JP6279409B2 - Oxidation of ketones to esters using post-treated tin-substituted zeolite beta - Google Patents

Description

  The present invention relates to a method for producing a lactone compound and / or a hydroxycarboxylic acid compound from a cyclic ketone compound.

  Lactone compounds and hydroxycarboxylic acid compounds are widely used as raw materials for organic compounds, intermediates, polymers, and the like useful as pharmaceuticals, perfumes, dyes and the like. As a method for producing the lactone compound or hydroxycarboxylic acid compound, a method is known in which a cyclic ketone compound is oxidized with a tin-substituted zeolite having a β-type zeolite structure and hydrogen peroxide (Patent Document 1).

International Publication No. 2001/081291

  Patent Document 1 describes that in the reaction for synthesizing ε-caprolactone from cyclohexanone, the selectivity for ε-caprolactone is 99% or more. However, when the present inventors made additional trials, ε-caprolactone and its hydrolyzate 6-hydroxycaproic acid were produced, and the total selectivity of ε-caprolactone and 6-hydroxycaproic acid was about 70 to 80%. I found out that

  Accordingly, an object of the present invention is to provide a method for more selectively producing a lactone compound and / or a hydroxycarboxylic acid compound from a cyclic ketone compound.

  As a result of intensive studies to solve the above problems, the present inventors have used as a catalyst a compound obtained by reacting a tin-substituted zeolite having a β-type zeolite structure with a compound containing an alkali metal, an alkaline earth metal, or ammonium. Then, the selectivity of a lactone compound or a hydroxycarboxylic acid compound can be improved, and it has been found that these compounds useful for various applications can be produced more efficiently. The present invention has been completed based on these findings.

（式中、Ｒは炭素数３〜１９の２価の炭化水素基を示す）
で表される環式ケトン化合物を過酸化水素及び下記触媒と反応させることにより、下記式（２）

（式中、Ｒは前記に同じ）
で表されるラクトン化合物及び／又は下記式（３）
ＨＯ−Ｒ−ＣＯＯＨ （３）
（式中、Ｒは前記に同じ）
で表されるヒドロキシカルボン酸化合物を製造するラクトン化合物及び／又はヒドロキシカルボン酸化合物の製造方法を提供する。
触媒：焼成、無水ベースで、下記式（４）
（Ｍ_wＳｎ_xＳｉ_1-x）Ｏ₂ （４）
（式中、Ｍは３価の電荷を有する金属、ｗは０〜２ｘ、ｘは０．００１〜０．１を示す）
で表される、β型ゼオライトのＸ線回折パターンの特徴を示す（但し、ｗが０の場合は近距離秩序性を有するアモルファスであるか、又はβ型ゼオライトのＸ線回折パターンの特徴を示す）スズ置換ゼオライトを、アルカリ金属、アルカリ土類金属、又はアンモニウムを含む化合物と反応させて得られる化合物 That is, the present invention provides the following formula (1):

(In the formula, R represents a divalent hydrocarbon group having 3 to 19 carbon atoms)
By reacting the cyclic ketone compound represented by the formula (2) with hydrogen peroxide and the following catalyst:

(Wherein R is the same as above)
And / or the following formula (3)
HO-R-COOH (3)
(Wherein R is the same as above)
The lactone compound which manufactures the hydroxycarboxylic acid compound represented by these, and / or the manufacturing method of a hydroxycarboxylic acid compound is provided.
Catalyst: calcined, anhydrous basis, formula (4)
(M _w Sn _x Si _1-x ) O ₂ (4)
(In the formula, M is a metal having a trivalent charge, w is 0 to 2x, and x is 0.001 to 0.1)
The characteristic of the X-ray diffraction pattern of the β-type zeolite represented by the formula (However, when w is 0, it is amorphous having short-range order, or the characteristic of the X-ray diffraction pattern of the β-type zeolite. ) Compounds obtained by reacting tin-substituted zeolite with compounds containing alkali metals, alkaline earth metals, or ammonium

  The present invention also provides the lactone compound and / or hydroxycarboxylic acid compound, wherein the compound containing alkali metal, alkaline earth metal, or ammonium is an alkali metal, alkaline earth metal, or a salt of ammonia and an acid. A manufacturing method is provided.

