JP2013209305A - Method for producing oxide of carbonyl compound using tin-containing catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reaction catalyst having a high reaction selectivity and being recyclable in a peroxidation reaction using a carbonyl compound, and to provide a method for highly efficiently producing, for example, ester, lactone and formyloxy compounds or derivatives thereof by subjecting a carbonyl compound to a peroxidation reaction using the reaction catalyst.SOLUTION: A specific tin-containing catalyst can be used for a peroxidation reaction of a carbonyl compound, and a recyclable specific tin-containing catalyst is reusable for the reaction. A method for producing an oxide carries out a peroxidation reaction of a carbonyl compound in the presence of the tin-containing catalyst or the tin-containing recyclable catalyst.

Description

  The present invention relates to a method for producing an oxide by oxidizing a carbonyl compound by a peroxidation reaction in the presence of a tin-containing catalyst. Furthermore, this invention relates to the manufacturing method which collect | recovers and uses repeatedly the tin containing catalyst used for the oxidation reaction.

  The method for producing an oxide by oxidizing a carbonyl compound by a peroxidation reaction as in the present invention includes, for example, reacting a ketone with an organic peracid such as peracetic acid or perbenzoic acid to produce an ester or lactone. The so-called Bayer-Villiger reaction for producing formyloxy compounds is generally known (see, for example, Non-Patent Document 1). The reaction products such as esters, lactones, and carboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, and alcohols obtained by side reactions of these compounds are, for example, pharmaceuticals, fragrances, dyes, and organic synthetic intermediates. And a compound useful as a resin raw material. (For example, refer nonpatent literature 2).

  In particular, when a cyclic ketone is used as a production raw material, lactone, hydroxycarboxylic acid, and dicarboxylic acid produced by reaction are attracting attention because they are useful starting materials for diol compound synthesis, respectively (for example, patents). Reference 1).

Furthermore, as the buyer-bilger reaction, various oxidation systems using hydrogen peroxide instead of the organic peracid as an oxidizing agent have been developed in recent years (for example, Patent Document 2, Patent Document 3, and Non-Patent Document 3).
For example, in Patent Document 1, an ester compound or a lactone compound is obtained by reacting a ketone compound with hydrogen peroxide in the presence of a compound containing a metal element selected from Group 3, Group 13, Group 14 and Group 15 of the periodic table. In the examples, the synthesis of ε-caprolactone from cyclohexanone is disclosed.
Patent Document 2 discloses a reaction example using a metal-containing mesopore silicate containing at least one selected from the group consisting of tungsten, molybdenum and vanadium, for example.
Further, Non-Patent Document 3 reports an oxidation reaction method using a metal catalyst such as beta zeolite (HZSM-5) supporting tin.

International Publication No. 1996/020909 Pamphlet JP 2000-256342 A JP2003-300722

Tetrahedron letters, 43, p.6925 (2002) J. Org. Chem., 51, p.2830 (1986) Nature, 412,424 (2001)

However, for example, organic peracids such as peracetic acid or m-chloroperbenzoic acid are sensitive to impact and difficult to handle, and in the concentrated state, there is a risk of explosion, so they are widely used for research purposes. When considering industrial use, it was difficult to say that it was a practical method in terms of safety and cost.
In order to avoid the use of organic peracids that are difficult to handle, various oxidation systems described in, for example, Patent Document 2, Patent Document 3, and Non-Patent Document 3 have been developed. However, even in these methods, for example, the cost problem that the metal catalyst to be used is expensive, the problem of the supply stability with respect to the industrial use that it is a rare metal, and further, it is used for production. In industrial production, it is difficult to say that the production method is highly practical due to the complicated problem of preparation that requires special catalyst preparation in advance.

In addition, for the purpose of obtaining ε-caprolactone, the present inventor actually tried this reaction using tin (II) chloride according to Example 12 of Patent Document 2, but the reaction selection of the desired ε-caprolactone was performed. It was confirmed that the rate was only 4.1% (see Comparative Example 1 of the present application).
Further, when considering industrial use, for example, whether the reaction catalyst can be recycled and reused is also an important issue in consideration of economics (cost) and environmental problems such as waste reduction.

  Then, this invention makes it a subject to provide the reaction catalyst which has high reaction selectivity and is recyclable in the peroxidation reaction using a carbonyl compound. Furthermore, the present invention provides a method for efficiently producing, for example, an ester, a lactone or a formyloxy compound, or a hydrolyzate of these compounds by peroxidizing a carbonyl compound as the reaction catalyst. The task is to do.

  From the above problems, the present inventors have intensively studied to achieve the object of the present invention, and as a result, have found a novel reaction catalyst containing specific tin that can be recycled and reused for the peroxidation reaction of the present invention. I found it. Further, the tin-containing catalyst is used to perform a peroxidation reaction of a carbonyl compound, for example, an ester, lactone, or formyloxy compound, and a carboxylic acid, dicarboxylic acid, hydroxycarboxylic acid obtained by side reaction of these compounds. And a method for producing alcohol with high efficiency, and the present invention was completed.

  That is, the problems of the present invention are solved by the inventions [1] to [14] shown below.

  [1] In the general formula (3), a carbonyl compound represented by the following general formula (2) is reacted with a peroxide in the presence of a tin-containing catalyst represented by the following general formula (1). The manufacturing method of the at least 1 sort (s) of oxide chosen from the group which consists of the ester compound shown, the carboxylic acid compound shown by General formula (4), and the compound containing the hydroxyl group shown by General formula (5).

(In the formula, R represents a hydrocarbon group having 1 to 24 carbon atoms (or an alkali metal atom), x represents the number of R groups and a real number of 0 to 3, and y represents the number of oxygen atoms. In addition, z is a real number from 0 to 1. Further, z represents the number of hydroxyl groups and is a real number from 0 to 4. However, the total number of x, y and z does not exceed 4. General formula (1) The number of carbon atoms of the tin-containing catalyst represented by is not more than 100.)

(In the formula, R ¹ represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent. R ² represents a hydrogen atom or a carbon atom which may have a substituent. The hydrocarbon group of the number 1 to 24 is shown.)

(In the formula, R ¹ and R ² are the same as the definitions of R ¹ and R ^{2 in} the general formula (2).)

(In the formula, R ² has the same definition as R ^{2 in} the general formula (2).)

(In the formula, R ¹ has the same definition as R ^{1 in} the general formula (2).)
[2] A cyclic carbonyl compound represented by the following general formula (6) is reacted with a peroxide in the presence of a tin-containing catalyst represented by the following general formula (1). ), A hydroxycarboxylic acid compound represented by the following general formula (8), and a dicarboxylic acid compound represented by the general formula (9).

(In the formula, R, x, y and z are the same as those represented by the general formula (1). The number of carbon atoms of the tin-containing catalyst represented by the general formula (1) does not exceed 100. .)

(In the formula, L represents an alkylene group having 3 to 24 carbon atoms or an aralkylene group having 7 to 24 carbon atoms, which may have a substituent.)

(In the formula, L is the same as the definition of L in the general formula (6).)

(In the formula, L is the same as the definition of L in the general formula (6).)

(In the formula, L ¹ represents an alkylene group having 2 to 23 carbon atoms, a phenylene group, or an aralkylene group having 7 to 23 carbon atoms, which may have a substituent.)
[3] The method for producing an oxide according to [1] or [2], wherein the tin-containing catalyst represented by the following general formula (1a) is used as the tin-containing catalyst represented by the general formula (1).

(Wherein y represents the number of oxygen atoms and is a real number from 0 to 1. z represents the number of hydroxyl groups and is a real number from 0 to 4. However, the total number of y and z is 4. Not exceed.)
[4] The above [3], wherein the tin-containing catalyst represented by the general formula (1a) is a catalyst prepared by hydrolyzing tin tetrachloride, tetraalkoxytin, stannate, or an organic acid salt of tin. The manufacturing method of oxide described in 2.

(Wherein y represents the number of oxygen atoms and is a real number from 0 to 1. z represents the number of hydroxyl groups and is a real number from 0 to 4. However, the total number of y and z is 4) Is not exceeded.)
[5] The tin-containing recycle catalyst obtained by collecting after completion of the reaction of [1] or [2] is repeatedly used as the tin-containing reaction catalyst according to [1] or [2]. 2. The method for producing an oxide according to 2.

[6] The tin-containing recycling catalyst obtained by recovering after reacting the carbonyl compound represented by the general formula (2) with a peroxide in the presence of tin acetate (Sn (OAc) ₂ ) is repeatedly used. The method for producing an oxide according to [1] or [2], which is used as the tin-containing reaction catalyst according to [1] or [2].

  [7] The method for producing an oxide according to any one of [1] to [6], wherein the peroxide is hydrogen peroxide.

  [8] A tin-containing recycling catalyst obtained by recovery after completion of the reaction according to [1] or [2].

[9] A tin-containing recycling catalyst obtained by recovering after reacting the carbonyl compound represented by the general formula (2) with a peroxide in the presence of tin acetate (Sn (OAc) ₂ ).

