KR20160087908A - Novel bis(hydroxyphenyl)benzoxazole compound - Google Patents

Abstract

(화학식 중 R₁은 탄소원자수 1~8의 알킬기, 탄소원자수 1~8의 알콕시기, 페닐기 또는 할로겐원자를 나타내고, R₂는 수소원자, 탄소원자수 1~8의 알킬기, 탄소원자수 1~8의 알콕시기, 페닐기 또는 할로겐원자를 나타내며, A는 탄소원자수 5~10의 시클로알킬리덴기를 나타내고, n은 0 또는 1~4의 정수를 나타낸다.)
로 표시되는 비스(히드록시페닐)벤즈옥사졸 화합물을 제공한다.The present invention aims to provide a novel bis (hydroxyphenyl) benzoxazole compound which is useful as a resin material such as an epoxy resin or a polybenzoxazole resin, as well as medicines, agricultural chemicals, dyes and electronic materials, or intermediates or raw materials thereof do.
In order to solve the above-mentioned problems,
[Chemical Formula 1]

(Wherein R ₁ represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, R ₂ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, An alkoxy group, a phenyl group or a halogen atom, A represents a cycloalkylidene group having 5 to 10 carbon atoms, and n represents 0 or an integer of 1 to 4.)
(Hydroxyphenyl) benzoxazole compound represented by the following formula (I).

Description

A novel bis (hydroxyphenyl) benzoxazole compound {Novel bis (hydroxyphenyl) benzoxazole compound}

The present invention relates to novel bis (hydroxyphenyl) benzoxazole compounds. (Hydroxyphenyl) benzoxazole compound useful as a resin material such as an epoxy resin, a medicament, an agricultural chemical, a dye and an electronic material, or an intermediate or raw material thereof.

Bis (hydroxyphenyl) benzoxazoles are expected as raw materials because they are excellent in tensile strength, bending strength, impact strength, heat resistance and electrical characteristics when used as a resin raw material such as epoxy resin.

As such bis (hydroxyphenyl) benzoxazoles, 2,2'-di (4-hydroxyphenyl) -6,6'-bibenzoxazole and 2,2-hexafluoropropylidene group -Bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] hexafluoropropane and the like are known (Patent Document 1, Patent Document 2).

Here, since 2,2'-di (4-hydroxyphenyl) -6,6'-bibenzoxazole has a high melting point and a low solubility in solvents, it is problematic in terms of workability and operability when it is industrially carried out 2,2-bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] hexafluoropropane having a 2,2-hexafluoropropylidene group is not sufficient in heat resistance.

Therefore, there is a strong demand for development of bis (hydroxyphenyl) benzoxazole compounds having a novel chemical structure with good workability, operability and excellent heat resistance.

U.S. Patent No. 5270432 Japanese Patent Application Laid-Open No. 2007-262204

The present invention provides a novel bis (hydroxyphenyl) benzoxazole compound useful as a resin raw material such as an epoxy resin or a polybenzoxazole resin, as well as medicines, agricultural chemicals, dyes and electronic materials, or intermediates or raw materials for the same.

The present inventors have intensively studied the problems of the bis (hydroxyphenyl) benzoxazole compound as described above. As a result, it has been found that by making the central skeleton of the bis (hydroxyphenyl) benzoxazole compound a cycloalkylidene group, a balance between solvent solubility and heat resistance And discovered a novel novel bis (hydroxyphenyl) benzoxazole compound and completed the present invention.

According to the present invention, there is provided a bis (hydroxyphenyl) benzoxazole compound represented by the following general formula (1).

(Wherein R ₁ represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, R ₂ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, An alkoxy group, a phenyl group or a halogen atom, A represents a cycloalkylidene group having 5 to 10 carbon atoms, and n represents 0 or an integer of 1 to 4.)

The bis (hydroxyphenyl) benzoxazole compound of the present invention has a cycloalkylidene skeleton in its central skeleton, and its central skeleton has an aliphatic cyclic structure, so that it has a relatively low melting point and is also excellent in solvent solubility.

