TW201738208A - Novel dihydroxy compound - Google Patents

Abstract

An object of the present invention is to provide a novel dihydroxy compound having an indoline skeleton. The above object can be solved by a method of producing the dihydroxy compound represented by the following general formula (1) of reacting an N-phenylisatin compound represented by the following general formula (2) with a phenoxy alcohol compound represented by the following general formula (3). (In the formula, R represents an alkylene group having 2 to 6 carbon atoms, each of R1 and R2 independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m represents an integer of 0 to 3, and n represents an integer of 0 to 2, provided that when m is 2 or more, R1 may be the same or different, and when n is 2, R2 may be the same or different.) (In the formula, R2 and n are the same as those in the general formula (1).) (In the formula, R, R1 and m are the same as those in the general formula (1).).

Description

Novel method for producing dihydroxy compound

This invention relates to a process for the manufacture of novel dihydroxy compounds.

Conventionally, bisphenoxy alcohols (compounds in which a hydrogen atom of a hydroxy group of a bisphenol is substituted with a hydroxyalkyl group) are used as a thermoplastic synthetic resin raw material such as a polycarbonate resin, a thermosetting resin material such as an epoxy resin, or an antioxidant. For applications such as raw materials, thermal recording material materials, and photosensitive resist materials, the performance required for these bisphenoxy alcohols has been increasing in recent years.

The bisphenoxy alcohol is known to have 3,3-bis(4-(2-hydroxyethoxy)phenyl)-2-phenylbenzylcarfenamide having an N-phenylisoindoline skeleton ( Non-patent document 1). Further, a method for producing a bisphenoxy alcohol is known by a method in which a bisphenol compound is reacted with an alkylene carbonate or an alkylene oxide, but in the method, a monohydroxy alkoxy group or a target of the intermediate is known. The bisphenoxy alcohols are further reacted with alkylene carbonates or alkylene oxides to form a compound in which the hydroxyl group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group, and the reaction selectivity is lowered. In addition, since a raw material or an intermediate having an aromatic hydroxyl group is present, the obtained compound is colored and has poor thermal stability. Therefore, it is necessary to repeat the purification when it is used as an optical application, and it is industrially disadvantageous (Non-Patent Document 1 and Patent Document 1) ).

Other manufacturing methods, for the production method of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene which is a compound having a cardo structure, are known to make anthrone and phenoxy a method of reacting with an ethanol, but the phenoxyethanol is less reactive than a phenol, and Patent Document 2 describes that in the production of a bisphenol by dehydration condensation of a phenol and a ketone, Generally, hydrogen chloride gas, a cation exchange resin, a solid acid or the like which is used as a catalyst does not exhibit activity at all.

Therefore, a method of reacting an anthrone with a phenoxyethanol in the presence of a sulfuric acid or a heteropoly acid catalyst is known (Patent Documents 3 and 4). However, if sulfuric acid is used as a catalyst, sulfuric acid will remain in the product, and the hue of the product will deteriorate. Further, when a heteropoly acid is used as a catalyst, it is necessary to set the reaction temperature to a high temperature, so that the reaction selectivity is lowered, and it is inefficient to react with a large excess of phenoxyethanol in order to increase the reaction selectivity.

Further, it is known that 3,3-bis(4-hydroxyphenyl)-2-benzene having an N-phenylisoindoline skeleton is produced by the reaction of N-phenylphthalimide with phenol. Method for benzylbenzamide (Patent Document 5).

However, in the compound having an N-phenylisoindoline skeleton or an N-phenylporphyrin skeleton, a method for producing a bisphenoxy alcohol by a condensation reaction of the same ketone with a phenoxy alcohol is not known. .

[Previous Technical Literature] [Non-patent literature]

Non-Patent Document 1: Izvestiya Akademii Nauk Gruzinskoi SSR, Seriya Khimicheskaya, 1985, vol. 11, p. 78-80.

[Non-patent literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 09-255609.

Patent Document 2: Japanese Laid-Open Patent Publication No. 2000-191577.

