JP2002193961A - Method for producing 5-hydroxy-2,6- norbornanecarbolactone and (meth)acrylic ester or the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing 5-hydroxy-2,6- norbornanecarbolactone and (meth)acrylic ester of the same in high yield and efficiently. SOLUTION: As to a method for producing 5-hydroxy-2,6- norbornanecarbolactone, 5-hydroxy-2,6-norbornanecarbolactone represented by formula (1) is obtained by reacting 5-norbornene-2-carboxylic acid or its ester having a ratio of endo-body of more than 70 mol% (i) with hydrogen peroxide in the presence of a metallic compound having a metal element selected from a group of W, Mo, V and Mn, (ii) with hydrogen peroxide having the metal element or (iii) with an organic peracid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to 5-hydroxy-2,6-norbornane carboractone and 5-hydroxy-2,6-norbornane carboractone which are useful as raw materials for functional polymers such as photosensitive resins, raw materials for pharmaceuticals, agricultural chemicals and other fine chemicals. The present invention relates to a method for producing the (meth) acrylic ester.

[0002]

2. Description of the Related Art As a method for producing 5-hydroxy-2,6-norbornane carboractone, Journal of Molecular Catalysis A: Chemical (Journal of
Molecular Catalysis A: Chemical) 142 (1999) 333-3
38 proposes a method of reacting 5-norbornene-2-carboxylic acid with hydrogen peroxide in the presence of methyltrioxorhenium. However, this method is not industrially advantageous because it uses expensive and toxic rhenium. Also, there is no known industrially satisfactory method for producing the (meth) acrylic acid ester of 5-hydroxy-2,6-norbornanecarboractone.

[0003]

Accordingly, an object of the present invention is to provide an industrially advantageous method for efficiently producing 5-hydroxy-2,6-norbornanecarboractone and its (meth) acrylate in high yield. It is to provide a manufacturing method.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have determined that the ratio of a specific stereoisomer is within a specific range. The present inventors have found that, when an ester is reacted with a specific peroxide, the corresponding 5-hydroxy-2,6-norbornanecarboractone can be efficiently produced in a high yield, and the present invention has been completed.

That is, according to the present invention, the ratio of the end body is 7
0-mol% or more of 5-norbornene-2-carboxylic acid or its ester is reacted with hydrogen peroxide in the presence of a metal compound containing a metal element selected from (i) W, Mo, V and Mn. , (Ii) reacting with a peroxide containing the metal element, or (iii) reacting with an organic peracid to obtain the following formula (1)

Embedded image The present invention provides a method for producing 5-hydroxy-2,6-norbornane carboractone, which obtains 5-hydroxy-2,6-norbornane carboractone represented by the formula:

In this production method, the reaction product is subjected to an extraction operation using an alkaline water and an organic solvent, and the reaction product is extracted from the organic solvent layer by 5 times.
The method may include a step of recovering -hydroxy-2,6-norbornane carboractone. The reaction product was subjected to a crystallization operation using a solvent containing an aliphatic hydrocarbon,
The method may include a step of recovering -hydroxy-2,6-norbornane carboractone as a crystal.

The present invention also provides a method of reacting 5-hydroxy-2,6-norbornanecarboractone obtained by the above method with (meth) acrylic acid or a reactive derivative thereof to obtain the following formula (2)

Embedded image (R represents a hydrogen atom or a methyl group)
5- (meth) acryloyloxy- to give (meth) acryloyloxy-2,6-norbornanecarboractone
Provided is a method for producing 2,6-norbornane carboractone.

[0008] In this specification, the term "peroxide" is used in a broad sense, and in a narrow sense, includes peroxide, hydroperoxide, peroxoacid or a salt thereof, peracid or a salt thereof, and the like.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Reaction raw material] 5-norbornene
2-Carboxylic acid is represented by the following formula (3), and there are endo- and exo-isomers as stereoisomers depending on the steric positional relationship of the carboxyl group.

Embedded image In the present invention, 5-norbornene-2-carboxylic acid or an ester thereof having a ratio of an end body of 70 mol% or more is used as a reaction raw material. If the ratio of the endo form is less than 70 mol%, the yield of the target compound, 5-hydroxy-2,6-norbornane carboractone (δ-hydroxynorbornane lactone), will be significantly reduced. In addition, since the thing with an extremely high ratio of an end body requires purification and the like,
From an industrial point of view, the ratio of the end body is preferably 70 to 90 mol%, particularly preferably about 75 to 85%.

