JP2009209062A - Method for producing epoxy compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an epoxy compound, by which the epoxy compound corresponding to an unsaturated compound having at least one carbon-carbon double bond can be produced in a high yield. <P>SOLUTION: Provided is a method for producing the epoxy compound, characterized by epoxidizing the unsaturated compound having at least one carbon-carbon double bond with hydrogen peroxide in the presence of a basic nitrogen-containing compound and a catalyst comprising a tungsten compound, a quaternary ammonium salt and a phosphoric acid-related compound to produce an epoxy compound corresponding to the unsaturated compound. The epoxidation reaction may be performed under a condition of pH 2 to 7. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention epoxidizes an unsaturated compound having at least one double bond with hydrogen peroxide in the presence of a catalyst composed of a tungsten compound, a quaternary ammonium salt and phosphoric acids, and a basic nitrogen-containing compound. And a method for producing the epoxy compound in a high yield.

  Conventionally, in the reaction of epoxidizing an unsaturated compound having at least one double bond with hydrogen peroxide, a metal compound (for example, a compound containing a Group 6 element of the periodic table such as tungsten, a periodic table of rhenium or the like) is used as a catalyst. A compound containing a Group 7 element, a compound containing a Group 8 element of the periodic table such as osmium, etc. are used, and industrially, a compound containing a Group 6 element of the periodic table (particularly a tungsten compound) from the viewpoint of low cost. ) Is widely used.

  For example, in Japanese Patent Application Laid-Open No. 2008-7466 (Patent Document 1), the following formula (1)

(In the formula, Y represents a linking group or a single bond. ^HA represents a hydrogen atom at the junction of the cyclohexane ring and the oxirane ring. The cyclohexane ring has a substituent other than the group shown in the formula. Also good)
Integrating the signal observed on the low magnetic field side of the proton at the junction of the cyclohexane ring and the oxirane ring in the ¹ H-NMR spectrum An alicyclic polyvalent epoxy compound having a ratio A / B between the value A and the integral value B of the signal observed on the high magnetic field side is 1.8 or more is disclosed. In this document, the alicyclic polyvalent epoxy compound is represented by the following formula (2):

(In the formula, Y represents a linking group or a single bond. The cyclohexene ring may have a substituent other than the group shown in the formula).
The cyclohexene ring containing compound represented by these is manufactured by oxidizing with hydrogen peroxide. Moreover, as a catalyst used in the said manufacturing method, the catalyst which consists of a combination of a tungsten compound, phosphoric acid, and onium salt is described, for example.

  However, in the method of Patent Document 1, since the pH of the reaction system is low and the resulting epoxy compound tends to be easily hydrolyzed or polymerized, it is difficult to produce in a high yield.

  In general, in an epoxidation reaction using a tungsten compound as a catalyst, it is known that the reaction proceeds at a higher reaction rate and reaction yield as the reaction pH is lower. For this reason, it is desirable to lower the pH of the reaction system, but as described above, the generated epoxy compound tends to be easily hydrolyzed or polymerized under conditions where the reaction pH is low (for example, the pH is about 2 or less). is there. Therefore, in the epoxidation reaction using a tungsten compound as a catalyst, it is important to adjust the reaction pH.

For example, Japanese Patent Publication No. 3-57102 (Patent Document 2) discloses C _6- having a cyclohexene ring that is substantially insoluble in water, hydrogen peroxide, and water in a reaction mixture composed of an aqueous phase and a liquid organic phase. C ₁₂ organic compound, a catalytic amount of hexavalent ions of a compound selected from the group consisting of molybdenum and tungsten, a catalytic amount of organic quaternary ammonium ions, and an inert strong acid selected from the group consisting of sulfuric acid and phosphoric acid A sufficient amount of soluble salt is mixed to adjust the pH of the aqueous phase to 2 to 6, and the strong acid soluble salt is mixed in an amount sufficient to bring the aqueous phase to 0.5 to 1.5 molar concentration. A method for producing cyclohexane epoxide of the organic compound is disclosed.

In this document, a soluble salt of an inert strong acid selected from the group consisting of sulfuric acid and phosphoric acid is used to adjust the reaction pH. Specifically, in the examples, sodium dihydrogen phosphate (NaH ₂ PO using ₄ · _2H 2 O). The method of this document uses a large amount of soluble salt (sodium dihydrogen phosphate) to increase epoxide selectivity and epoxide yield. However, when a large amount of a soluble salt (sodium dihydrogen phosphate) is used, various salts are generated as by-products, so that it is difficult to separate the epoxy compound in industrial scale production. Further, when a large amount of soluble salt (sodium dihydrogen phosphate) is used, it is necessary to treat a waste liquid containing sodium dihydrogen phosphate at a high concentration, which is not practical from the viewpoint of equipment and cost.
JP 2008-7466 A (Claim 1, Claim 3, Paragraph [0031]) Japanese Examined Patent Publication No. 3-57102 (claims, page 4, left column, lines 15 to 26, Examples)

  Accordingly, an object of the present invention is to provide a method capable of producing the epoxy compound with high yield.

  Another object of the present invention is to provide a method capable of producing the epoxy compound in a high yield over a wide pH range without using a large amount of a soluble salt.

  Still another object of the present invention is to provide a method for producing the epoxy compound which is inexpensive and excellent in productivity even on an industrial scale.

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that in a reaction system using a catalyst such as a tungsten compound, an unsaturated compound having at least one carbon-carbon double bond in the presence of a basic nitrogen-containing compound. It was found that when the compound is epoxidized with hydrogen peroxide, an epoxy compound corresponding to the unsaturated compound can be produced in a high yield, and the present invention has been completed.

