JP2003261506A - Method for producing (meth)acryloyloxybenzophenones - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a (meth)acryloyloxybenzophenone on an industrial scale without problems of corrosion even by using a usual reaction apparatus. <P>SOLUTION: A hydroxybenzophenone represented by formula (1) (R<SP>1</SP>and R<SP>2</SP>are each independently a hydrogen atom, a halogen atom, an amino group, a nitro group, a 1-10C alkyl group or a 1-10C alkoxy group) is reacted with (meth)acrylic acid anhydride in the presence of a basic substance to produce a (meth)acryloyloxybenzophenone represented by formula (2) (R<SP>1</SP>and R<SP>2</SP>are each independently a hydrogen atom, a halogen atom, an amino group, a nitro group, a 1-10C alkyl group or a 1-10C alkoxy group; R<SP>3</SP>is a hydrogen atom or a methyl group). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing (meth) acryloyloxybenzophenones.

[0002]

2. Description of the Related Art (Meth) acryloyloxybenzophenones such as 4- (meth) acryloyloxybenzophenone are useful substances as raw material monomers for polymers. For example, in Japanese Unexamined Patent Publication No. 2-273751, 4-
An example of using (meth) acryloyloxybenzophenone as a composition of a photosensitive recording element is described in J. Appl. Po
lym. Sci. , 51 (13) , 2139 (199 )
In 4), an example of use of acrylonitrile for photopolymerization is reported. Also, J. Appl. Polym. Sc
i. , 57 (8) , 997 (1995), it is reported that graft polymerization can be carried out by using it for the polymerization of styrene and the like. Also, European Patent No. 1026
No. 182 (1990), it is also reported as a raw material for hydrophilic polymers for contact lenses.

4- (meth) acryloyloxybenzophenone is generally produced by esterifying 4-hydroxybenzophenone with (meth) acrylic acid chloride. For example, a method of reacting in the presence of pyridine in a chloroform solvent (J. Appl. Polym. Sci., 51 (1
3) , 2139 (1994)), a method of reacting in anhydrous acetone in the presence of triethylamine (J. Appl. Polym. Sci., 57 .
(8) , 997 (1995)), a method of reacting with pyridine as a solvent (US Pat. No. 4,683,241 (1984)) and the like are known.

However, in any of the methods, since (meth) acrylic acid chloride, which is highly corrosive, is used as a raw material, a special apparatus having corrosion resistance is required for industrial scale production. A method for producing (meth) acryloyloxybenzophenones using a general stainless steel or iron reaction device without using a raw material that causes corrosion problems such as (meth) acrylic acid chloride is desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method capable of producing (meth) acryloyloxybenzophenones on an industrial scale without causing a problem of corrosion even if a general reactor is used. .

[0006]

The above problems of the present invention can be solved by the following present invention. A hydroxybenzophenone represented by the following formula (1) and a (meth) acrylic anhydride are reacted in the presence of a basic substance to produce a (meth) acryloyloxybenzophenone represented by the following formula (2). Method.

[0007]

[Chemical 3]

(In the formula (1), R ¹ and R ² are independently a hydrogen atom, a halogen atom, an amino group, a nitro group, or a carbon number of 1 to 1.
The alkyl group of 0, or a C1-C10 alkoxy group is shown. )

[0009]

[Chemical 4]