Examples of esters of 5-norbornene-2-carboxylic acid include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester,
Alkyl esters such as t-butyl ester (e.g., C
_1-4 alkyl esters); aryl ester such as phenyl ester; cycloalkyl esters such as cyclohexyl esters and aralkyl esters such as benzyl esters, but not limited thereto.

[Reaction Reagent] In the present invention, the above-mentioned 5-norbornene-2-carboxylic acid or an ester thereof is reacted with (i)
Reacting with hydrogen peroxide in the presence of a metal compound containing a metal element selected from W, Mo, V and Mn, or (ii)
Reacting with a peroxide containing the metal element, or (ii)
i) React with organic peracid.

As the metal compound in the above (i),
The compound is not particularly limited as long as it is a compound containing a metal element selected from W, Mo, V and Mn. For example, oxides, oxo acids or salts thereof containing the metal element, sulfides, halides, oxyhalides, Examples include boride, carbide, silicide, nitride, phosphide, peroxide, complex (inorganic complex and organic complex), and organometallic compound. These metal compounds can be used alone or in combination of two or more.

Examples of the oxide include tungsten oxide (WO ₂ , WO ₃ etc.), molybdenum oxide (MoO
₂ , MoO _3, etc.), vanadium oxide (VO, V ₂ O ₃ , V
O ₂ , V ₂ O _5, etc.), manganese oxide (MnO, Mn)
₂ O ₃ , Mn ₃ O ₄ , MnO ₂ , Mn ₂ O ₇ ), a composite oxide containing the metal, and the like.

The oxo acids include tungstic acid, molybdic acid, vanadic acid, manganic acid, etc., isopolyacids such as isopolytungstic acid, isopolymolybdic acid, isopolyvanadate; phosphotungstic acid, silicotungstic acid, Phosphomolybdenum sun, silico molybdic acid,
Heteropoly acids composed of the above-mentioned metal element such as limbanadomolybdic acid and other metal elements are included. As the other metal element in the heteropoly acid, phosphorus or silicon, particularly phosphorus is preferable.

Examples of the oxo acid salt include alkali metal salts such as the above-mentioned oxo acid sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; ammonium salt; transition metal salt and the like. Can be The salt of an oxo acid (for example, a salt of a heteropoly acid) may be a salt in which a part of a hydrogen atom corresponding to a cation is substituted with another cation.

Examples of the peroxide include peroxides, hydroperoxides, peroxo acids (eg, peroxotungstic acid, peroxomolybdate, peroxovanadate, etc.), and salts of peroxo acids (the alkali metal salts of the above peroxo acids, alkaline earth metal salts). Salts, ammonium salts, transition metal salts, etc.), peracids (permanganates, etc.), peracid salts (alkali metal salts, alkaline earth metal salts, ammonium salts, transition metal salts, etc. of the above peracids) and the like. Can be

The amount of the metal compound used is, for example, about 0.0001 to 2 mol, preferably 0.0005 to 0.5 mol per mol of 5-norbornene-2-carboxylic acid or its ester used in the reaction. It is about mol, more preferably about 0.001 to 0.2 mol.

In the above (i), as the hydrogen peroxide, pure hydrogen peroxide may be used, but from the viewpoint of handleability, it is usually diluted with an appropriate solvent, for example, water (for example, 30 weight%). % Hydrogen peroxide solution).

The amount of hydrogen peroxide used depends on the amount of 5-
For example, about 0.9 to 5 mol, preferably 0.1 mol, per 1 mol of norbornene-2-carboxylic acid or its ester.
It is about 9 to 3 mol, more preferably about 0.95 to 2 mol.

It is assumed that the active species in the case (i) is a peroxide or a peroxy radical containing the metal.

As the peroxide in the above (ii), those similar to the above-mentioned peroxides can be used. The peroxides can be used alone or in combination of two or more. The amount of peroxide used is, for example, 5-norbornene-2 used in the reaction.
-0.8 mol / mol of carboxylic acid or ester thereof
About 2 mol, preferably about 0.9 to 1.5 mol, and more preferably about 0.95 to 1.2 mol.

The organic peracid in the above (iii) includes:
Formic acid, peracetic acid, m-chloroperbenzoic acid and the like. The organic peracid may be an equilibrated peracid (eg, equilibrated formic acid, equilibrated peracetic acid, etc.). That is, for example, an organic acid such as formic acid or acetic acid may be used in combination with hydrogen peroxide to generate a corresponding organic peracid in the system. When using an equilibrium peracid, a small amount of a strong acid such as sulfuric acid may be added as a catalyst.

