JP2002284785A - Method of production for hydroxy-4- oxatricyclo[4.3.1.13,8]undecan-5-one and its methacrylate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method effectively and industrially advantageously producing a hydroxy-4-oxatricyclo[4.3.1.1<3> ,<8> ]undecan-5-one and its methacrylate in a high yield. SOLUTION: This method of production for hydroxy-4- oxatricyclo[4.3.1.1<3> ,<8> ]undecan-5-one reacts a hydroxyadamantanone expressed by formula (1) (The hydroxyl group is bonding to the bridgehead position of the adamantane ring) with a peroxy aliphatic carboxylic acid to obtain the hydroxy-4-oxatricyclo [4.3.1.1<3> ,<8> ]undecan-5-one expressed by formula (2). (The hydroxyl group is bonding to the bridgehead position of the 4- oxatricyclo[4.3.1.1<3> ,<8> ]undecane ring).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to hydroxy-4-oxatricyclo [4.3. Useful as a raw material for functional polymers such as photosensitive resins and a raw material for pharmaceuticals, agricultural chemicals and other fine chemicals. 1.1 ^3,8 ] undecane-5-one and its (meth) acrylate.

[0002]

2. Description of the Related Art A method for producing hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one is described in Sbornik. Vysokeno. Sko
ly. Chem. -Technol. , Paliv (1
984), D49, 205-15, reports a method of reacting 5-hydroxy-2-adamantanone with equilibrium peracetic acid or equilibrium formic acid. However, the method using such an equilibrium peracid has problems that the hydroxyl group of the substrate is easily acetylated in the initial stage of the reaction, temperature control is difficult, and the reaction time is long. The production method was not always satisfactory. In addition, the hydroxy-4-oxatricyclo [4.3.1.1.
^[3,8 ] Undecane-5-one (meth) acrylic acid ester has not been industrially satisfactorily known.

[0003]

Accordingly, an object of the present invention is to provide hydroxy-4-oxatricyclo [4.3.1.
[ ^3,8 ] undecane-5-one and its (meth) acrylic acid ester in an industrially advantageous production method capable of efficiently producing the same in a high yield.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, when hydroxyadamantanones are reacted with a specific peracid, the corresponding hydroxy-4-oxatricyclone is obtained. [4.3.1.1 ^3,8 ]
The present inventors have found that undecane-5-one can be efficiently produced in a high yield, and have completed the present invention.

That is, the present invention provides the following formula (1)

Embedded image (The hydroxyl group described in the formula is bonded to the bridgehead position of the adamantane ring), and a hydroxyadamantanone is reacted with an aliphatic percarboxylic acid to obtain the following formula (2)

Embedded image (The hydroxyl group described in the formula is bonded to the bridgehead of the 4-oxatricyclo [4.3.1.1 ^3,8 ] undecane ring). 3.1.1 ^3,8 ] undecane-5-one is provided, and a method for producing hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-5-one is provided. I do.

The present invention also relates to hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one represented by the formula (2) obtained by the above method,
By reacting with (meth) acrylic acid or a reactive derivative thereof, the following formula (3)

Embedded image (In the formula, R represents a hydrogen atom or a methyl group. The (meth) acryloyloxy group described in the formula binds to the bridgehead of the 4-oxatricyclo [4.3.1.1 ^3,8 ] undecane ring. (Meth) acryloyloxy-4- represented by
Oxatricyclo [4.3.1.1 ^3,8 ] undecane-
(Meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] characterized by obtaining 5-one
A method for producing undecane-5-one is provided.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Production of hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one] In the present invention, the hydroxyadaman represented by the above formula (1) is used. Reacting the tanones with the aliphatic percarboxylic acid,
Hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one represented by the above formula (2) is produced.

The hydroxyl group described in the above formula (1) is bonded to the bridgehead of the adamantane ring. That is, the hydroxyadamantanones represented by the formula (1) are either of the following two formulas (1a) and (1b).

Embedded image

The aliphatic percarboxylic acids include, for example, formic acid, peracetic acid, trifluoroperacetic acid, perpropionic acid and the like. Here, aliphatic percarboxylic acids have the meaning of excluding equilibrium peracids. The amount of the aliphatic percarboxylic acid to be used is, for example, about 0.8 to 2 mol, preferably about 0.9 to 1.5 mol, more preferably about 0.1 to 1 mol, per 1 mol of the hydroxyadamantanone used in the reaction. 95-
It is about 1.2 mol.