(In the formula (2), R ¹ and R ² are independently a hydrogen atom, a halogen atom, an amino group, a nitro group, and a carbon number of 1 to 1.
The alkyl group of 0, or a C1-C10 alkoxy group is shown. R ³ represents a hydrogen atom or a methyl group. ) The method for producing a (meth) acryloyloxybenzophenone represented by the above formula (2), wherein the basic substance is at least one of triethylamine, pyridine and 2,6-dimethylaminopyridine. The amount of the basic substance used is 0.01 to 5 mol per 1 mol of the hydroxybenzophenone represented by the formula (1) or represented by the formula (2) (meta).
A method for producing acryloyloxybenzophenones. The amount of the (meth) acrylic anhydride used is represented by the formula (1)
The method for producing a (meth) acryloyloxybenzophenone represented by the formula (2), which is 1 to 5 mol per 1 mol of the hydroxybenzophenone represented by. After reacting the hydroxybenzophenones represented by the formula (1) with the (meth) acrylic anhydride in the presence of a basic substance, alcohol is added to the reaction solution to remove the remaining (meth) acrylic anhydride. The above having a step of decomposing ~
A method for producing a (meth) acryloyloxybenzophenone represented by any one of the formulas (2).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, hydroxybenzophenones represented by the above formula (1) (hereinafter simply referred to as hydroxybenzophenones) and (meth) acrylic anhydride are reacted in the presence of a basic substance. Then, the (meth) acryloyloxybenzophenones represented by the formula (2) (hereinafter, simply referred to as (meth) acryloyloxybenzophenones) are produced. This reaction proceeds under mild conditions, and (meth) acryloyloxybenzophenones can be obtained in the same high yield as the conventional method using (meth) acrylic acid chloride. Moreover, unlike the (meth) acrylic acid chloride that has been conventionally used, the raw material (meth) acrylic anhydride has low corrosiveness to stainless steel and iron, which are generally used as the material of the reaction vessel. Therefore, according to the present invention, (meth) acryloyloxybenzophenones can be produced on an industrial scale without causing a problem of corrosion even if a general reaction apparatus is used.

In the present invention, it is preferable that after reacting the hydroxybenzophenones with the (meth) acrylic anhydride in the presence of a basic substance, alcohol is added to the reaction solution. The (meth) acrylic anhydride remaining after the reaction can become a polymerizable impurity when mixed in the product.
After the reaction, an alcohol, preferably a lower aliphatic alcohol, is added to easily decompose the remaining (meth) acrylic anhydride to form a (meth) acrylic ester,
Can be removed.

The present invention will be described in detail below.

The hydroxybenzophenones used as a raw material are represented by the above formula (1). Specifically, 4-hydroxybenzophenone, 2-hydroxybenzophenone, 4-hydroxy-4'-nitrobenzophenone, 4-hydroxy-2'-nitrobenzophenone, 2-hydroxy-2'-nitrobenzophenone, 2
-Hydroxy-4-nitrobenzophenone, 4-hydroxy-2-nitrobenzophenone, 4-hydroxy-
4'-aminobenzophenone, 4-hydroxy-2'-
Aminobenzophenone, 2-hydroxy-2'-aminobenzophenone, 2-hydroxy-4-aminobenzophenone, 4-hydroxy-2-aminobenzophenone,
4-hydroxy-4'-chlorobenzophenone, 4-hydroxy-2'-chlorobenzophenone, 2-hydroxy-2'-chlorobenzophenone, 2-hydroxy-4
-Chlorobenzophenone, 4-hydroxy-2-chlorobenzophenone, 4-hydroxy-4'-methylbenzophenone, 4-hydroxy-2'-methylbenzophenone, 2-hydroxy-2'-methylbenzophenone, 2
-Hydroxy-4-methylbenzophenone, 4-hydroxy-2-methylbenzophenone, 4-hydroxy-
4'-methoxybenzophenone, 4-hydroxy-2 '
-Methoxybenzophenone, 2-hydroxy-2'-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-hydroxy-2-methoxybenzophenone and the like can be mentioned.

The (meth) acryloyloxybenzophenones produced are those represented by the above formula (2).
Specifically, 4- (meth) acryloyloxybenzophenone, 2- (meth) acryloyloxybenzophenone, 4- (meth) acryloyloxy-4′-nitrobenzophenone, 4- (meth) acryloyloxy-2 ′.
-Nitrobenzophenone, 2- (meth) acryloyloxy-2'-nitrobenzophenone, 2- (meth) acryloyloxy-4-nitrobenzophenone, 4- (meth) acryloyloxy-2-nitrobenzophenone,
4- (meth) acryloyloxy-4'-aminobenzophenone, 4- (meth) acryloyloxy-2'-aminobenzophenone, 2- (meth) acryloyloxy-2'-aminobenzophenone, 2- (meth) acryloyloxy- 4-aminobenzophenone, 4- (meth)
Acryloyloxy-2-aminobenzophenone, 4-
(Meth) acryloyloxy-4'-chlorobenzophenone, 4- (meth) acryloyloxy-2'-chlorobenzophenone, 2- (meth) acryloyloxy-
2'-chlorobenzophenone, 2- (meth) acryloyloxy-4-chlorobenzophenone, 4- (meth) acryloyloxy-2-chlorobenzophenone, 4-
(Meth) acryloyloxy-4′-methylbenzophenone, 4- (meth) acryloyloxy-2′-methylbenzophenone, 2- (meth) acryloyloxy-
2'-methylbenzophenone, 2- (meth) acryloyloxy-4-methylbenzophenone, 4- (meth) acryloyloxy-2-methylbenzophenone, 4-
(Meth) acryloyloxy-4′-methoxybenzophenone, 4- (meth) acryloyloxy-2′-methoxybenzophenone, 2- (meth) acryloyloxy-2′-methoxybenzophenone, 2- (meth) acryloyloxy-4- Methoxybenzophenone, 4- (meth) acryloyloxy-2-methoxybenzophenone and the like can be mentioned.

