JP2888454B2 - Method for producing hydroxybenzoic acid having polymerizable group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a 4-hydroxybenzoic acid derivative having a polymerizable group, which is useful as a polymerizable monomer for a recording material.

[0002]

2. Description of the Related Art Various types of 4-hydroxybenzoic acid derivatives having a polymerizable group as a polymerizable monomer for a recording material are known, and some methods for producing the same are known.
It was not satisfactory in terms of handling.

[0003]

An object of the present invention is to provide a polymerizable monomer having a polymerizable group useful as a polymerizable monomer for a recording material.
-To provide a method for producing a hydroxybenzoic acid derivative which is simple and easy to purify.

[0004]

According to the present invention, a 4-hydroxybenzoic acid derivative having an alcoholic hydroxyl group represented by the following general formula (I) and an acrylic acid halide or a methacrylic acid halide are dissolved in an organic solvent : N-dimethyla
Cetamide, N, N-diethylacetamide, N, N-
Dimethylpropioamide, N-methylpyrrolidone, tet
Lamethylurea, tetraethylurea, N-methylacetate
Selected from the group of toanilide and 2-methylpyridine
And reacting in combination with a deoxidizing agent comprising a tertiary amide derivative as described above, which is characterized by comprising a method for producing a 4-hydroxybenzoic acid derivative having a polymerizable group represented by the following general formula (II).

[0005]

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[Wherein, X and Y may be the same or different and each represents a hydrogen atom or a hydroxy group, and Z represents a hydroxyalkyl group. General formula (II)

[0007]

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[In the above formula, X and Y may be the same or different and each represents a hydrogen atom or a hydroxy group, and R represents an acryloyloxyalkyl group or a methacryloyloxyalkyl group. ]

In the above general formula (I), Z represents 2 carbon atoms.
And a hydroxyalkyl group which may have a substituent of from 18 to 18, specifically, a hydroxyethyl group,
-Hydroxypropyl group, 2-hydroxypropyl group,
4-hydroxybutyl group, 6-hydroxyhexyl group,
8-hydroxyhexyl group, 10-hydroxydecyl group, 4- (hydroxymethyl) benzyl group, 3- (hydroxymethyl) benzyl group, 2- (hydroxymethyl)
Benzyl group, 12-hydroxydodecyl group, 2- (hydroxyethoxy) ethyl group, 3- (3-hydroxypropoxy) propyl group, 2,3-dihydroxypropyl group, 3-methacryloyloxy-2-hydroxypropyl group, 3- And acryloyloxy-2-hydroxypropyl group.

Specific examples of the 4-hydroxybenzoic acid derivative represented by the general formula (II) include acryloyloxyethyl 4-hydroxybenzoate, (2-methacryloyloxyethyl) 4-hydroxybenzoate, -Hydroxybenzoic acid (3-acryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-
(Methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (2-acryloyloxypropyl) ester, 4-hydroxybenzoic acid (2-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (4
-Methacryloyloxybutyl) ester, 4-hydroxybenzoic acid (6-acryloyloxyhexyl) ester, 4-hydroxybenzoic acid (6-methacryloyloxyhexyl) ester, 4-hydroxybenzoic acid (5
-Acryloyloxypentyl) ester, 4-hydroxybenzoic acid (5-methacryloyloxypentyl) ester, 4-hydroxybenzoic acid (8-methacryloyloxyoctyl) ester, 4-hydroxybenzoic acid (10-methacryloyloxydecyl) ester, 4 −
Hydroxybenzoic acid [4- (methacryloyloxymethyl) benzyl] ester, 4-hydroxybenzoic acid [2
-(Methacryloyloxyethoxy) ethyl] ester, 4-hydroxybenzoic acid [3- (methacryloyloxypropoxy) propyl] ester, 4-hydroxybenzoic acid [2,3-bis (methacryloyloxy) propyl] ester, 4-hydroxybenzoic acid Acid [2-acryloyloxy-3-methacryloyloxypropyl] ester, 4-hydroxybenzoic acid [2-methacryloyloxy-3-acryloyloxypropyl] ester,
2,4-dihydroxybenzoic acid (2-acryloyloxyethyl) ester, 2,4-dihydroxybenzoic acid (3-methacryloyloxyethyl) ester, 2,4
-Dihydroxybenzoic acid (3-acryloyloxypropyl) ester, 2,4-dihydroxybenzoic acid (3-
(Methacryloyloxypropyl) ester, 2,4-dihydroxybenzoic acid (2,3-dimethacryloyloxypropyl) ester and the like.

[0011] The production method according to the present invention comprises the step of acryloylating or methacryloylating an alcoholic hydroxyl group.
It is a production method with high yield, high purity, and easy purification.

The production method according to the present invention preferably uses an organic solvent, such as a nitrile solvent, a halogenated hydrocarbon solvent, an ether, an amide solvent, a ketone solvent, or an aromatic hydrocarbon. Is preferred. For example, acetonitrile, methylene chloride, acetone, chloroform, tetrahydrofuran, dioxane, N, N-dimethylacetamide, N-methylpyrrolidone, toluene and the like are preferable.

In the production method according to the present invention, a deoxidizing agent is used in combination. The deoxidizer, N, N- dimethylacetamide, N, N- diethylacetamide, N, N- dimethyl-propionitrile Ami de, N - methylpyrrolidone down, tetramethylurea, tetraethyl urea, N- methylacetoacetate <br/> Aniri And 2 -methylpyridine. These deoxidizing agents may be used as a solvent.