  That is, in the present invention, an unsaturated compound having at least one carbon-carbon double bond is passed in the presence of a catalyst composed of a tungsten compound, a quaternary ammonium salt and phosphoric acid, and a basic nitrogen-containing compound. Epoxidation with hydrogen oxide produces an epoxy compound corresponding to the unsaturated compound.

  In the said method, you may epoxidize on the conditions of about pH 2-7. Moreover, you may use the said basic nitrogen containing compound in the ratio of about 0.001-0.1 molar equivalent with respect to 1 mol of said unsaturated compounds on a carbon-carbon double bond basis. Furthermore, you may use the said tungsten compound in the ratio of about 0.0001-0.3 molar equivalent with respect to 1 mol of said unsaturated compounds on a carbon-carbon double bond basis. Furthermore, a quaternary ammonium salt may be used at a ratio of about 0.01 to 5 molar equivalents with respect to 1 mol of the tungsten compound, and 0.1 to 10 mol of phosphoric acid with respect to 1 mol of the tungsten compound. You may use it in the ratio of about an equivalent.

The unsaturated compound may be a compound having 6 or more carbon atoms, for example, a compound having at least one C _5-10 cycloalkene ring. The basic nitrogen-containing compound may be a tertiary amine, for example, a heterocyclic aromatic amine containing a nitrogen atom as a constituent atom of the ring.

  In the present invention, since the basic nitrogen-containing compound is used in the epoxidation reaction using a catalyst such as a tungsten compound, the epoxy compound can be produced in a high yield. Moreover, the said epoxy compound can be manufactured with a high yield over a wide pH range, without using a lot of soluble salts (for example, sodium hydrogenphosphate etc.). Furthermore, since the amount of the basic nitrogen-containing compound added is small, the production of by-products (for example, salts) is reduced, and even on an industrial scale, it is inexpensive and excellent. The said epoxy compound can be manufactured by productivity.

[Method for producing epoxy compound]
In the present invention, an unsaturated compound having at least one carbon-carbon double bond is formed with hydrogen peroxide in the presence of a catalyst composed of a tungsten compound, a quaternary ammonium salt and phosphoric acid and a basic nitrogen-containing compound. Epoxidation is performed to produce an epoxy compound corresponding to the unsaturated compound. In the epoxidation reaction, the double bond site of the unsaturated compound is usually epoxidized.

(Unsaturated compound)
The unsaturated compound as a substrate is not particularly limited as long as it has at least one carbon-carbon double bond (double bond or ethylene bond). That is, the unsaturated compound may have one or more double bonds in one molecule. The unsaturated compound includes (1) a linear or branched aliphatic hydrocarbon having a double bond, and (2) a cycloalkene ring (including a cycloalkapolyene ring such as a cycloalkadiene ring). Etc. are included. These compounds may have a substituent. In the case of performing an epoxidation reaction in a liquid phase, a liquid or solid (or miscible with a liquid) unsaturated compound is usually selected as the unsaturated compound under the reaction conditions.

(1) As a linear or branched aliphatic hydrocarbon having a double bond, for example, ethylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene 2,3-dimethyl-2-butene, 3-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene, 3-octene, 2-methyl-2-butene, 1-nonene, 2-nonene , Decene, undecene, dodecene, tetradecene, hexadecene, octadecene, etc. C _2-40 alkene (preferably C _2-30 alkene, more preferably C _2-20 alkene); butadiene, isoprene, 1,5-hexanediene, 1 C _4-4 such as 1,6-heptadiene, 1,7-octadiene, 2,6-octadiene, decadiene, undecadiene, dodecadiene ₀ alkadienes (preferably C _4-30 alkadienes, more preferably C _4-20 alkadienes); C _6-30 alkatrienes (preferably C _6-20 alkatrienes) such as undecatriene and dodecatriene. The linear or branched aliphatic hydrocarbon having a double bond may be used alone or in combination of two or more.

These linear or branched aliphatic hydrocarbons include, for example, aromatic hydrocarbon groups (for example, C _6-10 aryl groups such as phenyl groups), hydroxyl groups, halogen atoms (for example, fluorine atoms, chlorine atoms). , Bromine atom, etc.), mercapto group, alkoxy group (eg, C _1-10 alkoxy group such as methoxy, ethoxy, propoxy, butoxy, t-butoxy group (eg, C _1-6 alkoxy group), etc.), haloalkoxy Group, alkylthio group (for example, C _1-10 alkylthio group such as methylthio, ethylthio group, etc.), carboxyl group, alkoxycarbonyl group (for example, C _1-10 alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl group (for example, C1 _2-10 alkoxy carbonyl group), etc.), an acyl group (e.g. Acetyl, propionyl, etc. C _2-10 acyl group such as trifluoroacetyl group), an acyloxy group (e.g., acetoxy, propionyloxy, etc. C _1-10 acyloxy group such as trifluoroacetoxy group), an amino group, a substituted amino group , A nitro group, a cyano group, or a heterocyclic group (such as a nitrogen atom-containing heterocyclic group such as a pyridyl group). The number of substituents and the substitution position are not particularly limited.

Examples of the linear or branched aliphatic hydrocarbon having a substituent include the linear or branched aliphatic hydrocarbon having an aryl group (for example, a phenyl group) as a substituent (for example, phenylethylene). (Or styrene), 1-phenylpropene, 2-phenyl-1-butene, 1-phenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene, and the like. The linear or branched aliphatic hydrocarbon having an aryl group (for example, phenyl group) as a substituent is an alkenyl group (for example, C _2-10 such as vinyl, allyl, propenyl, isopropenyl, butenyl). Also referred to as an aromatic compound substituted with an alkenyl group (preferably a C _2-6 alkenyl group), and such an aromatic compound has at least one double bond in the side chain. As long as the alkenyl group and / or the aromatic ring may have a substituent (for example, the substituents exemplified above), a linking group (such as a linking group described later) may be interposed between the alkenyl group and the aromatic ring. ).