The amount of the (meth) acrylic acid anhydride used as a raw material is not particularly limited, but the hydroxybenzophenones as a raw material are expensive and it is economical to effectively use the hydroxybenzophenones. It is preferably 1 mol or more with respect to mol. Further, the amount of the (meth) acrylic anhydride used as a raw material is economically disadvantageous in a large excess, so 5 mol or less is preferable, and 1.5 mol or less is more preferable, relative to 1 mol of the hydroxybenzophenones. .

The basic substance used in the present invention is not particularly limited, and examples thereof include methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine,
Amines such as triethylamine, pyridine, and 2,6-dimethylaminopyridine, pyridines, basic ion exchange resins, and hydroxides of alkali metals or alkaline earth metals can be used. The basic substance may be used alone or in combination of two or more. As the basic substance, it is preferable to use amines and pyridines, particularly tertiary amines and pyridines, and among them, it is preferable to use at least one of triethylamine, pyridine, and 2,6-dimethylaminopyridine. When these are used as the basic substance, the raw material hydroxybenzophenones are uniformly dissolved, and the reaction proceeds well.

The amount of the basic substance used is not particularly limited, but in order to obtain a more sufficient reaction rate, it is preferably 0.01 mol or more, more preferably 0.1 mol or more, relative to 1 mol of the hydroxybenzophenones. . Further, the amount of the basic substance used is preferably 5 mol or less, more preferably 1.5 mol or less, relative to 1 mol of the hydroxybenzophenones, since a large excess thereof is economically disadvantageous.

The solvent used in the present invention is not particularly limited as long as it does not react with the (meth) acrylic anhydride, and general solvents such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, acetone, methyl ethyl ketone. , Methyl-i-butyl ketone, ethyl acetate, methyl (meth) acrylate, n-pentane, n-hexane, n-heptane, cyclohexane,
Toluene, o-xylene, m-xylene, p-xylene, N, N-dimethylformamide, dimethyl sulfoxide and the like can be used. As the solvent, one type may be used, or two or more types may be mixed and used. The amount of the solvent used may be appropriately determined, and in some cases, the reaction may be performed without using the solvent. The amount of the solvent used is usually 0.5 with respect to 1 mol of the hydroxybenzophenones.
L or more is preferable, and 2 L or less is preferable.

The reaction temperature is not particularly limited, but is preferably 0 ° C. or higher, more preferably 20 ° C. or higher. The reaction temperature is preferably 100 ° C or lower, more preferably 80 ° C or lower.

The order of addition of the raw materials is not particularly limited, but since many hydroxybenzophenones are solid, for example, the reaction solvent was first charged, the hydroxybenzophenones were suspended in the reaction solvent, and the basic substance was added. A method of adding (meth) acrylic anhydride (which may be a solution) later can be used.

After reacting the hydroxybenzophenones with the (meth) acrylic acid anhydride in the presence of a basic substance in this manner, the starting material (meth) acrylic acid anhydride may remain in the reaction solution to some extent. . In that case, it is preferable to add alcohol to the reaction liquid to decompose and remove the remaining (meth) acrylic anhydride.

The alcohol to be added is not particularly limited, but a lower aliphatic alcohol is preferable from the viewpoint of cost. Examples of the lower aliphatic alcohols include methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol and tert.
-Butanol and the like. Among them, it is preferable to use methanol and / or ethanol. The alcohols may be used alone or in combination of two or more.

