JPH0551349A - Novel phthalic ester derivative - Google Patents

Abstract

PURPOSE:To provide the title novel compound useful as a raw material for medicines, pesticides and various kinds of chemicals, also useful as a raw material for photosetting resins having especially excellent product characteristics. CONSTITUTION:The objective compound of formula I [R is H, lower alkenyl, of formula IV (m is 1-3) or of formula V (R<1> is H or OH; R<2> is lower alkenyl or phenylalkenyl; where, R<1> and R<2> are not Hs simultaneously)], for example, 4-trifluoromethyl-bis(3-acryloxy-2-hydroxypropyl)phthalate. The present compound can be obtained by the following processes: reaction is made between a phthalic acid compound of formula II or its anhydride of formula II' and an alcohol of formula III to form a phthalic ester derivative of formula I'', which is then halogenated into an acid halide of formula II''. followed by reaction with an alcohol of formula III; alternatively, reaction is made between the compound of the formula II or II' and an alcohol of the formula III.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula (I) [In the formula, R may be the same or different, and a hydrogen atom, a lower alkenyl group, (In the formula, m represents an integer of 1 to 3) or (In the formula, R ¹ represents a hydrogen atom or a hydroxyl group which may be the same or different, R ² represents a lower alkenyl or phenylalkenyl group, and n represents an integer of 1 to ^3. ). However, R ¹ and R ² do not represent hydrogen atoms at the same time. ] It is related with the phthalate ester derivative represented by. The phthalate derivative represented by the general formula (I) of the present invention is a compound useful as a raw material for medicines, agricultural chemicals, chemicals and the like, and as an intermediate for photocurable resins and the like.

[0002]

2. Description of the Related Art Many derivatives of phthalates have been reported as raw materials for medicines, agricultural chemicals, chemicals, resins and the like.

[0003]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have conducted extensive studies on a novel phthalate ester derivative, and as a result,
The phthalate derivative represented by the general formula (I) of the present invention is a novel compound which has not been described in the literature, and is useful as a raw material for medicines, agricultural chemicals and various chemicals, and particularly represented by the general formula (I). The present invention has been completed by finding that a photocurable resin derived from a phthalate derivative has excellent product characteristics as compared with a conventional similar resin.

[0004]

The phthalate derivative represented by the general formula (I) of the present invention can be produced, for example, by the following production method. (In the formula, R is the same as above, and X represents a halogen atom.)

A phthalic acid represented by the general formula (II) or an acid anhydride thereof represented by the general formula (II ') and an alcohol represented by the general formula (III) are combined with a base and an inert solvent. To give a phthalate ester derivative represented by the general formula (I '') by reacting in the presence or absence of, and further halogenating the phthalate ester derivative represented by the general formula (I ''), An acid halide represented by the general formula (II '') is prepared, and then the general formula (I
The phthalates represented by the general formula (I) can be produced by reacting with the alcohols represented by II). In addition, a phthalic acid represented by the general formula (II) or an acid anhydride represented by the general formula (II ′) and an alcohol represented by the general formula (III) are mixed with a base and an inert solvent. The phthalate derivative represented by the general formula (I) can also be produced by reacting in the presence or absence. This production method is a general production method of esterification, and can be produced, for example, by the method described in Shin Jikken Kagaku Koza 14-II (Maruzen), USP 3221043 or the like. In addition, the general formula (I
Instead of the alcohols represented by II), epoxidized products thereof such as glycidyl acrylate and glycidyl methacrylate can be used. Representative compounds of the phthalic acid derivative represented by the general formula (I) are shown in Table 1.
The present invention is not limited to these.

Table 1

[0007]

EXAMPLES Typical examples of the phthalate derivative represented by the general formula (I) of the present invention are shown below. Example 1 : Preparation of 4-trifluoromethyl-bis (3-acryloxy-2-hydroxypropyl) phthalate (Compound No. 1) In a 50 ml three-necked flask equipped with a condenser, 7.0 g (30 mmol) of 4-trifluoromethylphthalic acid, 8.1 g (63 mmol) of glycidyl acrylate, 0.06 g (0.6 mmol) of triethylamine, t -Butylcatechol 0.035 g (0.3 mmol) and toluene 30
ml was added and the reaction was carried out at 100 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled, washed with water, and the toluene layer was concentrated. The target product was isolated from the concentrate by wet column chromatography to obtain 8.7 g (yield 59.2%).

