KR102408697B1 - Method for producing novel dihydroxy compound - Google Patents

Abstract

(식중, R은 탄소원자수 2~6의 알킬렌기를 나타내고, R₁, R₂는 각각 독립적으로 탄소원자수 1~8의 알킬기 또는 탄소원자수 1~8의 알콕시기를 나타내며, m은 0~3의 정수를 나타내고, n은 0~2의 정수를 나타내며, 단, m이 2 이상인 경우 R₁은 동일해도 되고 상이해도 되며, n이 2인 경우 R₂는 동일해도 되고 상이해도 된다.)
[화학식 2]

(식중, R₂, n은 화학식 1의 그것과 동일하다.)
[화학식 3]

(식중, R, R₁, m은 화학식 1의 그것과 동일하다.) An object of the present invention is to provide a method for preparing a novel dihydroxy compound having an indoline skeleton.
The above problem can be solved by a method of preparing a dihydroxy compound represented by Formula 1 by reacting an N-phenylisatin compound represented by Formula 2 below with a phenoxy alcohol compound represented by Formula 3 below.
[Formula 1]

(Wherein, R represents an alkylene group having 2 to 6 carbon atoms, R ₁ , R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m is an integer of 0 to 3 , and n represents an integer of 0 to 2, with the proviso that when m is 2 or more, R ₁ may be the same or different, and when n is 2, R ₂ may be the same or different.)
[Formula 2]

(Wherein, R ₂ , n is the same as that of Formula 1.)
[Formula 3]

(Wherein, R, R ₁ , and m are the same as those of Formula 1.)

Description

Method for producing novel dihydroxy compound

The present invention relates to a process for the preparation of novel dihydroxy compounds.

Conventionally, bisphenoxy alcohols (compounds in which the hydrogen atom of the hydroxy group of bisphenols is substituted with a hydroxyalkyl group) is a raw material for a thermoplastic synthetic resin such as polycarbonate resin, a raw material for a thermosetting resin such as an epoxy resin, a raw material for an antioxidant, and a heat-sensitive recording medium. It is used as a raw material, a photosensitive resist raw material, etc., and in recent years, the performance required for these bisphenoxy alcohols is becoming more and more advanced.

As such bisphenoxy alcohols, 3,3-bis(4-(2-hydroxyethoxy)phenyl)-2-phenylphthalimidine having an N-phenylisoindoline skeleton is known (non-patent literature). One). Also, as a method for producing bisphenoxy alcohols, a method for producing by reacting a bisphenol compound with alkylene carbonates or alkylene oxides is known. Alcohols further react with alkylene carbonates or alkylene oxides to form a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group, resulting in a low reaction selectivity. In addition, since raw materials and intermediates having an aromatic hydroxyl group exist, the obtained compound is colored and has poor thermal stability. Therefore, repeated purification is required for optical use, which is industrially disadvantageous (Non-Patent Document 1, Patent Document) One).

As another production method, a method of reacting fluorenone with phenoxyethanol is known as a method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, which is a compound having a cardo structure. However, phenoxyethanols have lower reactivity compared to phenols, and in Patent Document 2, hydrogen chloride gas, cation exchange resins, solid acids, etc., which are generally used as catalysts in the production of bisphenols by dehydration condensation of phenols and ketones, are It is described as showing no activity at all.

Accordingly, a method of reacting fluorenones and phenoxyethanols in the presence of sulfuric acid or a heteropolyacid catalyst is known (Patent Documents 3 and 4). However, when sulfuric acid is used as the catalyst, the color deterioration of the product is concerned because the sulfuric acid remains in the product. In addition, when a heteropolyacid is used as a catalyst, the reaction selectivity is lowered because the reaction temperature needs to be high, and it is not efficient, such as the need to react with a large excess of phenoxyethanols to improve the reaction selectivity.

Also, a method for producing 3,3-bis(4-hydroxyphenyl)-2-phenylphthalimidine having an N-phenylisoindoline skeleton by reaction of N-phenylphthalimide with phenol is known (patent). Literature 5).

However, in the case of a compound having an N-phenylisoindoline skeleton or an N-phenylindoline skeleton, there is no known method for producing bisphenoxyalcohols by a condensation reaction between the same ketones and phenoxyalcohols.

Japanese Patent Laid-Open No. Hei 09-255609 Japanese Patent Laid-Open No. 2000-191577 Japanese Patent Laid-Open No. Hei 07-165657 Japanese Patent Laid-Open No. 2007-023016 International Publication No. 2015/107467

Izvestiya Akademii Nauk Gruzinskoi SSR, Seriya Khimicheskaya, 1985, vol.11, p.78-80

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a novel dihydroxy compound having an indoline skeleton having high heat resistance and high refractive index.