Patent Document 3: Japanese Laid-Open Patent Publication No. Hei 07-165657.

Patent Document 4: Japanese Laid-Open Patent Publication No. 2007-023016.

Patent Document 5: International Publication No. 2015/107467.

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

The present inventors have reviewed a method for producing a dihydroxy compound having a porphyrin skeleton, and as a result, found that a condensation reaction is carried out by using an N-phenylisatin compound and a phenoxy alcohol compound as a starting material as compared with the conventional reaction. Further, since the production method is carried out by a condensation reaction under mild conditions as compared with the conventional method, the present invention is completed as an industrially advantageous method as a method for producing a high-quality dihydroxy compound.

The present invention is as follows.

1. A method for producing a dihydroxy compound represented by the formula (1), which is an N-phenyl ruthenium compound represented by the following formula (2) and a phenoxy group represented by the following formula (3) The alcohol compound is reacted; (wherein R represents an alkylene group having 2 to 6 carbon atoms, and R ₁ and R ₂ each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m It is an integer from 0 to 3, and n is an integer from 0 to 2. However, 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 and n are the same as those of the formula (1)) (wherein R, R ₁ and m are the same as those of the formula (1))

The method for producing a dihydroxy compound of the present invention is particularly reactive with a phenoxy alcohol compound and a phenoxy alcohol compound, compared with the reactivity of a raw material ketone of a cardo structure and a phenoxy alcohol compound. A manufacturing method that is advantageous.

Further, since the N-phenyl ruthenium compound has high reactivity with the phenoxy alcohol compound, when compared under the same reaction conditions, the reaction can be carried out at a high yield and/or high conversion rate as compared with the conventional reaction, or The reaction time can be shortened, and the reaction can be carried out under mild conditions, so that it can be an industrially advantageous production method.

Further, the production method of the present invention can obtain a high-purity dihydroxy compound which contains almost no impurities, and thus can be used as an industrial production method.

The invention is described in detail below.

The dihydroxy compound of the present invention is represented by the following formula (1).

(wherein R represents an alkylene group having 2 to 6 carbon atoms, and R ₁ and R ₂ each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m It is an integer from 0 to 3, and n is an integer from 0 to 2. However, 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 above formula (1), R is each independently an alkylene group having 2 to 6 carbon atoms, and the alkylene group may specifically be, for example, 1,2-ethylenediamine or 1,2-propane. a dibasic group, a 1,3-propanediyl group, a pentamethylene group, a hexamethylene group or the like, but is preferably a linear or branched alkyl group having 2 to 4 carbon atoms, particularly preferably a carbon atom 2 or 3 alkylene. Here, the hydroxyalkoxy group represented by "-OR-OH" in the above formula (1) will be described, and the hydroxy bonding site bonded to the alkylene group R is not bonded to the direct bond with the ether group. A carbon atom of the alkyl group R (1 carbon atom). When R is an alkylene group having 3 or more carbon atoms, the hydroxy bonding position is preferably 2 or 3 positions of the alkyl group "R", and more preferably 2 positions. Specific examples thereof include 2-hydroxyethoxy group, 2-hydroxypropoxy group, 2-hydroxy-1-methylethoxy group, 3-hydroxypropoxy group and the like.

R ₁ and R ₂ are each independently an alkyl group having 1 to 8 carbon atoms and 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 is preferably an alkyl group. The linear or branched alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an isobutyl group. The alkyl group may have a substituent such as a phenyl group or an alkoxy group, within the range not impairing the effects of the present invention.

Further, when R ₁ and R ₂ are alkoxy groups having 1 to 8 carbon atoms, the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, and specific examples thereof include, for example, Methoxy, ethoxy, n-propoxy, isopropoxy and the like. The alkoxy group may have a substituent such as a phenyl group or an alkoxy group, within the range not impairing the effects of the present invention.

Preferably, R ₁ and R ₂ are methyl groups.

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

Further, in the above formula (1), a "-OR-OH" group substituted with a phenyl group directly bonded to a carbon atom at the 3-position of the porphyrin skeleton, and a substitution position of R _{1 are} first, "- The OR-OH" group is preferably substituted at the 4- or 2-position with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the porphyrin skeleton, and more preferably at the 4-position.