According to the production method of the present invention, from the carbonyl compound having a ketone group or a formyl group represented by the general formula (2), for example, an ester compound represented by the general formula (3) and / or the general formula ( A wide variety of compounds such as the carboxylic acid compound shown in 4) can be produced at a time. Similarly, from the cyclic carbonyl compound represented by the general formula (6), for example, a lactone compound represented by the general formula (7), a hydroxycarboxylic acid compound represented by the general formula (8), and / or the general formula ( 9) are produced, and these compounds are useful as, for example, pharmaceuticals, fragrances, dyes, organic synthetic intermediates, resin raw materials, and the like.
Furthermore, for example, when the cyclic carbonyl compound represented by the general formula (6) is used as the carbonyl compound represented by the general formula (2), the lactone compound represented by the general formula (7) obtained by the reaction of the present invention, In addition, both of the hydroxycarboxylic acid compound represented by the following general formula (8) and the dicarboxylic acid compound represented by the general formula (9) can be used as a raw material for synthesizing the alkylene diol. That is, this invention is also a manufacturing method of the raw material for alkylene diol manufacture. Furthermore, according to the production method of the present invention, since the used tin-containing catalyst can be recycled without unexpectedly deactivating, it is an economically suitable method for producing an oxide of a carbonyl compound.

<< Tin-containing catalyst represented by the general formula (1) >>
As a reaction catalyst used in the peroxidation reaction of the present invention, a tin-containing catalyst represented by the following general formula (1) is used.

  Here, in the general formula (1), R represents a hydrocarbon group having 1 to 24 carbon atoms (or an alkali metal atom) bonded to tin (Sn), which is the central metal of the reaction catalyst, and x represents an R group. Y is an average number of 0 to 3 and y is the average number of oxygen atoms bonded to tin (Sn), which is the central metal of the reaction catalyst, z is a real number of 0 to 1, The average number of hydroxyl groups bonded to tin (Sn), which is the central metal of the reaction catalyst, is indicated by a real number of 0-4. However, the total number of x, y and z does not exceed 4. Here, the average value is calculated from elemental analysis.

Here, in the general formula (1), the hydrocarbon group represented by R is a linear alkyl group having 1 to 24 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). Group, heptyl group, octyl group, decyl group, lauryl group, myristyl group, palmityl group, stearyl group, etc .; branched alkyl group having 3 to 24 carbon atoms (for example, 2-methylethylene group, 3,3- Dimethylpropylene group, 3,3-dimethylpentylene group, etc.); C3-C24 cyclic alkyl group (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclododecanyl group, etc.); carbon atom An aryl group having 6 to 24 carbon atoms (for example, a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group); an aralkyl group having 7 to 24 carbon atoms (for example, Njiru group, a hydrocarbon group having 1 to 24 carbon atoms phenethyl group), further, a group indicated above also include various isomers such as regioisomers and enantiomers.
Moreover, the C1-C24 hydrocarbon group of General formula (1) may have a substituent. Therefore, one or more of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group are, for example, a fluorine atom, a nitro group, a cyano group, an alkyloxy group having 1 to 6 carbon atoms, and / or a carbon atom having 1 to 6 carbon atoms. It may be substituted with a dialkylamino group or the like. Further, the number of these substituents is not limited, but the number of carbon atoms of the tin-containing catalyst represented by the general formula (1) does not exceed 100.

From the above, the tin-containing catalyst represented by the general formula (1) is preferably one or more tin-containing catalysts selected from the group consisting of the following general formula (1a), general formula (1b), and general formula (1c). More preferably, Sn (OH) ₄ , SnO (OH) ₂ , wherein R is a hydrocarbon group having 1 to 18 carbon atoms or an alkali metal atom, and General Formula (1c) One or more tin-containing catalysts selected from the group consisting of:

(In the general formulas (1a) to (1b), R represents a hydrocarbon group having 2 to 24 carbon atoms, y is a real number from 0 to 1, and z is a real number from 0 to 4. However, y The total number of z and z does not exceed 4.)

  Here, as a C1-C18 hydrocarbon group in the said General formula (1b) and the said General formula (1c), Preferably it has a C1-C18 linear alkyl group and a substituent. It may be a phenyl group or a benzyl group which may have a substituent.

  The tin-containing catalyst represented by the general formula (1) used in the present invention is a supported reaction catalyst further containing a tin component supported on a carrier selected from, for example, silica, alumina, zircon and the like. Also good. However, these catalysts indicate supported reaction catalysts containing a tin component in which one or more hydroxyl groups are bonded to tin. Therefore, the tin-containing catalyst represented by the general formula (1) used in the present invention includes all compounds having one or more hydroxyl groups bonded to a tin atom, and compositions containing the same.

  As for the tin-containing catalyst represented by the general formula (1) used in the present invention, a commercially available product may be used. For those having no commercially available product, for example, the production of the following reaction catalyst Separately manufactured and used according to the method.

<Method 1: Hydrolysis method of stannic acid compound>
Among the tin-containing catalysts represented by the general formula (1) used in the present invention, the tin-containing catalyst mainly represented by the general formula (1a) is, for example, an aqueous solution of a stannic acid compound represented by the general formula (1d). It can manufacture by the method of hydrolyzing in the inside (refer following reaction formula <I>).

Here, in general formula (1d), M represents an alkali metal atom or an alkaline earth metal atom, m represents the number thereof, and is 0 to 2. Moreover, in general formula (1a), y is a real number of 0-1 and z is a real number of 0-4. However, in the general formula (1a), the total number of y and z does not exceed 4.
Moreover, the stannic acid compound represented by the general formula (1d) may be used singly or in a plurality of types.

<Method 2: Method of hydrolysis of tin alkoxide compound>
Among the tin-containing catalysts represented by the general formula (1) used in the present invention, the tin-containing catalyst mainly represented by the general formula (1a) is, for example, an aqueous solution of a tin alkoxide compound represented by the general formula (1e). It can manufacture by the method of hydrolyzing in the inside (refer following reaction formula <II>).

Here, in the general formula (1e), R ′ has the same definition as R in the general formula (1). Moreover, in general formula (1a), y is a real number of 0-1 and z is a real number of 0-4. However, in the general formula (1a), the total number of y and z does not exceed 4.
Moreover, the stannic acid compound represented by the general formula (1e) may be used singly or in a plurality of types.

<Method 3: Method of hydrolysis of tin halide compound>
Among the tin-containing catalysts represented by the general formula (1) used in the present invention, the tin-containing catalysts mainly represented by the general formula (1a) to the general formula (1c) are, for example, the general formula (9). It can be produced by a method of hydrolyzing a tin halide compound which may contain the indicated hydrocarbon group (R) in an aqueous solution (see the following reaction formula <III>).

  Here, in general formula (1), R, x, y, and z, and R, x, and y in general formula (1f) are the same as those in general formula (1). Moreover, in general formula (1f), Hal shows a halogen atom, h represents the number, and is an integer of 1-4. However, in the general formula (1f), the total number of x, y, and h does not exceed 4. Moreover, the tin halide compound represented by the general formula (1f) may be used singly or in a plurality of types.

(Tin halide represented by the general formula (1f))
From the above, the tin halide represented by the general formula (1f) is preferably one or more tin halides selected from the group consisting of SnCl ₄ , RSnCl ₃ , and RSn (═O) Cl.

(Aqueous solution)
In the hydrolysis method, the aqueous solution used is not particularly limited as long as it does not inhibit the hydrolysis reaction of the present invention, and may be, for example, a mixed solution with an organic solvent.

  In the hydrolysis method, the aqueous solution used is preferably an alkaline aqueous solution, and specific examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate, potassium carbonate, and carbonate. An aqueous solution of an alkali metal salt of carbonic acid such as sodium hydrogen or potassium hydrogen carbonate, an alkaline earth metal hydroxide such as magnesium hydroxide or calcium hydroxide, or an alkaline earth metal salt of carbonate such as magnesium carbonate or calcium carbonate. used. In addition, these alkali metal salts or alkaline earth metal salts may be used alone or in combination of a plurality of types, and these alkali metal salts and alkaline earth metals may be used. You may mix and use a salt. Furthermore, these alkali metal salts and / or alkaline earth metal salts may be adjusted by adding them as they are during the hydrolysis reaction. Therefore, the concentration of the aqueous solution is not particularly limited.

  In the hydrolysis method, the mixing method of the aqueous alkali solution and tin halide is not particularly limited. That is, tin halide may be added to the alkaline aqueous solution, the alkaline aqueous solution may be added to the tin halide, or the alkaline aqueous solution and the tin halide may be added and mixed. In the hydrolysis, it is preferable to adjust the pH of the reaction solution. In addition, as pH, Preferably it is 0.5-10, More preferably, it is 1-7.

  From the method 1, the tin-containing catalyst represented by the general formula (1) of the present invention is obtained by, for example, mixing the tin halide represented by the general formula (1f) in an aqueous solution by a method such as stirring. The resulting reaction mixture is filtered or decanted to obtain a solid. In the above method, for example, the reaction environment such as reaction temperature and reaction pressure is not particularly limited.