As a result of examining a method for preparing a dihydroxy compound having an indoline skeleton, the present inventors found that the reaction was higher than that of the conventional reaction by a condensation reaction using an N-phenylisatin compound and a phenoxyalcohol compound as starting materials. In addition, since the condensation reaction proceeds under milder conditions than in the conventional method, the present invention has been completed by clarifying that the method is industrially advantageous as a method for producing a high-quality dihydroxy compound.

The present invention is as follows.

1. A method for preparing a dihydroxy compound represented by Formula 1 by reacting an N-phenylisatin compound represented by Formula 2 below with a phenoxyalcohol compound represented by Formula 3 below.

(Wherein, R represents an alkylene group having 2 to 6 carbon atoms, R ₁ , R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m is an integer of 0 to 3 , and n represents an integer of 0 to 2, with the proviso that when m is 2 or more, R ₁ may be the same or different, and when n is 2, R ₂ may be the same or different.)

(Wherein, R ₂ , n is the same as that of Formula 1.)

(Wherein, R, R ₁ , and m are the same as those of Formula 1.)

The method for producing a dihydroxy compound according to the present invention is characterized in that the reactivity between the N-phenylisatin compound and the phenoxy alcohol compound is specifically higher than the reactivity between the previously known cardo-structured raw ketones and the phenoxy alcohol compound. It is a manufacturing method with

In addition, since the reactivity of the N-phenyl isatin compound and the phenoxy alcohol compound is high, when compared under the same reaction conditions, the reaction proceeds with a high yield and/or high conversion rate compared to the conventional reaction, or the reaction time can be shortened. , and moreover, since the reaction proceeds under mild conditions, it can be an industrially advantageous manufacturing method.

In addition, the production method of the present invention is useful as an industrial production method because a high-purity dihydroxy compound containing almost no impurities can be obtained.

The present invention will be described in detail below.

The dihydroxy compound of the present invention is represented by Formula 1 below.

[Formula 1]

(Wherein, R represents an alkylene group having 2 to 6 carbon atoms, R ₁ , R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m is an integer of 0 to 3 , and n represents an integer of 0 to 2, with the proviso that when m is 2 or more, R ₁ may be the same or different, and when n is 2, R ₂ may be the same or different.)

In the formula (1), each R is independently an alkylene group having 2 to 6 carbon atoms, and specifically as the alkylene group, for example, 1,2-ethylenediyl group, 1,2-propanediyl group, 1,3- A propanediyl group, a pentamethylene group, a hexamethylene group, etc. are mentioned, Preferably it is a C2-C4 linear or branched alkylene group, Especially preferably, it is a C2-C3 alkylene group. Here, when describing the hydroxyalkoxy group represented by "-O-R-OH" in Formula 1, the bonding position of the hydroxy group bonded to the alkylene group R is a carbon atom (position 1) constituting the alkylene group R directly bonded to the ether group. does not bind to carbon atoms). When R is an alkylene group having 3 or more carbon atoms, the bonding position of the hydroxy group is preferably the 2-position or 3-position of the alkylene group "R", and among these, the 2-position is more preferable. Specific examples thereof include a 2-hydroxyethoxy group, a 2-hydroxypropoxy group, a 2-hydroxy-1-methylethoxy group, and a 3-hydroxypropoxy group.

R ₁ , R ₂ are each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and when R ₁ is an alkyl group having 1 to 8 carbon atoms, the alkyl group preferably has 1 to 4 carbon atoms is a linear or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an isobutyl group. Such an alkyl group may have a substituent, such as a phenyl group and an alkoxy group, in the range which does not impair the effect of this invention, for example.

Further, when R ₁ and R ₂ are an alkoxy group having 1 to 8 carbon atoms, the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, specifically, for example, a methoxy group, ethoxy time, n-propoxy group, isopropoxy group, and the like. The alkoxy group may have, for example, a substituent such as a phenyl group and an alkoxy group within the range that does not impair the effects of the present application.

Preferred R ₁ and R ₂ are methyl groups.

Further, in the formula (1), m is 0, 1, 2 or 3, preferably 0, 1 or 2, and particularly preferably 0 or 1. In the formula (1), n is 0, 1 or 2, preferably 0 or 1, particularly preferably 0.

In addition, in the "-OR-OH" group substituted with a phenyl group directly bonded to the carbon atom at position 3 of the indoline skeleton in Formula 1 and the substitution position of R ₁ , first, the "-OR-OH" group is an indole group. It is preferably substituted at the 4th or 2nd position with respect to the phenyl carbon atom directly bonded to the carbon atom at the 3rd position of the lean skeleton, and more preferably at the 4th position.