Further, R _{1 is} preferably substituted in the ortho or para position with respect to the above-mentioned "-OR-OH" group, and is a phenyl carbon atom which is directly bonded to the carbon atom at the 3-position of the porphyrin skeleton. When the "-OR-OH" group is substituted at the 4-position, it is preferably substituted at the 3-position or the 5-position. When the "-OR-OH" group is substituted at the 2-position, it is preferably at the 3 or 5 position. Replace it.

Further, when m is 2, the substitution position of R ₁ is preferably such that the "-OR-OH" group is at the 4-position with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the porphyrin skeleton. Substitution is carried out and R ₁ is substituted at the 3 and 5 positions, or the "-OR-OH" group is substituted at the 4 position and R ₁ is substituted at the 2 and 5 positions.

Further, when m is 3, the substitution position of R ₁ is preferably such that the "-OR-OH" group is at the 4-position with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the porphyrin skeleton. Substitution is carried out and R ₁ is substituted at the 2, 3 and 5 positions.

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

(wherein R ₂ and n are the same as those of the formula (1), and 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 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the total number of carbon atoms of R ₄ substituted in each hydroxyethoxy group is 4 or less.

In the above formula (4), preferred examples or specific examples of R ₂ and n are the same as those of the formula (1).

Further, in the above formula (4), when R ₃ 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 are those of the formula (1) R ₁ is the same as the alkyl group having 1 to 8 carbon atoms or the alkoxy group having 1 to 8 carbon atoms. More preferably, R ₃ is a hydrogen atom or a methyl group. As a preferred combination, it is preferred that at least one of R ₃ at the 3 and 5 positions is a hydrogen atom with respect to a phenyl carbon atom directly bonded to a carbon atom at the 3-position of the porphyrin skeleton, and The phenyl carbon atom directly bonded to the 3-position carbon atom of the porphyrin skeleton, and R _{3 at the} 2-position and the 5-position are preferably a hydrogen atom. Further, it is particularly preferred that R _{3 is} a hydrogen atom.

In the above formula (4), when R ₄ is an alkyl group having 1 to 4 carbon atoms, specifically, for example, a methyl group, an ethyl group, a n-propyl group or the like can be mentioned.

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-indole. -2-ketone; 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-methylbenzene 1-phenyl-1H-indol-2-one; 3,3-bis(3-ethyl-4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indole Indole-2-one; 3,3-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)-1-phenyl-1H-indol-2-one; 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- Indole-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; and 3,3-bis(4-(2-hydroxyl) Ethoxy)phenyl)-1-(4-methoxyphenyl)-1H-indol-2-one and the like.

In the method for producing a dihydroxy compound represented by the formula (1) of the present invention, one of the raw materials is an N-phenylasatin compound represented by the following formula (2).

(wherein R ₂ and n are the same as those of the formula (1))

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

Specific examples of the N-phenyl ruthenium compound represented by the above formula (2) include 1-phenyl-1H-indole-2,3-dione; 1-(4-methylphenyl group; -1H-indole-2,3-dione; 1-(2-methylphenyl)-1H-indole-2,3-dione; and 1-(4-methoxyphenyl)- 1H-indole-2,3-dione and the like.

Another raw material is a phenoxy alcohol compound represented by the following formula (3) Things.

(wherein R, R ₁ and m are the same as those of the formula (1))

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

The phenoxy alcohol compound represented by the above formula (3) is preferably a compound represented by the formula (6).

(wherein R ₃ and R ₄ are the same as those of the formula (4))

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

Specific examples of the compound represented by the above formula (6) include 2-phenoxyethanol; 2-phenoxypropanol; 1-phenoxy-2-propanol; 2-(2-A) Phenyloxy)ethanol; 2-(2-ethylphenoxy)ethanol; 2-(2,6-dimethylphenoxy)ethanol; 2-(2,5-dimethylphenoxy) Ethanol; and 2-(2,3,6-trimethylphenoxy)ethanol.