(2) Examples of the compound containing a cycloalkene ring (including a cycloalkapolyene ring such as a cycloalkadiene ring) include, for example, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cycloundecene C _3-20 cycloalkene (preferably C _4-14 cycloalkene, more preferably C _5-10 cycloalkene) such as cyclododecene; cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1, C _5-20 cycloalkadiene such as 3-cycloheptadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene, cyclodecadiene (preferably C _5-14 cycloalkadiene, more preferably C _{5 -10} Sik Alkadiene); and C _7-20 cycloalkadienyl triene such as cyclooctatriene may be mentioned. The compounds containing a cycloalkene ring may be used alone or in combination of two or more. Of these, C _3-20 cycloalkene is preferable, and C _5-10 cycloalkene [eg, C _6-8 cycloalkene (eg, C _5-6 cycloalkene such as cyclohexene)] and the like are preferably used. Is done.

These compounds may have a substituent on the cycloalkene ring. The number of substituents and the substitution position are not particularly limited. Examples of the substituent include (1) the substituent exemplified in the section of the straight-chain or branched aliphatic hydrocarbon having a double bond, for example, an alkyl group (for example, methyl, ethyl, isopropyl, butyl, isobutyl, a C _1-10 alkyl group such as a t-butyl group (preferably a C _1-6 alkyl group); a haloalkyl group; an alkenyl group (eg, an alkenyl group exemplified above); an aryl group (eg, a phenyl group) C _6-10 aryl group)] and the like.

  The unsaturated compound may be a compound containing a plurality of alkene units and / or cycloalkene units. The plurality of alkene units and / or cycloalkene units may be the same or different. Further, the plurality of alkene units and / or cycloalkene units may be bonded by a single bond (direct bond) or may be bonded through a linking group. 1 type may be sufficient as the said coupling group, and multiple types may be sufficient as it. The “alkene unit” may be a monovalent or polyvalent group corresponding to (1) the linear or branched aliphatic hydrocarbon having a double bond, and may be an alkapolyene such as an alkadiene unit. Used to include units. Further, the “cycloalkene unit” may be a monovalent or polyvalent group corresponding to the compound (2) containing a cycloalkene ring, and also includes a cycloalkapolyene unit such as a cycloalkadiene unit. Used in.

The linking group is usually a polyvalent group (for example, a divalent group). The linking group includes, for example, an alkylene group (for example, a C _1-20 alkylene group such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and 2-methylbutane-1,3-diyl group), a cycloalkylene group (for example, C _4-10 cycloalkylene group such as 1,4-cyclohexylene group), arylene group (for example, C _6-10 arylene group such as phenylene group and naphthalenediyl group), carbonyl bond, ester bond, amide bond And at least one selected from an ether bond and a urethane bond.

  The number of carbons of the unsaturated compound (in the case of containing a substituent and / or a linking group, the total number of carbons contained in the substituent and / or linking group) may be about 2 to 40, Preferably, it may be 6 or more (for example, 6 to 30), more preferably 6 to 25, particularly about 6 to 20 (for example, 7 to 20).

Such unsaturated compounds can be used alone or in combination of two or more. The unsaturated compound is preferably a compound containing (2) a cycloalkene ring (for example, a C _3-20 cycloalkene ring, preferably a C _6-20 cycloalkene ring, particularly a cyclohexene ring). The unsaturated compound may have one or more cycloalkene rings (particularly cyclohexene rings).

  Representative unsaturated compounds include, for example, the following formula (3)

(In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² represents a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, a carboxyl group, or an alkoxycarbonyl group.)
Or a compound represented by the following formula (4)

(In the formula, R ³ represents a linear or branched alkylene group, and R ¹ is the same as described above. M and n are the same or different and are 0 or an integer of 1 or more.)
And the like.

As the linear or branched alkylene group (including alkylidene group) represented by R ³ , an optionally substituted alkane (for example, C such as ethane, propane, isopentane, 2,2-dimethylpropane, etc.). _1-20 alkane etc.) [specifically, linear or branched C ₂ such as methylene group, ethylene group, propylene group, 2,2-dimethylpropane-1,3-diyl group, etc. _-20 alkylene group (or alkylidene group)] and the like. In the formula (4), m is usually 1.

Specifically, the unsaturated compound includes, for example, cyclohexene in the formula (3), wherein R ¹ and R ² are hydrogen atoms, R ¹ is a hydrogen atom, and R ² is a methoxycarbonyl group. Methyl 3-enecarboxylate (the following formula (3a)), R ¹ is a hydrogen atom, R ² is a vinyl group 4-vinylcyclohexene (the following formula (3b)), R ¹ is a methyl group, ² -methyl-4-vinylcyclohexene (the following formula (3c)) in which R ² is a vinyl group, 2-methyl-4- (2-propenyl) in which R ¹ is a methyl group and R ² is an isopropenyl group cyclohexene (formula (3d)); in the formula (4), ^{R 1} is hydrogen atom, ^{R 3} is a methylene group, m is 1, n is 0 cyclohex-3-ene-carboxylic acid cyclohexenyl Chill (formula (4a)), ^{R 1} is hydrogen atom, ^{R 3} is 2,2-dimethyl-1,3-diyl, bis m and n are 1 [1,3- ( Cyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester (the following formula (4b)), R ¹ is a methyl group, and R ³ is a 2,2-dimethylpropane-1,3-diyl group. And bis [1,3- (4-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester (the following formula (4c)) and bis [1,3, wherein m and n are 1 -(3-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester (the following formula (4d)) and the like are included.