In addition, R ₁ is preferably substituted at the o-position or the p-position with respect to the “-OR-OH” group, and with respect to the phenyl carbon atom directly bonded to the carbon atom at position 3 of the indoline skeleton, “- When the group "OR-OH" is substituted with the 4th position, it is preferably substituted with the 3rd or 5th position, and when the "-OR-OH" group is substituted with the 2nd position, the 3rd or 5th position It is preferred to be substituted.

In addition, when m is 2, the substitution position of R ₁ is the "-OR-OH" group at the 4th position, R ₁ is 3 with respect to the phenyl carbon atom directly bonded to the 3rd-position carbon atom of the indoline skeleton. It is preferable that it is substituted in the 2nd position and the 5th position, or the "-OR-OH" group is substituted in the 4th position and R ₁ is substituted at the 2nd position and the 5th position.

In addition, when m is 3, the substitution position of R ₁ is the "-OR-OH" group at the 4 position with respect to the phenyl carbon atom directly bonded to the carbon atom at the 3 position of the indoline skeleton, and R ₁ is 2 It is preferably substituted with the No., 3, and 5 positions.

Therefore, as the dihydroxy compound represented by the formula (1), a compound represented by the following formula (4) is preferable.

(Wherein, R ₂ , n is the same as that of Formula 1, R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, R ₄ is each independently hydrogen represents an atom or an alkyl group having 1 to 4 carbon atoms, provided that the total number of carbon atoms in R ₄ substituted with each hydroxyethoxy group is 4 or less.)

In Formula 4, preferred examples or specific examples of R ₂ , n are the same as those of Formula 1.

In addition, when R ₃ in Formula 4 is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, preferred examples or specific examples thereof include R ₁ in Formula 1 is an alkyl group or carbon source having 1 to 8 carbon atoms. It is the same as the case of an alkoxy group having 1 to 8 embroidery. More preferable R ₃ is a hydrogen atom or a methyl group. As a preferable combination, it is preferable that at least one of R ₃ in the 3-position and the 5-position with respect to the phenyl carbon atom directly bonded to the carbon atom in the 3-position of the indoline skeleton is a hydrogen atom, and further in the indoline skeleton It is preferable that R ₃ at the 2nd and 5th positions with respect to the phenyl carbon atom directly bonded to the carbon atom at the 3rd position is a hydrogen atom. Moreover, it is preferable that all R< ₃ > is especially a hydrogen atom.

In the above formula (4), when R ₄ is an alkyl group having 1 to 4 carbon atoms, specific examples thereof include a methyl group, an ethyl group, and an n-propyl group.

R ₄ is preferably a hydrogen atom or a methyl group.

Specific examples of the dihydroxy compound represented by the formula (1) of the present invention include 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxy-2-methylethoxy)phenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxy-1-methylethoxy)phenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(3-ethyl-4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-2,5-dimethylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-2,3,5-trimethylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(2-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one

3,3-bis(2-(2-hydroxyethoxy)-3-methylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-(4-methylphenyl)-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-(2-methylphenyl)-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-(4-methoxyphenyl)-1H-indol-2-one

and the like.

In the method for producing a dihydroxy compound represented by Formula 1 of the present invention, one of the raw materials is an N-phenylisatin compound represented by Formula 2 below.

[Formula 2]

(Wherein, R ₂ , n is the same as that of Formula 1.)

Preferred examples and specific examples of R ₂ , n are also the same as those of formula (1).

Specifically, as the N-phenylisatin compound represented by the above formula (2), for example,

1-phenyl-1H-indole-2,3-dione

1-(4-methylphenyl)-1H-indole-2,3-dione

1-(2-methylphenyl)-1H-indole-2,3-dione

1-(4-methoxyphenyl)-1H-indole-2,3-dione

and the like.

Another raw material is a phenoxy alcohol compound represented by Formula 3 below.

[Formula 3]

(Wherein, R, R ₁ , and m are the same as those of Formula 1.)

Preferred examples and specific examples of R, R ₁ , and m are also the same as those of formula (1).

As the phenoxy alcohol compound represented by the above formula (3), a compound represented by the formula (6) is preferable.

(Wherein, R ₃ , R ₄ are the same as those of Formula 4)

Preferred examples and specific examples of R ₃ and R ₄ are also the same as those of Formula (4).

As the compound represented by the above formula (6), specifically, for example,

2-phenoxyethanol

2-phenoxypropanol

1-phenoxy-2-propanol

2-(2-methylphenoxy)ethanol

2-(2-ethylphenoxy)ethanol

2-(2,6-dimethylphenoxy)ethanol

2-(2,5-dimethylphenoxy)ethanol

2-(2,3,6-trimethylphenoxy)ethanol

and the like.

