JPWO2014196269A1 - Ionic vinyl ether copolymer and method for producing organic compound using the same - Google Patents

Abstract

Provided is an ionic vinyl ether copolymer that enables an epoxidation reaction using hydrogen peroxide in an organic solvent / water two-phase system even when an olefin other than an allylic alcohol is used as a substrate. An ionic vinyl ether copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): In formula (1), X represents a group represented by the following formula (4) or a group represented by the following formula (5). [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4]

Description

  The present invention relates to an ionic vinyl ether copolymer and a method for producing an organic compound using the same. More specifically, the present invention relates to an ionic vinyl ether copolymer that can be preferably used as a phase transfer catalyst in an oxidation reaction in an organic solvent and water in a two-phase reaction field, and a method for producing an organic compound in the two-phase reaction field using the same. . This application claims the priority of Japanese Patent Application No. 2013-120342 for which it applied to Japan on June 7, 2013, and uses the content here.

  Oxidation reactions using oxidants are used in various applications. For example, production of aldehydes and carboxylic acids by oxidation of primary alcohols, production of ketones by oxidation of secondary alcohols, oxidation of unsaturated compounds. It is used for the production of various organic compounds such as the production of epoxy compounds and diols. In particular, the oxidation reaction using hydrogen peroxide as an oxidant has attracted attention in recent years from the viewpoint of reducing environmental impact because hydrogen peroxide is inexpensive, does not exhibit corrosivity, and the by-product is water. ing.

  As a method for producing an organic compound using hydrogen peroxide as an oxidizing agent, for example, a polymer obtained by radical polymerization of an acrylate monomer having a quaternary ammonium salt moiety and N-isopropylacrylamide is used as an organic solvent / water. A method of epoxidizing allyl alcohol by using as a phase transfer catalyst in a two-phase system is known (see Patent Document 1, Non-Patent Documents 1 and 2).

JP 2003-33659 A

Angelwante Chemie International Edition, 2005, 44, 4536-4538 Tetrahedron, 2004, 60, 4087-4096

  However, in the catalyst system including the phase transfer catalyst disclosed in the above prior art document, although catalytic activity for a compound having a double bond, which is considered to be susceptible to an oxidation reaction such as allyl alcohol, has been recognized, allyl No catalytic activity was observed for olefins other than type alcohols (particularly olefins having no oxygen atom at the allylic position). For example, Non-Patent Document 2 shows that the reaction does not proceed when cyclohexene is used as a substrate. For this reason, it is applicable to the case where olefins other than allyl alcohol are used as a substrate, and development of a method for producing an organic compound capable of using hydrogen peroxide as an oxidizing agent is desired at present. Representative examples of allyl alcohols include glycidol, geraniol, 2-cyclohexenol, 2-buten-1-ol, farnesol, phytol, and the like.

Accordingly, an object of the present invention is to provide an ionic vinyl ether copolymer that enables an epoxidation reaction using hydrogen peroxide in an organic solvent / water two-phase system even when an olefin other than an allyl alcohol is used as a substrate. There is to do.
Another object of the present invention is to oxidize an organic compound (sometimes referred to as “oxidizable organic compound”) in an organic solvent / water two-phase system and to produce a corresponding oxidized organic compound (“oxidized compound”). It is an object of the present invention to provide a method for producing an organic compound applicable to a wide range of substrates including allyl alcohol.
Furthermore, another object of the present invention is to provide an oxidation reaction catalyst that enables an epoxidation reaction using hydrogen peroxide in an organic solvent / water two-phase system even when an olefin other than an allyl alcohol is used as a substrate. Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have used an ionic vinyl ether copolymer having a specific structure as a phase transfer catalyst, so that even when an olefin other than an allyl alcohol is used as a substrate, The present invention was completed by finding that an epoxidation reaction using hydrogen peroxide in an organic solvent / water two-phase system was possible.

［式（１）中、Ｒ¹は、水素原子又は炭素数１〜５のアルキル基を示す。Ａ¹は、炭素数２〜４のアルキレン基を示す。ａは０〜３６の整数を示し、ａが２以上の整数の場合、複数のＡ¹は同一であってもよいし異なっていてもよい。ｂは１〜１８の整数を示す。Ｘは、下記式（４）

［式（４）中、Ｒ²、Ｒ³、及びＲ⁴は、同一又は異なって、炭素数１〜１８のアルキル基、又は炭素数２〜１８のアルケニル基を示す。Ｙ^-は、アニオンを示す。］
で表される基、又は、下記式（５）

［式（５）中、Ｒ⁵は、炭素数１〜６のアルキル基、又は炭素数２〜６のアルケニル基を示す。ｄは０〜５の整数を示す。Ｙ^-は、アニオンを示す。］
で表される基を示す。］
で表される構成単位、並びに下記式（２）

［式（２）中、Ｒ⁶は、水素原子又は炭素数１〜５のアルキル基を示す。Ｒ⁷は、水素原子、炭素数１〜１８のアルキル基、又は炭素数２〜１８のアルケニル基を示す。Ａ²は、炭素数２〜４のアルキレン基を示す。ｃは、１〜２４の整数を示し、ｃが２以上の整数の場合、複数のＡ²は同一であってもよいし異なっていてもよい。］
で表される構成単位を有することを特徴とするイオン性ビニルエーテルコポリマーを提供する。That is, the present invention provides the following formula (1):

[In Formula (1), R < ¹ > shows a hydrogen atom or a C1-C5 alkyl group. A ¹ represents an alkylene group having 2 to 4 carbon atoms. a represents an integer of 0 to 36. When a is an integer of 2 or more, a plurality of A ¹ may be the same or different. b shows the integer of 1-18. X is the following formula (4)

Wherein ^{(4), R 2, R} 3, and R ⁴ are the same or different and indicate an alkyl group, or an alkenyl group having 2 to 18 carbon atoms having 1 to 18 carbon atoms. Y ⁻ represents an anion. ]
Or a group represented by the following formula (5)

Wherein (5), R ⁵ represents an alkyl group, or an alkenyl group having 2 to 6 carbon atoms having 1 to 6 carbon atoms. d shows the integer of 0-5. Y ⁻ represents an anion. ]
The group represented by these is shown. ]
And the following formula (2)

[In Formula (2), R < ⁶ > shows a hydrogen atom or a C1-C5 alkyl group. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms. A ² represents an alkylene group having 2 to 4 carbon atoms. c represents an integer of 1 to 24. When c is an integer of 2 or more, a plurality of A ² may be the same or different. ]
The ionic vinyl ether copolymer characterized by having the structural unit represented by these is provided.

［式（３）中、Ｒ⁸は、水素原子又は炭素数１〜５のアルキル基を示す。Ｒ⁹は、炭素数１〜３６のアルキル基、又は炭素数２〜３６のアルケニル基を示す。］
で表される構成単位を有する前記のイオン性ビニルエーテルコポリマーを提供する。Further, the following formula (3)

[In Formula (3), R < ⁸ > shows a hydrogen atom or a C1-C5 alkyl group. R ⁹ represents an alkyl group having 1 to 36 carbon atoms or an alkenyl group having 2 to 36 carbon atoms. ]
The ionic vinyl ether copolymer having the structural unit represented by the formula:

  The present invention also relates to a method for producing an oxidized organic compound by proceeding an oxidation reaction of an organic compound in a two-phase reaction field between an organic solvent and water, and the phase transfer of the two-phase reaction field Provided is a method for producing an organic compound, characterized in that the ionic vinyl ether copolymer is used as a catalyst.

  Furthermore, the present invention provides a method for producing the organic compound, wherein the oxidation reaction proceeds in the presence of a complex oxide prepared from the ionic vinyl ether copolymer and a heteropolyacid or a salt thereof or a precursor compound thereof.

  Further, the production of the organic compound, wherein the heteropolyacid or a salt thereof is a heteropolyacid or a salt thereof containing a phosphorus atom and at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium. Provide a method.

  Further, the precursor compound is an inorganic acid containing at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium, or a salt thereof, and a phosphorus atom-containing oxo acid or an organic salt thereof. A method for producing a compound is provided.

  Furthermore, the manufacturing method of the said organic compound whose said oxidation reaction is the epoxidation reaction of the carbon-carbon double bond of the olefin using hydrogen peroxide is provided.