In addition, the resin containing the bis (hydroxyphenyl) benzoxazole compound of the present invention as a raw material is preferably a resin containing 2,2-bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] hexafluoropropane as a raw material It can be expected that heat resistance is superior to resin.

The bis (hydroxyphenyl) benzoxazole compound of the present invention will be described in detail below.

In the bis (hydroxyphenyl) benzoxazole compound represented by Formula 1 of the present invention, the alkyl group having 1 to 8 carbon atoms represented by R ₁ and R ₂ in the formula is a linear, branched or cyclic alkyl group , Preferably an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

Specific examples of such alkyl groups include methyl, ethyl, isopropyl, t-butyl, isobutyl, cyclohexyl, and cyclopentyl.

Such an alkyl group may be substituted with a halogen atom, an alkoxy group, a phenyl group or the like within the range not hindering the effect of the present invention, but is preferably not substituted.

The alkoxy group having 1 to 8 carbon atoms in the formula is preferably a linear, branched or cyclic alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms or a cycloalkoxy group having 5 to 8 carbon atoms, Is a linear or branched alkoxy group having 1 to 4 carbon atoms. Specific examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, cyclopentyloxy, cyclohexyloxy and the like. Such an alkoxy group may be substituted with a halogen atom, an alkoxy group, a phenyl group or the like within the range not hindering the effect of the present invention, but is preferably not substituted.

The phenyl group represented by R ₁ and R ₂ in the formula is preferably a phenyl group having no substituent. However, the phenyl group may be substituted with an alkyl group such as a methyl group, an alkoxy group such as a methoxy group, a halogen atom or the like to the extent that the effect of the present invention is not impaired.

Specific examples of the halogen atom represented by R ₁ and R ₂ in the formula include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the substituents R ₁ and R ₂ , preferable R ₁ is an alkyl group or a phenyl group, more preferably R ₁ is an alkyl group, and preferable R ₂ is an alkyl group, a phenyl group or a hydrogen atom, and more preferably R ₂ is a hydrogen atom.

The substitution number n of the substituent R ₁ of the hydroxyphenyl group represents 0 or an integer of 1 to 4, preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. [ The substitution position of R ₁ is preferably if the ortho position or para position to the hydroxyl group, and the substituted position of the hydroxyl group in the para position to the bonding site with the benzoxazole skeleton is a R ₁ The substitution position is preferably ortho to the hydroxyl group.

The substitution position of the hydroxy group of the hydroxyphenyl group is preferably a para position or a meta position with respect to the position bonded to the benzoxazole skeleton, particularly preferably a para position.

In the above formula (1), A represents a cycloalkylidene group having 5 to 10 carbon atoms.

Specific examples of such cycloalkylidene groups include cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, cycloheptane-1,1-diyl group, 3,3,5-trimethyl Cyclohexane-1,1-diyl group and the like.

More preferred is a 3,3,5-trimethylcyclohexane-1,1-diyl group from the viewpoint of heat resistance.

The cycloalkane skeleton may be substituted with an alkyl group, preferably a methyl group, and the preferred number of substituents is 1 to 3. [

Specific examples of the bis (hydroxyphenyl) benzoxazole compound of the present invention include, for example,

1,1-bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] -3,3,5-trimethylcyclohexane,

Butyl-4-hydroxyphenyl) -5-benzoxazolyl] -3,3,5-trimethylcyclohexane, 1,1-bis [2- (3,5-

1-bis [2- (3-tert-butyl-4-hydroxyphenyl) -5- benzoxazolyl] -3,3,5-trimethylcyclohexane,

1,1-bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] cyclohexane,

1,1-bis [2- (3-tert-butyl-4-hydroxyphenyl) -5-benzoxazolyl] cyclohexane,

1,1-bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] cyclopentane,

1,1-bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] cycloheptane,

Bis [2- (3-methyl-4-hydroxyphenyl) -5-benzoxazolyl] -3,3,5-trimethylcyclohexane,

1,1-bis [2- (4-hydroxyphenyl) -7-methyl-5-benzoxazolyl] -3,3,5-trimethylcyclohexane,