A method for preparing a dihydroxy compound represented by Formula 1 having an indoline skeleton by reacting an N-phenylisatin compound represented by Formula 2 with a phenoxyalcohol compound represented by Formula 3, which is the production method of the present invention will be described in detail.

The condensation reaction is carried out by reacting the N-phenylisatin compound and the phenoxy alcohol compound in the presence of an acid catalyst. First, a reaction mixture obtained by reacting an N-phenylisatin compound and a phenoxyalcohol compound in the presence of an acid catalyst is neutralized with an alkali, and then crystallized and filtered according to a known method to obtain a primary crystallized filtrate.

The molar ratio of the addition of the phenoxy alcohol compound to the N-phenylisatin compound during the reaction is not particularly limited as long as the molar ratio is greater than or equal to the theoretical value (2.0). range, particularly preferably in the range of 4.0 to 15 times the molar amount.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, hydrogen chloride gas, 60 to 98% sulfuric acid and 85% phosphoric acid, organic acids such as p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid or trifluoroacetic acid, and heteropolyacids. and solid acids such as ion exchange resins, activated clay, and silica-alumina. Preferably it is hydrogen chloride gas. A suitable amount of the acid catalyst used varies depending on the reaction conditions. For example, in the case of hydrogen chloride gas, after replacing the air in the reaction system with an inert gas such as nitrogen gas, hydrogen chloride gas is blown in to the concentration of hydrogen chloride gas in the gas phase in the reaction vessel. It is preferable to set the concentration of hydrogen chloride in the reaction solution as the saturation concentration by setting it to 75-100% by volume. In the case of 35% hydrochloric acid, it is used in the range of 5 to 70 parts by weight, preferably in the range of 10 to 40 parts by weight, and more preferably in the range of 20 to 30 parts by weight based on 100 parts by weight of the phenoxy alcohol compound. Here, when sulfuric acid is used as an acid catalyst, there is a concern that the color of the compound is deteriorated due to the sulfuric acid remaining in the desired compound, and when a heteropoly acid is used as an acid catalyst, the reaction temperature needs to be high, so that the reaction selectivity is lowered etc. is not efficient.

In the reaction, a cocatalyst may be used along with the acid catalyst as needed. For example, when hydrogen chloride gas is used as a catalyst, the reaction rate can be accelerated by using thiols as a co-catalyst. Examples of such thiols include alkyl mercaptans and mercaptocarboxylic acids, preferably alkyl mercaptans having 1 to 12 carbon atoms and mercaptocarboxylic acids having 1 to 12 carbon atoms, for example, methyl mercaptan and alkali metal salts such as ethyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan and their sodium salts, thioacetic acid, thioglycolic acid, and β-mercaptopropionic acid.

In addition, these can be used individually or in combination of 2 or more types.

The amount of thiol used as a co-catalyst is usually in the range of 0.5 to 20 mol%, preferably in the range of 2 to 10 mol%, based on the N-phenylisatin compound as a raw material.

In addition, the reaction solvent during the reaction has a low melting point of the raw materials N-phenyl isatin compound and phenoxy alcohol compound, and there is no need to use a solvent if there is no problem in operability. You may use it. The reaction solvent is not particularly limited as long as it does not flow out of the reactor at the reaction temperature and is inert to the reaction. For example, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as alcohol, hexane, heptane and cyclohexane; and carboxylate esters such as ethyl acetate and butyl acetate; and mixtures thereof. Of these, aliphatic alcohols are preferably used.

In addition, in order to promote the reaction of the acid catalyst by lowering the freezing point of the phenoxy alcohol compound, a small amount of water may be added as needed. In particular, when the acid catalyst is hydrogen chloride gas, water is preferable from the viewpoint of accelerating absorption of the hydrogen chloride gas as the catalyst. When adding water, the amount is preferably in the range of 0.5 to 15.0 parts by weight based on 100 parts by weight of the phenoxy alcohol compound.

The reaction temperature varies depending on conditions such as a catalyst to be used, but is preferably in the range of 20 to 70°C, more preferably in the range of 30 to 60°C. The reaction pressure is usually carried out under normal pressure, but depending on the boiling point of the organic solvent that may be used, the reaction may be carried out under pressure or reduced pressure so that the reaction temperature is within the above range. When the reaction is carried out under these conditions, the reaction is usually completed in about 1 to 30 hours.

The endpoint of the reaction can be confirmed by liquid chromatography or gas chromatography analysis. It is preferable that the end point of the reaction is the point at which the unreacted N-phenylisatin compound disappears and no increase in the target substance is observed.

The reaction yield for the phenoxy alcohol compound is usually about 75 to 95 mol%.