When the production method according to the present invention is carried out, 1.0 to 10.0 equivalents of acrylic acid chloride or methacrylic acid chloride are used per 1.0 mol of the compound represented by the general formula (I). It is preferable to use it, and it is particularly preferable to use 1.0 to 3.0 equivalents. The deoxidizing agent is preferably used in an amount of 1.0 equivalent or more based on the amount of acrylic acid chloride or methacrylic acid chloride used.
The reaction temperature is preferably from -10C to 100C, particularly preferably from 5C to 50C.

In the production method according to the present invention, a compound having an alcoholic hydroxyl group represented by the general formula (I):
-Hydroxybenzoic acid derivative is obtained by a conventional method.
For example, it can be easily obtained by esterification of 4-hydroxybenzoic acid with a halo alcohol or transesterification of a lower alkyl ester of 4-hydroxybenzoic acid with an alkylenediol.

[0016]

EXAMPLES Examples will be shown below, but the present invention is not limited to these examples. Unless otherwise specified in the examples, the percentages are by weight. Example-1 To a solution of 23 g of 4-hydroxybenzoic acid (3-hydroxypropyl) ester in 100 ml of acetonitrile, 20 ml of N-methylpyrrolidone was added with stirring, and 16 g of methacrylic acid chloride was further added. After reacting at 35 ° C. for 8 hours with stirring, the reaction mixture was poured into ice water, and the precipitated crystals were collected by filtration, recrystallized from ethyl acetate / n-hexane, and treated with 4-hydroxybenzoic acid (3-methacryloyl). Oxypropyl) ester (mp 70-72 ° C) was obtained.

Example-2 To a solution of 21 g of 4-hydroxybenzoic acid (2-hydroxyethyl) ester in 100 ml of acetonitrile, 20 ml of N, N-dimethylacetamide was added with stirring, and 20 g of methacrylic acid chloride was further added. 8 at 35 ° C
After reacting with stirring for a period of time, the reaction mixture was poured into ice-water, the precipitated crystals were collected by filtration, recrystallized from ethyl acetate / n-hexane, and 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester ( 87-89 °
C) was obtained.

Example 3 A reaction was carried out in the same manner as in Example 2 except that tetramethylurea was used as a deoxidizing agent to obtain 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester.

Example 4 2,4-Dihydroxybenzoic acid (2-hydroxyethyl) ester 20 g of N, N-dimethylacetamide 1
In a 00 ml solution, 25 g of methacrylic acid chloride was stirred.
Was added. After the reaction at 40 ° C. for 8 hours with stirring, the reaction mixture was poured into an aqueous layer, the precipitated crystals were collected by filtration, and recrystallized from ethyl acetate / n-hexane to give 2,4-
Dihydroxybenzoic acid (2-methacryloyloxyethyl) ester (melting point 112-114 ° C.) was obtained.

Examples 5 to 13 The following compounds were obtained in the same manner. However, those in which crystals were not precipitated even when the reaction mixture was poured into water were purified by silica gel column chromatography. 2,4-dihydroxybenzoic acid (3-methacryloyloxypropyl) ester (melting point 69-72 ° C), 4-hydroxybenzoic acid (4-methacryloyloxybutyl) ester (melting point 61-64)
C), 4-hydroxybenzoic acid (2-acryloyloxypropyl) ester (oil), 4-hydroxybenzoic acid (6-methacryloyloxyhexyl) ester (oil), 4-hydroxybenzoic acid (5-methacryloyloxypentyl) ) Esters (mp 38-42 ° C.)
4-hydroxybenzoic acid (2,3-bisacryloyloxypropyl) ester (oil), 4-hydroxybenzoic acid (3-acryloyloxypropyl) ester (oil).

Comparative Example To 80 g of N, N-dimethylacetamide was added to 15 g of 4-hydroxybenzoic acid and 5.4 g of sodium methylate, followed by stirring. To this solution was added 21.4 g of (2-methacryloyloxyethyl) -p-tosylate,
For 6 hours with stirring. The reaction mixture was poured into ice water, but no crystals were precipitated. Extraction with ethyl acetate and analysis of the product revealed that the product contained 4-hydroxybenzoic acid (2-methacryloyloxyethyl).
The ester contained 6% by weight of 4- (2-methacryloyloxyethoxy) benzoic acid (2-methacryloyloxyethyl) ester.

Claims (1)

(57) [Claims] 1. A method according to claim 1, wherein a 4-hydroxybenzoic acid derivative having an alcoholic hydroxyl group represented by the following general formula (I) and acrylic acid halide or methacrylic acid halide are mixed in an organic solvent with N, N-dimethylacetamide, N, N -Dieci
Luacetamide, N, N-dimethylpropioamide, N
-Methylpyrrolidone, tetramethylurea, tetraethyl
Luurea, N-methylacetanilide, and 2-methyl
4-hydroxybenzoate having a polymerizable group represented by the following general formula (II), wherein the reaction is carried out in combination with a deoxidizing agent comprising a tertiary amide derivative selected from the group consisting of pyridine. A method for producing an acid derivative. General formula (I) [In the above formula, X and Y may be the same or different, and a hydrogen atom or a hydroxy group, and Z represents a hydroxyalkyl group. General formula (II) [In the above formula, X and Y may be the same or different, and a hydrogen atom or a hydroxy group, and R represents an acryloyloxyalkyl group or a methacryloyloxyalkyl group. ]