The amount of the organic peracid used is, for example, about 0.8 to 2 mol, preferably 0.1 mol, per 1 mol of 5-norbornene-2-carboxylic acid or its ester used in the reaction.
About 9 to 1.5 mol, more preferably 0.95 to 1.
It is about 2 mol.

Among the above (i) to (iii), the reaction is highly selective, an organic acid which is liable to cause side reactions and complicated purification steps is not produced as a by-product, and the reaction is carried out in a heterogeneous system. From the point that the removal of the reaction reagent can be simplified by
The method (i) is particularly preferred.

[Reaction] The reaction is carried out in the presence or absence of a solvent. Examples of the solvent include alcohols such as t-butyl alcohol; halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane; aromatic hydrocarbons such as benzene; aliphatic hydrocarbons such as hexane, heptane and octane. An alicyclic hydrocarbon such as cyclohexane; N, N-dimethylformamide;
Amides such as N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; linear or cyclic ethers such as ethyl ether and tetrahydrofuran; esters such as ethyl acetate; organic acids such as acetic acid; Can be These solvents may be used alone or as a mixture of two or more. When the reaction is performed in a heterogeneous system, water or a solvent containing water is often used as the solvent.

The reaction temperature can be appropriately selected in consideration of the reaction rate and the reaction selectivity.
Preferably it is about 10 to 60 ° C. The reaction is batch type,
It may be performed by any method such as a semi-batch type and a continuous type.

By the above reaction, 5-hydroxy-2,6
The formation of norbornane calboractone; In this reaction, first, epoxidation of the double bond of 5-norbornene-2-carboxylic acid or an ester thereof occurs, and subsequently, an intramolecular cyclization reaction accompanied by ring opening of the epoxy ring proceeds, and the desired 5-hydroxy- It is assumed that 2,6-norbornane carboractone is produced. Further, at this time, if a raw material having a high content of exo-form 5-norbornene-2-carboxylic acid or an ester thereof is used, the cyclization reaction does not proceed,
It is presumed that the yield of the desired 5-hydroxy-2,6-norbornanecarboractone is greatly reduced.

When an ester of 5-norbornene-2-carboxylic acid is used as a substrate, an alcohol corresponding to the ester is by-produced. 5-Hydroxy-2,6-norbornanecarboractone produced by the reaction is separated and purified, for example, by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. it can.

In a preferred separation and purification method, the reaction product is subjected to an extraction operation using alkaline water and an organic solvent to recover 5-hydroxy-2,6-norbornane carboractone from the organic solvent layer and / or A step of subjecting the product to a crystallization operation using a solvent containing an aliphatic hydrocarbon to recover 5-hydroxy-2,6-norbornanecarboractone as crystals.

Examples of the alkaline water used in the extraction operation include an aqueous solution of an alkali metal hydroxide such as an aqueous solution of sodium hydroxide, an aqueous solution of an alkali metal carbonate such as an aqueous solution of sodium carbonate, and an aqueous solution of an alkali metal bicarbonate such as an aqueous solution of sodium hydrogen carbonate. And the like. The alkali concentration in the alkaline water varies depending on the type of the alkali, but is generally about 0.5 to 40% by weight, preferably 1 to 40% by weight.
It is about 15% by weight.

Organic solvents used in the extraction operation include aromatic hydrocarbons such as toluene; alicyclic hydrocarbons such as cyclohexane; ethers such as diethyl ether and diisopropyl ether; halogenated hydrocarbons such as methylene chloride; ethyl acetate. And the like; and mixed solvents thereof. Preferred organic solvents include esters such as ethyl acetate.

By an extraction operation using alkaline water and an organic solvent, by-products containing a carboxyl group such as unreacted exo-form 5-norbornene-2-carboxylic acid and epoxidized derivatives thereof are efficiently removed. be able to.

The aliphatic hydrocarbon used as a crystallization solvent in the crystallization operation includes, for example, pentane, hexane,
Examples thereof include linear or branched aliphatic hydrocarbons such as isohexane, heptane, octane, isooctane, decane, and dodecane. As the crystallization solvent, only the aliphatic hydrocarbon may be used, or the aliphatic hydrocarbon may be used in combination with the solvent exemplified as the organic solvent used in the extraction operation.

By this crystallization operation, high-purity 5-hydroxy-2,6-norbornanecarboractone can be obtained as crystals.

[5- (meth) acryloyloxy-2,
Production of 6-norbornane carboractone] 5- (meta)
Acryloyloxy-2,6-norbornane carboractone [δ- (meth) acryloyloxynorbornane lactone] is obtained by mixing 5-hydroxy-2,6-norbornane carboractone obtained by the above-mentioned method with (meth) acrylic acid or the same. It can be obtained by reacting with a reactive derivative.