After completion of the reaction, an alkali solution such as aqueous ammonia or aqueous sodium hydroxide solution is added to the obtained reaction mixture to neutralize the acid catalyst to obtain a reaction mixture solution containing the dihydroxy compound represented by the formula (1) of the present invention.

After the unreacted raw material phenoxy alcohol compound is removed by distillation of the neutralized reaction mixture, if necessary, water and an organic solvent insoluble in water are added, and the mixture is sufficiently stirred to perform water washing to separate the oil layer. The organic solvent used at this time needs to be an organic solvent that dissolves the dihydroxy compound of Formula 1 and has low solubility in water. As the organic solvent having this property, an aromatic hydrocarbon-based solvent such as toluene and xylene, an aliphatic hydrocarbon-based solvent such as cyclohexane and n-heptane, an aliphatic ketone-based solvent such as methyl isobutyl ketone, and an alcohol solvent such as butanol can be employed.

After the organic solvent layer obtained after neutralization and washing with water is partially removed by distillation, if necessary, the organic solvent layer is heated as it is or once heated to make a uniform solution, then cooled, or a crystallization solvent or poor solvent is added as appropriate. In the case where crystals are precipitated by cooling by filtration, the crude or high-purity target product can be obtained by filtering the crystals.

It is also possible to further refine the target product obtained above by recrystallization using a solvent. Examples of the organic solvent used at this time include aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and ester solvents such as ethyl acetate and butyl acetate, butanol, etc. Alcohol solvent is mentioned, These can be used individually or in mixture of 2 or more types.

Instead of the above crystallization operation, after completion of the reaction, the reaction solvent or the like is concentrated under reduced pressure, and the residue is purified by column chromatography or the like to obtain a high-purity product.

Here, as impurities that may be contained in the dihydroxy compound represented by Formula 1, 1EO (monohydroxyalkoxy) represented by Formula 7 below, and polyEO represented by Formula 8 below (hydroxyalkoxy group) a compound in which the hydroxy group of is further substituted with a hydroxyalkoxy group). However, by reacting the N-phenylisatin compound represented by Formula 2 with the phenoxyalcohol compound represented by Formula 3 by the production method of the present invention to prepare a dihydroxy compound represented by Formula 1, the following formula It is possible to prepare a dihydroxy compound represented by the formula (1) that does not contain impurities of the 1EO form represented by 7 or the polyEO form represented by the following formula (8).

The above-mentioned 1EO body is represented by the following formula (7).

(Wherein, R, R ₁ , R ₂ , m, and n are the same as those of Formula 1.)

Preferred examples and specific examples of R, R ₁ , R ₂ , m, and n are also the same as those of the formula (1).

The above-mentioned polyEO body is represented by the following formula (8).

(Wherein, R, R ₁ , R ₂ , m, and n are the same as those of Formula 1, and k each independently represents an integer of 1 to 5, except that k is 1 at the same time.)

Preferred examples and specific examples of R, R ₁ , R ₂ , m, and n are also the same as those of the formula (1).

Among the polyEOs represented by the above formula (8), the 3EO form, which is a compound that is more likely to be contained, is represented by the following formula (9).

(Wherein, R, R ₁ , R ₂ , m, and n are the same as those of Formula 1.)

Preferred examples and specific examples of R, R ₁ , R ₂ , m, and n are also the same as those of the formula (1).

Since the production method of the present invention has high reactivity compared to the conventional production method, the reaction proceeds under mild reaction conditions, and thus the desired dihydroxy compound can be obtained in high yield and/or high conversion rate compared to the conventional reaction.

In addition, since the dihydroxy compound represented by Chemical Formula 1 obtained by the production method of the present invention does not contain impurities of the polyEO form represented by the above-mentioned 1EO form and 3EO form, it is of high purity, so that the optical properties such as thermal stability and product color The characteristics are excellent.

Since the dihydroxy compound represented by the formula (1) obtained by the production method of the present invention is of high purity, it is expected to have high heat resistance and high refractive index, and particularly excellent effects are expected in polycarbonate for optical materials. That is, by using high molecular weight polycarbonate, it is excellent in transparency, heat resistance, mechanical properties, impact resistance, fluidity, etc. It can be expected to be used in the field.

In addition, as a polycarbonate oligomer, it can be used as a raw material for producing high molecular weight polycarbonate by various polymerization methods, as well as polymer modifiers such as surface modifiers, flame retardants, UV absorbers, flow modifiers, plasticizers, compatibilizers for resin alloys, etc. , can be widely used as an additive.