The amount of the alcohol used is not particularly limited, but if the (meth) acrylic anhydride remains, it becomes a polymerizable impurity. Therefore, in order to reduce this as much as possible, 1 mol of the remaining (meth) acrylic anhydride is used. On the other hand, it is preferably 1 mol or more. Further, the amount of alcohol used is preferably 5 mol or less with respect to 1 mol of the remaining (meth) acrylic acid anhydride, since it is economically disadvantageous if a large excess is used.

The reaction solution containing alcohol is usually 0
By maintaining the temperature at about 100 to 100 ° C for about 0.5 to 12 hours, the remaining (meth) acrylic anhydride can be decomposed and removed.

The reaction solution thus obtained is washed with water or the like and concentrated to obtain (meth) acryloyloxybenzophenones. And usually obtained (meta)
Acryloyloxybenzophenones are purified, for example, by recrystallization or distillation using a suitable solvent (a mixed system of diisopropyl ether and n-hexane, ethanol alone, or a mixed system of ethyl acetate, ethanol and water).

[0027]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.

In the examples, the analysis was carried out by gas chromatography (hereinafter referred to as GC).

The purity of the product was calculated from the peak area of GC by the following formula.

Purity (%) = (A / B) × 100 Here, A represents the peak area of (meth) acryloyloxybenzophenones which are the target products, and B represents the total area of all peaks other than the diluent solvent. .

All product yields were calculated on the starting hydroxybenzophenone bases.

The content of (meth) acrylic anhydride in the (meth) acryloyloxybenzophenones was calculated from the peak area of GC by the following formula.

Content of (meth) acrylic anhydride (%) =
{C / (C + D)} × 100 where C is the peak area of (meth) acrylic anhydride,
D represents the peak area of the (meth) acryloyloxybenzophenones which are the target products. In addition, when the reaction liquid was analyzed, the (meth) acrylic acid anhydride content was obtained in the same manner.

Example 1 Stirrer, two equal pressure dropping funnels,
SUS 500 equipped with thermometer and calcium chloride drying tube
In a mL separable flask, 218.0 g (1.10 mol) of 4-hydroxybenzophenone and 1 L of toluene were charged. Then, 122.4 g (1.21 mol) of triethylamine was charged into one dropping funnel, and a toluene solution 3 of 55 mass% methacrylic acid anhydride was charged into the other dropping funnel.
39.4 g (methacrylic anhydride 1.21 mol) was charged.

While stirring the suspension of 4-hydroxybenzophenone and toluene in a warm water bath, triethylamine was added dropwise at an internal temperature of 30 ° C, and then a toluene solution of methacrylic anhydride was added at an internal temperature of 30 ° C. And inside temperature 3
The reaction was carried out at 0 ° C for 6 hours. The content of methacrylic acid anhydride in the reaction solution after the reaction was 5.4%.

After the reaction was completed, 3.5 g of methanol was added to the reaction solution.
(0.11 mol) was added, and the internal temperature was kept at 30 ° C. for 3 hours. The content of methacrylic anhydride in the reaction solution after 3 hours was 0.3%. The amount of added methanol was 1 mol with respect to 1 mol of the remaining methacrylic anhydride.

Then, the reaction solution was washed twice with 1.1 L of water, and the organic layer was dried over anhydrous magnesium sulfate. Then, after filtration, the filtrate was concentrated under reduced pressure to obtain 331.9 g of crude 4-methacryloyloxybenzophenone. The content of methacrylic acid anhydride in the obtained crude 4-methacryloyloxybenzophenone was 0.2%.

The crude 4-methacryloyloxybenzophenone thus obtained was mixed with 550 mL of diisopropyl ether and n.
It was recrystallized from 440 mL of hexane, filtered off, and dried under reduced pressure to obtain 203.0 g of purified 4-methacryloyloxybenzophenone. The purified 4-methacryloyloxybenzophenone thus obtained had a purity of 99.5% and a methacrylic acid anhydride content of 0.1% or less. The melting point of the obtained crystal was 69.0-70.0 ° C. Yield 6
It was 9.0%.

When the inside of the SUS separable flask was visually observed after the reaction, no corrosion was observed.

No corrosion of the SUS separable flask was observed even after the 4-methacryloyloxybenzophenone was synthesized 10 times using the same SUS separable flask.