<Method 4: Production Method Using Tin Carboxylate Compound>
The tin-containing catalyst represented by the general formula (1a) used in the present invention is, for example, a method of treating a carboxylic acid tin compound represented by the general formula (10) in the presence of a peroxide (method 4-1). Or a method for treating a tin carboxylate compound represented by the general formula (10) in the presence of a peroxide and a carbonyl compound represented by the general formula (2) or the general formula (6) (Method 4-2). ) (See reaction formula <IV> below).

  Here, in the reaction formula <IV>, y and z in the tin-containing catalyst represented by the general formula (1a) are the same as those in the general formula (1a). In the general formula (1a), the total number of y and z does not exceed 4. The tin carboxylate compound represented by the general formula (10) will be described next.

(Tin carboxylate compound represented by the general formula (10))
In the tin carboxylate compound represented by the general formula (5) used in the present invention, the hydrocarbon group having 1 to 24 carbon atoms in R ³ is defined as the definition of the hydrocarbon group in R of the general formula (1). The same.

  Examples of the tin carboxylate compound represented by the general formula (5) used in the present invention include carbon such as tin formate, tin acetate, tin propionate, tin butanoate, tin hexanoate, tin 2-ethylhexanoate and the like. Tin salt of aliphatic monocarboxylic acid having 1 to 24 atoms; tin salt of aromatic monocarboxylic acid having 7 to 24 carbon atoms such as tin benzoate; tin pyridine carboxylate; tin oxalate, tin malonate, malee Tin salt of aliphatic dicarboxylic acid having 1 to 24 carbon atoms such as tin oxide; tin phthalate, tin isophthalate, tin terephthalate, benzenetetracarboxylic acid (mono or di) tin, naphthalene tetracarboxylic acid (mono or di) ) Tin salt of aromatic polycarboxylic acid having 8 to 24 carbon atoms such as tin, biphenyltetracarboxylic acid (mono or di) tin; pyridinecarboxylic acid , Tin pyrrole carboxylic acid, and heterocyclic tin salts of monocarboxylic acids having a carbon number of 4 to 24, such as furan carboxylic acid tin and the like.

  As the carboxylic acid tin compound, preferably one or more carboxylic acid tin compounds selected from the group consisting of tin salts of 1 to 24 aliphatic monocarboxylic acids and tin salts of aromatic monocarboxylic acids having 7 to 24 carbon atoms More preferably one or more carboxylic acid tin compounds selected from the group consisting of tin acetate, tin propionate, tin butanoate, tin hexanoate, tin 2-ethylhexanoate and tin benzoate.

(Carbonyl compound)
The carbonyl compound represented by the general formula (2) or the general formula (6) used in the method 4-2 of the present invention and the amount of the carbonyl compound described in << Method for producing an oxide of the present invention >> described later are used. It is the same kind as the compound and the same amount used.

(Peroxide)
Moreover, the peroxide used by this invention and its usage-amount are synonymous with the peroxide as described in the << manufacturing method of the oxide of this invention >> mentioned later.

  In addition, according to the method 4 of the present invention, the tin-containing catalyst represented by the general formula (1a) is, for example, in the aqueous solution of the tin carboxylate compound represented by the general formula (10), and, if necessary, In response, the carbonyl compound represented by the general formula (2) or the general formula (6) is added and mixed by a method such as stirring, and the obtained reaction mixture is filtered or decanted to obtain a solid. can do. In the above method, for example, the reaction environment such as reaction temperature and reaction pressure is not particularly limited.

<< Method for Producing Oxide of the Present Invention >>
In the method for producing an oxide of the present invention, for example, in the presence of a tin-containing catalyst represented by the general formula (1), a carbonyl compound represented by the general formula (2) and a peroxide are reacted to form a general formula The ester compound represented by (3) can be produced (reaction formula <V>).

Here, in the reaction formula <V>, R, x, y and z in the tin-containing catalyst represented by the general formula (1) are the same as those described in the general formula (1).
In the general formula (2), R ¹ represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and R ² may have a hydrogen atom or a substituent. A good hydrocarbon group having 1 to 24 carbon atoms is shown. Furthermore, R ¹ and R ² may combine to form a cyclic structure. In General Formula (3), R ¹ and R ² are the same as the definitions of R ¹ and R ^{2 in} General Formula (2).

<Carbonyl compound represented by formula (2)>
The carbonyl compound which is a raw material for production of the present invention is a compound having a ketone or aldehyde group represented by the following general formula (2).

In the general formula (2), in the formula, R ¹ represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent. R ² represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent. R ¹ and R ² may be bonded to form a cyclic structure.

In general formula (2), the hydrocarbon group in R ¹ or R ² is a linear alkyl group having 1 to 24 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). , Heptyl group, octyl group, decyl group, lauryl group, myristyl group, palmityl group, stearyl group, etc .; branched alkyl group having 3 to 24 carbon atoms (for example, 2-methylethylene group, 3,3-dimethyl) Propylene group, 3,3-dimethylpentylene group, etc.); cyclic alkyl group having 3 to 24 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclododecanyl group, etc.); Aryl group having 6 to 24 carbon atoms (for example, phenyl group, naphthyl group, anthranyl group, biphenyl group and the like); aralkyl group having 7 to 24 carbon atoms (for example, Njiru group, a phenethyl group, etc.), including various isomers, such as further positional isomers and optical isomers.

<Cyclic carbonyl compound represented by general formula (6)>
In the carbonyl compound represented by the general formula (2), R ¹ and R ² may combine to form a cyclic structure, that is, even a cyclic carbonyl compound represented by the following general formula (6). Good.

  In the cyclic carbonyl compound represented by the general formula (6), L represents an alkylene group having 3 to 24 carbon atoms or an aralkylene group having 7 to 24 carbon atoms, which may have a substituent.

  Therefore, examples of the cyclic carbonyl compound represented by the general formula (2) of the present invention include, for example, cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclohexane which may be unsubstituted or have a substituent. Octanone, cyclononanone, cyclodecanone, cyclododecanone, cycloundecanone, 2-decalon (Decahydro-2-naphthalenone), spiro [2,5] octane-6-one, spiro [3,5] nonane-7-one, etc. And arocyclic carbonyl compounds represented by the following general formulas (12) to (16).

The hydrocarbon group in R ¹ and R ² of the general formula (2) and the alkylene group and aralkylene group in L of the general formula (6) may have a substituent. Accordingly, examples of such a substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), an alkyl group having 1 to 8 carbon atoms (straight chain, branched chain, cyclic; various isomers also Substituted) with methoxy group, ethoxy group, trifluoromethyl group, difluoromethyl group, trichloromethyl group, trifluoroethyl group, trifluoromethoxy group, difluoromethoxy group, trifluoroethoxy group, phenyl group, halogen atom And phenyl group, phenyloxy group, and (phenyl substituted with a halogen atom) oxy group. Furthermore, the number of these substituents is not limited. However, the number of carbon atoms of the carbonyl compound represented by the general formula (2) and the cyclic carbonyl compound represented by the general formula (6) does not exceed 24.

  In addition, when the cyclic carbonyl compound shown by General formula (6) is used, the lactone compound shown by General formula (7) is obtained by reaction of this invention (reaction formula <V>).

  Here, in the reaction formula <V>, R, x, y and z in the tin-containing catalyst represented by the general formula (1) are the same as those described in the general formula (1). Moreover, L of the cyclic carbonyl compound represented by the general formula (6) represents an alkylene group having 3 to 24 carbon atoms or an aralkylene group having 7 to 24 carbon atoms, which may have a substituent.

Therefore, specifically, the carbonyl compound represented by the general formula (2) used in the present invention is preferably unsubstituted or optionally substituted with cyclohexyl carbaldehyde, methyl cyclohexyl ketone, benzaldehyde, acetophenone, 2 , 3-methylenedioxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 2,3-ethylenedioxybenzaldehyde, 3,4-ethylenedioxybenzaldehyde, 2,3-methylenedioxyacetophenone, 3,4-methylenedi Oxyacetophenone, 2,3-ethylenedioxyacetophenone, 3,4-ethylenedioxyacetophenone, cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, Rodekanon, be cyclododecanone, cycloalkyl undecanoic, the general formula (6) to (10);
More preferably methyl cyclohexyl ketone, 2,3-methylenedioxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 2,3-ethylenedioxybenzaldehyde, 3,4-ethylenedioxybenzaldehyde, 2,3-methylenedioxy Acetophenone, 3,4-methylenedioxyacetophenone, 2,3-ethylenedioxyacetophenone, 3,4-ethylenedioxyacetophenone, cyclopropanone, cyclopentanone, cyclobutanone, cyclopentanone, cyclohexanone, cyclododecanone .