More specifically, for example, (1) 5-hydroxy-2,6-norbornane carboractone may be added to a (meth) acrylic acid chloride or the like in the presence of a base such as triethylamine or pyridine if necessary. (Meth) such as (meth) acrylic halide and (meth) acrylic anhydride
Reacting active reactive derivatives of acrylic acid,
(2) 5-hydroxy-2,6-norbornanecarboractone is reacted with a (meth) acrylate such as methyl (meth) acrylate in the presence of a transesterification catalyst, or (3) 5-hydroxy-2 By reacting 2,6-norbornane carboractone with (meth) acrylic acid in the presence of a strong acid, 5- (meth) acryloyloxy-2,6-norbornane carboractone can be produced. The reaction conditions in these methods are the same as in the ordinary ester production method. At the time of the reaction, a polymerization inhibitor such as hydroquinone monomethyl ether or oxygen may be introduced in order to suppress the polymerization.

Among the above methods, the method (3) is preferable in terms of yield, operability and the like. In this method, the amount of (meth) acrylic acid used is 5-hydroxy-2,6-
For example, 1 mole per 1 mole of norbornane carboractone
It can be appropriately selected in the range of about 10 to 10 mol. Examples of the strong acid used in this method include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; methanesulfonic acid, ethanesulfonic acid,
Trifluoromethanesulfonic acid, benzenesulfonic acid,
Sulfonic acids such as t-toluenesulfonic acid; strongly acidic ion exchange resins. The amount of the strong acid to be used is, for example, about 0.1 to 15 parts by weight, preferably about 1 to 12 parts by weight, based on 100 parts by weight of 5-hydroxy-2,6-norbornane carboractone. In the method (3), in order to increase the reaction rate, it is preferable to advance the reaction while distilling off by-product water by azeotropic distillation or the like. As the azeotropic solvent, for example, toluene or the like can be used.

The 5- (meth) acryloyloxy-2,6-norbornanecarboractone produced by the reaction is separated, for example, by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography or other separation means, or Separation and purification can be performed by combining these. As a crystallization solvent used for crystallization, for example, a solvent containing at least a chain ether such as isopropyl ether is preferable.

The thus obtained 5- (meth) acryloyloxy-2,6-norbornane carboractone can be used as a raw material for a functional material such as a photosensitive resin or a raw material for a fine chemical such as a medicine or an agricultural chemical.

[0040]

According to the method of the present invention, 5-hydroxy-2,6-norbornanecarboractone and its (meth) acrylate can be efficiently produced in high yield. Therefore, the method of the present invention is extremely useful as an industrial production method.

[0041]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. The ratio between the endo form and the exo form of 5-norbornene-2-carboxylic acid was determined by gas chromatography.

Example 1 A flask equipped with a dropping funnel and a stirrer was charged with 200 g of 5-norbornene-2-carboxylic acid (purity: 98.5%, of which 82% was an endo-form and 18% exo-form).
(1.45 mol), 27 g of tungstic acid, 633 g of water
And raise the temperature to 50 ° C. while stirring.
While controlling the temperature at 60 ° C., 173 g (1.52 mol) of a 30% by weight aqueous hydrogen peroxide solution was dropped from the dropping funnel over 2 hours. Thereafter, stirring was continued at 50 to 55 ° C for 5 hours. The reaction solution was cooled to room temperature, and 10% by weight of sodium sulfite (Na
After adding 500 g of a ₂ SO ₃ ) aqueous solution, 870 ml of water was distilled off using a rotary evaporator, and then the concentrated solution was neutralized with a 10% by weight aqueous sodium carbonate solution. The neutralized solution was extracted twice with 1300 g of ethyl acetate, the ethyl acetate layers were combined, concentrated using a rotary evaporator, and mixed with 150 ml of n-hexane. The precipitated crystals were filtered and then dried to obtain 143 g (0.93 mol) of 5-hydroxy-2,6-norbornane carboractone.
Obtained. The yield of 5-hydroxy-2,6-norbornanecarboractone is 64.1% based on 5-norbornene-2-carboxylic acid, and the yield of 5-norbornene-endo-form is as follows.
It was 78.2% based on 2-carboxylic acid.