  For example, when cyclohexenylmethyl cyclohex-3-enecarboxylate represented by the above formula (4a) is used as the unsaturated compound, a corresponding epoxy compound (3,4-epoxycyclohexane represented by the following formula (5) is used. Hexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate) is obtained. Further, when 2-methyl-4-vinylcyclohexene represented by the above formula (3c) is used as the unsaturated compound, a corresponding epoxy compound (monoepoxy compound represented by the following formula (6a) and the following formula (6b) ) Is obtained.

(hydrogen peroxide)
Hydrogen peroxide (or hydrogen peroxide aqueous solution) for epoxidizing the unsaturated compound may be synthesized by a conventional method, or a commercially available product may be used. The concentration of hydrogen peroxide is not particularly limited, but it is, for example, 20 to 70 w / v%, preferably 22 to 67 w / v%, more preferably about 25 to 65 w / v% from the viewpoint of handleability. Also good.

(catalyst)
In the epoxidation reaction step of the present invention, the unsaturated compound is epoxidized with hydrogen peroxide in the presence of a catalyst. The catalyst is composed of a tungsten compound, a quaternary ammonium salt, and phosphoric acids.

(Tungsten compound)
The tungsten compound only needs to have at least a tungsten atom. For example, a tungsten halide (for example, tungsten chloride); a tungsten inorganic acid salt (for example, sulfate, nitrate, etc.); a tungsten organic acid salt (for example, tungsten chloride). For example, acetate etc. may be sufficient and the complex which makes tungsten a central metal may be sufficient. The tungsten compound may be a polyacid composed of tungstic acid or a salt thereof. Examples of the polyacid or a salt thereof include an isopolyacid or a salt thereof (for example, tungstic acid; an alkali metal salt of tungstic acid such as sodium tungstate and potassium tungstate, ammonium tungstate, etc.); a heteropolyacid or a salt thereof [ For example, tungstophosphoric acid (or phosphotungstic acid) (for example, 12-tungstophosphoric acid, 11-tungstophosphoric acid, etc.), vanadium tungstic acid, molybdenum tungstic acid, manganese tungstic acid, cobalt tungstic acid, silicotungstic acid, phosphovanad Tungstic acid, manganese molybdenum tungstic acid or a salt thereof (for example, alkali metal salt etc.) and the like. These tungsten compounds can be used alone or in combination of two or more. From the viewpoints of handling properties and cost, a polyacid composed of tungstic acid or a salt thereof is preferable. In particular, the isopolyacid or a salt thereof (for example, tungstic acid, sodium tungstate, etc.) is preferably used.

(Quaternary ammonium salt)
Quaternary ammonium salts include tetraalkylammonium salts [for example, tetraalkylammonium salts such as tetrabutylammonium chloride, tetrahexylammonium chloride, tetrahexylammonium hydrogensulfate, tetraoctylammonium chloride, tetraoctylammonium hydrogensulfate (tetraC _1-20 alkylammonium salt); trioctylmethylammonium chloride (TOMAC), hydrogen trioctylmethylammonium sulfate, trioctyl ethyl ammonium chloride, trialkyl alkylammonium salt (tri _{C 1-20} alkyl, such as hydrogen sulfate trioctyl ethyl ammonium -C _1-10 alkyl ammonium salt); dilauryl dimethyl ammonium chloride, dialkyldiarylammonium such bromide distearyldimethylammonium Kill ammonium salt (di _{C 1-20} alkyl - di _{C 1-10} alkyl ammonium salt); bromide lauryl trimethyl ammonium, trialkyl ammonium salts such as stearyl trimethyl ammonium chloride _{(C 1-20} alkyl - tri _{C 1-10} alkylammonium salts), etc.]; aryl - alkyl - trialkylammonium salts [e.g., chloride benzyltri _{C 1-10} alkylammonium (e.g., benzyltri _{C 1-10} alkyl ammonium salt such as benzyltrimethylammonium chloride, etc.); benzyldi chloride _{C 1 -10} alkyl _{-C 1-20} alkyl ammonium (e.g., benzyl chloride dimethyl stearyl ammonium) such as benzyl di _{C 1-10} alkyl _{-C 1-20} alkyl ammonium salts such as ; Cetylpyridinium chloride, cetylpyridinium bromide, iodide cetylpyridinium, etc. alkylpyridinium salts such as hydrogen sulfate, cetyl pyridinium (C _1-20 alkyl pyridinium salts). These quaternary ammonium salts can be used alone or in combination of two or more. Among these quaternary ammonium salts, a linear alkyl group having 6 or more carbon atoms is used as a side chain from the viewpoint of affinity with other reaction components such as the tungsten compound and the unsaturated compound as a substrate. A quaternary ammonium salt having at least one is preferred. Specifically, for example, trioctylmethylammonium chloride (TOMAC), stearyltrimethylammonium chloride, benzyldimethylstearylammonium chloride and the like are preferably used.