［式（１）中、Ｒ¹は、水素原子又は炭素数１〜５のアルキル基を示す。Ａ¹は、炭素数２〜４のアルキレン基を示す。ａは０〜３６の整数を示し、ａが２以上の整数の場合、複数のＡ¹は同一であってもよいし異なっていてもよい。ｂは１〜１８の整数を示す。Ｘは、下記式（４）

［式（４）中、Ｒ²、Ｒ³、及びＲ⁴は、同一又は異なって、炭素数１〜１８のアルキル基、又は炭素数２〜１８のアルケニル基を示す。Ｙ^-は、アニオンを示す。］
で表される基、又は、下記式（５）

［式（５）中、Ｒ⁵は、炭素数１〜６のアルキル基、又は炭素数２〜６のアルケニル基を示す。ｄは０〜５の整数を示す。Ｙ^-は、アニオンを示す。］
で表される基を示す。］
で表される構成単位、並びに下記式（２）

［式（２）中、Ｒ⁶は、水素原子又は炭素数１〜５のアルキル基を示す。Ｒ⁷は、水素原子、炭素数１〜１８のアルキル基、又は炭素数２〜１８のアルケニル基を示す。Ａ²は、炭素数２〜４のアルキレン基を示す。ｃは、１〜２４の整数を示し、ｃが２以上の整数の場合、複数のＡ²は同一であってもよいし異なっていてもよい。］
で表される構成単位を有するイオン性ビニルエーテルコポリマー含むことを特徴とする酸化反応用触媒を提供する。The present invention also provides a catalyst for an oxidation reaction of an organic compound in a two-phase reaction field between an organic solvent and water,
As a phase transfer catalyst, the following formula (1)

[In Formula (1), R < ¹ > shows a hydrogen atom or a C1-C5 alkyl group. A ¹ represents an alkylene group having 2 to 4 carbon atoms. a represents an integer of 0 to 36. When a is an integer of 2 or more, a plurality of A ¹ may be the same or different. b shows the integer of 1-18. X is the following formula (4)

Wherein ^{(4), R 2, R} 3, and R ⁴ are the same or different and indicate an alkyl group, or an alkenyl group having 2 to 18 carbon atoms having 1 to 18 carbon atoms. Y ⁻ represents an anion. ]
Or a group represented by the following formula (5)

Wherein (5), R ⁵ represents an alkyl group, or an alkenyl group having 2 to 6 carbon atoms having 1 to 6 carbon atoms. d shows the integer of 0-5. Y ⁻ represents an anion. ]
The group represented by these is shown. ]
And the following formula (2)

[In Formula (2), R < ⁶ > shows a hydrogen atom or a C1-C5 alkyl group. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms. A ² represents an alkylene group having 2 to 4 carbon atoms. c represents an integer of 1 to 24. When c is an integer of 2 or more, a plurality of A ² may be the same or different. ]
The catalyst for oxidation reaction characterized by including the ionic vinyl ether copolymer which has the structural unit represented by these.

That is, the present invention relates to the following.
[1] An ionic vinyl ether copolymer having a structural unit represented by the above formula (1) and a structural unit represented by the above formula (2).
[2] R ¹ in the above formula (1) is a hydrogen atom, A ¹ is a linear or branched alkylene group having 2 or 3 carbon atoms, a is an integer of 0 to 2, b The ionic vinyl ether copolymer according to [1], wherein is an integer of 1 to 4.
[3] In [1] or [2], R ² , R ³ , and R ⁴ in formula (4) are all alkyl groups having 4 to 8 carbon atoms or alkenyl groups having 4 to 18 carbon atoms. Ionic vinyl ether copolymer.
[4] In the above formula (2), R ⁶ is a hydrogen atom, R ⁷ is an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and A ² is a straight or branched chain having 2 or 3 carbon atoms. The ionic vinyl ether copolymer according to any one of [1] to [3], which is a chain alkylene group.
[5] The ionic vinyl ether copolymer according to any one of [1] to [4], further having a structural unit represented by the above formula (3).
[6] The ionic vinyl ether copolymer according to [5], wherein R ⁸ in the above formula (3) is a hydrogen atom, and R ⁹ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. .
[7] The proportion of the structural unit represented by the above formula (1) is 1 mol% or more with respect to the total amount of the structural units constituting the ionic vinyl ether copolymer (total structural unit: 100 mol%). ] The ionic vinyl ether copolymer in any one of-[6].
[8] The proportion of the structural unit represented by the formula (2) is 1 to 99 mol% with respect to the total amount (100 mol%) of the structural units constituting the ionic vinyl ether copolymer. 7] The ionic vinyl ether copolymer according to any one of [7].
[9] The proportion of the structural unit represented by the above formula (3) is 0 to 90 mol% with respect to the total amount (100 mol%) of the structural units constituting the ionic vinyl ether copolymer. [8] The ionic vinyl ether copolymer according to any one of [8].
[10] The ionic vinyl ether copolymer according to any one of [1] to [9], wherein the degree of polymerization of all the structural units is 10 to 10,000.
[11] The ionic vinyl ether copolymer according to any one of [1] to [10], which has a weight average molecular weight of 1,000 to 100,000.
[12] A method for producing an oxidized organic compound by proceeding an oxidation reaction of an organic compound in a two-phase reaction field between an organic solvent and water, as a phase transfer catalyst in the two-phase reaction field, The manufacturing method of the organic compound characterized by using the ionic vinyl ether copolymer in any one of [1]-[11].
[13] The organic solvent is a cyclo C _3-10 alkanol, a chain ether, a ketone, an ester (chain ester), an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, The method for producing an organic compound according to [12], which is at least one organic solvent selected from the group consisting of halogenated hydrocarbons and phenols.
[14] The method for producing an organic compound according to [12] or [13], wherein the ratio of water to the organic solvent is the former / the latter (weight ratio) 90/10 to 5/95.
[15] The method for producing an organic compound according to any one of [12] to [14], wherein the amount of the organic solvent used is 0.01 to 20 parts by weight with respect to 1 part by weight of the organic compound to be oxidized.
[16] Any one of [12] to [15], wherein the oxidation reaction proceeds in the presence of an oxide of a complex prepared from the ionic vinyl ether copolymer and a heteropolyacid or a salt thereof or a precursor compound thereof. The manufacturing method of the organic compound as described in any one of.
[17] The heteropolyacid or salt thereof is a heteropolyacid or salt thereof containing a phosphorus atom and at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium. 16] The manufacturing method of the organic compound in any one of.
[18] The precursor compound includes an inorganic acid or a salt thereof containing at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium, and a phosphorus atom-containing oxo acid or a salt thereof. ] The manufacturing method of the organic compound in any one of [17].
[19] The method for producing an organic compound according to any one of [12] to [18], wherein the oxidation reaction is an epoxidation reaction of an olefin carbon-carbon double bond using an oxidizing agent.
[20] The method for producing an organic compound according to any one of [12] to [19], wherein the oxidation reaction is an epoxidation reaction of an olefin carbon-carbon double bond using hydrogen peroxide as an oxidizing agent.
[21] The olefin is (i) a linear or branched aliphatic hydrocarbon having a carbon-carbon double bond, and / or (ii) a cycloalkene ring (a cycloalkapolyene ring such as a cycloalkadiene ring). And the method for producing an organic compound according to [19] or [20].
[22] The method for producing an organic compound according to any one of [19] to [21], wherein the olefin is a compound represented by the following formula (a) and / or the following formula (b).
[23] The olefin is cyclohexene, vinylcyclohexene (3-vinylcyclohexene), methyl cyclohex-3-enecarboxylate, 4-allylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4- (2-propenyl) ) Cyclohexene, 1-methyl-4- (1-methylethenyl) cyclohexene (limonene), cyclohexenylmethyl cyclohex-3-enecarboxylate, bis [1,3- (cyclohex-3-enecarboxylic acid)]-2,2 -Dimethylpropyl ester, bis [1,3- (4-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester [4-methylcyclohex-3-enecarboxylic acid = 2,2- Dimethyl-3- (4-methylcyclohex-3-enecarbonyloxy ) Propyl] and bis [1,3- (3-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester [3-methylcyclohex-3-enecarboxylic acid = 2,2 The method for producing an organic compound according to any one of [19] to [22], which is at least one selected from the group consisting of -dimethyl-3- (3-methylcyclohex-3-enecarbonyloxy) propyl] .
[24] The method for producing an organic compound according to any one of [12] to [23], wherein the amount of the ionic vinyl ether copolymer used is 0.1 to 50 parts by weight with respect to 100 parts by weight of the organic compound to be oxidized. .
[25] The amount of the heteropolyacid or salt thereof or the precursor compound used (the amount corresponding to 1 mol of the heteropolyacid or salt thereof in the case of the precursor compound) is 1 mol of the oxidizable group of the oxidizable organic compound. The method for producing an organic compound according to any one of [16] to [24], which is 0.01 to 3.00 mol.
[26] When the amount of the oxidizing agent used in the method for producing an organic compound of the present invention is hydrogen peroxide as the oxidizing agent, the amount of the hydrogen peroxide (substantially added hydrogen peroxide) is The oxidizable organic compound (olefin) according to any one of [19] to [25], which is 0.5 to 3.0 moles per mole of an oxidizable group (such as an olefin carbon-carbon double bond). A method for producing an organic compound.
[27] The method for producing an organic compound according to any one of [19] to [26], wherein the reaction temperature (temperature of the reaction system) is 50 to 70 ° C. when hydrogen peroxide is used as an oxidizing agent.
[28] The method for producing an organic compound according to any one of [12] to [27], wherein the pH of the reaction system (aqueous phase) is 2 to 7.
[29] A catalyst for an oxidation reaction of an organic compound in a two-phase reaction field between an organic solvent and water, the structural unit represented by the above formula (1) as a phase transfer catalyst, and the above formula (2) An oxidation reaction catalyst comprising an ionic vinyl ether copolymer having a structural unit represented by:

  Since the ionic vinyl ether copolymer of the present invention has the above-described structure, the ionic vinyl ether copolymer is used as a phase transfer catalyst, so that not only allyl alcohol but also olefin other than allyl alcohol is used as a substrate. In addition, the epoxidation reaction using hydrogen peroxide in the organic solvent / water two-phase system can be efficiently advanced.