<Peroxide>
The peroxide used in the present invention is at least one selected from the group consisting of hydrogen peroxide, persulfuric acid, persulfate alkaline salt compounds, and persulfate alkaline earth salt compounds. The peroxide used in the present invention may be used by dissolving or suspending in water or an organic solvent described later. In addition, the said peroxide may use a commercial item as it is, or may manufacture and use it by arbitrary well-known methods, for example.

  As the peroxide of the present invention, preferably hydrogen peroxide, persulfuric acid, alkali metal salt of persulfuric acid, more preferably hydrogen peroxide solution, sodium persulfate, potassium persulfate, and a mixture of sodium persulfate and potassium persulfate More preferably, it is a hydrogen peroxide solution, particularly preferably 30% to 60% hydrogen peroxide solution.

  The amount of the peroxide of the present invention is appropriately adjusted depending on the uniformity and stirring properties of the reaction solution, but the carbonyl compound represented by the general formula (2) (or the cyclic carbonyl compound represented by the general formula (6)). Preferably it is 0.1-100 mol with respect to 1 mol, More preferably, it is 0.3-50 mol, Most preferably, it is 0.5-10 mol.

<Tin-containing catalyst used in the present invention>
The tin-containing catalyst used in the present invention is a composition containing a tin component represented by the general formula (1). Moreover, you may use the tin containing catalyst of this invention individually or in mixture of multiple types. Further, the reaction catalyst may be used as it is, or may be used by dissolving or suspending in, for example, water, an organic solvent described later, or a mixed solvent thereof.

(Amount used: reaction catalyst)
Although the usage-amount of the tin-containing catalyst of this invention is suitably adjusted with the uniformity of a reaction liquid, stirring property, etc., with respect to 1 mol of carbonyl compounds shown by General formula (2), 0.001 mol or more and 2.0. Or less, preferably 0.001 mol or more and less than 1.0 mol, more preferably 0.003 mol or more and less than 1.0 mol, and particularly preferably 0.004 mol or more and 0.5 mol or less.

<Reaction solvent>
The oxidation reaction of the present invention can be carried out without a solvent or in the presence of a reaction solvent. Further, the reaction system may be either a homogeneous system or a heterogeneous system. Furthermore, in the case of a homogeneous system, even if it is a single-phase system, for example, a multiphase system such as a two-phase system composed of a water-organic phase. Or in either case.

  When the reaction of the present invention is performed in the presence of a reaction solvent, examples of the solvent that can be used include water, alcohols such as methanol, ethanol, propanol, isopropanol, and hexafluoroisopropanol; nitriles such as acetonitrile and propionitrile. Ketones such as acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, carbonates such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate; 1,2-dimethoxyethane, tetrahydrofuran, 1,4 -Ethers such as dioxane; carboxylic acids such as formic acid and acetic acid; amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; N Ureas such as N'- dimethylimidazolidinone; benzene, toluene, xylene and the like aromatic hydrocarbons; halogens dichloroethane and the like; ethyl acetate, and carboxylic acid esters such as ethyl propionate. These may be used alone or in combination of two or more.

  The reaction solvent is preferably at least one mixed solvent selected from the group consisting of water, nitriles, ketones, carbonates, ethers, carboxylic acids, aromatic hydrocarbons, halogens, carboxylic acid esters, More preferably, at least selected from the group consisting of water, acetonitrile, acetone, dimethyl carbonate, 1,4-dioxane, 1,2-dimethoxyethane, acetic acid, methyl acetate, ethyl acetate, ethyl propionate, benzene, and toluene, xylene. One mixed solvent, particularly preferably, at least one mixed solvent selected from the group consisting of water, acetonitrile, acetone, 1,4-dioxane, acetic acid, ethyl propionate, and toluene can be used.

  The mixed solvent with water is not particularly limited, but the amount of water relative to the total amount of solvent is usually 0.01 to 80% by weight, preferably 0.1 to 40% by weight, More preferably, it is 0.3-20 weight%, More preferably, it is 0.5-10 weight%, Most preferably, it is 0.5-7.5 weight%.

(Amount used: reaction solvent)
The amount of the reaction solvent used is appropriately adjusted depending on the uniformity of the reaction solution, the stirring ability, etc., and is preferably 0.1 to 1000 g with respect to 1 g of the cyclic ketone compound represented by the general formula (1). More preferably, it is 0.3-750g, Most preferably, it is 0.5-500g.

<Other additives>
In the reaction of the present invention, for example, phosphoric acid, a phosphate compound, a surfactant or the like may be added as an additive to carry out the reaction of the present invention.

  Examples of the phosphate used include, for example, alkali metal phosphates such as potassium phosphate, sodium phosphate, calcium phosphate, magnesium phosphate, potassium hydrogen phosphate, sodium hydrogen phosphate, alkali metal hydrogen phosphate, and phosphorus Examples include acid alkaline earth metal salts and ammonium phosphate salts. In the reaction of the present invention, a surfactant such as an alkali metal alkyl sulfonate may be used to increase the reaction rate. In addition, you may adjust pH of the reaction liquid mentioned later using said additive.

<Reaction conditions>
The peroxidation reaction of the present invention is performed, for example, in the air or in an inert gas atmosphere. Moreover, the mixing order of the tin-containing catalyst of the present invention, the carbonyl compound represented by the general formula (2) (or the cyclic carbonyl compound represented by the general formula (6)), the peroxide, and the reaction solvent is not particularly limited. However, the carbonyl compound represented by the general formula (2) (or the cyclic formula represented by the general formula (6) is used so that the dangerous peroxide is surely consumed during the reaction and does not remain excessively after the completion of the reaction. A mode in which a peroxide is added to a mixture of a carbonyl compound), a tin-containing catalyst, and a reaction solvent under reaction temperature conditions is desirable. In order to ensure that the peroxide is consumed during the reaction, the reaction is preferably carried out with stirring.

(Reaction temperature)
The reaction temperature of the present invention is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, more preferably 20 ° C to 100 ° C, particularly preferably 60 ° C to 90 ° C, and the reaction pressure is particularly limited. Not. In the above reaction, the reaction itself may be difficult to proceed because the peroxide is decomposed depending on the pH of the reaction system. Therefore, the pH of the reaction system is preferably 6.0 to 10.5, more preferably 8.0 to 9.5. In addition, it is desirable to carry out the progress of the reaction of the present invention while confirming with an analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), nuclear magnetic resonance spectrum ( ¹ H-NMR).

  In the reaction of the present invention, after completion of the reaction, for example, if necessary, the reaction mixture is separated, with a sulfite such as sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, or a reducing agent such as sodium thiosulfate. After treatment, the resulting mixture of lactone compound and hydroxycarboxylic acid compound can subsequently be used for the production of diol compounds. In addition, the obtained mixture of the lactone compound and the hydroxycarboxylic acid compound is separated into, for example, a lactone compound into an organic layer solution by separating the mixture using a weak alkaline aqueous solution such as potassium carbonate or sodium hydrogen carbonate and an organic solvent. Carboxylic acid compounds can be distributed to aqueous solution and isolated and purified, respectively, or can be isolated and purified by methods such as distillation, recrystallization or column chromatography.

<< Oxide obtained by the production method of the present invention and its hydrolyzate >>
In the present invention, the ester represented by the general formula (3) is efficiently obtained from various carbonyl compounds represented by the general formula (2) and peroxides by performing the peroxidation reaction under the above-described oxidation reaction conditions. A compound and an oxide such as a lactone compound represented by the general formula (7) are obtained.