1,1-bis [2- (3-methyl-4-hydroxyphenyl) -5-benzoxazolyl] cyclohexane,

Bis [2- (3-methyl-4-hydroxyphenyl) -5-benzoxazolyl] cyclopentane,

And 1,1-bis [2- (3-phenyl-4-hydroxyphenyl) -5-benzoxazolyl] cyclohexane.

The method for producing the bis (hydroxyphenyl) benzoxazole compound of the present invention as described above is not limited in any way. For example, the following method can be used.

(Method 1)

A method in which a condensation reaction is carried out in an organic solvent at an elevated temperature using a bisaminophenol compound represented by the following formula (3) and a hydroxybenzoic acid compound corresponding to the target bis (hydroxyphenyl) benzoxazole compound as a raw material (Japanese Patent Application Laid-Open No. 2007-262204 And the like). As to the production method, for example, 1,1-bis (3-amino-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane as a bisaminophenol, 4-hydroxybenzoic acid Phenyl ester is used as a raw material. The reaction formula thereof is represented by the following formula, for example.

Reaction formula (1)

Examples of the hydroxybenzoic acids used in the above reaction include hydroxybenzoic acid phenyl esters represented by the following formula (2).

(Wherein R < ₁ > and n are the same as those in formula (1)).

The molar ratio of the raw materials of the bisaminophenols and the hydroxybenzoic acid phenyl esters in the reaction is usually 2 to 5 moles, preferably 2 to 3 moles, of the hydroxybenzoic acid phenyl ester per mole of bisaminophenols, . The reaction solvent is preferably used, and examples thereof include N-alkylamide solvents such as N-methyl-2-pyrrolidone and the like, aromatic hydrocarbons such as biphenyl, and mixed solvents thereof. The amount of the solvent to be used is usually in the range of 1 to 20 parts by weight based on 1 part by weight of bisaminophenols. The reaction temperature may be in the range of 150 to 250 占 폚, and the reaction pressure may be atmospheric pressure, reduced pressure, or pressurized, but may be reduced to easily remove by-product water or phenols.

For example, raw materials and reaction solvents are collectively charged into a reaction vessel, and the mixture is heated to a reaction temperature of about 150 ° C. to 180 ° C. After the system is depressurized, water and phenolics Distillation). Thereafter, the system is further heated to about 200 to 250 ° C to complete the cyclic dehydration reaction. After completion of the reaction, the desired product can be obtained from the obtained reaction product as a crude product or a purified product using a known purification method.

For example, a solid or a crystal precipitated or reprecipitated by cooling the obtained reaction solution or by adding water may be filtered off, washed with water and methanol, and dried to obtain the desired product.

In the above method, the bisaminophenols are represented by the following formula (3).

(R ₂ in the formula, A is the same as that in formula (1)).

Accordingly, such bisaminophenols correspond to the bis (hydroxyphenylbenzoxazole) compounds of the present invention, and specific examples thereof include 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane (3-amino-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (1,1-bis , 1,1-bis (3-amino-4-hydroxyphenyl) cyclopentane, and 1,1-bis (3-amino-4-hydroxyphenyl) cycloheptane.

These bisaminophenols can be obtained by, for example, nitration of the bis (nitrophenol) compound obtained by nitrating the corresponding bisphenol compound in the presence of nitric acid as shown in reaction formula (2), for example, a hydrogenation catalyst such as palladium carbon or nickel (Japanese Patent Application Laid-Open No. 2003-12611, Japanese Patent Application Laid-Open No. 2003-81925, etc.), for example, by reacting with hydrogen gas in the presence of a catalyst.

Reaction formula (2)

(R ₂ in the formula, A is the same as that in formula (1)).