  The present invention also provides a method for producing the above lactone compound and / or hydroxycarboxylic acid compound, wherein the compound containing alkali metal, alkaline earth metal, or ammonium is sodium nitrate and / or ammonium nitrate.

  The present invention also provides the lactone compound and / or hydroxycarboxylic acid compound, wherein the catalyst is a compound containing 0.1 to 0.9 mol of alkali metal, alkaline earth metal, or ammonium with respect to 1 mol of tin. A manufacturing method is provided.

  In the present invention, the reaction between the cyclic ketone compound, hydrogen peroxide and the catalyst may be selected in the absence of a solvent or from an alcohol solvent, an ether solvent, an ester solvent, a hydrocarbon solvent, and a nitrile solvent. And a method for producing the lactone compound and / or hydroxycarboxylic acid compound, which is carried out in the presence of at least one solvent.

  The present invention also provides a method for producing the above lactone compound and / or hydroxycarboxylic acid compound, wherein hydrogen peroxide is reacted in an amount of 0.1 to 10 moles per mole of the cyclic ketone compound.

  The present invention also provides that the cyclic ketone compound is at least one compound selected from cyclopentanone, cyclohexanone, methylcyclopentanone, methylcyclohexanone, n-pentylcyclopentanone, t-butylcyclohexanone, and adamantanone. A process for producing the lactone compound and / or hydroxycarboxylic acid compound is provided.

  In the method for producing a lactone compound and / or hydroxycarboxylic acid compound of the present invention, the above catalyst is used, so that the lactone compound is useful as a raw material or intermediate of an organic compound useful as a medicine, a fragrance, a dye, or a raw material of a polymer. Or a hydroxycarboxylic acid compound can be selectively produced.

[catalyst]
The method for producing a lactone compound and / or hydroxycarboxylic acid compound of the present invention is characterized by using the following catalyst.
Catalyst: calcined, anhydrous basis, formula (4)
(M _w Sn _x Si _1-x ) O ₂ (4)
(In the formula, M is a metal having a trivalent charge, w is 0 to 2x, and x is 0.001 to 0.1)
The β-zeolite is a tin-substituted zeolite having the characteristics of an X-ray diffraction pattern of β-type zeolite (however, when w is 0, it is amorphous having short-range order or X-rays of β-type zeolite) A compound obtained by reacting a tin-substituted zeolite (showing the characteristics of a diffraction pattern) with a compound containing an alkali metal, an alkaline earth metal, or ammonium.

  M in the formula (4) is a metal having a trivalent charge, and examples thereof include aluminum, boron, gallium, and iron.

The tin-substituted zeolite represented by the formula (4) is a compound having at least a microporous three-dimensional framework structure of SiO ₂ and SnO ₂ tetrahedral units and a crystallographically regular pore system. This is a compound having a peak in the diffraction angle (2θ) range of 5 to 50 degrees, which is a feature of the X-ray diffraction pattern of

  In addition, when the elements constituting the tin-substituted zeolite are only tin atoms, silicon atoms, and oxygen atoms (that is, when w is 0), the tin-substituted zeolite is amorphous having short-range order, or β-type zeolite It has either a structure.