In addition, the dihydroxy compound of the present invention obtained by the production method of the present invention uses a terminal hydroxy group, in addition to polycarbonate, epoxy resin, oxetane resin, acrylic resin, polyester, polyarylate, polyether ether ketone, It can also be expected to be used as a raw material for resins such as polysulfone, novolac, and resol, as a raw material for other photosensitive compositions, as a resist additive, as a developer, and as an antioxidant.

In particular, use as an acrylic monomer such as diacrylate obtained by reacting the dihydroxy compound of the present invention with acrylic acid or the like, as a raw material for an acrylic resin, and use as an optical hard coating material using these can be expected.

Example

The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples.

In addition, the softening point in an Example, refractive index, and purity were measured by the following method.

[Analysis method]

1. Measurement of softening point

Device: manufactured by Shimadzu Corporation 　DSC-60 DIFFERENTIAL SCANNING CALORIMETER

Temperature rise condition: 10℃/min　(30℃→200℃)

Atmospheric gas: nitrogen gas (flow: 50 ml/min)

How to measure :

The first measurement was performed under the above-mentioned temperature rising condition, and the melting point was measured from the endothermic peak thereof.

Thereafter, the same material was cooled to room temperature, and measurement was performed a second time under the same conditions, and the endothermic peak thereof was taken as the softening point.

2. Measurement of refractive index

Apparatus: Refractometer RA-500N manufactured by Kyoto Electronics Industry Co., Ltd.

How to measure :

THF solutions (THF refractive index 1.40) having concentrations of 10, 15, and 30% were prepared, and the refractive index of the compound to be measured was calculated by extrapolation from the refractive index of the solution.

3. Purity Determination

Equipment: manufactured by Shimadzu Corporation 　CLASS-LC10

Pump: LC-10ATvp

Column oven: CTO-10Avp

Detector: SPD-10Avp

Column: Shim-pack　CLC-ODS　Inner diameter 6 mm, length 150 mm

Oven temperature: 50℃

Flow rate: 1.0 ml/min

Mobile phase: (A) methanol, (B) 0.2 vol% aqueous acetic acid solution

Gradient conditions: (A) Volume % (time from the start of analysis)

60%(0min)→60%(20min)→100%(40min)→100%(50min)

Sample injection amount: 20 μl

Detection wavelength: 280 nm

<Example 1>

Preparation of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one-1

331.2 g (2.40 mol) of 2-phenoxyethanol and 44.6 g (0.20 mol) of 1-phenyl-1H-indole-2,3-dione were placed in a 4-neck flask equipped with a thermometer, a stirrer, and a cooling tube, and the reaction vessel was purged with nitrogen. After the substitution, hydrogen chloride gas was blown at 40° C. so that the concentration of hydrogen chloride gas in the gas phase was 95% or more. Then, 4.2 g of 15% sodium methyl mercaptan aqueous solution (0.009 mol as sodium methyl mercaptan) was added, and the mixture was stirred at 40° C. for 22 hours.

After completion of the reaction, the conversion rate of 1-phenyl-1H-indole-2,3-dione was 99.7%, 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indole-2- The reaction yield of ion (vs. 1-phenyl-1H-indole-2,3-dione) was 93.7%.

After completion of the reaction, 304.5 g of a 16% aqueous sodium hydroxide solution (1.22 mol as sodium hydroxide) was added to adjust the pH to 6. The resulting solution was heated to 150 DEG C, unreacted 2-phenoxyethanol was distilled off under a reduced pressure of 2.4 kPa, and then 268.3 g of toluene was added. 45.0 g of water was added to the obtained solution, stirred at 80° C., and then left still to perform a water washing operation to extract the aqueous layer twice. After washing with water, the temperature of the obtained oil layer was raised to 160°C, the solvent was removed by distillation under a reduced pressure of 1.0 kPa, followed by cooling, and 582.2 g of toluene was added at 110°C, and 72.3 g of methanol was added at 70°C. Then, it cooled to 30 degreeC, and the precipitated crystal|crystallization was separated by filtration to obtain 61.4 g of crude crystals as white crystals.

After adding 226.5 g of 1-butanol to 55.5 g of the obtained crude crystal and dissolving it at 110°C, 112.7 g of 1-butanol was removed by distillation under normal pressure, followed by cooling to 30°C, and the precipitated crystals were separated by filtration. 48.5 g of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one was obtained by drying the obtained crystals at 80°C under reduced pressure.