Example 2 A flask equipped with a dropping funnel and a stirrer was charged with 200 g of 5-norbornene-2-carboxylic acid (purity: 98.5%, of which 82% of endo-form and 18% of exo-form).
(1.45 mol), 860 g of acetic acid and 7 g of sulfuric acid were added, the temperature was raised to 50 ° C. while stirring, and 30 wt.
73 g (1.52 mol) were added dropwise over 2 hours. Thereafter, stirring was continued at 50 to 55 ° C for 5 hours. The reaction solution was cooled to room temperature, and neutralized by adding 153 g of a 30% by weight aqueous sodium hydroxide solution. The solution after neutralization is diluted with 550 g of ethyl acetate.
The mixture was extracted twice, 500 g of a 10% by weight aqueous sodium sulfite solution was added to the ethyl acetate layer, and the mixture was stirred and separated. The organic layer was neutralized by adding 460 g of a 10% by weight aqueous sodium carbonate solution, and separated. The aqueous layer was extracted with 990 g of ethyl acetate. The ethyl acetate layer was mixed with the ethyl acetate layer obtained by extracting the above neutralized solution, and concentrated using a rotary evaporator. 150 ml of n-hexane was added to the concentrate and mixed.
The precipitated crystals were filtered and dried to obtain 5-hydroxy-2,6-norbornane carboractone.
g (0.84 mol). The yield of 5-hydroxy-2,6-norbornanecarboractone is 58.3% based on 5-norbornene-2-carboxylic acid, and 71.1% based on 5-norbornene-2-carboxylic acid in an endo form.
Met.

Comparative Example 1 The same operation as in Example 1 was performed, except that 5-norbornene-2-carboxylic acid having an endo-form ratio of 60% and an exo-form ratio of 40% was used as a raw material. as a result,
5-methacryloyloxy-2,6 obtained as crystals
The amount of norbornane calboractone is 100 g (0.6 g);
5 mol), and the yield was 45%.

Example 3 The 5-hydroxy-2,6-norbornane obtained by the method of Example 1 was placed in a distillation can at the bottom of a 10-stage perforated plate batch distillation column equipped with a condenser and a decanter at the top. 100 g (0.65 mol) of carboractone, 140 g of methacrylic acid
(1.63 mol), 0.9 g of hydroquinone monomethyl ether, 6 g of sulfuric acid and 400 g of toluene were charged and 5%
The reaction was carried out while circulating a nitrogen gas containing oxygen at a flow rate of 40 ml / min and distilling off by-produced water. The distillation was terminated when about 11 ml of water was distilled off from the decanter at the top of the column.
The liquid in the distillation can was cooled to room temperature, and 250 g of toluene was added. After washing this mixture with 1000 ml of water, 10% by weight
1000 ml of aqueous sodium carbonate solution, 10% by weight saline 10
Washed sequentially with 00 ml and 1000 ml of water. After washing, the toluene layer was concentrated using a rotary evaporator, and isopropyl ether was added to precipitate crystals. After filtering the crystals, the crystals were rinsed with 30 ml of isopropyl ether and dried to obtain 98.2 g (0.44 mol) of 5-methacryloyloxy-2,6-norbornanecarboractone. The yield was 67%.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shinya Nagano 610-1-3-2 F-term (reference) 4C037 AA02 4H039 CA42 CA60 CC50

Claims (4)

[Claims] 1. A method for preparing a metal compound containing a metal element containing a metal element selected from the group consisting of (i) W, Mo, V and Mn. Reacting with hydrogen peroxide in the presence, (ii) reacting with a peroxide containing the metal element, or (iii) reacting with an organic peracid to give the following formula (1): Wherein 5-hydroxy-2,6-norbornane carboractone represented by the formula:
A method for producing 2,6-norbornane carboractone. 2. The method according to claim 1, further comprising the step of subjecting the reaction product to an extraction operation using alkaline water and an organic solvent to recover 5-hydroxy-2,6-norbornane carboractone from the organic solvent layer. A method for producing hydroxy-2,6-norbornane carboractone. 3. The method according to claim 1, further comprising the step of subjecting the reaction product to a crystallization operation using a solvent containing an aliphatic hydrocarbon to recover 5-hydroxy-2,6-norbornanecarboractone as crystals. For producing 5-hydroxy-2,6-norbornane carboractone. 4. A method of reacting 5-hydroxy-2,6-norbornane carboractone obtained by the method according to claim 1 with (meth) acrylic acid or a reactive derivative thereof. And the following formula (2) (R represents a hydrogen atom or a methyl group)
A method for producing 5- (meth) acryloyloxy-2,6-norbornane carboractone, wherein (meth) acryloyloxy-2,6-norbornane carboractone is obtained.