The graph which shows the result of the epoxidation reaction of 3-vinylcyclohexene of an Example [A horizontal axis | shaft: Reaction time (unit: time), a vertical axis | shaft: The ratio of the peak area of 1, 2- epoxy- 4-vinylcyclohexane in gas chromatography (Unit: area%)].

[Ionic vinyl ether copolymer]
The ionic vinyl ether copolymer of the present invention is a copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) as essential structural units (monomer units).

R ¹ in the formula (1) is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n -C1-C5 linear or branched alkyl groups, such as a pentyl group, are mentioned. Among these, as R ¹ , a hydrogen atom is preferable.

A ¹ in formula (1) represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include linear or branched alkylene groups having 2 to 4 carbon atoms such as an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group. Among them, as A ¹ , a linear or branched alkylene group having 2 or 3 carbon atoms is preferable. Also, a in the formula (1) represents an integer of 0 to 36, when a is an integer of 2 or more, to the plurality of A ¹ may be the same or different. a is preferably an integer of 0 to 2. When two or more oxyalkylene structural units [A ¹ O] are present in the formula (1), the addition form of these oxyalkylene structural units is not particularly limited, and may be a random type, It may be a block type.

  B in Formula (1) shows the integer of 1-18. b is preferably an integer of 1 to 4.

X in the formula (1) represents a group represented by the following formula (4) or a group (ionic group) represented by the following formula (5).

In formula (4), R ² , R ³ , and R ⁴ are the same or different and represent an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms. Examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-propyl group, n-butyl group, i-butyl group, hexyl group, octyl group and the like. And a linear or branched alkyl group having 1 to 18 carbon atoms. As said C2-C18 alkenyl group, C2-C18 linear or branched alkenyl groups, such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, are mentioned, for example. Among these, from the viewpoint of allowing the oxidation reaction to proceed with higher efficiency, R ² , R ³ , and R ⁴ in the formula (4) include an alkyl group having 2 to 18 carbon atoms and an alkenyl group having 2 to 18 carbon atoms. More preferably, they are a C3-C18 alkyl group, a C3-C18 alkenyl group, More preferably, a C4-C8 alkyl group and a C4-C18 alkenyl group. In particular, all of R ² , R ³ , and R ⁴ are preferably an alkyl group having 2 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, more preferably an alkyl group or carbon having 4 to 10 carbon atoms. It is a C3-C18 alkenyl group, More preferably, it is a C4-C8 alkyl group or a C4-C18 alkenyl group.

In formula (4), Y ⁻ represents an anion. Y ⁻ is not limited to a monovalent anion, for example, an anion represented by Y ²⁻ , Y ^3−, etc. as a counter ion of two or more (—NR ² R ³ R ⁴ ) ⁺ . May be. Examples of Y ⁻ include halide ions such as chloride ion, fluoride ion and bromide ion; inorganic anions obtained by removing protons from inorganic acids such as sulfuric acid and phosphoric acid; methosulfate, ethosulfate, methophosphate, etho Examples thereof include organic anions obtained by removing protons from phosphates and various organic acids (for example, acetic acid, lactic acid, citric acid, etc.).

In Formula (5), R ⁵ is a substituent on the aromatic heterocyclic ring (pyridine ring), and represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. D is the number of R ⁵ (the number of substitutions) on the aromatic heterocyclic ring and represents an integer of 0 to 5. Y ⁻ represents an anion similarly to the formula (4).

  The ionic vinyl ether copolymer of the present invention may have one of the structural units represented by the formula (1), or may have two or more.

In formula (2), R < ⁶ > shows a hydrogen atom or a C1-C5 alkyl group. Specific examples of R ⁶ include the same as R ¹ described above. Among them, R ⁶ is preferably a hydrogen atom.

In Formula (2), R ⁷ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms. Specific examples of R ⁷ include the same as R ^{2 to} R ⁴ described above. Among them, as R ^7, preferably an alkenyl group having an alkyl group or a C2-10 having 1 to 4 carbon atoms.

In the formula (2), A ² represents an alkylene group having 2 to 4 carbon atoms. Specific examples of A ² include the same as A ¹ described above. Among these, as A ² , a linear or branched alkylene group having 2 or 3 carbon atoms is preferable. Moreover, c in Formula (2) shows the integer of 1-24, and when c is an integer greater than or equal to ² , some A2 may be the same and may differ. In addition, when two or more kinds of oxyalkylene structural units [A ² O] are present in the formula (2), the addition form of these oxyalkylene structural units is not particularly limited, and may be a random type, It may be a block type.

  The ionic vinyl ether copolymer of the present invention may have one of the structural units represented by the formula (2), or may have two or more.

The ionic vinyl ether copolymer of the present invention may further have a structural unit represented by the following formula (3).

In formula (3), R ⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of R ⁸ include those similar to R ¹ described above. Among these, as R ⁸ , a hydrogen atom is preferable.

In formula (3), R ⁹ represents an alkyl group having 1 to 36 carbon atoms or an alkenyl group having 2 to 36 carbon atoms. Specific examples of R ⁹ include, for example, the same alkyl groups having 1 to 18 carbon atoms and alkenyl groups having 2 to 18 carbon atoms in the above-described R ^{2 to} R ⁴ . Among them, as R ^9, preferably an alkenyl group having an alkyl group or a C2-10 having 1 to 10 carbon atoms.

  The ionic vinyl ether copolymer of the present invention may have one of the structural units represented by the formula (3), or may have two or more.

  The ionic vinyl ether copolymer of the present invention may have structural units other than the structural units represented by the above formulas (1) to (3) (sometimes referred to as “other structural units”).

  The proportion of the structural unit represented by the formula (1) in the ionic vinyl ether copolymer of the present invention is not particularly limited, but is based on the total amount of the structural units constituting the ionic vinyl ether copolymer (total structural unit: 100 mol%). 1 mol% or more is preferable, More preferably, it is 5-90 mol%, More preferably, it is 10-70 mol%, Especially preferably, it is 12-40 mol%, Most preferably, it is 30 mol% or more. By setting the proportion of the structural unit represented by the formula (1) to 1 mol% or more (particularly 30 mol% or more), the oxidation reaction of the organic compound (particularly olefin epoxidation with hydrogen peroxide) can be further enhanced. There is a tendency to be able to proceed with efficiency.

  The proportion of the structural unit represented by the formula (2) in the ionic vinyl ether copolymer of the present invention is not particularly limited, but is 1 to 99 with respect to the total amount (100 mol%) of the structural units constituting the ionic vinyl ether copolymer. The mol% is preferable, more preferably 5 to 90 mol%, still more preferably 10 to 70 mol%, particularly preferably 12 to 40 mol%, and most preferably 30 mol% or more. By setting the proportion of the structural unit represented by the formula (2) to 1 mol% or more (particularly 30 mol% or more), hydrophilicity is improved, and this tends to increase the function as a phase transfer catalyst.

  The proportion of the structural unit represented by the formula (3) in the ionic vinyl ether copolymer of the present invention is not particularly limited, but is 0 to 90 with respect to the total amount (100 mol%) of the structural units constituting the ionic vinyl ether copolymer. The mol% is preferable, more preferably 10 to 50 mol%, still more preferably 30 to 45 mol%. By setting the proportion of the structural unit represented by the formula (3) to 90 mol% or less, the organic compound oxidation reaction (particularly, olefin epoxidation with hydrogen peroxide) tends to proceed with higher efficiency. There is.

  Although the polymerization degree of all the structural units in the ionic vinyl ether copolymer of the present invention is not particularly limited, it is preferably 10 to 10,000, more preferably 100 to 5000, and further preferably 120 to 3000. By setting the degree of polymerization to 10 or more, there is a tendency that an oxidation reaction of an organic compound (particularly, olefin epoxidation with hydrogen peroxide) can proceed with higher efficiency. On the other hand, when the degree of polymerization is 10,000 or less, when the reaction is carried out in a two-phase reaction field of organic solvent / water, there is a tendency that good reactivity can be secured without the viscosity of the aqueous phase becoming too high.

  Although the weight average molecular weight of the ionic vinyl ether copolymer of this invention is not specifically limited, 1000-100000 are preferable, More preferably, it is 3000-75000. The molecular weight distribution (= weight average molecular weight / number average molecular weight) of the ionic vinyl ether copolymer of the present invention is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. is there. The average molecular weight (weight average molecular weight, number average molecular weight) of the ionic vinyl ether copolymer of the present invention is calculated from the molecular weight in terms of standard polystyrene measured by gel permeation chromatography.