(Phosphoric acids)
Phosphoric acids include phosphoric acid, polyphosphoric acid (including pyrophosphoric acid and metaphosphoric acid), (poly) phosphate {ammonium salt such as (poly) ammonium phosphate; metal salt of (poly) phosphoric acid [for example, phosphorus (Poly) alkali metal phosphates such as potassium phosphate and sodium phosphate; (Poly) alkaline earth metal salts such as calcium phosphate; (Poly) alkali metal phosphates such as potassium hydrogen phosphate and sodium hydrogen phosphate Salts; (Poly) hydrogen phosphate alkaline earth metal salts such as calcium hydrogen phosphate; (Poly) metal phosphates such as (poly) aluminum phosphate salts (including aluminum phosphate pyrophosphate double salts)}, etc. Is mentioned. The phosphoric acid includes a material (or raw material) for synthesizing phosphoric acid such as diphosphorus pentoxide. These phosphoric acids may be used alone or in combination of two or more. Of these phosphoric acids, phosphoric acid or phosphate (particularly phosphoric acid) is preferable from the viewpoints of handleability and cost.

(Ratio of each component in the catalyst)
In the catalyst, the quaternary ammonium salt is, for example, 0.01 to 5 molar equivalents, preferably 0.03 to 3 molar equivalents, more preferably about 0.05 to 1 molar equivalents with respect to 1 mol of the tungsten compound. It may be included in proportion. The phosphoric acid may be, for example, about 0.1 to 10 molar equivalents, preferably about 0.2 to 5 molar equivalents, and more preferably about 0.3 to 3 molar equivalents with respect to 1 mol of the tungsten compound.

  Hydrogen peroxide (substantially added hydrogen peroxide) is 0.1 to 10 mole equivalents, preferably 0.2 to 8 mole equivalents, more preferably 0.3 to 5 moles per mole of the unsaturated compound. You may add in the ratio of about a molar equivalent.

  The tungsten compound is 0.0001 to 0.3 molar equivalent (for example, 0.0001 to 0.1 molar equivalent), preferably 0.0005 to 1 mole of the unsaturated compound on a carbon-carbon double bond basis. 0.25 molar equivalent (e.g. 0.0005-0.05 molar equivalent), more preferably 0.001-0.2 molar equivalent, especially 0.001-0.01 molar equivalent (e.g. 0.002-0 (0.008 molar equivalent). That is, the tungsten compound is, for example, 0.01 to 30 mol%, preferably 0.05 to 25 mol%, more preferably 0, based on the carbon-carbon double bond (1 mol) contained in the unsaturated compound. You may use in the ratio of about 1-20 mol%. Here, for example, when the unsaturated compound has two carbon-carbon double bonds in one molecule, 1 mol of the unsaturated compound contains 2 mol of carbon-carbon double bonds. Let's say.

  Moreover, a quaternary ammonium salt is 0.01-5 mol% with respect to the carbon-carbon double bond (1 mol) contained in the said unsaturated compound, for example, Preferably it is 0.03-3 mol%, Furthermore, Preferably, you may use it in the ratio of about 0.05-2 mol%. Furthermore, phosphoric acid is 0.05-3 mol% with respect to the carbon-carbon double bond (1 mol) contained in the said unsaturated compound, for example, Preferably it is 0.1-2 mol%, More preferably, it is 0. You may use in the ratio of about 2-1 mol%.

(Basic nitrogen-containing compounds)
The feature of the present invention is that the unsaturated compound is epoxidized with hydrogen peroxide in the presence of a basic nitrogen-containing compound in a reaction system using a catalyst such as a tungsten compound. In the epoxidation reaction, by using a basic nitrogen-containing compound, the epoxidation reaction of the unsaturated compound can be performed in a wide pH range. In addition, when a basic nitrogen-containing compound is used, in a catalyst system composed of a tungsten compound, a quaternary ammonium salt and phosphoric acid, reactive reactive species involved in the epoxidation reaction are stably formed, Epoxy compounds can be produced with high yield. In addition, since the basic nitrogen-containing compound works effectively even if the addition amount is small, the yield is reduced (or the epoxy compound is destabilized) due to the addition of a large amount, and by-products (for example, , Salts, etc.) are effectively suppressed. Therefore, the epoxy compound can be produced in a high yield over a wide pH range.

  Examples of the basic nitrogen-containing compound include ammonia and amines (monoamines, polyamines, etc.).

Monoamines include, for example, primary amines [eg, primary aliphatic amines (eg, C _1-20 alkyl amines such as methylamine, ethylamine, etc.), primary alicyclic amines (eg, , C _4-10 cycloalkylamines such as cyclohexylamine), primary aromatic amines (eg, C _6-10 arylamines such as aniline, toluidine, etc.)]; secondary amines [eg, primary secondary aliphatic amines (e.g., dimethylamine, and di _{C 1-20} alkyl amines such as diethylamine), second Kyuabura; aromatic amines (e.g., such as _{di-C 4-10} cycloalkyl amines such as dicyclohexylamine) , secondary aromatic amines (e.g., such as _{di-C 6-10} aryl amines such as diphenylamine), etc.]; tertiary amine {For example, aliphatic tertiary amines [e.g., trialkylamines (triethylamine, tripropylamine, tributylamine, trihexylamine, tri C _2-20 alkyl amines such as trioctylamine (preferably tri C _{2- 16} alkyl amines)), dialkyl alkyl amines (diC _1-10 alkyl C _1-20 alkyl amines such as diethylmethylamine) etc.]; alicyclic tertiary amines [eg tricycloalkylamines (TriC _4-10 cycloalkylamine such as tricyclohexylamine), dicycloalkylalkylamines (diC _4-10 cycloalkyl C _1-10 alkylamine such as dicyclohexylmethylamine), cycloalkyldialkylamines (Cyclohexyl dimethyl ester _{C 4-10,} such as cycloalkyl-di _{C 1-10} alkyl amines), etc.], such as triethanolamine; aromatic tertiary amines [such as triaryl amines (such as _{tri-C 6-10} aryl amines such as triphenylamine) Aryldialkylamines (C _6-10 aryldiC _1-10 alkylamines such as N, N-dimethylaniline)]; heterocyclic amines (eg pyridine, methylpyridine (or picoline), ethylpyridine, quinoline) , Isoquinoline, quinoxaline, quinazoline, phthalazine, 1-methylimidazole, N, N-dimethylaminopyridine, heterocyclic aromatic amines containing a nitrogen atom as a ring constituent atom, and the like.