(Method 2)

As another method for obtaining the bis (hydroxyphenyl) benzoxazole compound of the present invention, bisnitrophenols represented by the following formula (4) corresponding to the aimed bis (hydroxyphenyl) benzoxazole compound and bis Methylphenol as a raw material and performing a dehydration condensation reaction in an organic solvent, preferably at a temperature in the presence of a catalyst.

(3-nitro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane as a bis (nitrophenol), 2,6-di-t- The case where p-cresol is used as a raw material is described. The reaction is represented, for example, by the following reaction formula (3).

Reaction formula (3)

In the above method, the bis-nitrophenols are represented by the following formula (4).

(R ₂ in the formula, A is the same as that in formula (1)).

Accordingly, such bisnitrophenols correspond to the bis (hydroxyphenylbenzoxazole) compound of the present invention, and specifically include 1,1-bis (3-nitro-4-hydroxyphenyl) cyclohexane, 1,1- Bis (3-nitro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1- Bis (3-nitro-4-hydroxyphenyl) cyclopentane, and 1,1-bis (3-nitro-4-hydroxyphenyl) cycloheptane.

Such bis-nitrophenols can be prepared by, for example, treating bisphenols represented by the following formula (6) corresponding to the bis-nitrophenols represented by the above formula (4) with 5 to 80% nitric acid under conditions that substantially no other acid exists Or by nitration with a known method (WO01 / 81293, Japanese Patent Application Laid-Open No. 11-106365, etc.).

(R ₂ in the formula, A is the same as that in formula (2)).

The methyl phenols of the raw materials in the above method are represented by the following formula (5).

(Wherein R ₁ and n are the same as those in formula (1)).

Accordingly, such methylphenols correspond to the bis (hydroxyphenylbenzoxazole) compounds of the present invention, and specific examples thereof include 2,6-di-t-butyl-4-methylphenol, 2,4- -6-t-butylphenol, 2-t-butyl-4-methylphenol, 2,4,6-trimethylphenol and 2-methoxy-4-methylphenol.

The molar ratio of the starting materials of the bis-nitrophenols and the methyl phenols in the reaction is usually in the range of 2 to 10 moles, preferably 3 to 5 moles, per 1 mole of the bis-nitrophenols.

The catalyst is not required to be used but is preferably used for improving the yield. When the catalyst is used, the catalyst is preferably iron (iron powder), sulfur or sodium sulfide or a mixture thereof. The amount of the catalyst is usually in the range of 0.01 to 3 moles per 1 mole of the raw material bisnitrophenol, To 0.3 mol, and in the case of sulfur, it is preferably in the range of 1.5 to 2.5 mol, more preferably 2 mol.

The reaction solvent is preferably used, and for example, a halogenated aromatic compound such as o-dichlorobenzene, an aromatic hydrocarbon solvent such as biphenyl, an alkyl naphthalene such as 2,6-dimethyl naphthalene and 2,6- Amide solvents such as N-methyl-2-pyrrolidone, polyalkylene glycol ethers such as tetraethylene glycol dimethyl ether and diethylene glycol dibutyl ether, and mixtures thereof. The amount of the solvent to be used is preferably in the range of 1 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 1 part by weight of the bis (nitrophenols).

The reaction temperature is preferably in the range of 160 占 폚 to 200 占 폚, and more preferably in the range of 170 to 190 占 폚. The reaction pressure may be atmospheric pressure, pressure or reduced pressure. And may be adjusted by pressurization to raise the temperature, for example, when the boiling point of the reaction solvent at normal pressure is lower than the reaction temperature.

The reaction is carried out, for example, by adding a predetermined amount of a bis-nitrophenol, a methyl phenol, a catalyst and a reaction solvent to a reaction vessel, raising the reaction temperature to a predetermined reaction temperature while stirring under a nitrogen stream, and maintaining the temperature.