The manufacturing method of the present invention will be described in detail, that is, the general formula (2) A method of producing a dihydroxy compound represented by the formula (1) having a porphyrin skeleton by reacting the N-phenyl ruthenium compound shown and the phenoxy alcohol compound represented by the formula (3).

The condensation reaction is carried out by reacting the above N-phenyl ruthenium compound and phenoxy alcohol compound in the presence of an acid catalyst. First, the N-phenyl ruthenium compound and the phenoxy alcohol compound are reacted in the presence of an acid catalyst, and the obtained reaction mixture is neutralized with a base, and then crystallized and filtered according to a known method to obtain a crystallization filter once.

In the reaction, the molar ratio of the phenoxy alcohol compound to the N-phenyl ruthenium compound is not more than a theoretical value (2.0) or more, but it is preferably 3.0 times or more, more preferably 3.0 times or more. It is in the range of 3.5 to 20 times the molar amount, and particularly preferably in the range of 4.0 to 15 times the molar amount.

The acid catalyst may, for example, be an inorganic acid such as hydrochloric acid, hydrogen chloride gas, 60 to 98% sulfuric acid or 85% phosphoric acid; an organic acid such as p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid or trifluoroacetic acid; Acid, ion exchange resin, activated clay, solid acid such as cerium oxide-alumina, and the like. Hydrogen chloride gas is preferred. The preferred amount of the acid catalyst to be used varies depending on the reaction conditions. However, when the hydrogen chloride gas is used, for example, the air of the reaction system may be substituted with an inert gas such as nitrogen gas, and then hydrogen chloride gas may be blown to make the gas in the reaction vessel. The concentration of hydrogen chloride gas is 75 to 100% by volume, and the concentration of hydrogen chloride in the reaction liquid becomes a saturated concentration. When it is 35% hydrochloric acid, it is used in the range of 5 to 70 parts by weight, preferably 10 to 40 parts by weight, more preferably 20 to 30 parts by weight, based on 100 parts by weight of the phenoxy alcohol compound. Here, if sulfuric acid is used as the acid catalyst, sulfuric acid remains in the target compound and is chemicalized. When the hue of the compound is deteriorated, when the heteropoly acid is used as the acid catalyst, the reaction temperature must be set to a high temperature, so that the reaction selectivity is lowered, and the efficiency is not obtained.

In the reaction, a catalytic catalyst may be used in addition to the acid catalyst. For example, when hydrogen chloride gas is used as a catalyst, a mercaptan is used as a catalyst, whereby the reaction rate can be accelerated. Examples of the mercaptan include alkyl mercaptans and mercaptocarboxylic acids, preferably an alkyl mercaptan having 1 to 12 carbon atoms and a mercaptocarboxylic acid having 1 to 12 carbon atoms, and examples thereof include methyl sulfur. Alcohol, ethyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, etc., alkali metal salts such as these sodium salts, thioacetic acid, indole acetic acid, β-mercaptopropionic acid, and the like.

Further, these may be used alone or in combination of two or more.

The amount of the mercaptan used in the catalyst is usually in the range of 0.5 to 20 mol%, preferably 2 to 10 mol%, based on the N-phenyl isatin compound of the starting material.

Further, in the reaction, there is a reaction solvent, and as long as the melting point of the N-phenyl ruthenium compound and the phenoxy alcohol compound of the raw material is low and the workability is not problematic, the solvent is not required, but the operability and reaction in industrial production are improved. It can also be used for reasons such as speed. The reaction solvent is not particularly limited as long as it is not distilled from the reactor at the reaction temperature and is inert to the reaction, and examples thereof include aromatic hydrocarbons such as toluene and xylene; and aliphatic alcohols such as methanol, n-propanol and isobutanol. An aliphatic hydrocarbon such as hexane, heptane or cyclohexane; a carboxylic acid ester such as ethyl acetate or butyl acetate; or a mixture thereof. It is preferred to use an aliphatic alcohol in these.