[0010] The reaction is carried out in the presence or absence of a solvent. Examples of the solvent include alcohols such as t-butyl alcohol; chloroform, dichloromethane,
Halogenated hydrocarbons such as 1,2-dichloroethane; aromatic hydrocarbons such as benzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; N, N-dimethylformamide; N
Amides such as dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; linear or cyclic ethers such as ethyl ether and tetrahydrofuran; esters such as ethyl acetate; and organic acids such as acetic acid. These solvents may be used alone or as a mixture of two or more.

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, the above-mentioned formula (1a) or (1
From the hydroxyadamantanones represented by b), hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane represented by the following formula (2a), (2b) or (2c) 5-one is produced.

Embedded image

The hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one produced by the reaction is, for example, filtered, concentrated, distilled, extracted, crystallized, recrystallized,
Separation and purification can be performed by separation means such as column chromatography, or a combination thereof.

[(Meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5
Production of on] (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one is obtained by preparing hydroxy-4-oxatricyclo [4 3.3.1.1 ^3,8 ] undecane-5
It can be obtained by reacting ON with (meth) acrylic acid or a reactive derivative thereof.

More specifically, for example, (1) hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one may be added with triethylamine, if necessary,
In the presence of a base such as pyridine, an active reactive derivative of (meth) acrylic acid such as (meth) acrylic halide or (meth) acrylic anhydride such as (meth) acrylic chloride or (2) ) Hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one is reacted with a (meth) acrylate such as methyl (meth) acrylate in the presence of a transesterification catalyst Let me
(3) Hydroxy-4-oxatricyclo [4.3.
1.1 ^3,8 ] undecane-5-one in the presence of a strong acid with (meth) acrylic acid to give (meth)
Acryloyloxy-4-oxatricyclo [4.3.
1.1 ^3,8 ] undecane-5-one. 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.

Of the above methods, the methods (1) and (3) are preferable in terms of yield, operability, and the like. In the method (1), the active reactive derivative of (meth) acrylic acid is used in an amount of hydroxy-4-oxatricyclo [4.3.
1.1 ^3,8 ] undecane-5-one can be suitably selected, for example, in the range of about 1 to 10 mol per 1 mol. Examples of the base used in this method include, for example, hydroxides, carbonates, bicarbonates, and alkaline earth metals (eg, magnesium,
Inorganic bases such as hydroxides and carbonates of calcium and the like);
Organic bases such as triethylamine and pyridine are exemplified. Preferably, an organic base such as triethylamine is used. The amount of the base used is, for example, 0 to 10 mol, preferably 1 mol, per 1 mol of hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one.
About 2 mol.

In the method (3), the amount of (meth) acrylic acid used is based on 1 mol of hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one. For example, it can be appropriately selected within a range of about 1 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; sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and t-toluenesulfonic acid; Strong acid ion exchange resins and the like can be mentioned. The amount of the strong acid used is hydroxy-4-oxatricyclo [4.3.
1.1 ^3,8 ] undecane-5-one 100 parts by weight, for example, 0.1 to 15 parts by weight, preferably about 1 to 12 parts by weight. 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.

By the above reaction, the above formulas (2a) and (2
From hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one represented by b) or (2c), by the following formula (3a), (3b) or (3c) The (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one represented is produced.

Embedded image (Wherein, R represents a hydrogen atom or a methyl group)

The (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one produced by the reaction is, for example, filtered, concentrated, distilled, extracted, crystallized, Separation and purification can be performed by separation means such as recrystallization, column chromatography, or a combination thereof.

The (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one thus obtained is used as a raw material for a functional material such as a photosensitive resin, a medicine, It can be used as a raw material for fine chemicals such as pesticides.

[0021]

According to the method of the present invention, hydroxy-4
-Oxatricyclo [4.3.1.1] ^3,8] Undecane
-5-one and its (meth) acrylate
It can be produced efficiently with a high yield. Also equilibrated as a reaction reagent
Since aliphatic percarboxylic acids are used instead of peracids, acetyl
Is difficult to form, and the reaction can be easily controlled.
In both cases, the reaction time can be reduced. Therefore, the method of the present invention
Is extremely useful as an industrial production method.

[0022]

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.

