JPH0454150A - Production of 3-chloro-4-hydroxybenzoic acid derivative having polymerizable group - Google Patents

Abstract

PURPOSE:To readily obtain a 3-chloro-4-hydroxybenzoic acid derivative with facilitated purification by using a specific hydroxybenzoic acid derivative as a raw material and reacting the raw material with a halogenating agent. CONSTITUTION:A hydroxybenzoic acid derivative [e.g. (3-acryloyloxypropyl) 4-hydroxybenzoate] expressed by formula I (Y is H, alkyl, alkoxy, acyloxy or OH; R is monofunctional group having polymerizable group) is halogenated with a halogenating agent to provide a 3-chloro-4-hydroxybenzoic acid derivative [e.g. 3-acryloyloxypropyl 3-chloro-4-hydroxybenzoate], expressed by formula II (X is halogen) and having the polymerizable group. The resultant compound is useful as an electron accepting compound for recording materials.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention provides an electron-accepting compound useful as an electron-accepting compound for recording materials.
The present invention relates to a method for producing a 3-chloro-4 hydroxybenzoic acid derivative having a novel polymerizable group.

(Prior art) 3 having a polymerizable group as an electron-accepting compound for recording materials
-Chloro-4-hydroxybenzoic acid derivatives have not been studied until now.1 The present inventors found that 3-chloro-4-hydroxybenzoic acid derivatives having a specific polymerizable group have extremely excellent performance. I found out. However, there is no known method for industrially producing 3-chloro-4-hydroxybenzoic acid derivatives having such polymerizable groups.

(Object of the Invention) An object of the present invention is to provide a method for producing a 3-chloro-4-hydroxybenzoic acid derivative having a polymerizable group that is simple and easy to purify.

(Structure of the Invention) The present invention is based on the following general formula (1) [In the above general formula (I), Y is a hydrogen atom, an alkyl group,
Alkoxy group, acyloxy group or hydroxy group,
R represents a monovalent group having a polymerizable group. ] The hydroxybenzoic acid derivative represented by the following general formula (n) is halogenated in the presence of a halogenating agent. [In the above general formula (n), Y and R represent the same thing as in general formula (I), and X represents a halogen atom.

] Consists of a method for producing a 3-chloro-4-hydroxybenzoic acid derivative having a polymerizable group.

In the general formula (I), the group represented by R has 5 to 2 carbon atoms.
An alkyl group having 0 polymerizable vinyl groups.

An aralkyl group having a polymerizable vinyl group having 9 to 20 carbon atoms is preferred, particularly an alkyl group having 5 to 15 carbon atoms having an acryloyloxy group or a methacryloyloxy group, and an aralkyl group having 9 to 15 carbon atoms having a vinyl group. Aralkyl groups are preferred.

Moreover, these groups may have two or more polymerizable groups.

The halogen atom represented by X is preferably a chlorine atom or a bromine atom.

Among the substituents represented by Y, hydrogen atoms, carbon atoms 1 to 4
an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 8 carbon atoms, and specifically a hydrogen atom, a methyl group, and an ethyl group.

Preferred are methoxy, ethoxy, acetyloxy, propionyloxy, acryloyloxy, methacryloyloxy and the like.

The production method of the present invention is preferably carried out using a solvent, and the solvent is preferably an aromatic hydrocarbon, a halogenated hydrocarbon, an ether, a fatty acid, etc., for example,
Benzene, toluene, methylene chloride, chloroform, dichloroethane, methylchloroform, tetrahydrofuran, dioxane, acetic acid and the like are preferred.

The halogenating agent used in the production method of the present invention is:

Common halogenating agents used for halogenating aromatic compounds are listed, and are described, for example, in Shin Jikken Kagaku Koza (Maruzen), Vol. 14, pages 307 to 450. Preferred examples of the halogenating agent include chlorine, bromine, sulfuryl chloride, N-kufurosucciimide, N-bromosuccimide, and the like.

What is the reaction temperature when carrying out the production method of the present invention?

-10°C to 100°C, especially 5°C to 50°C
°C is preferred.

(Example-1) To a solution of 26 g of 4-hydroxybenzoic acid (3-acryloyloxypropyl) ester in 90 ml of chloroform, 11 ml of sulfuryl chloride was added under stirring at a reaction temperature of 20 ml.
The addition was carried out over a period of 0.5 hour while controlling the temperature to ~25°C. The 8 reaction mixture was reacted at 25°C for 2 hours with further stirring, poured into water, the chloroform layer was separated, the chloroform was distilled off, and 3-chloro-4-hydroxybenzoic acid (3-acryloyloxypropyl) ester I got it.

(Example-2) To a solution of 27 g of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester in 100 ml of methylene chloride, 11 ml of sulfuryl chloride was added under stirring while controlling the reaction temperature at 20 to 25°C. , was added over 5 hours. The 8-reaction mixture was reacted for 2 hours at 25°C with further stirring, poured into water, separated the methylene chloride layer, and then distilled off the methylene chloride. ) ester was obtained.

(Example-3) To a solution of 26 g of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester in 80 ml of tetrahydrofuran, 11 ml of sulfuryl chloride was added under stirring.2 While controlling the reaction temperature at 20 to 25°C, 0.5 I added it over time. The reaction mixture, which was reacted at 25°C for 2 hours with further stirring, was poured into water, and the precipitated crystals were collected by filtration and recrystallized using ethyl acetate/n-hexane as a solvent.

3-chloro-4-hydroquine benzoic acid (2-methacryloyloxyethyl) ester was obtained.

(Example 4) To a solution of 24 g of 4-hydroxybenzoic acid (2-acryloyloxyethyl) ester in 80 ml of tetrahydrofuran, 11 ml of sulfuryl chloride was added under stirring, while controlling the reaction temperature at 20 to 25°C. I added it over time. The reaction mixture, which was reacted for 2 hours at 25°C with further stirring, was poured into water, the precipitated oil was extracted with ethyl acetate, and the ethyl acetate was distilled off, resulting in 3chloro-4-hydroxybenzoic acid. (2-acryloyloxyethyl)ester was obtained.

(Examples 5 to 10) The following compounds were obtained in the same manner.

3-chloro-4-hydroxybenzoic acid vinylbenzyl ester, 3-chloro-4-hydroxybenzoic acid (2-methacryloyloxypropyl) ester, 3-chloro-
4-Hydroquine benzoic acid (2-acryloyloxypropyl) ester.

3-Chloro-4-hydroxybenzoic acid (4-methacryloyloxybutyl) ester, 3-chloro4-hydroxybenzoic acid (2-acryloyloxybutyl) ester, 3-chloro-4-7droxybenzoic acid (2,3- bisacryloyloxypropyl) ester

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the above general formula (I), Y is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a hydroxyl group. group, R represents a monovalent group having a polymerizable group. ] There are ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (II) represented by the following general formula (II), which is characterized by halogenating the hydroxybenzoic acid derivative represented by the following in the presence of a halogenating agent. In the above general formula (II), Y and R represent the same as those in general formula (I), and X represents a halogen atom. ] A method for producing a 3-chloro-4-hydroxybenzoic acid derivative having a polymerizable group.