[Method for producing ionic vinyl ether copolymer]
Although the ionic vinyl ether copolymer of this invention is not specifically limited, For example, it can manufacture by the following method.
A monomer (sometimes referred to as "monomer (i)") corresponding to a structural unit (sometimes referred to as "structural unit (i)") that can be converted into the structural unit represented by formula (1); and , A monomer corresponding to the structural unit represented by formula (2) (sometimes referred to as “monomer (2)”), and, if necessary, a monomer corresponding to the structural unit represented by formula (3) ( The monomer (sometimes referred to as “monomer (3)”) or a monomer corresponding to another structural unit (sometimes referred to as “other monomer”) is copolymerized, and then the structural unit (i) is represented by the formula (1). )

As described above, the method includes the following step 1 and step 2 as essential steps.
Step 1: Copolymerizing a monomer mixture containing monomer (i) and monomer (2) as essential components to form a precursor of the ionic vinyl ether copolymer of the present invention (sometimes referred to as “precursor copolymer”). Step of generating Step 2: Converting the structural unit (i) in the precursor copolymer obtained in Step 1 into the structural unit represented by the formula (1) to generate the ionic vinyl ether copolymer of the present invention.

The structural unit (i) is not particularly limited as long as it is a structural unit that can be converted into the structural unit represented by the formula (1). Examples of the monomer (monomer (i)) corresponding to the structural unit (i) include a compound represented by the following formula (i-1).

In formula (i-1), R ¹ , A ¹ , a, and b are the same as those in formula (1). Z in Formula (i-1) represents an amino group, a halogen atom, or a sulfate group protected by a protecting group. Examples of the protecting group in the amino group protected by the protecting group as Z include known or commonly used protecting groups for amino groups, specifically, Protective Groups in Organic Synthesis 3rd Ed. T. W. Greene, P.M. G. M.M. Wuts, John Wiley and Sons, Inc. , Protecting groups described in 1999, and the like. Specifically, for example, phthaloyl group; alkoxycarbonyl such as t-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, allyloxycarbonyl group Group; acyl group such as trifluoroacetyl group; arylsulfonyl group such as p-toluenesulfonyl group and 2,2-nitrobenzenesulfonyl group; and the like. Examples of the halogen atom as Z include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the sulfate group as Z include a methane sulfate group and a p-toluene sulfate group.

  Examples of the compound represented by the formula (i-1) in which Z is an amino group protected by a protecting group include 2-phthalimidoethyl vinyl ether. The phthaloylimide group of 2-phthalimidoethyl vinyl ether is deprotected by, for example, reacting with hydrazine in Step 2, and then reacting with an alkyl halide having 1 to 18 carbon atoms or an alkenyl halide having 2 to 18 carbon atoms. Can be converted into a group represented by the above formula (4). Moreover, when Z is a halogen atom, it can be converted into a group represented by the above formula (5) by reacting with pyridine or substituted pyridine in Step 2, for example.

  The copolymerization of the monomer (vinyl ether monomer) in step 1 can be advanced by a cationic polymerization method. In particular, living cationic polymerization is preferred from the viewpoint of easy control of the molecular weight, composition, and structure of the resulting copolymer and easy obtaining of a uniform polymer having a narrow molecular weight distribution and composition distribution.

  The copolymerization of the monomer in step 1 can be allowed to proceed in the absence of a solvent, or can be allowed to proceed in the presence of a solvent. Examples of the solvent (polymerization solvent) include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-pentane and n-hexane; halogenated hydrocarbons such as dichloromethane and dichloroethane; diethyl ether and tetrahydrofuran. Examples include ether. In addition, a polymerization solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Although the usage-amount of a polymerization solvent is not specifically limited, For example, it can select suitably from the range of 0-2000 weight part with respect to 100 weight part of whole quantity of a monomer.

  As the polymerization initiator used when copolymerizing the monomer in Step 1, a known or conventional polymerization initiator can be used, and is not particularly limited, but hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, hydrogen iodide, acetic acid, Protonic acids such as trifluoroacetic acid; metal oxides such as phosphorus oxide, titanium oxide, aluminum oxide and other solid acids; halogens such as chlorine, bromine, iodine, iodine chloride, bromine chloride, iodine bromide; magnesium, zinc, Metal halides such as chlorides, bromides, iodides such as aluminum, titanium, iron and boron; organometallic compounds such as alkylates such as aluminum or zinc; magnesium alkylations such as Grignard reagents; triphenylmethylcarbonium ions Stable carbonium ions such as boron trifluoride-diethyl ether complex and other Lewis acids It is. In the above copolymerization, if necessary, a compound that generates protons such as water, alcohol, and proton acid; a compound that generates carbonium ions such as alkyl halides, and the like are used as a cocatalyst together with a polymerization initiator. You can also.

Among the above polymerization initiators, examples of living cationic polymerization initiators include known or conventional polymerization initiators such as HI / I ₂ -based initiators, initiators combining organic aluminum compounds and additives such as ethers or esters. Agents can be used.

  The usage-amount of a polymerization initiator is not specifically limited, It can select suitably from a known usage-amount.

  The temperature at the time of copolymerizing the monomer in Step 1 (polymerization temperature) varies depending on the kind of polymerization initiator, monomer, polymerization solvent and the like to be used, and is not particularly limited, but is preferably −80 to 150 ° C., more preferably − 78-80 ° C. The polymerization time varies depending on the type of polymerization initiator, monomer, solvent and the like used, and is not particularly limited, but is preferably 10 minutes to 100 hours. The copolymerization reaction can be carried out in any form such as a batch form, a semibatch form, and a continuous form.

［式（ｉ）中、Ｒ¹、Ａ¹、ａ、ｂ、及びＺは、は、式（ｉ−１）におけるものと同じ。］By the step 1, a precursor copolymer having a structural unit represented by the following formula (i) and a structural unit represented by the formula (2) as essential structural units is obtained. The precursor copolymer may be purified by a conventional method, for example, separation means such as concentration, extraction, column chromatography, or a combination means combining these before or after being subjected to Step 2. Good.

[In the formula (i), R ¹ , A ¹ , a, b and Z are the same as those in the formula (i-1). ]

  Although the weight average molecular weight of the said precursor copolymer is not specifically limited, 500-100,000 are preferable, More preferably, it is 1000-75000. The molecular weight distribution (= weight average molecular weight / number average molecular weight) of the precursor copolymer is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. The average molecular weight (weight average molecular weight, number average molecular weight) of the precursor copolymer is calculated from the molecular weight in terms of standard polystyrene measured by gel permeation chromatography.

  In step 2, the structural unit (i) in the precursor copolymer is converted into the structural unit represented by the formula (1) to produce the ionic vinyl ether copolymer of the present invention. The method for converting the structural unit (i) into the structural unit represented by the formula (1) is not particularly limited, and a well-known method can be used in the field of organic synthesis. As described above, when Z is an amino group (phthaloylimide group) protected by a phthaloyl group, it is deprotected by reacting with hydrazine, and then an alkyl halide having 1 to 18 carbon atoms or 2 carbon atoms. Z can be converted to a group represented by the formula (4) by reacting with -18 alkenyl halides. Moreover, when Z is a halogen atom, it can be converted into a group represented by the above formula (5) by reacting with pyridine or substituted pyridine in Step 2, for example.

  The ionic vinyl ether copolymer of the present invention can be purified by a conventional method, for example, separation means such as dialysis, concentration, filtration, column chromatography, or a separation means combining these.

[Method for producing organic compound]
The ionic vinyl ether copolymer of the present invention is a method for producing an oxidized organic compound (oxidized compound) by advancing an oxidation reaction of an organic compound (oxidized organic compound) in a two-phase reaction field between an organic solvent and water. And can be preferably used as a phase transfer catalyst in the above two-phase reaction field. By using the ionic vinyl ether copolymer of the present invention as a phase transfer catalyst, not only allyl alcohols but also olefins other than allyl alcohols can be used as substrates for oxidation reactions (particularly due to hydrogen peroxide). Epoxidation reaction) can be carried out efficiently. In addition, in this specification, the manufacturing method of the said organic compound which uses the ionic vinyl ether copolymer of this invention as a phase transfer catalyst is called "the manufacturing method of the organic compound of this invention."

The oxidation reaction in the method for producing an organic compound of the present invention is carried out in a two-phase reaction field of an organic solvent and water. As the organic solvent, a known or conventional organic solvent capable of forming a two-phase with water (aqueous solution or the like) can be used, and it is appropriately selected according to the kind of the organic compound to be oxidized (especially olefin). For example, cyclo C _3-10 alkanols such as cyclopropanol and cyclohexanol; chain ethers such as dimethyl ether and diethyl ether; methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone Ketones such as cyclohexanone; esters (chain esters) such as ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate; hydrocarbons (eg, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methyl) Cycloaliphatic hydrocarbons such as cyclohexane, toluene, Ren, aromatic hydrocarbons such as ethylbenzene); and the like phenols; chloroform, methylene chloride, halogenated hydrocarbons such as chlorobenzene. The said organic solvent can be used individually by 1 type or in combination of 2 or more types. Of these, esters and aromatic hydrocarbons are preferred from the viewpoint of reaction efficiency.