Examples of polyamines include polyamines corresponding to the monoamines such as chain polyamines [eg, alkane diamines (C _2-20 alkane diamines such as ethylene diamine, propylene diamine, tetramethylene diamine, hexamethylene diamine), etc. Diamines; primary polyamines such as polyalkylene polyamines (or polyalkylene imines such as poly _C2-4 alkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine)], cyclic polyamines [e.g. Cyclic secondary polyamines (eg, piperazine, 1,4,8,11-tetraazacyclotetradecane, etc.), cyclic tertiary polyamines (pyrimidine, hexamethylenetetramine, 1,4-diazabicyclo [2, , 2] octane (triethylenediamine, DABCO), 1,5-diazabicyclo [4,3,0] -5-nonene (DBN), 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) Etc.) etc.].

  The basic nitrogen-containing compounds may be used alone or in combination of two or more. Of these basic nitrogen-containing compounds, tertiary amines are preferable because they do not hinder the generation of reactive species formed in the catalyst system, and suppress the cleavage reaction of the generated epoxy compound. Group tertiary amines, in particular, heterocyclic aromatic amines containing a nitrogen atom as a ring-constituting atom [for example, pyridine, methylpyridine (or picoline), quinoline, etc.] are preferably used.

  The basic nitrogen-containing compound is, for example, 0.001 to 0.1 molar equivalent, preferably 0.002 to 0.07 molar equivalent, based on a carbon-carbon double bond, relative to 1 mole of the unsaturated compound. More preferably, you may use it in the ratio of about 0.003-0.05 molar equivalent. That is, for example, 0.1 to 10 mol%, preferably 0.2 to 7 mol%, more preferably 0.3 to 5 mol% with respect to the carbon-carbon double bond (1 mol) contained in the unsaturated compound. You may use it in the ratio of about mol%. The basic nitrogen-containing compound is, for example, 0.01 to 8 molar equivalents, preferably 0.05 to 6 molar equivalents, and more preferably about 0.1 to 5 molar equivalents per 1 mol of the tungsten compound. It may be used in proportion.

(Epoxidation reaction)
The epoxidation reaction is carried out in the presence of a catalyst composed of a tungsten compound, a quaternary ammonium salt and phosphoric acid, and a basic nitrogen-containing compound, and the unsaturated compound is epoxidized with hydrogen peroxide, and the unsaturated An epoxy compound corresponding to the compound is produced.

  In the epoxidation reaction, the tungsten compound, quaternary ammonium salt, phosphoric acid, basic nitrogen-containing compound, unsaturated compound and hydrogen peroxide (hereinafter collectively referred to as “raw material (or reaction component)”) May be mixed and reacted together, or may be mixed and reacted individually. For example, from the viewpoint of reaction efficiency, the raw materials excluding hydrogen peroxide (specifically, the tungsten compound, the quaternary ammonium salt, the phosphoric acid, the basic nitrogen-containing compound and the unsaturated compound) among the raw materials are previously stored. After mixing, hydrogen peroxide may be added to the resulting mixed solution to initiate the epoxidation reaction. In addition, when adding and mixing each raw material, in each raw material, the whole quantity may be added at once (or at once), and may be added in batches (or divided into a plurality of times). In addition, when hydrogen peroxide is added, the whole amount may be added at once (or at a time), but in order to suppress the rapid temperature rise of the reaction solution due to reaction heat and the accompanying decomposition of hydrogen peroxide, It is preferable to add them in batches (or in several batches). The method of adding hydrogen peroxide in batches (or divided into multiple times) is not particularly limited. For example, if a method of dropping hydrogen peroxide into the reaction solution is used, the reaction rate can be easily adjusted and the reaction can be performed. The rapid temperature rise of the solution can be effectively prevented.

The epoxidation reaction may be performed in the absence of a solvent, but is usually performed in the presence of a solvent in many cases. In the epoxidation reaction, hydrogen peroxide is used for epoxidation, and thus the solvent usually includes an aqueous solvent. Examples of the aqueous solvent include water, water-soluble organic solvents [eg, cyclic ethers (eg, dioxane, tetrahydrofuran, etc.); cellosolve acetates (C _1-4 alkyl cellosolve acetates such as ethyl cellosolve acetate], etc.] Can be mentioned. These aqueous solvents may be used alone or in combination of two or more. From the viewpoint of versatility, water is usually used.

In the epoxidation reaction, the solvent is preferably a mixed solvent of the aqueous solvent and the organic solvent. The organic solvent is not particularly limited as long as it can be separated from an aqueous solvent, and can be appropriately selected depending on the type of the unsaturated compound. For example, cyclo C _3-10 alkanols such as cyclopropanol and cyclohexanol Chain ethers such as dimethyl ether and diethyl ether; ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone and cyclohexanone; esters (chains such as ethyl acetate, butyl acetate, methyl lactate and ethyl lactate) Hydrocarbons (for example, aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, Chloroform, methylene chloride, chloro Halogenated hydrocarbons such as benzene, phenols, etc.). The organic solvents may be used alone or in combination of two or more. Of these organic solvents, aromatic hydrocarbons (for example, toluene, xylene, ethylbenzene and the like) and halogenated hydrocarbons (for example, chloroform, methylene chloride, chlorobenzene and the like) are preferable from the viewpoint of reaction efficiency, Aromatic hydrocarbons (such as toluene) are preferred.

