JPS6242952A - Salicylic acid phenyl ester derivative - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R1 is H or CH3; X is Br, Cl or I; n is 0-4; R2 is phenyl). EXAMPLE:1-Phenyloxycarbonyl-2-acryloyloxybenzene. USE:Useful as a lens material and a modified monomer for a resin having improved impact resistance and high refractive index. PREPARATION:A compound shown by the formula II is halogenated to give a compound shown by the formula III and then 1mol compound shown by the formula III is dehydrohalogenated with 1mol compound shown by the formula IV (X' is halogen; preferably Cl) to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel and useful compounds, particularly compounds useful as modifying monomers for high refractive index resins used in lens materials.

Synthetic resins have long been used as lens materials to replace inorganic glass, but for eyeglass lenses, synthetic resins are mainly made by polymerizing a radically polymerizable monomer called diethylene glycol bis(allyl carbonate) (hereinafter abbreviated as CR-39). resin is used. However, although this CR-39 resin has good transparency, dyeability, and mechanical properties, it has a refractive index of 1.49, which is lower than 1.53 for lens glass, so it is molded into concave lenses for myopia. In this case, the disadvantage was that the edges were thicker than glass lenses when compared with the same power. The biggest reason why synthetic resin lenses are unpopular with eyeglass wearers is this problem of edge thickness.

Conventionally, polystyrene has been the most universally rigid colorless transparent resin with a high refractive index, but polystyrene has the disadvantage of poor impact resistance and has not been used for eyeglass lenses.

In general, it is effective to introduce a benzene ring into the molecular structure to increase the refractive index, but the introduction of a benzene ring tends to make the resin brittle. It has been hoped that a synthetic resin useful as a synthetic resin would emerge.

The present inventors conducted intensive research to obtain a synthetic resin that has a high refractive index, excellent impact resistance, and is useful as a lens material. As a result, it happened that the compound represented by the general formula (1) below was found to be similar to polystyrene. We have discovered that it is useful as a modifying monomer for resins that have a high refractive index but poor impact resistance, and have thus come to form the present invention.

That is, the present invention provides a salicylic acid phenyl ester derivative represented by general formula (I):

However, in General 2 (I), R5 is H or CH3.
X is a halogen atom selected from Br, Cp or I, n is an integer of 0 to .1, and R7 is phenyl.

Here, representative examples of specific compounds included in general formula (1) are as follows.

1-phenyloxysulfonyl-2-acryloyloxybenzene; 5-chloro-1-phenyloxycarbonyl-2-acryloyloxybenzene; 3.5-dichloro-1-phenyloxycarbonyl-2
-acryloyloxybenzene; 3.4,5.6-tetrachloro-1-phenyloxycarbonyl-2-acryloyloxybenzene; 5-bromo-1-phenyloxycarbonyl-2=acryloyloxybenzene; 3.5-dibromo- 1-phenyloxycarbonyl-2
-acryloyloxybenzene; 3.4.5.6-tetrabromo-1-phenyloxycarponyl-2-acryloyloxyhenzene; 3.5-
Short-1-phenyloxycarbonyl-2-acryloyloxybenzene; ■-phenyloxycarbonyl-2-methacryloyloxybenzene; 5-chloro-1-phenyloxycarbonyl-2-methacryloyloxybenzene; 3.5-dichloro-1- Tsuyunyloxy luponyl 2
-methacryloyloxybenzene; 3.4, 5.6--
Tetrachloro-1-phenyloxycarbonyl-2-methacryloyloxybenzene; 5-phyromo-1-phenyloxycarbonyl-methacryloyloxybenzene; 3,5-dib is mo-1-phenyloxycarbonyl-2
-methacryloyloxybenzene; 3,4,5.6-tetrabromo-1-phenyloxyca, l+/bonyl-
2-methacryloylogicibenzene; 3,5-short-1-phenyloxycarbonyl-2-methacryloylogicibenzene; The compound of general formula (T) is a new compound that has not been reported in the literature. can be synthesized, for example, by the following method.

General formula (■): O (However, R2 in the formula has the same meaning as above.) Compound ■ (ester of salicylic acid) is halogenated, and general formula (■) D (However, in the formula, R2 , X and n have the above-mentioned meanings).
The mole is expressed by the general formula (■); cH. When a dehydrohalogenation reaction is carried out with 1 mole of the compound (2) represented by =cc-c-x' (wherein R1 has the above-mentioned meaning, and Xo is a halogen, preferably chlorine), the final objective is achieved. A compound of general formula (T) is obtained.