Example 2 : Preparation of 4-trifluoromethyl-bis (3-methacryloxy-2-hydroxypropyl) phthalate (Compound No. 2) In place of the glycidyl acrylate of Example 1, 9.0 g (63 mmol) of glycidyl methacrylate was used and reacted in the same manner as in Example 1 to give 11.
6 g was obtained (yield 74.6%).

Example 3 : 4-trifluoromethyl-
Production of (2-acryloxyethyl) phthalate In a 50 ml three-necked flask equipped with a condenser, 4-trifluoromethylphthalic anhydride 4.3 g (20 mmol), acrylic acid (2-hydroxyethyl) 4.9 g (42 mmol), triethylamine 0.4 g (4 mmol) Millimolar) and
0.012 g (0.1 mmol) of t-butyl catechol was added, and the reaction was carried out at 100 ° C. for 4 hours. After completion of the reaction, the reaction solution was cooled, washed with water, and the toluene layer was concentrated. The concentrate was subjected to wet column chromatography to obtain 6.0 g of the desired product as a mixture of two isomers (yield 90.4%).

Example 4 : 4-trifluoromethyl-bis (3-acryloxyethyl) phthalate (Compound No.
3) Manufacturing In a 50 ml three-necked flask equipped with a condenser, 6.0 g of 4-trifluoromethyl- (2-acryloxyethyl) phthalate obtained in Example 3 (mixture of two isomers) was obtained.
And thionyl chloride 3.2 g (27 mmol)
Was added and reacted at room temperature for 1.5 hours and at 50 ° C. for 1 hour. After completion of the reaction, excess thionyl chloride was distilled off, and the concentrate was added with 2.1 g of (2-hydroxyethyl) acrylate (1
(8 mmol) and 20 ml of dichloromethane were added, 1.7 g (21 mmol) of pyridine was gradually added under cooling, and the reaction was carried out at room temperature for 1 hour. After completion of the reaction, the reaction solution was washed with water and concentrated. Wet column chromatography of the concentrate
Thus, 5.5 g of the target product was obtained (yield 71.1%).

Example 5 : 4-trifluoromethyl-
Production of (2-methacryloxyethyl) phthalate 5.5 g of methacrylic acid (2-hydroxyethyl) instead of acrylic acid (2-hydroxyethyl) of Example 3
(42 mmol) was used and the reaction was carried out in the same manner as in Example 3 to obtain 6.7 g of the desired product as a mixture of two isomers (yield).
96.8%).

Example 6 : 4-trifluoromethyl-bis (3-methacryloxyethyl) phthalate (Compound N
o. 4) Manufacturing In a 50 ml three-necked flask equipped with a condenser, 8.7 g (2-isomer mixture) of 4-trifluoromethyl- (2-methacryloxyethyl) phthalate obtained in Example 5 (2 isomers)
(5 mmol) and thionyl chloride (4.5 g, 38 mmol) were added, and the reaction was carried out at room temperature for 1.5 hours and at 50 ° C. for 1 hour. After completion of the reaction, excess thionyl chloride was distilled off,
(2-hydroxyethyl) methacrylate 3.3 in the concentrate
g (25 mmol) and 20 ml of dichloromethane were added,
2.4 g (30 mmol) of pyridine was gradually added under cooling, and the reaction was carried out at room temperature for 1 hour. After completion of the reaction, the reaction solution was washed with water and concentrated. The concentrate was subjected to wet column chromatography to obtain 9.7 g of the desired product (yield 84.7%).

Claims (2)

[Claims] 1. General formula (I) [In the formula, R may be the same or different, and a hydrogen atom, a lower alkenyl group, (In the formula, m represents an integer of 1 to 3) or (In the formula, R ¹ represents a hydrogen atom or a hydroxyl group which may be the same or different, R ² represents a lower alkenyl or phenylalkenyl group, and n represents an integer of 1 to ^3. ). However, R ¹ and R ² do not represent hydrogen atoms at the same time. ] The phthalate ester derivative represented by these. 2. The phthalic acid ester derivative according to claim 1, wherein the phthalic acid ester derivative represented by the general formula (I) is represented by the following general formula (I ′). (In the formula, R is the same as above.)