Example 1 5-A flask equipped with a dropping funnel, a condenser and a stirrer was used.
20 g (120 mmol) of hydroxy-2-adamantanone and 200 mL of ethyl acetate were added, and 50 g was stirred.
The temperature was raised to 50 ° C, and a solution of 9.3 g (120 mmol) of 30 wt% peracetic acid in ethyl acetate (21.7 g) was added dropwise from the dropping funnel over 30 minutes while controlling the internal temperature to 50 to 60 ° C. Thereafter, stirring was continued at 50 ° C. for 3 hours. The reaction mixture was analyzed by gas chromatography to find that the desired 1-hydroxy-4-oxatricyclo [4.3.
1.1 ^3,8 ] undecane-5-one was produced in an amount of 21 g (116 mmol). The yield was 97%. The obtained reaction solution was concentrated, and the mixture was stirred under ice-cooling to be cooled and crystallized. Then, n-hexane was further added and aged for 30 minutes. The obtained slurry solution is filtered, and the filtrate is then filtered with n
After rinsing with -hexane and drying under reduced pressure,
1-hydroxy-4-oxatricyclo [4.3.1.
[ ^1,3,8 ] undecane-5-one was obtained as a white solid (19.3 g, 106 mmol). The isolation yield was 88%.

Example 2 1-Hydroxy-4-oxatricyclo obtained by the method of Example 1 was placed in a 1 L round bottom flask equipped with a stirrer, a thermometer, a condenser, and a dean-stark device. 1.
[ ^3,8 ] undecane-5-one 50 g (274.39 mmol), methacrylic acid 118.10 g (1371.9)
7 mmol), hydroquinone monomethyl ether 0.
5 g (4.03 mmol) and 400 g of toluene were added,
Stir at room temperature. While circulating air at 400 mL / min, 2.69 g (27.44 mmol) of sulfuric acid was added, and the mixture was stirred under reflux for 20 hours and cooled to room temperature. 400 mL of a 10% by weight aqueous solution of sodium carbonate is added to the reaction mixture.
And washed with 400 mL of a 10% by weight saline solution.
After washing twice, the mixture was concentrated at 50 ° C. until the reaction mixture became 125 g. The mixture was stirred under ice-cooling to be cooled and crystallized, and then 75 g of diisopropyl ether was added dropwise and aged for 30 minutes. The resulting slurry solution was filtered, rinsed with diisopropyl ether, and dried under reduced pressure, to give 1-methacryloyloxy-4-oxatricyclo [4.3.
1.1 ^3,8 ] undecane-5-one in 43.60 g (1
74.19 mmol) obtained as a white solid. The yield was 63.5%.

Example 3 In a 2000 mL round bottom flask equipped with a stirrer and a thermometer,
100 g (548.7 mmol) of 1-hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one obtained by the method of Example 1 and 83.3 g of triethylamine (823. 1 mmol), hydroquinone monomethyl ether 0.1 g, tetrahydrofuran (TH
F) 600 g was added, and the mixture was stirred at room temperature under a nitrogen atmosphere.
74.5 g of acrylic acid chloride (82
(3.1 mmol) and 240 g of THF were added dropwise at room temperature over 1 hour. After stirring at room temperature for 30 hours,
The reaction was stopped by adding 840 g of pure water to obtain a uniform solution. This was concentrated under reduced pressure to remove THF, and the pH was adjusted to about 10 by adding a 10% by weight aqueous sodium carbonate solution. Extraction was performed twice using the same amount of ethyl acetate as this aqueous solution to obtain a target product in ethyl acetate. This was concentrated under reduced pressure to remove ethyl acetate, and then purified by column chromatography (n-hexane / ethyl acetate = 2/1) to give 1-acryloyloxy-4 as a white solid.
- give the oxatricyclo [4.3.1.1 ^{3, 8]} undecane-5-one 106.2 g (449.4 mmol). The yield was 81.9%.

Claims (2)

[Claims] [Claim 1] The following formula (1) (The hydroxyl group described in the formula is bonded to the bridgehead position of the adamantane ring), and a hydroxyadamantanone is reacted with an aliphatic percarboxylic acid to give the following formula (2): (The hydroxyl group described in the formula is bonded to the bridgehead of the 4-oxatricyclo [4.3.1.1 ^3,8 ] undecane ring). 3.1.1 ^3,8 ] undecane-5-one; a process for producing hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one. 2. The method according to claim 1, wherein the hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one represented by the formula (2) is By reacting with (meth) acrylic acid or a reactive derivative thereof, the following formula (3) is obtained. (In the formula, R represents a hydrogen atom or a methyl group. The (meth) acryloyloxy group described in the formula binds to the bridgehead of the 4-oxatricyclo [4.3.1.1 ^3,8 ] undecane ring. (Meth) acryloyloxy-4- represented by
Oxatricyclo [4.3.1.1 ^3,8 ] undecane-
(Meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] characterized by obtaining 5-one
A method for producing undecane-5-one.