The compound of general formula (1) according to the present invention obtained in this way is usually obtained as a white powder, but it has a radically polymerizable double bond at the terminal, and when polymerized alone, a high refractive index resin can be obtained. In addition, it can also be copolymerized with other radically polymerizable monomers. When the compound of the present invention itself is polymerized, a high refractive index resin having a refractive index Nd of 1.59 or more is obtained, so it is also useful as a modifying monomer for increasing the refractive index of a low refractive index resin.

Examples of the present invention will be shown below.

(Example 1) 5-bromo-1-phenyloxycarbonyl-2-methacryloyloxybenzene (hereinafter B
(referred to as IMPhS): (1) Synthesis of intermediate compound (1) with the following structural formula: 214, Og phenyl salicylate was dissolved in about 500 ml of 1,4-dioxane, and while stirring at room temperature, 160, O g of bromine was slowly added dropwise. After the dropwise addition was completed, this solution was allowed to react at room temperature for 5 hours and then under reflux for 1 hour. The resulting mixture was sufficiently cooled and concentrated, and the precipitated crystals were recrystallized with a chloroform-methanol (1:4) mixed solvent to give 21
9. 8 g of product was obtained. Yield: 75% (2) Synthesis of final target product: 136.9 g of the product from 1) in the previous section was dissolved in about 250 ml of tetrahydrofuran and cooled to 0°C. 3. Keep this solution at 0°C. 7 g of methacrylic acid chloride followed by 2 1. Approximately 70 ml of an aqueous solution containing 2 g of sodium hydroxide was slowly added dropwise, and the mixture was allowed to react at O'C for 2 hours.

When the reaction product was allowed to stand still, it separated into two layers, an organic layer and an aqueous layer, so the aqueous layer was removed and the organic layer was concentrated.

The obtained concentrate was dropped into a dilute aqueous sodium hydroxide solution, and the resulting precipitate was recrystallized twice with ethanol, filtered, and dried to obtain 142.0 g of white powder. Yield 85% (3) Melting point of target product: 85.8-87.6°C (
4) Elemental analysis value of target product: CI6.7: H12.8: 0 3.8
: Br 1.1 Theoretical value: C17 : R13
:04 :Brl(5) NMR chart of target product: Figure 1 (Example 2) 5-bromo-1-phenyloxycarbonyl-2-acryloyloxybenzene (hereinafter referred to as B,
(referred to as APhS): (1) Synthesis of the final target product: 74.8 g of the product synthesized in section (1) of Example 1 was
It was dissolved in 4.0 ml of tetrahydrofuran and cooled to 0°C. While maintaining this solution at Q'C, about 40 ml of an aqueous solution containing 25:4 g of acrylic acid chloride and then 11.6 g of sodium hydroxide was slowly added dropwise, and the reaction was continued at 0° C. for 2 hours.

When the reaction product was allowed to stand still, it separated into two layers, an organic layer and an aqueous layer, so the aqueous layer was removed and the organic layer was concentrated.

The obtained concentrate was dropped into a dilute aqueous sodium hydroxide solution, and the resulting precipitate was recrystallized twice with ethanol, filtered, and dried to obtain 57.3 g of white powder. Yield 64% (2) Melting point of target product: 119. O~120.3
'c(3) Elemental analysis value of target product; C16,2: H10,5: 03.9: Br 1
．． 0 theoretical value: C16:HI3:04 +Br
1(4) NMR chart of target product: Figure 2 (Example 3) 3,5-dibromo-1-phenyloxycarbonyl-2-acryloyloxybenzene (hereinafter referred to as B2APhS) having the following structural formula. Synthesis: Br (1) Synthesis of intermediate compound (1) of the following structural formula: Dissolve phenyl salicylate of Br 107, Og in about 600 ml of methanol, and add 240.0 g of it while stirring at room temperature.
of bromine was slowly added dropwise. After the completion of the dropwise addition, 6 hours under reflux.
After reacting for a while, a white solid precipitated. After cooling the resulting reaction mixture, the precipitate was filtered off, and the solid was washed with methanol and dried to obtain 136.6 g of product. Yield: 73% (2) Synthesis of final target product: 95.3 g of the product obtained in the previous section (1) was dissolved in about 150 mβ of tetrahydrofuran and cooled to Q'C. While maintaining this solution at Q'C, about 70 ml of an aqueous solution containing 40.6 g of acrylic acid chloride and then 18.5 g of sodium hydroxide was slowly added dropwise, and the solution was heated to 0.
The reaction was carried out at ℃ for 3 hours.