Also, in order to lower the freezing point of the phenoxy alcohol compound and promote the acid catalyst Reaction, add a small amount of water as needed. In particular, when the acid catalyst is hydrogen chloride gas, it is preferred because water promotes the absorption of the hydrogen chloride gas of the catalyst. When water is added, the amount of water added 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 the 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 it may be carried out under pressure or reduced pressure so that the reaction temperature becomes within the above range, depending on the boiling point of the organic solvent which can be used. If the reaction is carried out under such conditions, the reaction usually ends in about 1 to 30 hours.

The end point of the reaction can be confirmed by liquid chromatography or gas chromatography analysis. Preferably, the time point at which the unreacted N-phenyl ruthenium compound disappears and the increase in the object is not confirmed is the end point of the reaction.

The reaction yield relative to 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, and the acid catalyst is neutralized to obtain a reaction-end mixed liquid containing the dihydroxy compound represented by the general formula (1) of the present invention.

The neutralized reaction mixture is subjected to distillation to remove the unreacted raw material phenoxy alcohol compound, and then subjected to a water washing treatment in which water and a water-insoluble organic solvent are added and thoroughly stirred and the oil layer is separated. The organic solvent to be used at this time is required to be an organic solvent which can dissolve the dihydrocarbyl compound of the formula (1) and has a low solubility in water. The organic solvent having such a property may be an aromatic hydrocarbon such as toluene or xylene; an aliphatic hydrocarbon such as cyclohexane or n-heptane; an aliphatic ketone such as methyl isobutyl ketone; or an alcohol solvent such as butanol.

The organic solvent layer obtained after the neutralization/water washing is removed by distillation to remove a part of the solvent, and then the organic solvent is directly cooled or temporarily heated to a uniform solution and cooled, or a suitable crystallization solvent, a poor solvent is added, and cooled. When crystals are precipitated, the crystals are filtered, whereby a crude or high-purity target can be obtained.

The object obtained above can be further recrystallized and purified using a solvent. The organic solvent to be used in this case may be an aromatic hydrocarbon solvent such as toluene, xylene or mesitylene; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; and ethyl acetate. An ester solvent such as butyl acetate or an alcohol solvent such as butanol, which may be used singly or in a mixture of two or more types.

In place 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, the impurity which may be contained in the dihydroxy compound represented by the formula (1) is a 1 EO (monohydroxy alkoxy) represented by the following formula (7), and the following formula (8) is shown. a plurality of EO bodies (compounds in which the hydroxyl group of the hydroxyalkoxy group is further substituted by a hydroxyalkoxy group). However, the N-phenylisatin compound represented by the formula (2) is reacted with the phenoxy alcohol compound represented by the formula (3) by the production method of the present invention, and the second formula (1) is produced. A hydroxy compound, whereby a dihydroxy compound represented by the formula (1) which does not contain an impurity of a 1 EO represented by the following formula (7) or a poly-EO represented by the following formula (8) can be produced. .

The above 1EO system is represented by the following formula (7).

(wherein R, R ₁ , R ₂ , m, and n are the same as those of the formula (1))

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

The above multiple EO system is represented by the following formula (8).

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

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

The 3EO system of the compound which is more likely to be contained in the multi-EO body represented by the above formula (8) is represented by the following formula (9).

(wherein R, R ₁ , R ₂ , m, and n are the same as those of the formula (1))

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

Compared with the conventional production method, the production method of the present invention has high reactivity, so that the reaction can be carried out under mild reaction conditions, and the desired dihydroxy group can be obtained with high yield and/or high conversion ratio as compared with the conventional reaction. Compound.

In addition, the dihydroxy compound represented by the formula (1) obtained by the production method of the present invention does not contain impurities of a plurality of EO bodies represented by the above-mentioned 1EO body or 3EO body, and has high purity, so thermal stability, The color of the product is excellent in optical properties.