The tin-substituted zeolite represented by the above formula (4) is Avelino Corma, Laszlo T. Nemeth, Michael Renz, Susana Valencia, Nature, 412 (2001) 423-425, Zihua Kang, Xiongfu Zhang, Haiou Liu, Jieshan Qiu. , King Lun Yeung, Chemical Engineering Journal, 218 (2013) 425-432, HF method and DGC method (Dry-gel conversion), specifically, silicon compounds (for example, tetraethyl orthosilicate, silica powder, etc.) Structure directing agents (for example, organic bases such as tetraethylammonium hydroxide) and tin compounds (for example, tin halides such as SnCl ₄ ; tin alkoxides such as tin butoxide, tin ethoxide, tin propoxide, etc.) and fluorine compounds (for example, Hydrofluoric acid, ammonium fluoride, sodium fluoride, silicon fluoride, ammonium fluorosilicate, sodium fluorosilicate, etc.) and metal compounds (trivalent Compounds containing a metal (M) having a load, for example, can be produced by the method subjecting the AlCl ₃ and the like) in hydrothermal synthesis.

  The amount of the structure directing agent used is, for example, about 0.1 to 1 mol with respect to 1 mol of the silicon compound.

  The usage-amount of the said tin compound is about 0.001-0.1 mol with respect to 1 mol of silicon compounds.

  The usage-amount of the said fluorine compound is about 0.1-1 mol with respect to 1 mol of silicon compounds.

  The usage-amount of the said metal compound is about 0.1 mol or less with respect to 1 mol of silicon compounds.

  The reaction temperature in the HF method is, for example, about 100 to 200 ° C, preferably 130 to 150 ° C. The reaction pressure is, for example, about 100 to 500 kPa. The reaction time is, for example, about 1 to 30 days, preferably 15 to 25 days.

  The reaction temperature in DGC method is about 100-200 degreeC, for example, Preferably it is 150-190 degreeC. The reaction pressure is, for example, about 100 to 1500 kPa. The reaction time is, for example, about 1 hour to 5 days, preferably 12 hours to 3 days.

  The tin-substituted zeolite obtained by the above method can be separated and purified by, for example, separation means such as filtration, concentration, and distillation, or a separation means that combines these. The separated and purified tin-substituted zeolite is then preferably subjected to a calcination treatment to remove the structure-directing agent and the like. The firing temperature is, for example, about 500 to 650 ° C, preferably 550 to 600 ° C. The firing treatment time is, for example, about 1 to 100 hours, preferably 5 to 10 hours.

  The molar ratio of silicon to tin (the former / the latter) contained in the tin-substituted zeolite obtained by the above method is, for example, about 10 to 1000, preferably 25 to 500, particularly preferably 50 to 250.

  The catalyst of the present invention is subjected to a treatment (hereinafter sometimes referred to as “post-treatment”) in which the tin-substituted zeolite obtained by the above method is reacted with a compound containing an alkali metal, an alkaline earth metal, or ammonium. It is characterized by. By performing the post treatment, it is possible to preferentially reduce the Bronsted acid point among the Lewis acid point and Bronsted acid point of the tin-substituted zeolite.

  Examples of the compound containing alkali metal, alkaline earth metal, or ammonium include alkali metal (for example, sodium, potassium, etc.), alkaline earth metal (for example, magnesium, calcium, etc.), or ammonia and acid (for example, nitric acid, A salt with hydrochloric acid or the like is preferred, and sodium nitrate, ammonium nitrate or the like can be suitably used. These can be used alone or in combination of two or more.

  The amount of the alkali metal, alkaline earth metal, or ammonium-containing compound is, for example, about 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the tin-substituted zeolite. When the amount of the alkali metal, alkaline earth metal, or ammonium-containing compound exceeds the above range, the Lewis acid point of the tin-substituted zeolite tends to decrease and the catalytic activity tends to decrease. On the other hand, when the usage-amount of the said compound containing an alkali metal, alkaline-earth metal, or ammonium is less than the said range, there exists a tendency for the effect which improves the selectivity of a lactone compound and a hydroxycarboxylic acid compound to become difficult to be acquired.

  The reaction temperature during the post treatment is, for example, about 0 to 100 ° C., preferably 70 to 90 ° C. The reaction pressure is, for example, about 100 kPa. The reaction time is, for example, about 1 to 24 hours, preferably 5 to 15 hours.