Purity 　　　　　　　99.2% (high-speed liquid chromatography area%)

1EO represented by the formula (7) (below the detection limit)

3EO body represented by the formula (9) (below the detection limit)

Yield 　　　　　　　55% (vs. 1-phenyl-1H-indole-2,3-dione)

Melting point　　　　　　　153℃ (differential scanning calorimetry)

Softening temperature　　　　　73℃ (differential scanning calorimetry)

Refractive index (n _D 20) 1.60

Proton nuclear magnetic resonance spectrum (400 MHz, solvent DMSO-D ₆ , standard TMS) chemical shift (signal shape, number of protons):

<Example 2>

Preparation of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one-2

34.8 g (0.25 mol) of 2-phenoxyethanol, 10.0 g (0.045 mol) of 1-phenyl-1H-indole-2,3-dione, n-octylmercaptan in a 4-neck flask equipped with a thermometer, stirrer, and cooling tube 0.35 g (0.0024 mol) was added, and 20.7 g of methanesulfonic acid was added while maintaining the temperature in the system at 50-55° C., followed by stirring at 50-55° C. for 4.5 hours.

After completion of the reaction, the conversion ratio of 1-phenyl-1H-indole-2,3-dione was 100%, 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indole-2- The reaction yield of ion (vs. 1-phenyl-1H-indole-2,3-dione) was 85.3%, and all of the 1EO compounds represented by Chemical Formula 7 and 3EO compounds represented by Chemical Formula 9 were below the detection limit.

From the results of Examples 1 and 2, it is found that the production method of the present invention is a method for obtaining a high-purity dihydroxy compound containing almost no impurities of 1EO represented by Formula 7 or 3EO represented by Formula 9. It was confirmed and it became clear that it is useful as an industrial manufacturing method.

In addition, with reference to the manufacturing method described in Japanese Patent Publication No. 2010-505011, etc., the N-phenylisatin compound represented by the formula (2) and a phenol compound are reacted, and then the obtained bisphenol compound having an indoline skeleton is alkylated In the method of producing a dihydroxy compound represented by Formula 1 by reacting with rencarbonate and the like to hydroxyalkylate, the generation of impurities of 1EO represented by Formula 7 or 3EO represented by Formula 9 cannot be suppressed. , as a result, a high-purity dihydroxy compound cannot be obtained. This will be specifically demonstrated in "Comparative Example 1" below.

<Comparative Example 1>

Preparation of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one

(Process 1)

Preparation of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one

225.9 g (2.40 mol) of phenol and 44.6 g (0.20 mol) of 1-phenyl-1H-indole-2,3-dione were placed in a 4-neck flask equipped with a thermometer, a stirrer, and a cooling tube, and the reaction vessel was substituted with nitrogen, Hydrogen chloride gas was blown at 40° C. so that the concentration of hydrogen chloride gas in the gas phase was 95% or more. Then, it stirred at 30 degreeC for 22 hours. After completion of the reaction, the conversion rate of 1-phenyl-1H-indole-2,3-dione was 100%, and the reaction yield of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one (vs. 1-phenyl-1H-indole-2,3-dione) was 88.8%.

After completion of the reaction, 57.4 g of 16% aqueous sodium hydroxide solution (0.23 mol as sodium hydroxide), 0.3 g of 75% phosphoric acid, 3.0 g of water, and 40.0 g of toluene were added, and the mixture was heated to 75° C. and stirred. Then, it cooled to 30 degreeC, and obtained 86.8 g of crude crystals by filtering the precipitated crystal|crystallization.

To the obtained crude crystal, 151.9 g of toluene, 325.5 g of methyl ethyl ketone, and 87.0 g of water were added and dissolved at 70° C., and then left still to extract an aqueous layer. After adding water and stirring at 70°C, the water washing operation of extracting the aqueous layer by standing still was performed twice. After washing with water, the obtained oil layer was heated to 110°C and the solvent was removed by distillation, then toluene was added and cooled to 30°C, and the precipitated crystals were separated by filtration. The obtained crystals were dried at 60°C under reduced pressure to obtain 56.1 g of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one.

Purity 　　　99.5% (high-speed liquid chromatography area%)

Yield 　　　71.3% (vs. 1-phenyl-1H-indole-2,3-dione)

Melting point　　　300℃ (differential scanning calorimetry)

(Process 2)

Preparation of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one

40.0 g (0.10 mol) of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one obtained in step 1, 1- 60.0 g of butanol, 26.0 g (0.30 mol) of ethylene carbonate, 0.60 g of 48% aqueous potassium hydroxide solution (0.0051 mol as potassium hydroxide), 0.33 g (0.0010 mol) of tetrabutylammonium bromide were added, and the reaction vessel was substituted with nitrogen, and then 118~ The mixture was stirred for 12 hours while maintaining 120° C., and then 5.1 g of water was added, followed by stirring while maintaining 105 to 107° C. for an additional 4 hours.