  The ratio of water and organic solvent is not particularly limited, but is preferably selected from the range of the former / the latter (weight ratio) 90/10 to 5/95, more preferably 85/15 to 10/90, and even more preferably. Is 80/20 to 15/85, particularly preferably 75/25 to 20/80. The amount of the organic solvent used is not particularly limited, but is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight with respect to 1 part by weight of the organic compound to be oxidized (olefin or the like). More preferably, it is 0.1-10 weight part (for example, 0.2-5 weight part).

  The oxidation reaction in the method for producing an organic compound of the present invention proceeds particularly in the presence of an oxide of a complex prepared from the ionic vinyl ether copolymer of the present invention and a heteropolyacid or a salt thereof or a precursor compound thereof. It is preferable in that the oxidation reaction can proceed with higher efficiency. For example, the oxide of the above complex coexists with the ionic vinyl ether copolymer of the present invention and the heteropolyacid or a salt thereof or a precursor compound thereof in the reaction system in the presence of an oxidizing agent (particularly hydrogen peroxide). Can be generated.

  That is, the method for producing an organic compound of the present invention comprises a catalyst (oxidation reaction) for an oxidation reaction of an organic compound in a two-phase reaction field of an organic solvent and water, which contains at least the ionic vinyl ether copolymer of the present invention as a phase transfer catalyst. In this case, the oxidation reaction proceeds in the presence of a catalyst. As described above, the oxidation reaction catalyst preferably includes at least the ionic vinyl ether copolymer of the present invention and a heteropolyacid or a salt thereof or a precursor compound thereof. The oxidation catalyst is a complex oxide prepared from the ionic vinyl ether copolymer of the present invention and a heteropolyacid or a salt thereof or a precursor compound thereof by coexisting with an oxidizing agent (particularly hydrogen peroxide). Is considered to generate.

  As the heteropolyacid or salt thereof, various known heteropolyacids or salts thereof can be used, and are not particularly limited. For example, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, Examples thereof include ribdophosphoric acid, tungstomolybdosilicic acid, and phosphovanadmolybdic acid. Among them, the heteropolyacid includes phosphorus (phosphorus atom) and a heteropolyacid containing at least one (one or more) metal (metal atom) selected from the group consisting of tungsten, manganese, molybdenum, and vanadium. preferable. Examples of such heteropolyacids include phosphotungstic acid, phosphomanganic acid, phosphomolybdic acid, and phosphovanadic acid. Among these, phosphotungstic acid is particularly preferable from the viewpoint of cost. Examples of the salt of the heteropolyacid include onium salts, alkali metal salts, alkaline earth metal salts, transition metal salts of the above exemplified heteropolyacids.

  The precursor compound of the heteropolyacid or a salt thereof means one or more compounds that can form (prepare) a heteropolyacid or a salt thereof. The precursor compound does not necessarily form a heteropolyacid or a salt thereof in the reaction system. Examples of the precursor compound include metal atoms such as tungsten, manganese, vanadium, molybdenum, titanium, aluminum, and niobium (preferably at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium). ) And at least one heteroatom selected from the group consisting of phosphorus, silicon, and arsenic (preferably phosphorus (phosphorus atom)) Combinations with compounds can be used. That is, the heteropolyacid or salt thereof is a heteropolyacid or salt thereof prepared from a compound containing at least one metal atom selected from the group consisting of tungsten, manganese, and vanadium and a compound containing at least phosphorus. Preferably there is.

  Examples of the compound containing a hetero atom include phosphoric acid, polyphosphoric acid (including pyrophosphoric acid and metaphosphoric acid), (poly) phosphate {metal salt of (poly) phosphoric acid [for example, a compound containing a phosphorus atom] (Poly) alkali metal phosphates such as potassium phosphate, sodium phosphate; (Poly) alkaline earth metal salts such as calcium phosphate; potassium hydrogen phosphate, sodium hydrogen phosphate, disodium hydrogen phosphate, etc. (Poly) alkali metal hydrogen phosphate; (Poly) alkaline earth metal phosphate such as calcium hydrogen phosphate; (Poly) aluminum phosphate (including aluminum pyrophosphate double salt) ) Metal phosphate]} and the like. In addition, the compound (or raw material) which synthesize | combines the compound containing the said phosphorus atoms, such as a phosphorus pentoxide, is also contained in the compound containing the said phosphorus atom. The said compound containing a phosphorus atom can be used individually by 1 type or in combination of 2 or more types. Among these, phosphorus atom-containing oxo acids such as phosphoric acid or phosphates (particularly phosphoric acid) or salts thereof are preferable from the viewpoints of handleability and cost. Examples of the compound containing a hetero atom include silicic acid (orthosilicate, metasilicic acid, etc.) as a compound containing a silicon atom, and arsenic acid, arsenous acid, etc. as a compound containing an arsenic atom.

  Examples of the metal compound include halides of metals such as tungsten, manganese, vanadium, molybdenum, titanium, aluminum, and niobium, inorganic acid salts, organic acid salts, complexes, and polyacids or salts thereof composed of the above metal atoms. Etc. These metal compounds can be used individually by 1 type or in combination of 2 or more types.

  Among the above metal compounds, examples of the compound containing tungsten (tungsten compound) include tungsten halides (tungsten chloride, etc.); tungsten inorganic acid salts (sulfates, nitrates, etc.); tungsten organic acid salts (acetates) Complex with tungsten as the central metal; isopolyacid or its salt of tungsten (tungstic acid; alkali metal salt of tungstic acid such as sodium tungstate, potassium tungstate, etc.), heteropolyacid or its salt (tungstophosphoric acid ( Or tungstophosphate) (for example, 12-tungstophosphoric acid, 11-tungstophosphoric acid, etc.), vanadium tungstic acid, molybdenum tungstic acid, manganese tungstic acid, cobalt tungstic acid, silicotungstic acid, phosphovanadotan Sten acid, manganese molybdate tungstate or salts thereof (e.g., alkali metal salts), etc.).

  In particular, the metal compound is preferably an inorganic acid (polyacid, isopolyacid) or a salt thereof containing at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium.

  That is, as a precursor compound of the heteropolyacid or a salt thereof, an inorganic acid or a salt thereof containing at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium, and a phosphorus atom-containing oxoacid Or the combination of the salt is preferable.

  In the method for producing an organic compound of the present invention, other components can be allowed to coexist in the reaction system. Examples of other components include hydroquinones, trialkylamines, and polyethylene glycol. The usage-amount of these other components can be set suitably, and is not specifically limited.

(Oxidant)
As the oxidizing agent used in the oxidation reaction in the method for producing an organic compound of the present invention, a known or conventional oxidizing agent can be used, and is not particularly limited. As described above, in the two-phase system of organic solvent / water, It is preferable to use hydrogen peroxide from the viewpoint that the advantage of the present invention that a wide range of substrates such as olefins other than allyl alcohol can be applied is effective. Hydrogen peroxide is preferably used in the form of an aqueous solution (aqueous hydrogen peroxide solution) from the viewpoint of safety. Hydrogen peroxide (or hydrogen peroxide aqueous solution) may be synthesized by a conventional method, or a commercially available product may be used. The concentration of hydrogen peroxide in the case of using an aqueous hydrogen peroxide solution is not particularly limited, but is preferably 20 to 70 w / v%, more preferably 22 to 67 w / v%, and still more preferably from the viewpoint of handleability and the like. 25 to 65 w / v%.

(Organic compounds)
Although it does not specifically limit as an organic compound (oxidized organic compound) as a substrate used in the manufacturing method of the organic compound of the present invention, for example, a compound having an ethylenically unsaturated double bond (when referred to as “olefin”) And alcohol, ketone and the like. When an olefin is oxidized with an oxidizing agent, usually a carbon-carbon double bond (ethylenically unsaturated double bond) is epoxidized to produce a corresponding epoxy compound. Depending on conditions, a diol is generated. Oxidation of primary alcohol with an oxidizing agent produces aldehyde, carboxylic acid and the like. When secondary alcohol is oxidized with an oxidizing agent, ketone, carboxylic acid and the like are produced. Further, when the ketone is oxidized with an oxidizing agent, Bayer-bilger oxidation proceeds to produce an ester (in the case of oxidation of a chain ketone) and a lactone (in the case of oxidation of a cyclic ketone). In particular, the most typical oxidation reaction when hydrogen peroxide is used as the oxidizing agent is olefin oxidation, in particular, olefin carbon-carbon double bond epoxidation reaction. Hereinafter, although olefin epoxidation (epoxidation of olefin carbon-carbon double bond) will be described in detail, the oxidation reaction in the method for producing an organic compound of the present invention is not limited to this reaction, and any of the above oxidation reactions It may be. The method for producing an organic compound of the present invention is particularly useful in that it can be applied to a wide range of substrates such as olefins other than allyl alcohol as the substrate (oxidized organic compound) as well as allyl alcohol. .

  The olefin is not particularly limited as long as it has at least one ethylenically unsaturated double bond (non-aromatic carbon-carbon double bond) in the molecule (in one molecule). That is, the olefin may have one or more ethylenically unsaturated double bonds in the molecule. The olefin contains (i) a linear or branched aliphatic hydrocarbon having a carbon-carbon double bond, and (ii) a cycloalkene ring (including a cycloalkapolyene ring such as a cycloalkadiene ring). And the like. These compounds may have a substituent. When the oxidation reaction is performed in a liquid phase, a liquid or solid (or miscible with the liquid) olefin is usually selected as the olefin usually under reaction conditions.