<Ester compound represented by general formula (3) and lactone compound represented by general formula (7)>
Therefore, examples of the ester compound represented by the general formula (3) and the lactone compound represented by the general formula (7) that are oxides produced in the present invention include, for example, cyclohexyl formate, phenyl formate, Formic acid (2,3-methylenedioxybenzyl) ester, formic acid (3,4-methylenedioxybenzyl) ester, formic acid (2,3-ethylenedioxybenzyl) ester, formic acid (3,4-ethylenedioxybenzyl) Ester, acetic acid cyclohexyl ester, acetic acid phenyl ester, acetic acid (2,3-methylenedioxybenzyl) ester, acetic acid (3,4-methylenedioxybenzyl) ester, acetic acid (2,3-ethylenedioxybenzyl) ester , Acetic acid (3,4-ethylenedioxybenzyl) ester, ε-caprolactone, α-methyl-ε Caprolactone, β-methyl-ε-caprolactone, γ-methyl-ε-caprolactone, α-methyl-ε-propyl-ε-caprolactone, α-ethyl-ε-caprolactone, β-ethyl-ε-caprolactone, γ-ethyl- ε-caprolactone, α-ethyl-ε-methyl-ε-caprolactone, α-ethyl-ε-butyl-ε-caprolactone, α-ethyl-ε-isopropyl-ε-caprolactone, α-ethyl-ε-isobutyl-ε- Caprolactone, α-ethyl-ε-tert-butyl-ε-caprolactone, α-propyl-ε-caprolactone, α-butyl-ε-caprolactone, α-butyl-ε-methyl-ε-caprolactone, α-butyl-ε- Propyl-ε-caprolactone, α-isopropyl-ε-caprolactone, α-isopropyl-ε-methyl-ε-cap Lolactone, α-isopropyl-ε-propyl-ε-caprolactone, α-isopropyl-ε-butyl-ε-caprolactone, α-isopropyl-ε-tert-butyl-ε-caprolactone, α-isobutyl-ε-caprolactone, α- Isobutyl-ε-methyl-ε-caprolactone, α-isobutyl-ε-propyl-ε-caprolactone, α-isobutyl-ε-butyl-ε-caprolactone, α-isobutyl-ε-isopropyl-ε-caprolactone, α-isobutyl- ε-tert-butyl-ε-caprolactone, α-tert-butyl-ε-caprolactone, β-tert-butyl-ε-caprolactone, γ-tert-butyl-ε-caprolactone, α-tert-butyl-ε-methyl- ε-caprolactone, α-tert-butyl-ε-propyl-ε-cap Lolactone, α-tert-butyl-ε-butyl-ε-caprolactone, α, β-dimethyl-ε-caprolactone, α, γ-dimethyl-ε-caprolactone, α, δ-dimethyl-ε-caprolactone, α, ε- Dimethyl-ε-caprolactone, β, γ-dimethyl-ε-caprolactone, β, δ-dimethyl-ε-caprolactone, α, β-diethyl-ε-caprolactone, α, γ-diethyl-ε-caprolactone, α, δ- Diethyl-ε-caprolactone, α, ε-diethyl-ε-caprolactone, β, γ-diethyl-ε-caprolactone, β, δ-diethyl-ε-caprolactone, α, ε-dipropyl-ε-caprolactone, α, ε- Dibutyl-ε-caprolactone, α, ε-diisopropyl-ε-caprolactone, α, ε-diisobutyl-ε-caprolactone, α, ε-diter Examples include t-butyl-ε-caprolactone.

<< Hydrolysate from oxide obtained by the production method of the present invention >>
In the production method of the present invention, the oxide as described above is further hydrolyzed during the reaction, for example, containing a carboxylic acid compound represented by the general formula (4) and a hydroxyl group represented by the general formula (5). The compound, or a hydrolyzate such as a hydroxycarboxylic acid compound represented by the general formula (8), and a dicarboxylic acid compound represented by the general formula (9) obtained by further peroxidizing the hydroxycarboxylic acid compound are purified. (Reaction Formula <VI>).

Here, in each compound in the reaction formula <VI>, R ¹ represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and R ² represents a hydrogen atom or a substituent. A hydrocarbon group having 1 to 24 carbon atoms which may have L represents an alkylene group having 3 to 24 carbon atoms or an aralkylene group having 7 to 24 carbon atoms, which may have a substituent, and L ¹ may have a substituent. A good alkylene group having 2 to 23 carbon atoms, a phenyl group, or an aralkylene group having 7 to 23 carbon atoms is preferable.

Among such compounds, in particular, the ester compound represented by the general formula (3) is an ester compound such as formic acid cyclohexyl ester, formic acid phenyl ester, or formic acid (3,4-methylenedioxyphenyl) ester. In this case, the compound containing a hydroxyl group represented by the above general formula (5) such as cyclohexanol, phenol, or sesamol to be purified by hydrolysis is industrially used as a solvent, a raw material for organic synthesis, or a raw material for perfume. Useful.
Furthermore, according to the production method of the present invention, for example, the cyclic carbonyl compound represented by the general formula (6) and the hydrolyzate thereof, the hydroxycarboxylic acid compound represented by the above general formula (8) and / or the hydroxycarboxylic compound. In some cases, the dicarboxylic acid compound represented by the general formula (9) in which the acid compound further undergoes a peroxidation reaction can be produced at the same time. The cyclic carbonyl compound represented by the general formula (6), the hydroxycarboxylic acid compound represented by the general formula (8), and the dicarboxylic acid compound represented by the general formula (9) are each independently or a mixture thereof. The alkylene diol can be produced by hydrogenolysis.
Therefore, the production method of the present invention comprises the group consisting of the cyclic carbonyl compound represented by the general formula (6), the hydroxycarboxylic acid compound represented by the general formula (8), and the dicarboxylic acid compound represented by the general formula (9). It is also a method for producing at least one raw material for producing an alkylene diol selected from the above.

  In the present invention, in particular, when hydrogen peroxide is used as a peroxide, this hydrogen peroxide is decomposed into water and oxygen after the reaction, so there is no need to treat by-products derived from the peroxide. Since the hydrogen peroxide can be decomposed into water after the reaction, it is a so-called production method in which harmful waste is reduced, so-called environmental load is suppressed.

  In addition, since the tin-containing catalyst used in the reaction of the present invention is separated as a solid filtrate by the filtration operation at the time of the post-reaction treatment, the product ester compound, lactone compound and / or formyloxy compound is removed. Can be easily obtained. That is, it can be said that the production method of the present invention is an industrially simple production method.

  Furthermore, according to the production method of the present invention, for example, the solid recovered by filtration or the like after the reaction is surprisingly lost as a tin-containing catalyst even if it is reused in the next buyer-bilger reaction as it is. An oxide of a carbonyl compound can be obtained without activation. Many production methods for recycling reaction catalysts have been known so far, but in many cases, the recovered catalyst cannot be reused as it is. For example, the catalyst regeneration process and the like are complicated. Operation is required. However, since the solid collected after the reaction of the present invention can be recycled as it is, it is a reaction catalyst capable of obtaining an oxide of a carbonyl compound from an economical viewpoint.

  Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto. In the following examples and comparative examples, “%” means “% by mass” unless otherwise specified.

Analyzer: GC-14B (manufactured by SHIMADZU)
Column used: TC-WAX (manufactured by GL Science); 0.53 mmI. D. × 30m, film thickness 1μm
Analysis temperature: start temperature: 60 ° C. (hold for 5 minutes) → (temperature increase rate: 7 ° C./min)→end temperature: 220 ° C. (hold for 12 minutes).
Inlet: Splitless, 250 ° C
Detector: FID, 250 ° C
Internal standard: Anisole

<Analysis conditions for high performance liquid chromatography (HPLC)>
Column: ODS-80TsQA φ4.6 mm × 250 mm (manufactured by TOSOH) + Union C-18 φ4.6 mm × 100 mm (manufactured by Imact)
Eluent: acetonitrile / 20 mM NaH2PO4 aqueous solution; Vol / Vol) = 5/95 (adjusted to pH = 3.0 with phosphoric acid).
Column temperature: 40 ° C
Detector: 210nm
Flow rate: 1.0 ml / min

Example 1 (Production of tin-containing catalyst represented by the general formula (1): Method 1)
1.00 g (3.749 mmol) of sodium stannate and 100 g of water were added to a glass container equipped with a stirrer and a thermometer, and 7.5 ml (7.5 mmol) of 1 mol / L hydrochloric acid was added dropwise at room temperature. The reaction was stirred at 25 ° C. for 1 hour. Thereafter, the insoluble matter in the reaction solution is filtered, and the filtrate is dried under reduced pressure, whereby the tin-containing catalyst represented by the general formula (1) as the target product is used as the tin-containing catalyst of the general formula (c). 0.608 g (white solid) was obtained.

Example 2 (Production of tin-containing catalyst represented by the general formula (1): Method 2)
100 g of water was added to a glass container equipped with a stirrer and a thermometer, and 1.00 g (2.432 mmol) of tetra-t-butoxytin was added dropwise at room temperature. The reaction was stirred at 25 ° C. for 1 hour. Thereafter, the insoluble matter in the reaction solution is filtered, and the filtrate is dried under reduced pressure, whereby the tin-containing catalyst represented by the general formula (1) as the target product is used as the tin-containing catalyst of the general formula (c). 0.420 g (white solid) was obtained.

Example 3 (Production of tin-containing catalyst represented by the general formula (1): Method 3)
In a glass container equipped with a stirrer and a thermometer, 20 ml of water was added, and at 25 ° C, the pH of the reaction solution was in the range of 2.5 to 3.5, and 3.00 g (8.555 mmol) of tin tetrachloride pentahydrate. ) Was dissolved in 34 ml of water and a 1 mol / L aqueous sodium hydroxide solution was added dropwise. The reaction was stirred at 25 ° C. for 30 minutes. Thereafter, the insoluble matter in the reaction solution is filtered, and the filtrate is dried under reduced pressure, whereby the tin-containing catalyst represented by the general formula (1) as the target product is used as the tin-containing catalyst of the general formula (c). 1.369 g (white solid) was obtained.

Example 4 (Production of tin-containing catalyst represented by the general formula (1): Method 3)
To a glass container equipped with a stirrer and a thermometer, 30.6 ml (61.2 mmol) of a 2 mol / L aqueous sodium hydroxide solution was added, and 3.57 g (10.185 mmol) of tin tetrachloride pentahydrate was added to water at 25 ° C. An aqueous solution dissolved in 10 ml was added dropwise. The reaction was stirred at 25 ° C. for 30 minutes. 20.4 ml (20.4 mmol) of 1 mol / L hydrochloric acid was added dropwise. The reaction was stirred at 25 ° C. for 30 minutes. Thereafter, the insoluble matter in the reaction solution is filtered, and the filtrate is dried under reduced pressure, whereby the tin-containing catalyst represented by the general formula (1) as the target product is used as the tin-containing catalyst of the general formula (c). 1.6532 g (white solid) was obtained.