  The reaction atmosphere at the time of the post treatment is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.

  After completion of the post-treatment, the obtained product can be separated and purified by separation means such as filtration, concentration and distillation, or a separation means combining these.

  The catalyst of the present invention obtained through the post-treatment has a Bronsted acid point decreased while leaving a Lewis acid point. Further, it contains about 0.1 to 0.9 mol, preferably 0.2 to 0.6 mol of alkali metal, alkaline earth metal, or ammonium with respect to 1 mol of tin. It contains about 0.001 to 0.3 mmol, preferably 0.01 to 0.1 mmol of an earth metal or ammonium.

  Since the catalyst of the present invention has the above properties, a lactone compound and a hydroxycarboxylic acid compound can be selectively produced from a cyclic ketone compound under mild conditions.

（式中、Ｒは炭素数３〜１９の２価の炭化水素基を示す）
で表される。 [Cyclic ketone compounds]
The cyclic ketone compound of the present invention has the following formula (1):

(In the formula, R represents a divalent hydrocarbon group having 3 to 19 carbon atoms)
It is represented by

  R is a divalent hydrocarbon group having 3 to 19 carbon atoms, for example, linear or branched having 3 to 19 carbon atoms (preferably 3 to 11 carbon atoms, particularly preferably 3 to 7 carbon atoms). A chain alkylene group, a linear or branched alkenylene group, a linear or branched alkynylene group, a cycloalkylene group (including a cycloalkylidene group), a cycloalkenylene group, a bridged cyclic group, etc. Can be mentioned.

  In the formula (1), R is bonded to a carbon atom constituting a carbonyl group (—C (═O) —) to form an alicyclic ring. The alicyclic ring includes a monocyclic hydrocarbon ring and a polycyclic hydrocarbon ring (spiro hydrocarbon ring, ring assembly hydrocarbon ring, bridged cyclic hydrocarbon ring, condensed ring hydrocarbon ring, and bridged condensed ring ring. Including hydrocarbon rings).

Examples of the monocyclic hydrocarbon ring include C _3-12 cycloalkane rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane; C _3-12 cycloalkenes such as cyclopentene and cyclohexene. Can be mentioned.

Examples of the spiro hydrocarbon ring include C _5-16 spiro hydrocarbon rings such as spiro [4.4] nonane, spiro [4.5] decane, and spirobicyclohexane.

Examples of the ring assembly hydrocarbon ring include a ring assembly hydrocarbon ring including a plurality of C _5-12 cycloalkane rings such as bicyclohexane.

Examples of the bridged cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, norbornene, bicycloheptane, bicycloheptene, bicyclooctane (bicyclo [2.2.2] octane, bicyclo [3.2.1] octane, etc. Bicyclic hydrocarbon rings such as homobredane, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane, etc. Ring: Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene.

  Examples of the condensed cyclic hydrocarbon ring include 5 to 8 such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene. A condensed ring in which a plurality of membered cycloalkane rings are condensed can be exemplified.

  Examples of the bridged condensed cyclic hydrocarbon ring include dimers of dienes (for example, dimers of cycloalkadiene such as cyclopentadiene, cyclohexadiene, cycloheptadiene), hydrogenated products thereof, and the like. it can.

  The alicyclic ring has various substituents [eg, halogen atom, oxo group, hydroxyl group, substituted oxy group (eg, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group etc.), substituted or unsubstituted carbamoyl group, A cyano group, a nitro group, a substituted or unsubstituted amino group, a sulfo group, a heterocyclic group, and the like. The alicyclic ring may be condensed with an aromatic or non-aromatic heterocyclic ring.

Specific examples of the cyclic ketone compound of the present invention include monocyclic ketone compounds such as cyclopropanone, cyclopentanone, methylcyclopentanone, n-pentylcyclopentanone, cyclohexanone, methylcyclohexanone, t-butylcyclohexanone; Bicyclo [2.1.0] pentan-5-one, bicyclo [3.1.0] hexane-6-one, bicyclo [4.1.0] heptane-7-one, adamantanone, and the following formula (1 And polycyclic ketone compounds such as compounds represented by (-1) to (1-11).