(I) Examples of linear or branched aliphatic hydrocarbons having a carbon-carbon double bond include ethylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, and 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 A C _2-40 alkene (preferably a C _2-30 alkene, more preferably a C _2-20 alkene) such as nonene, 2-nonene, decene, undecene, dodecene, tetradecene, hexadecene, octadecene; butadiene, isoprene, 1, C _4-40 alkadiene (preferably C ₄ ) such as 5-hexanediene, 1,6-heptanediene, 1,7-octadiene, decadiene, undecadiene, dodecadiene _-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 carbon-carbon double bond can 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 (for example, C _1-10 alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc. (for example, C _1-6 alkoxy group), etc. ), A haloalkoxy group, an alkylthio group (eg, a C _1-10 alkylthio group such as a methylthio group or an ethylthio group), a carboxyl group, an alkoxycarbonyl group (eg, a C _1-10 alkoxy such as a methoxycarbonyl group or an ethoxycarbonyl group) carbonyl group (e.g., a C _2-10 alkoxycarbonyl group), etc.), an acyl group (e.g., acetyl, pro Onyl group, such as C _2-10 acyl group such as trifluoroacetyl group), an acyloxy group (e.g., acetoxy group, propionyloxy group, C _1-10 acyloxy group such as trifluoroacetoxy group), an amino group, substituted amino A substituent such as a group, a nitro group, a cyano group, or a heterocyclic group (such as a nitrogen atom-containing heterocyclic group such as a pyridyl group) may be included. 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. In addition, the linear or branched aliphatic hydrocarbon having an aryl group (for example, phenyl group) as a substituent is an alkenyl group (for example, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, etc.) _Or an aromatic compound substituted with a C _2-10 alkenyl group (preferably a C _2-6 alkenyl group), and the aromatic compound has at least one carbon in the side chain. -As long as it has a carbon double bond, the alkenyl group and / or aromatic ring may have a substituent (for example, the above exemplified substituent), and between the alkenyl group and the aromatic ring. May have a linking group (such as a linking group described below).

(Ii) 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 such as cyclododecene (preferably C _4-14 cycloalkene, more preferably C _5-10 cycloalkene); 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} cycloalkadiene); cycloocta Such as C _7-20 cycloalkadienyl triene such as Lien and the like. The compound which has a cycloalkene ring can be used individually by 1 type or in combination of 2 or more types. Among these, C _3-20 cycloalkene is preferable, and C _5-10 cycloalkene [for example, C _6-8 cycloalkene (for example, C _5-6 cycloalkene such as cyclohexene)] can be preferably used.

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 (i) a substituent exemplified in the section of a linear or branched aliphatic hydrocarbon having a carbon-carbon double bond, and an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group). Group, butyl group, isobutyl group, C _1-10 alkyl group (preferably C _1-6 alkyl group) such as t-butyl group, etc .; haloalkyl group; alkenyl group (for example, alkenyl group exemplified above); aryl Group (for example, C _6-10 aryl group such as phenyl group) and the like.

  The olefin may be a compound containing a plurality of alkene units and / or cycloalkene units. The plurality of alkene units and / or cycloalkene units in the compound containing the plurality of alkene units and / or cycloalkene units may be the same or different. 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 the above (i) a linear or branched aliphatic hydrocarbon having a carbon-carbon double bond, such as an alkadiene unit. It is used in the meaning including the alkapolyene unit. The “cycloalkene unit” may be a monovalent or polyvalent group corresponding to the compound (ii) containing a cycloalkene ring, and 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, _C4-10 cycloalkylene group such as 1,4-cyclohexylene group), arylene group (eg C _6-10 arylene group such as phenylene group, naphthalenediyl group, etc.), carbonyl bond, ester bond, amide bond And at least one selected from an ether bond and a urethane bond.

  Carbon contained in the carbon number of the olefin (when a substituent and / or a linking group is included, a substituent and / or a linking group (a substituent and a linking group when both a substituent and a linking group are included)) The total number) is not particularly limited, but is preferably 2 to 40, more preferably 6 or more (for example, 6 to 30), further preferably 6 to 25, and particularly preferably 6 to 20 (For example, 7 to 20).

Such olefin can be used individually by 1 type or in combination of 2 or more types. The olefin is preferably a compound containing (ii) a cycloalkene ring (for example, a C _3-20 cycloalkene ring, preferably a C _6-20 cycloalkene ring, particularly a cyclohexene ring). The olefin may have one or more cycloalkene rings (particularly cyclohexene rings).

［式（ａ）中、Ｒ¹¹は、水素原子又はアルキル基を示し、Ｒ¹²は、水素原子、アルキル基、アルケニル基、ヒドロキシル基、アルコキシ基、カルボキシル基、又はアルコキシカルボニル基を示す。］
で表される化合物や、下記式（ｂ）

［式（ｂ）中、Ｒ¹³は単結合、又は、直鎖若しくは分岐鎖状アルキレン基を示す。Ｒ¹¹は、同一又は異なって、前記に同じ。ｐ及びｑは、同一又は異なって、０又は１以上の整数である。］
で表される化合物などが含まれる。なお、ｐ及びｑが０であり、Ｒ¹³が単結合である場合には、上記式（ｂ）で表される化合物は、２つのシクロヘキセン環が直接結合した構造を有する。Representative olefins include, for example, the following formula (a)

[In Formula (a), R ¹¹ represents a hydrogen atom or an alkyl group, and R ¹² 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 (b)

[In the formula (b), R ¹³ represents a single bond or a linear or branched alkylene group. R ¹¹ is the same or different and the same as above. p and q are the same or different and are 0 or an integer of 1 or more. ]
And the like. When p and q are 0 and R ¹³ is a single bond, the compound represented by the above formula (b) has a structure in which two cyclohexene rings are directly bonded.

As the linear or branched alkylene group (including alkylidene group) represented by R ¹³ , for example, an alkane optionally having a substituent (for example, ethane, propane, isopentane, 2,2-dimethylpropane, etc.) A divalent group corresponding to a C _1-20 alkane, etc. [specifically, a linear or branched chain such as a methylene group, an ethylene group, a propylene group, a 2,2-dimethylpropane-1,3-diyl group, etc. And a C _2-20 alkylene group (or alkylidene group)]. In the above formula (b), p and q are preferably 1.

Specifically, the olefin includes, for example, cyclohexene in which R ¹¹ and R ¹² are hydrogen atoms, R ¹¹ is a hydrogen atom, and vinyl cyclohexene (3) in which R ¹² is a vinyl group in the above formula (a). -Vinylcyclohexene, etc.), R ¹¹ is a hydrogen atom, R ¹² is a methoxycarbonyl group methyl cyclohex-3-enecarboxylate (the following formula (a-1)), R ¹¹ is a hydrogen atom, R ¹² Is an allyl group, 4-allylcyclohexene (following formula (a-2)), R ¹¹ is a methyl group, and R ¹² is a vinyl group (following formula (a-3) ), R ¹¹ is a methyl group, R ¹² is an isopropenyl group 2-methyl-4- (2-propenyl) cyclohexene (the following formula (a-4)), R ¹¹ is a methyl group, R ¹² Is an isopropenyl group There l-methyl-4- (1-methylethenyl) cyclohexene (limonene); in the formula (b), a R ¹¹ is a hydrogen atom, R ¹³ is methylene group, p is is 1, q is 0 cyclohex Cyclohexenylmethyl-3-enecarboxylate (following formula (b-1)), R ¹¹ is a hydrogen atom, R ¹³ is 2,2-dimethylpropane-1,3-diyl, and p and q are 1 Bis [1,3- (cyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester (the following formula (b-2)), R ¹¹ is a methyl group, R ¹³ is 2,2 Bis [1,3- (4-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester [4- which is dimethylpropane-1,3-diyl and p and q are 1 Methylcyclohex-3-encar Acid = 2,2-dimethyl-3- (4-methylcyclohex-3-enecarbonyloxy) propyl] (the following formula (b-3)) and bis [1,3- (3-methylcyclohexa) -3-enecarboxylic acid)]-2,2-dimethylpropyl ester [3-methylcyclohex-3-enecarboxylic acid = 2,2-dimethyl-3- (3-methylcyclohex-3-enecarbonyloxy) Propyl] (the following formula (b-4)) and the like.