Example 5 (Production of tin-containing catalyst represented by the general formula (1): Method 4)
To a glass container equipped with a stirrer and a thermometer, 2.00 g (8.446 mmol) of tin (II) acetate and 20 ml of water were added, and 8.5 ml (17.00 mmol) of a 2 mol / L aqueous sodium hydroxide solution was added. The reaction was stirred at 25 ° C. for 3 hours. 3 mol / L sulfuric acid was added dropwise until the pH of the reaction solution reached 3.5. The reaction was stirred at 25 ° C. for 30 minutes. Thereafter, the insoluble matter in the reaction solution is filtered, and the filtrate is dried under reduced pressure, whereby the tin-containing catalyst represented by the general formula (1) as the target product is used as the tin-containing catalyst of the general formula (c). Obtained 1.1867 g (tan solid).

Example 6 (Production of tin-containing catalyst represented by the general formula (1): Method 4)
To a glass container equipped with a stirrer and a thermometer, 2.00 g (8.446 mmol) of tin (II) acetate, 15 ml of water and 15 ml of acetonitrile were added, and the reaction solution was stirred at 75 ° C. for 4 hours. Thereafter, the insoluble matter in the reaction solution is filtered, and the filtrate is dried under reduced pressure, whereby the tin-containing catalyst represented by the general formula (1) as the target product is used as the tin-containing catalyst of the general formula (c). 1.2126 g (black gray solid) was obtained.

Example 7 (Production of tin-containing catalyst represented by the general formula (1): Method 4)
To a glass container equipped with a stirrer and a thermometer, 2.00 g (5.636 mmol) of tin (IV) acetate, 15 ml of water and 15 ml of acetonitrile were added, and the reaction solution was stirred at 75 ° C. for 4 hours. Thereafter, the insoluble matter in the reaction solution is filtered, and the filtrate is dried under reduced pressure, whereby the tin-containing catalyst represented by the general formula (1) as the target product is used as the tin-containing catalyst of the general formula (c). 0.9240 g (white solid) was obtained.

Example 8 (Production of tin-containing catalyst represented by the general formula (1): Method 4)
In a glass container equipped with a stirrer and a thermometer, 20.00 g (0.204 mol) of cyclohexanone, 80 g of acetonitrile, 11.46 g (0.204 mol) of 60% hydrogen peroxide, 4.827 g of tin acetate (II. 020 mol) was added and the mixture was stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution is cooled to room temperature, insoluble matters in the reaction solution are filtered, and the filtrate is dried under reduced pressure, whereby the tin-containing catalyst represented by the general formula (1) as the target product is converted into the general formula. As a tin-containing catalyst (c), 3.833 g (white solid) was obtained.

Example 9 (Production of tin-containing catalyst represented by the general formula (1): Method 4)
To a glass container equipped with a stirrer and a thermometer, tin acetate (II) 2.414 g (10.194 mmol) acetonitrile 40 g, 60% hydrogen peroxide 8.597 g (152.91 mmol) were added, and 70 ° C. Stir for hours. Thereafter, the reaction solution is cooled to room temperature, insoluble matters in the reaction solution are filtered, and the filtrate is dried under reduced pressure, whereby the tin-containing catalyst represented by the general formula (1) as the target product is converted into the general formula. As a tin-containing catalyst (c), 1.8021 g (white solid) was obtained.

  In the tin-containing catalysts obtained in Examples 1 to 9, quantitative analysis of tin atoms was performed by inductively coupled plasma emission spectroscopy (ICP-AES), and quantitative analysis of oxygen and hydrogen by inert gas melting-infrared absorption method. Went. The results are summarized in Table 1 below.

* 1: Inductively coupled plasma optical emission spectrometry (ICP-AES).
* 2: Inert gas melting-infrared absorption method.

Reference Example 1 (Synthesis of HPLC sample: aqueous solution of 6-hydroxyhexanoic acid)
To a glass container equipped with a stirrer and a thermometer, ε-caprolactone (0.20 g, manufactured by Tokyo Chemical Industry Co., Ltd.), purified water (8 ml), and 8M aqueous sodium hydroxide solution (2 ml) were added, and 1 in an oil bath at 100 ° C. Stir for hours to react. After completion of the reaction, the resulting reaction solution was cooled, and the pH of the reaction solution was adjusted to 2.5 to 3.0 using a 3M aqueous sulfuric acid solution to obtain an aqueous solution of 6-hydroxyhexanoic acid.

Example 10 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 1, amount of hydrogen peroxide used; 1.5 equivalents per mole of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.867 g (15.3 mmol) of 60% hydrogen peroxide, 0.19 g of the tin-containing catalyst of Example 1 (About 1 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion of cyclohexanone was 33.8%, the yield of ε-caprolactone was 22.8%, and the selectivity was 67.5% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid is 3.7%, the selectivity is 11.0% (based on the amount of used cyclohexanone), and the yield of adipic acid is 0.8. %, The selectivity is 2.4% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 80.9%. there were.

Example 11 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 2, amount of hydrogen peroxide used; 1.5 equivalents per mole of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.867 g (15.3 mmol) of 60% hydrogen peroxide, 0.19 g of the tin-containing catalyst of Example 2 (About 1 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Then, when the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method), the conversion of cyclohexanone was 38.0%, the yield of ε-caprolactone was 24.2%, and the selectivity was 63.7% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid is 4.9%, the selectivity is 12.9% (based on the amount of cyclohexanone used), and the yield of adipic acid is 1.0. %, The selectivity is 2.6% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 79.2%. there were.

Example 12 (Synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 3, use amount of hydrogen peroxide; 1.5 equivalent to 1 mol of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.867 g (15.3 mmol) of 60% hydrogen peroxide, 0.19 g of the tin-containing catalyst of Example 3 (About 1 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion of cyclohexanone was 36.1%, the yield of ε-caprolactone was 24.3%, and the selectivity was 67.3% (based on the usage amount of cyclohexanone), the yield of 6-hydroxyhexanoic acid is 4.4%, the selectivity is 12.2% (based on the usage amount of cyclohexanone), and the yield of adipic acid is 1. .3%, selectivity is 3.6% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 83.1. %Met.

Example 13 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 4, amount of hydrogen peroxide used; 1.5 equivalents per mole of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.867 g (15.3 mmol) of 60% hydrogen peroxide, 0.19 g of the tin-containing catalyst of Example 4 (About 1 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion of cyclohexanone was 34.7%, the yield of ε-caprolactone was 22.7%, and the selectivity was 65.4% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid is 4.1%, the selectivity is 11.8% (based on the amount of used cyclohexanone), and the yield of adipic acid is 1.0. %, Selectivity is 2.9% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 80.1%. there were.

Example 14 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 5, use amount of hydrogen peroxide; 1.5 equivalents per 1 mol of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.867 g (15.3 mmol) of 60% hydrogen peroxide, 0.19 g of the tin-containing catalyst of Example 5 (About 1 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion of cyclohexanone was 28.7%, the yield of ε-caprolactone was 18.3%, and the selectivity was 63.8% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid is 4.3%, the selectivity is 15.0% (based on the amount of used cyclohexanone), and the yield of adipic acid is 0.7%. %, The selectivity is 2.4% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 81.2%. there were.

Example 15 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 6, amount of hydrogen peroxide used; 1.5 equivalents per mole of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.867 g (15.3 mmol) of 60% hydrogen peroxide, 0.19 g of the tin-containing catalyst of Example 6 (About 1 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion of cyclohexanone was 22.5%, the yield of ε-caprolactone was 14.2%, and the selectivity was 63.1% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid was 2.7%, the selectivity was 12.0% (based on the amount of used cyclohexanone), and the yield of adipic acid was 0.5. %, Selectivity is 2.2% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 77.3%. there were.

Example 16 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 7, use amount of hydrogen peroxide; 1.5 equivalents per 1 mol of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.867 g (15.3 mmol) of 60% hydrogen peroxide, 0.19 g of the tin-containing catalyst of Example 7 (About 1 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, when the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method), the conversion of cyclohexanone was 45.2%, the yield of ε-caprolactone was 27.8%, and the selectivity was 61.5% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid was 9.4%, the selectivity was 20.8% (based on the amount of used cyclohexanone), and the yield of adipic acid was 1.7. %, The selectivity is 3.8% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 86.1%. there were.

Example 17 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 8, use amount of hydrogen peroxide; 1.5 equivalents per mole of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.867 g (15.3 mmol) of 60% hydrogen peroxide, 0.19 g of the tin-containing catalyst of Example 8 (About 1 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, when the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method), the conversion of cyclohexanone was 33.8%, the yield of ε-caprolactone was 23.9%, and the selectivity was 70.7% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid is 4.2%, the selectivity is 12.4% (based on the amount of used cyclohexanone), and the yield of adipic acid is 0.9. %, The selectivity is 2.7% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 85.5%. there were.