After the completion of the reaction, a known preparation of bis (hydroxyphenyl) benzoxazoles is obtained from the obtained reaction mixture according to a conventional method by appropriately using known methods such as catalyst separation, outflow separation of low boiling point fractions, and crystallization filtration If necessary, it is purified again by crystallization filtration, column separation or the like to obtain a high-purity product.

For example, when the crystals precipitate by cooling the reaction liquid as it is or cooling it by adding a poor solvent, the crystals are separated by filtration to obtain a desired product with high purity. Alternatively, after completion of the reaction, the reaction solvent and the like are concentrated under reduced pressure, and the residue thereof is purified by column chromatography or the like to obtain a high-purity product.

(Method 3)

As another method for obtaining the bis (hydroxyphenyl) benzoxazole compound of the present invention, n is 1 or more and at least _one of the substituents R ₁ is a tertiary alkyl group such as a tert-butyl group in the above formula (1) / And substituent R < ₂ > (hydroxyphenyl) benzoxazole compound as an intermediate which is a tertiary alkyl group such as a t-butyl group and the like. The bis (hydroxyphenyl) benzoxazole compound in which the tertiary alkyl group is substituted as the intermediate is obtained, Butyl group or the like is cleaved and substituted with a hydrogen atom in accordance with a known method such as a method in which a tertiary alkyl group such as t-butyl is removed according to a known method (Japanese Patent Application Laid-open No. Hei 2-169530 and Japanese Unexamined Patent Publication No. 8-143494) To obtain a target bis (hydroxyphenyl) benzoxazole.

(3-nitro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane as a bis (nitrophenol), 2,6-di-t- bis [2- (3,5-di-tert-butyl-4-hydroxyphenyl) -5-benzoxazolyl] pyrimidine as an intermediate obtained by the reaction of the above- The t-butyl group was removed from -3,3,5-trimethylcyclohexane to obtain the desired 1,1-bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] -3,3,5-trimethylcyclo Hexane is obtained.

The reaction is represented by, for example, the following reaction formula (4).

Reaction formula (4)

In the de-butylation reaction, an acid having a high boiling point such as p-toluenesulfonic acid and p-toluenesulfonic acid anhydride is preferable, and as the amount of the catalyst, To 50 mol%, and more preferably from 10 to 30 mol%. In the reaction, a usual solvent is used, and preferred examples of the solvent include phenols such as phenol and m-cresol. The amount of the solvent is not particularly limited, but is usually about 10 to 500 parts by weight based on 1 part by weight of the bis (hydroxyphenyl) benzoxazole compound. The reaction temperature is usually in the range of about 200 to 250 ° C.

The reaction is carried out, for example, by adding a predetermined amount of t-butyl substituted-bis (hydroxyphenyl) benzoxazole compound, catalyst, and reaction solvent to a reaction vessel and heating to a predetermined reaction temperature while stirring in a nitrogen atmosphere, The reaction is carried out.

After completion of the reaction, a known purification method such as crystallization and concentration can be used to obtain the desired product from the reaction mixture. For example, a solvent or water is added to the reaction mixture, or the mixture is concentrated or the mixture is crystallized, and the precipitated crystals of the objective substance are separated by filtration. The water-soluble impurities may be removed by adding water to the reaction solution before the above operation is performed, followed by washing with water. It is also possible to remove the catalyst from the reaction solution by neutralization with an aqueous alkaline solution, washing with water, or the like, or purify it by column chromatography after treatment to remove low boiling point or the like by concentration.

Example

(Production example)

Synthesis of 1,1-bis (3-nitro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane

9.32 g (0.030 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 50 ml of dichloromethane and a magnet for stirring were placed in a 100 ml three-necked flask, 6.10 g (0.067 mol) of 70% nitric acid was added dropwise over 3 hours while maintaining the temperature at 0 to 5 占 폚. Further, the reaction was carried out for 3 hours while maintaining the temperature. After completion of the reaction, the reaction solution was filtered, and 1% aqueous solution of sodium hydrogencarbonate and then distilled water were poured into the filtered crystals and washed well. After drying, 6.0 g of 1,1-bis (3-nitro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane having a purity of 99.9% (high performance liquid chromatography) was obtained.