  For example, when cyclohexenyl methyl cyclohex-3-enecarboxylate represented by the above formula (b-1) is used as the olefin, a corresponding epoxy compound (3,4-epoxycyclohexane represented by the following formula (c) is used. Hexenylmethyl (3,4-epoxy) cyclohexanecarboxylate) is obtained. Further, when 2-methyl-4-vinylcyclohexene represented by the above formula (a-3) is used as the olefin, the corresponding epoxy compound (monoepoxy compound represented by the following formula (d-1) and the following formula: A diepoxy compound represented by (d-2) is obtained. Furthermore, when 1-methyl-4- (1-methylethenyl) cyclohexene (limonene) is used as the olefin, the corresponding 1,2-epoxy-4- (2-methyloxiranyl) -1-methylcyclohexane ( Limonene diepoxide). Further, as the olefin, bis [1,3- (4-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester represented by the above formula (b-3) [4-methylcyclohexa When -3-enecarboxylic acid = 2,2-dimethyl-3- (4-methylcyclohex-3-enecarbonyloxy) propyl] is used, a corresponding epoxy compound represented by the following formula (e) is obtained. . In addition, as the olefin, bis [1,3- (3-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester represented by the above formula (b-4) [3-methylcyclohexa When -3-enecarboxylic acid = 2,2-dimethyl-3- (3-methylcyclohex-3-enecarbonyloxy) propyl] is used, a corresponding epoxy compound represented by the following formula (f) is obtained. .

  The oxidation reaction (epoxidation reaction, etc.) in the method for producing an organic compound of the present invention includes an organic phase containing an oxidizable organic compound (olefin, etc.) and an aqueous phase (heteropolyacid or a salt thereof or a precursor compound thereof). It is preferable that hydrogen peroxide or an aqueous solution thereof be added to a two-phase solution composed of The abundance ratio of the ionic vinyl ether copolymer of the present invention in each of the aqueous phase and the organic phase depends on the structure and temperature.

  In the method for producing the organic compound of the present invention, the method for allowing the ionic vinyl ether copolymer of the present invention and the heteropolyacid or a salt thereof or a precursor compound thereof to coexist in the reaction system is not particularly limited. For example, the ionic vinyl ether copolymer of the present invention and a heteropolyacid or a salt thereof or a precursor compound thereof may be added to the reaction system in the form of a composition, or the ionic vinyl ether of the present invention. You may add a copolymer and heteropoly acid or its salt, or these precursor compounds separately in a reaction system.

  The amount of the ionic vinyl ether copolymer of the present invention used in the method for producing the organic compound of the present invention is not particularly limited, but is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the oxidizable organic compound (olefin or the like). More preferably, it is 0.5-30 weight part, More preferably, it is 1.0-15 weight part. When the amount of the ionic vinyl ether copolymer of the present invention is 0.1 parts by weight or more, the oxidation reaction tends to proceed more efficiently.

  When a heteropolyacid or a salt thereof or a precursor compound thereof is used in the method for producing an organic compound of the present invention, the amount used (in the case of a precursor compound, an amount corresponding to 1 mol of the heteropolyacid or a salt thereof) is particularly limited. Although it is not, 0.01 to 3.00 mol is preferable with respect to 1 mol of an oxidizable group (for example, a carbon-carbon double bond of an olefin) of an oxidizable organic compound (olefin or the like), more preferably 0.01 It is -1.00 mol, More preferably, it is 0.01-0.05 mol. When the amount used is 0.01 mol or more, the oxidation reaction tends to proceed more efficiently.

  The amount of the oxidant used in the method for producing an organic compound of the present invention can be appropriately set depending on the kind of the oxidant and is not particularly limited. For example, when hydrogen peroxide is used as the oxidant, the amount of hydrogen peroxide (substantially added hydrogen peroxide) is not particularly limited, but the oxidizable group of the oxidizable organic compound (olefin, etc.). (For example, carbon-carbon double bond of an olefin) The amount is preferably 0.5 to 3.0 mol, more preferably 0.7 to 2.8 mol, still more preferably 0.9 to 2 with respect to 1 mol. 0.0 mole.

  In the above oxidation reaction, when hydrogen peroxide is used as the oxidizing agent, the ionic vinyl ether copolymer, heteropolyacid or salt thereof or precursor compound thereof (hereinafter referred to as oxidation reaction) of the present invention is used for the purpose of suppressing the rate of oxygen generation during the reaction. Catalyst), oxidizable organic compounds (olefins, etc.) (these may be collectively referred to as “raw materials”), and other components (for example, hydroquinones, etc.), and then a mixed solution ( The oxidation reaction (epoxidation reaction etc.) should be initiated by adding hydrogen peroxide to (usually a two-phase system). In addition, when adding and mixing each raw material, in each raw material, the whole quantity may be added collectively (or once), and may be added in batch (or divided into multiple times). In addition, when hydrogen peroxide is added all at once (or at one time), 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 desirable to add (or divide into multiple times). 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 reaction temperature (or the temperature of the reaction system) can be appropriately set according to the type of the organic compound to be oxidized, the oxidizing agent, etc., and is not particularly limited. For example, when hydrogen peroxide is used as the oxidizing agent, it is preferably 50 to 70 ° C., more preferably 55 to 65 ° C. in consideration of oxygen generation due to decomposition of hydrogen peroxide. By setting the reaction temperature to 70 ° C. or lower, the generation of oxygen can be suppressed, and the production can be more safely performed. Moreover, the said reaction may be performed under a normal pressure and can also be performed under reduced pressure or pressurization.

  Moreover, the pH of the reaction system (aqueous phase) is not particularly limited, but is preferably 2 to 7, more preferably 3 to 5, and still more preferably 3.5 to 4.5.

  Although the reaction time is not particularly limited, for example, when hydrogen peroxide is used as the oxidizing agent, it is preferable to terminate the reaction immediately after the target oxide is formed in order to avoid generation of excess oxygen. .

  The obtained oxidized compound (epoxy compound, etc.) is separated and purified from the raw materials and the like according to the purpose by a conventional method, for example, separation means such as filtration, concentration, column chromatography, etc., or a separation means combining these. be able to.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
[Production of copolymer represented by the following formula (I-1)]
2-Phthalimidoethyl vinyl ether (4.31 g) was dissolved in dichloromethane (15 mL), and at room temperature, 2-ethoxyethyl vinyl ether (2.49 g), isobutyl vinyl ether (2.6 mL), and 1,4-dioxane (2 .1 mL) was added sequentially and stirred. Subsequently, it cooled to -68 degreeC and boron trifluoride diethyl ether complex 0.1M dichloromethane solution (4.0 mL) was dripped over 5 minutes. After completion of dropping, the temperature was raised to 10 ° C. over 30 minutes, methanol (containing 0.3 wt% ammonia aqueous solution; 5.0 mL) was added, and the mixture was stirred for 10 minutes. Thereafter, dichloromethane (50 mL) was added to the reaction mixture, and this solution was washed successively with ion-exchanged water (50 mL) and saturated brine (50 mL), and anhydrous sodium sulfate (10 g) and anhydrous magnesium sulfate (5 g) were added simultaneously. , Dried. The solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a white slurry liquid (8.41 g, sometimes referred to as “white slurry liquid (1)”).
The white slurry liquid (1) was dissolved in 1,4-dioxane (20 mL), and methanol (10 mL) was added to make a uniform solution. Next, hydrazine monohydrate (2.4 mL) was added at room temperature, the temperature was raised to 65 ° C. with stirring, and stirring was continued for another 3 hours. Thereafter, the precipitated solid was removed by filtration, and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by dialysis to obtain a white slurry (4.09 g, sometimes referred to as “white slurry (2)”).
The white slurry (2) is dissolved in a mixed solvent of N, N-dimethylformamide (20 mL) and ethanol (10 mL), 1-bromobutane (9.59 g) is added at room temperature, and the mixture is heated to 120 ° C. and stirred. did. After 13 hours, it was cooled to room temperature and concentrated under reduced pressure. Ethyl acetate was added to the obtained crude product to precipitate a white solid, which was collected by filtration and dried to obtain PTC-1 (6.1 g) as a pale yellow liquid. By ¹ H-NMR spectrum measurement of the obtained PTC-1, it was confirmed that it was a copolymer represented by the following formula (I-1).
¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.89 (t, 9H, J = 7.0 Hz, CH ₃ ), 1.23-1.38 (m, 30H, CH ₂ ), 1.58-1 .94 (m, 6H, CH ₂ ), 2.75 (s, 3H, CH ₃ ), 3.28-3.31 (m, 6H, CH ₂ ), 3.38 (s, 3H, CH ₃ ) , 3.54-3.69 (m, 26H, CH 2), 3.80-3.82 (m, 2H, CH 2), 3.91-3.93 (m, 2H, CH 2)

  In addition, ratio (molar ratio) of n1 / n2 / n3 in PTC-1 was 32.4 / 35.0 / 32.6. In addition, “ran” in formula (I-1) means that each structural unit is added by random copolymerization, and the same applies to the following.