Example 18 (Synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 8, use amount of hydrogen peroxide; 1.2 equivalent to 1 mol of cyclohexanone, no organic solvent use)
In a glass container equipped with a stirrer and a thermometer, 2.00 g (20.2 mmol) of cyclohexanone, 1.388 g (24.5 mmol) of 60% hydrogen peroxide, 0.38 g (about 2 mmol) of the tin-containing catalyst of Example 8 ) And stirred at 70 ° C. for 8 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, when the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method), the conversion of cyclohexanone was 52.3%, the yield of ε-caprolactone was 7.7%, and the selectivity was 14.7% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid is 33.6%, the selectivity is 64.3% (based on the amount of used cyclohexanone), and the yield of adipic acid is 2.7. %, Selectivity is 5.2% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 84.2%. there were.

Example 19 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of tin-containing catalyst of Example 9, use amount of hydrogen peroxide; 1.5 equivalents per mole of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.867 g (15.3 mmol) of 60% hydrogen peroxide, 0.19 g of the tin-containing catalyst of Example 9 (About 1 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, when the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method), the conversion of cyclohexanone was 40.5%, the yield of ε-caprolactone was 25.7%, and the selectivity was 63.5% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid was 7.7%, the selectivity was 19.0% (based on the amount of used cyclohexanone), and the yield of adipic acid was 1.6. %, Selectivity is 4.0% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 86.5%. there were.

Example 20 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of metastannic acid (SnO (OH) ₂ ), use amount of hydrogen peroxide; 1.5 equivalents to 1 mol of cyclohexanone)
In a glass container equipped with a stirrer and thermometer, chlorhexanone 2.00 g (20.4 mmol), acetonitrile 8 g, 60% hydrogen peroxide 1.719 g (30.6 mmol), metastannic acid 0.38 g (Mitsuwa Chemical) Chemicals, 2.25 mmol) and 1.224 g (20.4 mmol) of acetic acid were added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion of cyclohexanone was 34.7%, the yield of ε-caprolactone was 27.5%, and the selectivity was 79.3% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid was 2.8%, the selectivity was 8.1% (based on the amount of cyclohexanone used), and the yield of adipic acid was 1.4. %, The selectivity is 4.0% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 91.4%. there were.

Example 21 (synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; use of metastannic acid (SnO (OH) ₂ ), use amount of hydrogen peroxide; 1.5 equivalent to 1 mol of cyclohexanone)
In a glass container equipped with a stirrer and thermometer, chlorhexanone 2.00 g (20.4 mmol), acetonitrile 8 g, 60% hydrogen peroxide 1.719 g (30.6 mmol), metastannic acid 0.38 g (Mitsuwa Chemical) (Manufactured by Yakuhin Co., Ltd., 2.25 mmol) was added and stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion of cyclohexanone was 15.3%, the yield of ε-caprolactone was 10.5%, and the selectivity was 68.6% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid is 1.5%, the selectivity is 9.8% (based on the amount of cyclohexanone used), and the yield of adipic acid is 0.6. %, Selectivity was 3.9% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) was 82.4%. It was.

Example 22 (synthesis of ε-caprolactone and 6-hydroxyhexanoic acid; butyltin hydroxide oxide: (BuSnO (OH)) used, amount of hydrogen peroxide used; 1.2 equivalents per 1 mol of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, to 2.00 g (20.4 mmol) of cyclohexanone, 1.146 g (20.4 mmol) of 60% hydrogen peroxide, 0.426 g of butyltin hydroxide oxide (manufactured by Tokyo Chemical Industry, 2.04 mmol) and 1.224 g (20.4 mmol) of acetic acid were added and stirred at 70 ° C. for 8 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, when the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method), the conversion of cyclohexanone was 94.4%, the yield of ε-caprolactone was 1.9%, and the selectivity was 2.0% (based on the usage amount of cyclohexanone), the yield of 6-hydroxyhexanoic acid is 87.0%, the selectivity is 92.2% (based on the usage amount of cyclohexanone), and the yield of adipic acid is 4.9. %, The selectivity is 5.1% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount used of cyclohexanone) is 99.3%. there were.

Example 23 (Synthesis of ε-caprolactone and 6-hydroxyhexanoic acid; triphenyltin hydroxide: (Ph3SnOH) used, amount of hydrogen peroxide used; 1.5 equivalents per mol of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 1.146 g (20.4 mmol) of 60% hydrogen peroxide, 0.374 g of triphenyltin hydroxide (manufactured by ALDRICH, 1 0.02 mmol) was added and the mixture was stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, when the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method), the conversion of cyclohexanone was 28.5%, the yield of ε-caprolactone was 14.3%, and the selectivity was 50.2% (based on the amount of cyclohexanone), the yield of 6-hydroxyhexanoic acid is 6.1%, the selectivity is 21.4% (based on the amount of cyclohexanone), and the yield of adipic acid is 1.0 %, Selectivity is 3.6% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 75.2%. there were.

Example 24 (Synthesis of butyrolactone and 6-hydroxybutanoic acid; use of tin-containing catalyst of Example 8, use amount of hydrogen peroxide; 1.5 equivalents per mole of cyclobutanone)
In a glass container equipped with a stirrer and a thermometer, 1.43 g (20.4 mmol) of cyclobutanone, 1.723 g (30.6 mmol) of 60% hydrogen peroxide, 0.380 g (about 2 mmol) of the tin-containing catalyst of Example 8 ), 8 g of acetonitrile was added, and the mixture was stirred at 55 to 60 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion of cyclobutanone was 98.7%, the butyrolactone yield was 69.2%, and the selectivity was 70. 1% (based on the amount of cyclobutanone), the yield of 4-hydroxybutanoic acid is 12.3%, and the selectivity is 12.4% (based on the amount of cyclobutanone used). The total of butyrolactone and 4-hydroxybutanoic acid The selectivity (based on the amount of cyclobutanone used) was 82.5%, and the reaction yield was 81.5%.

Example 25 (Synthesis of ethyl propionate and propionic acid; use of tin-containing catalyst of Example 8, use amount of hydrogen peroxide; 2.0 equivalents per mole of 3-pentanone)
In a glass container equipped with a stirrer and a thermometer, 1.72 g (20.0 mmol) of 3-pentanone, 2.268 g (40.0 mmol) of 60% hydrogen peroxide, 0.426 g of the tin-containing catalyst of Example 8 ( About 2 mmol), 8 g of toluene, and 1.20 g (20.0 mmol) of acetic acid were added and stirred at 70 ° C. for 6 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Next, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion of 3-pentanone was 42.5%, and the yield of ethyl propionate was 36.8%. The rate is 86.6% (based on the usage amount of 3-pentanone), the yield of propionic acid is 2.7%, and the selectivity is 6.4% (based on the usage amount of 3-pentanone). The total selectivity for propionic acid (based on the amount of 3-pentanone used) was 92.9%, and the reaction yield was 39.5%.

Example 26 (Synthesis of acetic acid (3,4-methylenedioxyphenyl) ester; use of tin-containing catalyst of Example 8, use amount of hydrogen peroxide; 2. per mole of 3,4-methylenedioxyacetophenone. 0 equivalent)
In a glass container equipped with a stirrer and a thermometer, 1.64 g (10.0 mmol) of 3,4-methylenedioxyacetophenone, 1.134 g (20.0 mmol) of 60% hydrogen peroxide, tin of Example 8 0.186 g (about 1 mmol) of catalyst, 4 g of toluene, and 0.600 g (10.0 mmol) of acetic acid were added and stirred at 45 ° C. for 10 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion rate of 3,4-methylenedioxyacetophenone was 58.8%, and acetic acid (3,4-methylenedi). The selectivity of oxyphenyl) ester was 87.8% (based on the amount of 5-acetyl-1,3-benzodioxole used), and the reaction yield was 51.6%.

Example 27 (Synthesis of cyclohexyl acetate; use of tin-containing catalyst of Example 8, use amount of hydrogen peroxide; 2.0 equivalents per mole of cyclohexyl methyl ketone)
In a glass container equipped with a stirrer and a thermometer, 1.26 g (10.0 mmol) of cyclohexyl methyl ketone, 1.134 g (20.0 mmol) of 60% hydrogen peroxide, 0.186 g of the tin-containing catalyst of Example 8 ( About 1 mmol), 4 g of toluene, and 0.600 g (10.0 mmol) of acetic acid were added and stirred at 70 ° C. for 6 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion rate of cyclohexyl methyl ketone was 92.7%, and the selectivity of acetic acid cyclohexyl ester was 92.2% (cyclohexyl). Based on the amount of methyl ketone used), the reaction yield was 85.5%.