Example 2 Addition of methanol after completion of the reaction (methanol was added to the reaction solution at an internal temperature of 30 ° C.
4-Methacryloyloxybenzophenone was obtained in the same manner as in Example 1 except that the (holding time) was not performed.

As a result, 335.2 g of crude 4-methacryloyloxybenzophenone was obtained, and the content of methacrylic acid anhydride in the crude 4-methacryloyloxybenzophenone was 5.1%. Then, this was purified in the same manner as in Example 1 to give purified 4-methacryloyloxybenzophenone 2
04.2 g was obtained. The purified 4-methacryloyloxybenzophenone thus obtained had a purity of 98.3% and a methacrylic acid anhydride content of 1.3%. The yield was 68.5%.

When the inside of the SUS separable flask was visually observed after the reaction, no corrosion was observed.

No corrosion of the SUS separable flask was observed even after synthesizing 4-methacryloyloxybenzophenone 10 times using the same SUS separable flask.

Comparative Example 1 Stirrer, two equal pressure dropping funnels,
SUS 500 equipped with thermometer and calcium chloride drying tube
In a mL separable flask, 218.0 g (1.10 mol) of 4-hydroxybenzophenone and toluene 1.1.
I charged L. Then, 122.4 g (1.21 mol) of triethylamine was charged into one dropping funnel, and 126.5 g of methacrylic acid chloride (1.
21 mol) was charged.

While stirring the suspension of 4-hydroxybenzophenone and toluene in a warm water bath, triethylamine was added dropwise at an internal temperature of 30 ° C., and then methacrylic acid chloride was added dropwise at an internal temperature of 30 ° C. Then, the reaction was performed at an internal temperature of 30 ° C. for 6 hours.

After the reaction was completed, 3.5 g of methanol was added to the reaction solution.
(0.11 mol) was added, and the internal temperature was kept at 30 ° C. for 3 hours. Then, the reaction solution was washed with water twice as in Example 1, the organic layer was dried, and the filtrate was concentrated to obtain 325.4 g of crude 4-methacryloyloxybenzophenone.

When the inside of the SUS separable flask was visually observed after the reaction, corrosion was found.

[0049]

EFFECTS OF THE INVENTION According to the present invention, (meth) acryloyloxybenzophenones can be produced on an industrial scale without causing a problem of corrosion even if a general reactor is used.

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Claims (6)

[Claims] 1. A hydroxybenzophenone represented by the following formula (1) and a (meth) acrylic acid anhydride are reacted in the presence of a basic substance to give a (meth) represented by the following formula (2).
A method for producing acryloyloxybenzophenones. [Chemical 1] (In the formula (1), R ¹ and R ² independently represent a hydrogen atom, a halogen atom, an amino group, a nitro group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. ) [Chemical 2] (In the formula (2), R ¹ and R ² independently represent a hydrogen atom, a halogen atom, an amino group, a nitro group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. R
³ represents a hydrogen atom or a methyl group. ) 2. The basic substance is triethylamine,
The method for producing a (meth) acryloyloxybenzophenone represented by the formula (2) according to claim 1, which is at least one of pyridine and 2,6-dimethylaminopyridine. 3. The formula (2) according to claim 1 or 2, wherein the amount of the basic substance used is 0.01 to 5 mol with respect to 1 mol of the hydroxybenzophenone represented by the formula (1). A method for producing a (meth) acryloyloxybenzophenone represented by: 4. The hydroxybenzophenone 1 represented by the formula (1) is used in the amount of the (meth) acrylic anhydride used.
It is 1-5 mol with respect to mol, The manufacturing method of the (meth) acryloyloxy benzophenone represented by Formula (2) in any one of Claims 1-3. 5. A hydroxybenzophenone represented by the formula (1) is reacted with a (meth) acrylic anhydride in the presence of a basic substance, and then alcohol is added to the reaction liquid to remain (meth). The method for producing a (meth) acryloyloxybenzophenone represented by the formula (2) according to any one of claims 1 to 4, which comprises a step of decomposing acrylic acid anhydride. 6. The method for producing a (meth) acryloyloxybenzophenone represented by the formula (2) according to claim 5, wherein the alcohol is a lower aliphatic alcohol.