Example 2
[Production of copolymer represented by the following formula (I-2)]
2-Chloroethyl vinyl ether (1.0 mL), 2-ethoxyethyl vinyl ether (1.06 g), and isobutyl vinyl ether (1.3 mL) were dissolved in dichloromethane (8.0 mL). Subsequently, 1,4-dioxane (1.0 mL) was added and cooled to −70 ° C., and boron trifluoride diethyl ether complex 0.1 M dichloromethane solution (2.0 mL) was added dropwise over 5 minutes. After completion of the dropwise addition, the temperature was gradually raised to 15 ° C., methanol (containing 0.3 wt% ammonia aqueous solution; 3.0 mL) was added, and the mixture was stirred for 10 minutes. Thereafter, dichloromethane (30 mL) was added to the reaction mixture, and this solution was washed successively with ion-exchanged water (50 mL) and saturated brine (50 mL), and dried over anhydrous sodium sulfate (10 g). The solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a pale yellow liquid (2.96 g). This was refluxed in a mixed solvent of toluene (3.0 mL) and pyridine (4.0 mL) for 8 hours. Unreacted pyridine was then removed by concentration under reduced pressure and diethyl ether was added to precipitate the product. Thereafter, the diethyl ether phase was removed, and the residue was concentrated under reduced pressure to obtain PTC-2 (4.04 g) as a red liquid. By ¹ H-NMR spectrum measurement of the obtained PTC-2, it was confirmed to be a copolymer represented by the following formula (I-2).
¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.89 (t, 9H, J = 7.0 Hz, CH ₃ ), 1.23-1.38 (m, 30H, CH ₂ ), 1.58-1 .94 (m, 6H, CH ₂ ), 2.75 (s, 3H, CH ₃ ), 3.28-3.31 (m, 6H, CH ₂ ), 3.38 (s, 3H, CH ₃ ) , 3.54-3.69 (m, 26H, CH 2), 3.80-3.82 (m, 2H, CH 2), 3.91-3.93 (m, 2H, CH 2)

  The ratio (molar ratio) of n4 / n5 / n6 in PTC-2 was 34.5 / 31.5 / 34.0.

Example 3
[Epoxidation of 3-vinylcyclohexene using PTC-1 as a phase transfer catalyst]
PTC-1 (0.124 g) was dissolved in ion exchange water (2.04 g). To this, sodium tungstate dihydrate (0.197 g), 85% phosphoric acid (0.114 g), and disodium hydrogen phosphate dodecahydrate (0.0525 g) were sequentially added and stirred. . After 5 minutes, ethyl acetate (9.05 g) and 3-vinylcyclohexene (3.64 g) were added, the temperature was raised to 60 ° C., and 35% hydrogen peroxide (4.08 g) was added and stirred.
FIG. 1 is a graph showing the results of the epoxidation reaction of 3-vinylcyclohexene. The horizontal axis represents the reaction time (unit: hours), and the vertical axis represents 1,2-epoxy-4-vinylcyclohexane in gas chromatography. This is the peak ratio (unit: area%). The ratio of the peak of 1,2-epoxy-4-vinylcyclohexane is the peak area of 1,2-epoxy-4-vinylcyclohexane, the peak area of 3-vinylcyclohexene and 1,2-epoxy-4-vinylcyclohexane. It is calculated by dividing by the sum of.
As shown in FIG. 1, by using PTC-1 as a phase transfer catalyst, epoxidation of a double bond in an aliphatic ring (cyclohexene ring) of 3-vinylcyclohexene proceeds, and 1,2-epoxy- It was confirmed that 4-vinylcyclohexane was formed.

Example 4
[Epoxidation of 3-vinylcyclohexene using PTC-2 as a phase transfer catalyst]
PTC-2 (0.373 g) was dissolved in ion exchange water (1.97 g). To this, sodium tungstate dihydrate (0.193 g), 85% phosphoric acid (0.108 g), and disodium hydrogen phosphate dodecahydrate (0.0558 g) were sequentially added and stirred. . After 5 minutes, ethyl acetate (9.03 g) and 3-vinylcyclohexene (3.19 g) were added, the temperature was raised to 60 ° C., 35% hydrogen peroxide (4.10 g) was added, and the mixture was stirred.
As shown in FIG. 1, by using PTC-2 as a phase transfer catalyst, epoxidation of a double bond in the aliphatic ring of 3-vinylcyclohexene proceeds, and 1,2-epoxy-4-vinylcyclohexane Was confirmed to generate.

Example 5
[Epoxidation of 3-vinylcyclohexene using PTC-2 as a phase transfer catalyst]
The epoxidation reaction of 3-vinylcyclohexene was carried out in the same manner as in Example 4 except that the amount of PTC-2 was changed to 0.673 g.
As shown in FIG. 1, by using PTC-2 as a phase transfer catalyst, epoxidation of a double bond in the aliphatic ring of 3-vinylcyclohexene proceeds, and 1,2-epoxy-4-vinylcyclohexane Was confirmed to generate.

Example 6
[Epoxidation of 3-vinylcyclohexene using PTC-2 as a phase transfer catalyst]
The epoxidation reaction of 3-vinylcyclohexene was carried out in the same manner as in Example 4 except that ethyl acetate was changed to toluene.
As shown in FIG. 1, by using PTC-2 as a phase transfer catalyst, epoxidation of a double bond in the aliphatic ring of 3-vinylcyclohexene proceeds, and 1,2-epoxy-4-vinylcyclohexane Was confirmed to generate.

  Since the ionic vinyl ether copolymer of the present invention has the above-described structure, the ionic vinyl ether copolymer is used as a phase transfer catalyst, so that not only allyl alcohol but also olefin other than allyl alcohol is used as a substrate. In addition, the epoxidation reaction using hydrogen peroxide in the organic solvent / water two-phase system can be efficiently advanced.

Claims (8)

Following formula (1)

[In Formula (1), R < ¹ > shows a hydrogen atom or a C1-C5 alkyl group. A ¹ represents an alkylene group having 2 to 4 carbon atoms. a represents an integer of 0 to 36. When a is an integer of 2 or more, a plurality of A ¹ may be the same or different. b shows the integer of 1-18. X is the following formula (4)

Wherein ^{(4), R 2, R} 3, and R ⁴ are the same or different and indicate an alkyl group, or an alkenyl group having 2 to 18 carbon atoms having 1 to 18 carbon atoms. Y ⁻ represents an anion. ]
Or a group represented by the following formula (5)

Wherein (5), R ⁵ represents an alkyl group, or an alkenyl group having 2 to 6 carbon atoms having 1 to 6 carbon atoms. d shows the integer of 0-5. Y ⁻ represents an anion. ]
The group represented by these is shown. ]
And the following formula (2)

[In Formula (2), R < ⁶ > shows a hydrogen atom or a C1-C5 alkyl group. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms. A ² represents an alkylene group having 2 to 4 carbon atoms. c represents an integer of 1 to 24. When c is an integer of 2 or more, a plurality of A ² may be the same or different. ]
An ionic vinyl ether copolymer having a structural unit represented by: Further, the following formula (3)

[In Formula (3), R < ⁸ > shows a hydrogen atom or a C1-C5 alkyl group. R ⁹ represents an alkyl group having 1 to 36 carbon atoms or an alkenyl group having 2 to 36 carbon atoms. ]
The ionic vinyl ether copolymer of Claim 1 which has a structural unit represented by these.   A method for producing an oxidized organic compound by advancing an oxidation reaction of an organic compound in a two-phase reaction field between an organic solvent and water, wherein the phase transfer catalyst is used as the phase transfer catalyst in the two-phase reaction field. Or an ionic vinyl ether copolymer as described in 2 above.   The method for producing an organic compound according to claim 3, wherein the oxidation reaction proceeds in the presence of an oxide of a complex prepared from the ionic vinyl ether copolymer and a heteropolyacid or a salt thereof or a precursor compound thereof.   The organic compound according to claim 4, wherein the heteropolyacid or a salt thereof is a heteropolyacid or a salt thereof containing a phosphorus atom and at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium. Manufacturing method.   The said precursor compound contains the inorganic acid or its salt containing at least 1 type of metal atom selected from the group which consists of tungsten, manganese, molybdenum, and vanadium, and its phosphorus atom containing oxo acid or its salt. A method for producing the organic compound.   The method for producing an organic compound according to any one of claims 3 to 6, wherein the oxidation reaction is an epoxidation reaction of an olefin carbon-carbon double bond using hydrogen peroxide. A catalyst for an oxidation reaction of an organic compound in a two-phase reaction field between an organic solvent and water,
As a phase transfer catalyst, the following formula (1)

[In Formula (1), R < ¹ > shows a hydrogen atom or a C1-C5 alkyl group. A ¹ represents an alkylene group having 2 to 4 carbon atoms. a represents an integer of 0 to 36. When a is an integer of 2 or more, a plurality of A ¹ may be the same or different. b shows the integer of 1-18. X is the following formula (4)

Wherein ^{(4), R 2, R} 3, and R ⁴ are the same or different and indicate an alkyl group, or an alkenyl group having 2 to 18 carbon atoms having 1 to 18 carbon atoms. Y ⁻ represents an anion. ]
Or a group represented by the following formula (5)

Wherein (5), R ⁵ represents an alkyl group, or an alkenyl group having 2 to 6 carbon atoms having 1 to 6 carbon atoms. d shows the integer of 0-5. Y ⁻ represents an anion. ]
The group represented by these is shown. ]
And the following formula (2)

[In Formula (2), R < ⁶ > shows a hydrogen atom or a C1-C5 alkyl group. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms. A ² represents an alkylene group having 2 to 4 carbon atoms. c represents an integer of 1 to 24. When c is an integer of 2 or more, a plurality of A ² may be the same or different. ]
A catalyst for oxidation reaction, comprising an ionic vinyl ether copolymer having a structural unit represented by:

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