Example 28 (Synthesis of cyclohexyl acetate; use of tin-containing catalyst of Example 8, use amount of hydrogen peroxide; 2.0 equivalents per mole of cyclohexyl methyl ketone)
In a glass container equipped with a stirrer and a thermometer, 1.26 g (10.0 mmol) of cyclohexyl methyl ketone, 1.134 g (20.0 mmol) of 60% hydrogen peroxide, 0.186 g of the tin-containing catalyst of Example 8 ( About 1 mmol), 4 g of acetonitrile, and 0.600 g (10.0 mmol) of acetic acid were added and stirred at 70 ° C. for 6 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method). As a result, the conversion rate of cyclohexyl methyl ketone was 79.4%, and the selectivity of acetic acid cyclohexyl ester was 82.9% (cyclohexyl). Based on the amount of methyl ketone used), the reaction yield was 65.8%.

Examples 29 to 32 (recycle production method: synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; repetitive use of tin-containing catalyst of Example 8, amount of hydrogen peroxide used; 5 equivalents)
In a glass vessel equipped with a stirrer and a thermometer, cyclohexanone 2.00 g (20.4 mmol), 60% hydrogen peroxide 1.735 g (30.6 mmol), and the tin-containing catalyst of Example 8 0.38 g (about 2 mmol) ), 8 g of acetonitrile, and 1.224 g (20.4 mmol) of acetic acid were added, and the mixture was stirred at 70 ° C. for 4 hours. Thereafter, the reaction solution was cooled to room temperature, and the tin-containing catalyst was recovered by filtration. To the recovered tin-containing catalyst, 1.735 g (30.6 mmol) of 60% hydrogen peroxide, 8 g of acetonitrile, and 1.224 g (20.4 mmol) of acetic acid were added to 2.00 g (20.4 mmol) of cyclohexanone. For 4 hours. Thereafter, the reaction solution was cooled to room temperature, and the tin-containing catalyst was recovered by filtration. The tin-containing catalyst was repeatedly used four times in total by the same reaction operation. The filtrate obtained in each reaction is analyzed (GC; internal standard method, HPLC; absolute calibration curve method). The conversion rate of cyclohexanone, the yield of ε-caprolactone, the selectivity (based on the amount of cyclohexanone used), 6- The yield and selectivity of hydroxyhexanoic acid (based on the amount of cyclohexanone used), the yield of adipic acid, and the selectivity (based on the amount of cyclohexanone used) were measured. The results are summarized in Table 2 below.

* 1: Total selectivity (%) = [selectivity of ε-caprolactone (%)] + [selectivity of 6-hydroxyhexanoic acid (%)] + [selectivity of adipic acid (%)]

Comparative Example 1 (Synthesis of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid; tin (II) chloride used, hydrogen peroxide used; 1 equivalent per 1 mole of cyclohexanone)
In a glass container equipped with a stirrer and a thermometer, 1.00 g (10.2 mmol) of cyclohexanone, 4 g of acetonitrile, 0.573 g (10.2 mmol) of 60% hydrogen peroxide, 0.097 g of tin (II) chloride (0 0.5 mmol), and the mixture was stirred at 70 ° C. for 6 hours. Thereafter, the reaction solution was cooled to room temperature, and insoluble matters were removed by filtration. Subsequently, when the obtained filtrate was analyzed (GC; internal standard method, HPLC; absolute calibration curve method), the conversion of cyclohexanone was 60.4%, the yield of ε-caprolactone was 2.5%, and the selectivity was 4.1% (based on the amount of cyclohexanone used), the yield of 6-hydroxyhexanoic acid is 12.9%, the selectivity is 21.4% (based on the amount of used cyclohexanone), and the yield of adipic acid is 3.9. %, Selectivity is 6.5% (based on the amount of cyclohexanone used), and the total selectivity of ε-caprolactone, 6-hydroxyhexanoic acid and adipic acid (based on the amount of cyclohexanone used) is 32.0%. there were.

  From the above Examples and Comparative Examples, the production method of the present invention uses a tin-containing catalyst, for example, from a carbonyl compound having a ketone group or a formyl group, to oxides such as esters, lactones and formyloxy compounds, and Hydrolysates such as carboxylic acids, hydroxycarboxylic acids and alcohols obtained by decomposing these compounds can be obtained with a safe and high reaction selectivity without complicating the production process.

  Moreover, even if the recovered tin-containing catalyst after use in the production method is repeatedly used in the peroxidation reaction of the present invention, the target ester compound, lactone compound, etc. can be obtained with high selectivity. it can.

  In the present invention, by using a specific tin-containing catalyst, an oxide such as an ester compound or a lactone compound can be produced from a carbonyl compound having a ketone group or a formyl group by an industrially advantageous method. it can. Among the products obtained by the method of the present invention, in particular, ester compounds, lactone compounds, and compounds containing carboxylic acids, hydroxycarboxylic acids, and hydroxyl groups obtained by hydrolysis of these compounds (alcohols) And phenols) are useful compounds as, for example, pharmaceuticals, fragrances, dyes, organic synthetic intermediates, resin raw materials and the like.

Claims (9)

An ester compound represented by the general formula (3), characterized by reacting a carbonyl compound represented by the general formula (2) and a peroxide in the presence of a tin-containing catalyst represented by the general formula (1); A method for producing at least one oxide selected from the group consisting of a carboxylic acid compound represented by the general formula (4) and a hydroxyl group-containing compound represented by the general formula (5).

(In the formula, R represents a hydrocarbon group having 1 to 24 carbon atoms (or an alkali metal atom), x represents the number of R groups and a real number of 0 to 3, and y represents the number of oxygen atoms. In addition, z is a real number from 0 to 1. Further, z represents the number of hydroxyl groups and is a real number from 0 to 4. However, the total number of x, y and z does not exceed 4. General formula (1) The number of carbon atoms of the reaction catalyst containing a tin component represented by the formula does not exceed 100.)

(In the formula, R ¹ represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent. R ² represents a hydrogen atom or a carbon atom which may have a substituent. (This represents a hydrocarbon group of 1 to 24.)

(In the formula, R ¹ and R ² are the same as the definitions of R ¹ and R ^{2 in} the general formula (2).)

(In the formula, R ² has the same definition as R ^{2 in} the general formula (2).)

(In the formula, R ¹ has the same definition as R ^{1 in} the general formula (2).)
A lactone compound represented by general formula (7), wherein a cyclic carbonyl compound represented by general formula (6) and a peroxide are reacted in the presence of a tin-containing catalyst represented by general formula (1). A process for producing at least one oxide selected from the group consisting of a hydroxycarboxylic acid compound represented by the general formula (8) and a dicarboxylic acid compound represented by the general formula (9).

(In the formula, R, x, y and z are the same as those represented by the general formula (1). The number of carbon atoms of the reaction catalyst containing the tin component represented by the general formula (1) is 100 is not exceeded.)

(In the formula, L represents an alkylene group having 3 to 24 carbon atoms or an aralkylene group having 7 to 24 carbon atoms, which may have a substituent.)

(In the formula, L is the same as the definition of L in the general formula (6).)

(In the formula, L is the same as the definition of L in the general formula (6).)

(In the formula, L ¹ represents an alkylene group having 2 to 23 carbon atoms, a phenylene group, or an aralkylene group having 7 to 23 carbon atoms, which may have a substituent.)
The manufacturing method of the oxide of Claim 1 or 2 which uses the tin containing catalyst shown by General formula (1a) as a tin containing catalyst shown by General formula (1).

(Wherein y represents the number of oxygen atoms and is a real number from 0 to 1. z represents the number of hydroxyl groups and is a real number from 0 to 4. However, the total number of y and z is 4) Is not exceeded.)
The oxidation according to claim 3, wherein the tin-containing catalyst represented by the general formula (1a) is a catalyst prepared by hydrolyzing tin tetrachloride, tetraalkoxytin, stannate, or an organic acid salt of tin. Manufacturing method.

(Wherein y represents the number of oxygen atoms and is a real number from 0 to 1. z represents the number of hydroxyl groups and is a real number from 0 to 4. However, the total number of y and z is 4) Is not exceeded.)
The tin-containing recycled catalyst obtained by recovery after completion of the reaction according to claim 1 or 2 is repeatedly used as the tin-containing reaction catalyst according to claim 1 or 2, wherein the oxide of claim 1 or 2 is used. Production method.
A tin-containing recycle catalyst obtained by recovering after reacting the carbonyl compound represented by the general formula (2) with a peroxide in the presence of tin acetate (Sn (OAc) ₂ ) is repeatedly claim 1 or The method for producing an oxide according to claim 1 or 2, which is used as the tin-containing reaction catalyst according to claim 2.
The method for producing an oxide according to any one of claims 1 to 6, wherein the peroxide is hydrogen peroxide.
A tin-containing recycling catalyst obtained by recovery after completion of the reaction according to claim 1.
A tin-containing recycling catalyst obtained by recovering after reacting the carbonyl compound represented by the general formula (2) with a peroxide in the presence of tin acetate (Sn (OAc) ₂ ).