After adding 12.7 g of a 10% aqueous acetic acid solution at 70°C to the obtained reaction solution, 20.0 g of methyl isobutyl ketone and 40.0 g of water were added and dissolved at 80°C, and then left still to extract the aqueous layer. Further, after adding water and stirring, the water washing operation in which the water layer was extracted by standing still was performed once. After washing with water, the obtained oil layer was heated to 126°C to remove the solvent by distillation, and then toluene and water were added. It cooled to 25 degreeC, and 75.1 g of crude crystals were obtained by filtering the precipitated crystal|crystallization.

300.4 g of 1-butanol was added to the obtained crude crystals, dissolved at 75°C, the temperature was raised to 120°C, the solvent was removed by distillation, and then cooled to 25°C, and the precipitated crystals were separated by filtration. 31.5 g of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one was obtained by drying the obtained crystal|crystallization at 80 degreeC under reduced pressure.

Purity 　　　 97.1% (high-speed liquid chromatography area%)

1EO represented by the formula (7): 0.06%

3EO body represented by the formula (9): 2.76%

Yield 　　　 71.7% (vs. 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one)

Total yield 　51.1% (vs. 1-phenyl-1H-indole-2,3-dione)

Melting point　　　150.2℃ (differential scanning calorimetry)

<Comparative Example 2>

Preparation of 9,9-((4-hydroxyethoxy)phenyl)fluorene

Put 78.3 g (0.57 mol) of 2-phenoxyethanol into a 4-neck flask equipped with a thermometer, stirrer, and cooling tube, purify the reaction vessel with nitrogen, and then blow hydrogen chloride gas at 40° C. to reduce the hydrogen chloride gas concentration in the gas phase to 98% above. Subsequently, 11.3 g of 21% sodium methyl mercaptan aqueous solution (0.034 mol as sodium methyl mercaptan) was added, and then 50.0 g (0.28 mol) of 9-fluorenone dissolved in 75 g (0.54 mol) of 2-phenoxyethanol was added for 2 hours. was dropped over. After stirring at 40° C. for 30 hours, the conversion rate of 9-fluorenone was 27%, and the reaction yield of 9,9-((4-hydroxyethoxy)phenyl)fluorenone was 15%.

<Comparative example 3>

Preparation of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-2-phenylphthalimidine

331.6 g (2.40 mol) of 2-phenoxyethanol and 44.8 g (0.20 mol) of N-phenylphthalimide were placed in a 4-neck flask equipped with a thermometer, a stirrer, and a cooling tube, the reaction vessel was substituted with nitrogen, and then at 40°C Hydrogen chloride gas was blown in so that the concentration of hydrogen chloride gas in the gas phase was 95% or more. Then, 4.2 g of 15% sodium methyl mercaptan aqueous solution (0.009 mol as sodium methyl mercaptan) was added, and the mixture was stirred at 40° C. for 22 hours.

In the reaction solution after 22 hours of reaction, no formation of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-2-phenylphthalimidine was observed.

From the results of Comparative Examples 2 and 3, the reactivity of the N-phenylisatin compound represented by Formula 2 and the phenoxyethanol compound represented by Formula 3 in the preparation method of the present invention is 9-fluorenone and 2-phenoxyethanol It was confirmed that it was specifically higher than the reaction of (Comparative Example 2) or the reaction of N-phenylphthalimide and 2-phenoxyethanol (Comparative Example 3).

That is, in the method for producing the dihydroxy compound represented by Formula 1 of the present invention, the reactivity between the N-phenylisatin compound and the phenoxy alcohol compound is related to the reactivity between the previously known cardo-structured raw material ketones and the phenoxy alcohol compound. It is a manufacturing method in which a feature that is specifically higher than that is a feature.

Due to this high reactivity, the production method of the present invention can proceed with a high yield and/or a high conversion rate or shorten the reaction time compared to the conventionally known production method, and furthermore, because the reaction proceeds under mild conditions, It can be an industrially advantageous manufacturing method.

In addition, the production method of the present invention is useful as an industrial production method because a high-purity dihydroxy compound containing almost no impurities can be obtained.

Claims (1)

A method for preparing a dihydroxy compound represented by Formula 1 by reacting an N-phenylisatin compound represented by Formula 2 below with a phenoxyalcohol compound represented by Formula 3 below.
[Formula 1]

(Wherein, R represents an alkylene group having 2 to 6 carbon atoms, R ₁ , R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and m is 0, 1 or 2 , n represents 0 or 1, and the "-OR-OH" group is substituted at the 4th position with respect to the phenyl carbon atom directly bonded to the 3rd-position carbon atom of the indoline skeleton, provided that m is In the case of 2, R ₁ may be the same or different.)
[Formula 2]

(Wherein, R ₂ , n is the same as that of Formula 1.)
[Formula 3]

(Wherein, R, R ₁ , and m are the same as those of Formula 1, and the substitution position of R ₁ is not the 4th position.)