（式中、Ｒは前記に同じ）
で表されるラクトン化合物、及び／又は下記式（３）
ＨＯ−Ｒ−ＣＯＯＨ （３）
（式中、Ｒは前記に同じ）
で表されるヒドロキシカルボン酸化合物が得られる。例えば、シクロヘキサノンからはε−カプロラクトン及び／又は６−ヒドロキシカプロン酸が得られる。 [Method for producing lactone compound and / or hydroxycarboxylic acid compound]
In the method for producing a lactone compound and / or a hydroxycarboxylic acid compound of the present invention, the cyclic ketone compound is reacted with hydrogen peroxide and the catalyst, whereby the following formula (2) corresponding to the cyclic ketone compound is obtained.

(Wherein R is the same as above)
And / or the following formula (3)
HO-R-COOH (3)
(Wherein R is the same as above)
The hydroxycarboxylic acid compound represented by this is obtained. For example, cyclohexanone provides ε-caprolactone and / or 6-hydroxycaproic acid.

  The amount of the catalyst used is, for example, about 1 to 1000 g, preferably 5 to 500 g, particularly preferably 10 to 100 g, with respect to 1 mol of the cyclic ketone compound.

  As hydrogen peroxide, pure hydrogen peroxide may be used, but from the viewpoint of handling, it is usually diluted with an appropriate solvent (for example, water) (for example, 5 to 70% by weight of hydrogen peroxide water). ). The usage-amount of hydrogen peroxide is about 0.1-10 mol with respect to 1 mol of cyclic ketone compounds, Preferably it is 0.15-5 mol, Most preferably, it is 0.2-3 mol.

  The above reaction is carried out in the presence of a solvent or in the absence of a solvent.

  When the reaction is performed in the presence of a solvent, examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, and butanol; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, dioxolane, 1,2-dimethoxy. Examples include ether solvents such as ethane and cyclopentyl methyl ether; ester solvents such as butyl acetate and ethyl acetate; hydrocarbon solvents such as pentane, hexane, heptane and octane; nitrile solvents such as acetonitrile and benzonitrile. it can. These can be used alone or in combination of two or more. The usage-amount of a solvent is about 5-50 mL with respect to 1g of cyclic ketone compounds. When the usage-amount of a solvent exceeds the said range, the density | concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.

  The reaction atmosphere is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.

  The reaction temperature is, for example, about 20 to 100 ° C, preferably 40 to 100 ° C. The reaction time is, for example, about 0.2 to 12 hours. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  When the reaction is performed continuously, the cyclic ketone compound and hydrogen peroxide as raw materials may be separately charged into the reactor, or may be charged into the reactor in a premixed state. The feed rate of the raw material to the reactor [liquid space velocity; LHSV (Liquid Hourly Space Velocity)] is, for example, about 0.05 to 20 / hr, preferably 0.1 to 15 / hr, particularly preferably 0.15 to 8 / hr.

  After completion of the reaction, the obtained product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc., or a separation means combining these.

  In the method for producing a lactone compound and / or hydroxycarboxylic acid compound of the present invention, the lactone compound and / or hydroxycarboxylic acid compound can be selectively produced because the catalyst is used, and the selectivity of the lactone compound is: For example, it is 50% or more, preferably 65% or more, more preferably 70% or more, particularly preferably 80% or more, and most preferably 85 to 95%. The selectivity of the hydroxycarboxylic acid compound is, for example, 1% or more, preferably 2 to 50%. Furthermore, the total selectivity of the lactone compound and the hydroxycarboxylic acid is, for example, 85% or more, preferably 90% or more, and particularly preferably 95 to 99%.

