comparative Example 6
A 10% by weight molybdenum oxide-supporting silica (comparative catalyst 5) using silica as a support was prepared in the same manner as in Example Catalyst 3 except that silica was used instead of titania as the support. The reaction was conducted under the same conditions as in Example 1 except that 10% by weight molybdenum oxide-supported silica (comparative catalyst 5) using silica as a support was used instead of 10% by weight molybdenum oxide-supported titania (Example catalyst 3). went. As a result, the reaction hardly proceeded and the yield of allyl octyl ether was 7%.

Comparative Example 7
The reaction was carried out under the same conditions as in Example 1 except that styrene polymer-supported paratoluenesulfonic acid (manufactured by Sigma-Aldrich, comparative catalyst 6) was used instead of 10 wt% molybdenum oxide-supported titania (Example catalyst 3). went. As a result, the yield of allyl octyl ether was 25%. It was also considered difficult to recover this catalyst.

Comparative Example 8
The reaction was carried out under the same conditions as in Example 1 except that Nafion NR50 (manufactured by DuPont, comparative catalyst 7) was used instead of 10% by weight molybdenum oxide-supporting titania (Example catalyst 3). As a result, the yield of allyl octyl ether was 21%. It was also considered difficult to recover this catalyst.

Examples 9-16
The reaction was carried out under the same conditions as in Example 1 except that various alcohols, phenols, thiols, or amines were used instead of octanol, and the reaction temperature and time were slightly changed. The results are shown in Table 1.

Example 17
Instead of 10 wt% molybdenum oxide-supported titania (Example catalyst 3), 10 wt% molybdenum oxide-supported titania once used in Example 1 was washed with acetonitrile and then refired at 500 ° C (once regenerated catalyst) The reaction was conducted under the same conditions as in Example 1 except that was used again as a catalyst. As a result, the conversion of octanol was 95%, and the yield of allyl octyl ether was 84%.

Example 18
In place of 10% by weight molybdenum oxide-supported titania (Example Catalyst 3), 10% by weight molybdenum oxide-supported titania (regenerated catalyst) used in Example 17 was washed with acetonitrile and then refired at 500 ° C. ( The reaction was carried out under the same conditions as in Example 1 except that the twice-regenerated catalyst was used again as the catalyst. As a result, the conversion of octanol was 94%, and the yield of allyl octyl ether was 86%.

Summarizing the results of the above examples and comparative examples, the following can be said.
(1) In the production of allyl compounds using allyl alcohol as an allylating agent, molybdenum oxide, tungsten oxide, rhenium oxide is selected from transition metal oxides used as catalyst components, and titania is selected as a catalyst carrier. Only when this is done, the allyl compound can be produced efficiently.
(2) Various allyl compounds corresponding to them can be produced from various alcohols, phenols, thiols and amines.
(3) The catalyst having a transition metal oxide supported on titania can be recovered and reused at least twice by washing and re-firing after the allylation reaction.
(4) Of molybdenum oxide, tungsten oxide, and rhenium oxide, molybdenum oxide and tungsten oxide are particularly preferable, and molybdenum oxide is most preferable.
(5) The ratio of the transition metal oxide to titania is preferably 1 to 20% by weight, more preferably 5 to 15% by weight.
(6) The yield of allyl compounds was relatively high when alcohols or amines were used, and was highest when alcohols were used.

  Allyl compounds are industrially important as intermediates for medicines and agricultural chemicals and as raw materials for resins. According to the present invention, allyl compounds can be efficiently produced using allyl alcohol as a raw material, a by-product of water only, and a recoverable and reusable catalyst. It can be used widely in fields such as intermediates and resin raw materials.

Claims (6)

  Using a catalyst in which a transition metal oxide is supported on titania, allyl alcohol is allowed to act on one or more compounds selected from the group consisting of alcohols, phenols, thiols, and amines. A method for producing allyl compounds, wherein an allyl group is introduced with dehydration to produce one or more allyl compounds selected from the group consisting of allyl ethers, allyl thioethers, and allylamines.   2. The method for producing allyl compounds according to claim 1, wherein the transition metal oxide is one type or two or more types selected from the group consisting of molybdenum oxide, tungsten oxide, and rhenium oxide.   The manufacturing method of the allyl compounds of Claim 1 or 2 whose oxide of the said transition metal is 1-20 weight percent with respect to titania.   The method for producing allyl compounds according to any one of claims 1 to 3, wherein an allyl ether is produced using an alcohol.   The allyl according to any one of claims 1 to 4, wherein the alcohol is selected from the group consisting of an aliphatic alcohol, an aromatic alcohol, an alicyclic alcohol, and an alcohol containing a hetero element. Method for producing compounds.   The said allyl compound manufactured contains at least 1 sort (s) selected from the group which consists of an aromatic ring, an alkyl group, a cycloalkyl group, and a sulfur atom in any one of Claims 1-5. The manufacturing method of allyl compounds.