  The ratio of the aqueous solvent to the organic solvent can be selected from the range of the former / the latter (weight ratio) = 90/10 to 5/95, for example, 85/15 to 10/90, preferably 80/20 to 15 / 85, more preferably about 75/25 to 20/80. Moreover, the usage-amount of an organic solvent is 0.01-20 weight part with respect to 1 weight part of said reaction components, Preferably it is 0.05-15 weight part, More preferably, 0.1-10 weight part ( For example, it may be about 0.2 to 5 parts by weight.

  The reaction temperature (or the temperature of the reaction system) may be about 20 to 100 ° C., preferably 30 to 90 ° C., more preferably about 40 to 80 ° C. (for example, 50 to 80 ° C.). Moreover, the said reaction may be performed under a normal pressure, and can also be performed under pressure reduction or pressurization. Furthermore, the reaction may be performed in the air or in an inert gas (nitrogen, helium, argon, etc.) atmosphere.

  Although reaction time can be suitably selected according to reaction conditions (for example, kind and amount of reaction components, reaction temperature, etc.), for example, 10 minutes to 20 hours, preferably 30 minutes to 15 hours, more preferably 1 to 1. It may be about 10 hours (for example, 2 to 8 hours).

  Further, the pH of the reaction system (aqueous phase) may be about 2 to 7, preferably about 3 to 7, more preferably about 3.5 to 6.5. As described above, in the epoxidation reaction using a tungsten compound, generally, the lower the reaction pH, the higher the activity and yield of the epoxy compound can be produced, and the reaction activity and yield decrease as the reaction pH approaches neutrality. Tend to. However, in the present invention, since an epoxidation reaction using a tungsten compound is performed in the presence of a basic nitrogen-containing compound, it is high even in a neutral (or weakly acidic) region (for example, about pH 6 to 7). The reaction activity and yield can be maintained, and an epoxy compound can be produced at a high yield over a wide pH range.

  The yield of the epoxy compound produced through the epoxidation reaction is about 80 to 100%, preferably 85 to 99%, more preferably 90 to 98% (for example, 92 to 97%) based on the unsaturated compound. It is.

  The obtained epoxy compound is separated and purified from the reaction product by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, or a combination means combining them. Also good.

  In the present invention, an epoxy compound corresponding to an unsaturated compound (for example, a compound having a cyclohexene ring) can be produced in a high yield, and the resulting epoxy compound is a pharmaceutical, a fragrance, a dye, a food, an organic synthetic intermediate, It is useful as an intermediate compound for molecular resin materials.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the evaluation method in an Example and a comparative example is as follows.

[Evaluation methods]
(PH measurement)
The pH was measured using a portable meter ("SEVENGO" manufactured by METTLER TOLEDO Co., Ltd.).

[Example 1]
After replacing the 1 L four-necked flask with nitrogen, disodium tungstate 4.0 g (12 mmol), phosphoric acid (purity 85%) 1.40 g (12 mmol), benzyldimethylstearyl ammonium chloride 1.03 g (2 Mmol), 0.96 g (12 mmol) of pyridine, 200 g (2.4 mol) of cyclohexene, and 200 g of toluene, and heated to 70 ° C. with stirring. Next, 303 g of a 30 w / v% hydrogen peroxide aqueous solution (2.7 mol of hydrogen peroxide) was added dropwise to the obtained mixed solution over 5 hours. At 2 hours after the start of the reaction (start of dropping), the reaction solution was collected (sampled), and the pH of the lower layer (aqueous phase) was measured and found to be 4.5. After dropping the entire amount of the aqueous hydrogen peroxide solution, the reaction solution was allowed to cool to room temperature, and the upper layer and the lower layer were separated. When the upper layer was analyzed using gas chromatography, the yield of the produced epoxy compound (based on cyclohexene) was 95%.

[Example 2]
The reaction was conducted in the same manner as in Example 1 except that 2.88 g (37 mmol) of pyridine was used. At 2 hours after the start of the reaction (start of dropping), the reaction solution was collected (sampled), and the pH of the lower layer (aqueous phase) was measured and found to be 6.2. After dropwise addition of the entire amount of the aqueous hydrogen peroxide solution, the reaction solution was allowed to cool to room temperature, the upper layer and the lower layer were separated, and the upper layer was analyzed using gas chromatography. The yield of the produced epoxy compound (cyclohexene) Standard) was 93%.

[Comparative Example 1]
The reaction was conducted in the same manner as in Example 1 except that 3.45 g (25 mmol) of disodium hydrogen phosphate was used instead of pyridine. At 2 hours after the start of the reaction (start of dropping), the reaction solution was collected (sampled), and the pH of the lower layer (aqueous phase) was measured and found to be 6.3. After dropwise addition of the entire amount of the aqueous hydrogen peroxide solution, the reaction solution was allowed to cool to room temperature, the upper layer and the lower layer were separated, and the upper layer was analyzed using gas chromatography. The yield of the produced epoxy compound (cyclohexene) Criteria) was 27%.