  In the method for producing the lactone compound and / or hydroxycarboxylic acid compound of the present invention, the conversion rate of the cyclic ketone compound is, for example, 18% or more, preferably 20% or more, and particularly preferably 30 to 95%. The unreacted raw material can be recycled into the reaction system, and the utilization rate of the raw material can be improved by recycling the unreacted raw material.

  Furthermore, the catalyst used in the reaction can be easily recovered by subjecting the reaction solution to filtration treatment, etc., and after performing regeneration treatment (for example, water washing treatment, firing treatment, etc.) as necessary, the lactone of the present invention It can be reused as a catalyst in the production method of the compound and / or hydroxycarboxylic acid compound. Therefore, the production method of the lactone compound and / or hydroxycarboxylic acid compound of the present invention can minimize the cost, and provide a lactone compound and / or hydroxycarboxylic acid compound useful for various applications at a low cost. it can. Therefore, the method for producing a lactone compound and / or a hydroxycarboxylic acid compound of the present invention is particularly useful as a method for industrially producing a lactone compound and / or a hydroxycarboxylic acid compound.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Preparation Example 1
(Preparation of tin-substituted zeolite by HF method)
41.7 g of tetraethylorthosilicate (hereinafter sometimes referred to as “TEOS”) and 45.4 g of tetraethylammonium hydroxide (hereinafter referred to as “TEAOH”) in a Teflon (registered trademark) beaker. ) Aqueous solution (35 wt%), 13.7 g distilled water was added. Thereafter, 0.70 g of SnCl ₄ .5H ₂ O was added and stirred at 60 ° C. 4.35 g of hydrofluoric acid (46 wt%) was added to the clear solution obtained by stirring the mixture until ethanol formed by hydrolysis of TEOS was completely evaporated, and a thick paste [SiO ₂ : ((C ₂ H ₅ ) ₄ N) ₂ O: SnO ₂ : HF: H ₂ O (molar ratio) = 1: 0.27: 0.01: 0.5: 8] was obtained.
The obtained paste was put in a stainless steel autoclave coated with Teflon (registered trademark) and heated at 140 ° C. with stirring for 21 days. Thereafter, the reaction solution was subjected to filtration to recover the product, and the obtained product was dried at 100 ° C. overnight.
The product after drying was shown to have a β-type zeolite structure by X-ray diffraction analysis.
The product after drying was further subjected to a calcination treatment at 580 ° C. for 5 hours to obtain a tin-substituted zeolite (1). When the chemical analysis of the tin-substituted zeolite (1) was conducted, it was determined that the composition on an anhydrous basis was (Si _0.99 Sn _0.01 ) O ₂ .

Preparation Example 2
(Preparation of tin-substituted zeolite by DGC method)
In a Teflon (registered trademark) beaker, 18.2 g of TEAOH aqueous solution (35% by weight), 3.7 g of distilled water, and 4.8 g of powdered silica were added and stirred at room temperature for 2 hours. Thereafter, a solution prepared by dissolving 0.28 g of SnCl ₄ .5H ₂ O in 1.4 g of distilled water was added, and the mixture was further stirred for 30 minutes. Finally, 1.60 g of ammonium fluoride was added, and the composition [SiO ₂ : ((C ₂ H ₅ ) ₄ N) ₂ O: SnO ₂ : NH ₄ F: H ₂ O (molar ratio) = 1: 0 .27: 0.01: 0.54: 11].
When the obtained composition was transferred into a bath kept at 70 ° C. and stirring was continued, a thick paste was formed. This paste was dried until 14.4 g of water was distilled off to form a dry gel.
The obtained dry gel was transferred to another Teflon (registered trademark) beaker, and this beaker was placed in a stainless steel autoclave coated with Teflon (registered trademark) together with 0.5 g of distilled water and allowed to stand at 180 ° C. for 2 days. Heated.
Thereafter, the reaction solution was subjected to filtration to recover the product, and the obtained product was dried at 100 ° C. overnight.
The product after drying was shown to have a β-type zeolite structure by X-ray diffraction analysis.
The product after drying was further subjected to a calcination treatment at 580 ° C. for 5 hours to obtain a tin-substituted zeolite (2). When the chemical analysis of the tin-substituted zeolite (2) was conducted, the composition on an anhydrous basis was determined to be (Si _0.99 Sn _0.01 ) O ₂ .