(Example 1)

Synthesis of 1,1-bis [2- (3,5-di-t-butyl-4-hydroxyphenyl) -5-benzoxazolyl] -3,3,5-trimethylcyclohexane

To a 100 ml test tube were added 600.5 mg (1.50 mmol) of 1,1-bis (3-nitro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,6- , 96.2 mg (3.00 mmol) of sulfur powder, 16.8 mg (0.30 mmol) of iron powder and 8 ml of o-dichlorobenzene were placed, and the inside of the tube was replaced with argon at room temperature.

Thereafter, the temperature was raised to 180 캜 while stirring, and the reaction was carried out for 48 hours while refluxing at the temperature. After the completion of the reaction, the low boiling point product was distilled off under reduced pressure, and the concentrated residue was purified by silica gel column chromatography to obtain 1,1-bis [2- (3,5-di-t- butyl-4-hydroxyphenyl) Oxazolyl] -3,3,5-trimethylcyclohexane (571.5 mg). The yield for 1,1-bis (3-nitro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane was 50%.

Molecular weight (HRMS / MALDI-TOF): 769.4964 (M + H) ⁺

¹ H NMR identification result (300 MHz, solvent: CDCl ₃ , internal standard: tetramethylsilane)

(Example 2)

Synthesis of 1,1-bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] -3,3,5-trimethylcyclohexane

Bis [2- (3,5-di-t-butyl-4-hydroxyphenyl) -5-benzoxazolyl] -3,3,3- (4.9 × 10 ^-2 mmol) of p-toluenesulfonic anhydride were introduced, and the temperature was raised to 210 ° C. with stirring in a microwave reactor, and the temperature For 4 hours.

After further raising the temperature to 230 占 폚, the reaction was carried out for 3 hours, then the temperature was raised to 250 占 폚 and the reaction was carried out for 5 hours.

After completion of the reaction, the reaction mixture was cooled to room temperature, and the resulting reaction solution was added to water. Further, an aqueous alkaline solution was added to neutralize the solution to a pH of about 6, and the aqueous layer was removed. The obtained oil layer was purified by silica gel column chromatography to obtain 42.0 mg of 1,1-bis [2- (4-hydroxyphenyl) -5-benzoxazolyl] -3,3,5-trimethylcyclohexane. The yield based on 1,1-bis [2- (3,5-di-t-butyl-4-hydroxyphenyl) -5-benzoxazolyl] -3,3,5-trimethylcyclohexane was 39%.

Melting point 344 占 폚 (differential scanning calorimetry)

Molecular weight (HRMS / MALDI-TOF): 545.2461 (M + H) ⁺

¹ H NMR identification result (300 MHz, solvent: THF-d ₈ , internal standard: tetramethylsilane)

(Comparative Example)

Di (4-hydroxyphenyl) -5,5'-bibenzoxazole (comparative compound) synthesized in the same manner as in Example and the compound obtained in Example 2 were dissolved in methanol, toluene, methyl Was dissolved in isobutyl ketone (MIBK) at room temperature to prepare a saturated solution. The supernatant of the saturated solution was collected and the concentration was measured by high performance liquid chromatography. The results of each measurement are shown in the following table. The melting point of the comparative compound was 410 占 폚 (differential scanning calorimetry).

As is clear from the above results, the benzoxazole compound of the present invention is much more excellent in solubility in methanol, toluene, and MIBK than the comparative compound.

Claims (1)

(1)
[Chemical Formula 1]

(Wherein R ₁ represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, R ₂ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, An alkoxy group, a phenyl group or a halogen atom, A represents a cycloalkylidene group having 5 to 10 carbon atoms, and n represents 0 or an integer of 1 to 4.)
(Hydroxyphenyl) benzoxazole compound represented by the formula (I).