[Example 3]
After replacing the 1 L four-necked flask with nitrogen, disodium tungstate 1.0 g (3.1 mmol), phosphoric acid (purity 85%) 0.36 g (3.1 mmol), benzyldimethylstearylammonium chloride 0 .39 g (0.93 mmol), 0.24 g (3.1 mmol) of pyridine, bis [1,3- (cyclohex-3-enecarboxylic acid)]-2,2- represented by the above formula (4b) 100 g (0.31 smol) of dimethylpropyl ester and 300 g of toluene were charged, and the temperature was raised to 70 ° C. with stirring. Subsequently, 78 g (hydrogen peroxide 0.68 mol) of 30 w / v% hydrogen peroxide aqueous solution was dropped into the obtained mixed solution over 5 hours. At 2 hours after the start of the reaction (start of dropping), the reaction solution was collected (sampled), and the pH of the lower layer (aqueous phase) was measured to be 4.7. After dropping the entire amount of the aqueous hydrogen peroxide solution, the reaction solution was allowed to cool to room temperature, and the upper layer and the lower layer were separated. When the upper layer was analyzed using gas chromatography, the yield of the produced epoxy compound {bis [1,3- (cyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester standard} was determined as diepoxy. The body (the following formula (7a)) was 92%, and the monoepoxy body (the following formula (7b)) was 3%.

[Example 4]
Instead of bis [1,3- (cyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester, bis [1,3- (4-methylcyclohexa--) represented by the above formula (4c) is used. 3-enecarboxylic acid)]-2,2-dimethylpropyl ester was reacted in the same manner as in Example 3 except that 108 g (0.31 mol) was used. At 2 hours after the start of the reaction (start of dropping), the reaction solution was collected (sampled), and the pH of the lower layer (aqueous phase) was measured to be 4.6. After dropwise addition of the entire amount of the aqueous hydrogen peroxide solution, the reaction solution was allowed to cool to room temperature, the upper layer and the lower layer were separated, and the upper layer was analyzed using gas chromatography. [1,3- (4-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester standard} is 93% diepoxy (formula (8a) below), monoepoxy (formula below) (8b)) was 3%.

[Example 5]
Instead of bis [1,3- (cyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester, 87 g of methyl cyclohex-3-enecarboxylate represented by the above formula (3a) (0. 62 mol) The reaction was carried out in the same manner as in Example 3 except that it was used. At 2 hours after the start of the reaction (start of dropping), the reaction solution was collected (sampled), and the pH of the lower layer (aqueous phase) was measured and found to be 5.4. After dropping the entire amount of the aqueous hydrogen peroxide solution, the reaction solution was allowed to cool to room temperature, the upper layer and the lower layer were separated, and the upper layer was analyzed using gas chromatography. As a result, the produced epoxy compound (the following formula (9 The yield of the epoxy compound represented by ()) (based on methyl cyclohex-3-enecarboxylate) was 95%.

[Example 6]
The reaction was carried out in the same manner as in Example 1 except that 1.13 g (12 mmol) of β-picoline was used instead of pyridine. At 2 hours after the start of the reaction (start of dropping), the reaction solution was collected (sampled), and the pH of the lower layer (aqueous phase) was measured to be 4.6. After dropwise addition of the entire amount of the aqueous hydrogen peroxide solution, the reaction solution was allowed to cool to room temperature, the upper layer and the lower layer were separated, and the upper layer was analyzed using gas chromatography. The yield of the produced epoxy compound (cyclohexene) Standard) was 94%.

[Example 7]
The reaction was carried out in the same manner as in Example 1 except that 1.57 g (12 mmol) of quinoline was used instead of pyridine. At 2 hours after the start of the reaction (start of dropping), the reaction solution was collected (sampled), and the pH of the lower layer (aqueous phase) was measured to be 4.6. After dropwise addition of the entire amount of the aqueous hydrogen peroxide solution, the reaction solution was allowed to cool to room temperature, the upper layer and the lower layer were separated, and the upper layer was analyzed using gas chromatography. The yield of the produced epoxy compound (cyclohexene) Standard) was 94%.

  As is apparent from the examples, in the epoxidation reaction using a tungsten compound as a catalyst, an epoxy compound corresponding to the unsaturated compound could be produced in a high yield by using a basic nitrogen-containing compound. On the other hand, in Comparative Example 1 in which the reaction is carried out in the presence of disodium hydrogen phosphate, the production of reactive species that can be formed in the catalyst system is inhibited (or suppressed). The compound yield was very low. In the examples, since the epoxidation reaction is performed in the presence of a basic nitrogen-containing compound, as is clear from the comparison between Example 2 and Comparative Example 1, the neutral (or weakly acidic) region ( For example, a high yield could be maintained even at a pH of about 6-7.

Claims (6)

  Epoxidizing an unsaturated compound having at least one carbon-carbon double bond with hydrogen peroxide in the presence of a catalyst composed of a tungsten compound, a quaternary ammonium salt and phosphoric acid and a basic nitrogen-containing compound, A method for producing an epoxy compound corresponding to the unsaturated compound.   The production method according to claim 1, wherein epoxidation is performed under conditions of pH 2-7.   The manufacturing method of Claim 1 or 2 which uses a basic nitrogen containing compound in the ratio of 0.001-0.1 molar equivalent with respect to 1 mol of unsaturated compounds on a carbon-carbon double bond basis.   The tungsten compound is used in a proportion of 0.0001 to 0.3 molar equivalent based on the carbon-carbon double bond with respect to 1 mol of the unsaturated compound, and the quaternary ammonium salt is 0 with respect to 1 mol of the tungsten compound. The manufacturing method in any one of Claims 1-3 which uses 0.01-5 molar equivalent and phosphoric acids in the ratio of 0.1-10 molar equivalent.   The production method according to any one of claims 1 to 4, wherein the unsaturated compound is a compound having 6 or more carbon atoms, and the basic nitrogen-containing compound is a tertiary amine. The unsaturated compound is a compound having at least one C _5-10 cycloalkene ring, and the basic nitrogen-containing compound is a heterocyclic aromatic amine containing a nitrogen atom as a constituent atom of the ring. 6. The production method according to any one of 5 above.