Preparation Example 3
(Post treatment (1): Sodium nitrate treatment)
In a plastic bottle, 100 mL of an aqueous solution of sodium nitrate (1 mol / L) and 1 g (0.017 mol) of tin-substituted zeolite [(Si _0.99 Sn _0.01 ) O ₂ ] obtained in Preparation Example 1 or 2 were charged at 80 ° C. Stir for 12 hours.
Thereafter, the reaction solution was subjected to filtration treatment to recover the product. The obtained product was sufficiently washed with pure water and then dried at 100 ° C. overnight to obtain a catalyst (1).
Catalyst (1) was shown to retain the β-type zeolite structure by X-ray diffraction analysis.
When the chemical analysis of the catalyst (1) was carried out, the amount of tin element was the same as before the post-treatment, and 0.05 milligrams of sodium element was newly added per 1 g of the catalyst (1) by the post-treatment, and 1 mol of tin. It was shown that 0.32 mol of sodium element was contained.

Preparation Example 4
(Post treatment (2): Ammonium nitrate treatment)
A plastic bottle was charged with 100 mL of an aqueous ammonium nitrate solution (1 mol / L) and 1 g (0.017 mol) of tin-substituted zeolite [(Si _0.99 Sn _0.01 ) O ₂ ] obtained in Preparation Example 1 or 2, and 12 at 80 ° C. Stir for hours.
Thereafter, the reaction solution was subjected to filtration treatment to recover the product. The obtained product was sufficiently washed with pure water and then dried at 100 ° C. overnight to obtain a catalyst (2).
The catalyst (2) was shown to retain the β-type zeolite structure by X-ray diffraction analysis.
When the chemical analysis of the catalyst (2) was conducted, the amount of elemental tin was not changed from that before the post-treatment, and 0.06 mmol of ammonium was newly added per 1 g of the catalyst (2) by the post-treatment. On the other hand, it was shown to contain 0.36 mol of ammonium.

Example 1 (reacts batchwise in the presence of a catalyst)
125 mg of the catalyst (1) obtained in Preparation Example 3, 3 mmol of cyclohexanone, 2 mmol of hydrogen peroxide, and 8.5 mL of dioxane were added to a glass container equipped with a stirrer, a heating device, and a thermometer. (1 atm) was stirred at 90 ° C. for 1 hour to obtain ε-caprolactone and 6-hydroxycaproic acid.

Examples 2-6, Comparative Examples 1-3
It carried out like Example 1 except having changed reaction conditions as described in a table | surface. In the comparative example, tin-substituted zeolite (1) before post-treatment was used as the catalyst (3).

The results are summarized in the following table. The conversion rate and selectivity were measured by a standard measurement method using GC-FID.

Example 7 (fixed bed, reaction in the presence of a solvent in a continuous manner)
Catalyst (1) 6.3 mL (3.28 g) was filled in a glass reaction tube (reaction tube inner diameter 10 mm, sheath tube outer diameter 6 mm, length 130 mm), the air in the reaction tube was replaced with nitrogen gas, The reaction temperature was raised to 75 ° C. After the temperature rise, a mixed solution of dioxane and cyclohexanone (weight ratio; 1: 1.3) and a mixed solution of dioxane and 35% hydrogen peroxide (weight ratio; 2.5: 1) were charged separately (feed rate) LHSV = 1.03 / hr), and the reaction was performed at normal pressure.
As a result of analyzing the obtained reaction crude liquid, the conversion of cyclohexanone was 72.6%, the conversion of 35% hydrogen peroxide was 67.8%, the selectivity of ε-caprolactone was 54.9%, and 6-hydroxy The selectivity of caproic acid was 41.8%, and the total selectivity of ε-caprolactone and 6-hydroxycaproic acid was 96.7%.