When the reaction product was allowed to stand still, it was separated into an organic layer and a 2N aqueous layer, so the aqueous layer was removed and the organic layer was concentrated. The obtained concentrate was dropped into a dilute aqueous sodium hydroxide solution, and the resulting precipitate was recrystallized twice with ethanol, filtered,
Upon drying, 64.0 g of white powder was obtained. Yield 58% (3) Melting point of target product: xoo, o ~ 1.0
5.0℃ (4) Elemental analysis value of target product: C15,9: H9,6: 03.6: Br 2.1
Theoretical value: C16:HICl:04:Br2(5)
NMR chart of target product: Figure 3 (Example 4) 3,5-dibromo-1-phenyloxycarbonyl-2-methacryloyloxybenzene (having the following structural formula)
(hereinafter referred to as 82MPIIS): (1) Synthesis of the final target product: 40.0 g of the product synthesized in section (1) of Example 3 was
Dissolved in 50ml of tetrahydrofuran and cooled to 0°C. While maintaining this solution at 0° C., 13.8 g of methacrylic acid chloride and then approximately 40 ml of an aqueous solution containing 5.5 g of sodium hydroxide were slowly added dropwise, and the reaction was continued at 0° C. for 3 hours.

When the reaction product was allowed to stand, it separated into two layers, an organic layer and an aqueous layer, so the aqueous layer was removed and the organic layer was concentrated. The obtained concentrate was dropped into a dilute aqueous sodium hydroxide solution, and the resulting precipitate was recrystallized twice with ethanol, filtered,
Upon drying, 16.3 g of white powder was obtained. Yield 34% (2) Melting point of target product: 95.2-97.
5°C (3) Elemental analysis value of target product: C16,13: 1 (11,6: O3,7: Br
2.1 Theoretical value: C17:H12:04 :Br2(4
) NMR Char 1 of the desired product: Figure 4 (Example 5) 5-chloro-1-phenyloxycarbonyl-2-methacryloyloxyhenzene (hereinafter referred to as
(1) Synthesis of intermediate compound (2) of the following structural formula: 300 ml of sulfuryl chloride was added to 107.0 g of phenyl salicylate, and the mixture was reacted at room temperature for 3 days.

The resulting reaction mixture was concentrated, and the precipitated crystals were recrystallized with chloroform-methanol (1:4> mixed solvent).
7.0 g of product was obtained. Yield: 62% (2) Synthesis of final target product: 37.7 g of the product obtained in the previous section (1) was dissolved in about 100 ml of tetrahydrofuran and cooled to 0°C. This solution is 0
Approximately 30 mj of an aqueous solution containing 17.2 g of methacrylic acid chloride followed by 6.8 g of sodium hydroxide while being maintained at °C! was slowly added dropwise, and the mixture was allowed to react at O'C for 2 hours.

When the reaction product was allowed to stand still, it separated into an organic layer and a 2N aqueous layer, so the aqueous layer was removed and the organic layer was concentrated.

The obtained concentrate was dropped into a dilute aqueous sodium hydroxide solution, and the resulting precipitate was recrystallized twice with ethanol, filtered, and dried to obtain 37.9 g of white powder. Yield 79% (3) Melting point of target product: SO, t~84.8°C (
4) Elemental analysis values of target product: C16,9: H13,4: O3,7: C7! 1
．． 2 theoretical value: C17:HI3:04:czl
(5) NMR chart of target product: Figure 5 (Application example) Of 100 parts by weight of the monomer mixture (hereinafter simply referred to as parts), 30 parts were the compound of the above example, and 10 parts were as a crosslinking agent. 1,3-bis(3,5-
Dibromo-4-methacryloyl-benzoyloxy)propane (hereinafter referred to as BMBP): (1) (CHz)a was used, the remaining 60 parts was styrene, and 0.0% of benzoylperoxyl- was added as a radical polymerization initiator. 2
After heating to 50°C and thoroughly mixing, the mixture was poured into an aluminum cup and cast polymerization was carried out. Polymerization was carried out in a nitrogen gas atmosphere by keeping the atmosphere at 100° C. and leaving it for 5 hours. The properties of the resin obtained are shown in Table 1 below.

[Brief explanation of drawings]

1 to 5 are NMR charts of compounds of each example of the present invention.

Claims (1)

[Claims] General formula below: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is H or CH_3, X is a halogen selected from Br, Cl or I, n is an integer from 0 to 4, and R_2 is a phenyl group) Salicylic acid phenyl ester derivative represented by