Example 8 (Fixed bed, solventless, continuous reaction)
Catalyst (1) 6.3 mL (3.28 g) was filled in a glass reaction tube (reaction tube inner diameter 10 mm, sheath tube outer diameter 6 mm, length 130 mm), the air in the reaction tube was replaced with nitrogen gas, The reaction temperature was raised to 75 ° C. After the temperature rise, cyclohexanone and 35% hydrogen peroxide (molar ratio; 4: 1) were charged separately (feed rate; LHSV = 2.08 / hr) and reacted at normal pressure.
As a result of analyzing the obtained reaction crude liquid, the conversion of cyclohexanone was 71.6%, the conversion of 35% hydrogen peroxide was 65.8%, the selectivity of ε-caprolactone was 57.0%, 6-hydroxy The selectivity of caproic acid was 35.5%, and the total selectivity of ε-caprolactone and 6-hydroxycaproic acid was 92.5%.

Claims (7)

Following formula (1)

(In the formula, R represents a divalent hydrocarbon group having 3 to 19 carbon atoms)
By reacting the cyclic ketone compound represented by the formula (2) with hydrogen peroxide and the following catalyst:

(Wherein R is the same as above)
And / or the following formula (3)
HO-R-COOH (3)
(Wherein R is the same as above)
The manufacturing method of the lactone compound and / or hydroxycarboxylic acid compound which manufactures the hydroxycarboxylic acid compound represented by these.
Catalyst: calcined, anhydrous basis, formula (4)
(M _w Sn _x Si _1-x ) O ₂ (4)
(In the formula, M is a metal having a trivalent charge, w is 0 to 2x, and x is 0.001 to 0.1)
The characteristic of the X-ray diffraction pattern of the β-type zeolite represented by the formula (However, when w is 0, it is amorphous having short-range order, or the characteristic of the X-ray diffraction pattern of the β-type zeolite. ) Compounds obtained by reacting tin-substituted zeolite with compounds containing alkali metals, alkaline earth metals, or ammonium   The method for producing a lactone compound and / or a hydroxycarboxylic acid compound according to claim 1, wherein the compound containing an alkali metal, an alkaline earth metal, or ammonium is an alkali metal, an alkaline earth metal, or a salt of ammonia and an acid. .   The method for producing a lactone compound and / or a hydroxycarboxylic acid compound according to claim 1, wherein the compound containing an alkali metal, an alkaline earth metal, or ammonium is sodium nitrate and / or ammonium nitrate.   The lactone compound according to any one of claims 1 to 3, wherein the catalyst is a compound containing 0.1 to 0.9 mol of alkali metal, alkaline earth metal, or ammonium with respect to 1 mol of tin. Alternatively, a method for producing a hydroxycarboxylic acid compound.   The reaction of the cyclic ketone compound, hydrogen peroxide and the catalyst is carried out in the absence of a solvent or at least one solvent selected from alcohol solvents, ether solvents, ester solvents, hydrocarbon solvents, and nitrile solvents. The manufacturing method of the lactone compound and / or hydroxycarboxylic acid compound of any one of Claims 1-4 performed in presence of this.   The method for producing a lactone compound and / or a hydroxycarboxylic acid compound according to any one of claims 1 to 5, wherein hydrogen peroxide is reacted in an amount of 0.1 to 10 mol with respect to 1 mol of the cyclic ketone compound.   The cyclic ketone compound is at least one compound selected from cyclopentanone, cyclohexanone, methylcyclopentanone, methylcyclohexanone, n-pentylcyclopentanone, t-butylcyclohexanone, and adamantanone. 7. A process for producing a lactone compound and / or a hydroxycarboxylic acid compound according to any one of 6 above.