Since the dihydroxy compound represented by the formula (1) obtained by the production method of the present invention has high purity, it is expected to have high heat resistance/high refractive index, and in particular, an excellent effect of polycarbonate for optical materials can be expected. In other words, the high molecular weight polycarbonate is excellent in transparency, heat resistance, mechanical properties, impact resistance, fluidity, etc., and can be expected to be used for optical applications such as optical disks and lenses, or can be expected as an engineering plastic. Used in various fields such as automotive, electrical/electronic, and various containers.

Further, the polycarbonate oligomer can be used not only as a raw material for producing a high molecular weight polycarbonate by various polymerization methods, but also as a surface modifier, a flame retardant, an ultraviolet absorber, and a fluidity modification. Additives such as a polymer modifier such as a solvent, a plasticizer, or a solvent for a resin alloy.

Further, the dihydroxy compound of the present invention obtained by the production method of the present invention can be expected to be used as an epoxy resin, an oxetane resin, an acrylic resin, or a polyester, in addition to polycarbonate. Resin raw materials such as polyarylate, polyetheretherketone, polyfluorene, novolak, resol, other photosensitive material, resist additive, color developer, and antioxidant.

In particular, it is expected that the dihydroxy compound of the present invention can be reacted with acrylic acid or the like to obtain a diacrylate or the like, which is used as an acrylic monomer or an acrylic resin raw material, and can be expected to be used as an optical hard coat material.

(Example)

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

Further, the softening point, refractive index, and purity in the examples were measured by the following methods.

[Analytical method] Softening point determination

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

Heating conditions: 10 ° C / min (30 ° C → 200 ° C).

Ambient gas: nitrogen (flow: 50 ml / min).

test methods:

The first measurement was carried out under the above-described temperature rising conditions, and the melting point was measured from the endothermic peak.

Thereafter, the same sample was cooled to room temperature and subjected to the second measurement under the same conditions, and the endothermic peak was used as a softening point.

2. Refractive index determination

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

test methods:

The THF solution (THF refractive index 1.40) at a concentration of 10, 15, and 30% was adjusted, and the refractive index of the measured compound was calculated from the solution refractive index extrapolation method.

3. Purity determination

Device: CLASS-LC10 manufactured by Shimadzu Corporation.

Pump: LC-10ATvp.

Column oven: CTO-10Avp.

Detector: SPD-10Avp.

Column: Shim-pack CLC-ODS has an inner diameter of 6 mm and a length of 150 mm.

Oven temperature: 50 ° C.

Flow rate: 1.0 ml/min.

Mobile phase: (A) methanol, (B) 0.2 vol% acetic acid water.

Gradient conditions: (A) Volume % (time from the start of the analysis) 60% (0 min) → 60% (20 min) → 100% (40 min) → 100% (50 min) Sample injection amount: 20 μl.

Detection wavelength: 280 nm.

<Example 1>

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

In a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, 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 added. After the reaction vessel was replaced with nitrogen, hydrogen chloride gas was blown at 40 ° C to adjust the concentration of hydrogen chloride gas in the gas phase portion to 95% or more. Thereafter, 4.2 g of a 15% aqueous sodium methylthiolate solution (0.009 mol of sodium methyl mercaptan) was added, and the mixture was stirred at 40 ° C for 22 hours.

The conversion of 1-phenyl-1H-indole-2,3-dione after the end of the reaction was 99.7%, 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl The reaction yield of -1H-indol-2-one (relative to 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 of sodium hydroxide) was added, and the pH was adjusted to 6. The obtained solution was heated to 150 ° C, and unreacted 2-phenoxyethanol was removed by distillation under reduced pressure of 2.4 kPa, and then 268.3 g of toluene was added. Two water washing operations were carried out, and 45.0 g of water was added to the obtained solution, and after stirring at 80 ° C, the aqueous layer was allowed to stand and removed. After washing with water, the obtained oil layer was heated to 160 ° C, and the solvent was distilled off under 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. Thereafter, the mixture was cooled to 30 ° C, and the precipitated crystals were filtered, whereby 61.4 g of a white crystal was obtained.

226.5 g of 1-butanol was added to 55.5 g of the obtained crude crystals, and after dissolving at 110 ° C, 112.7 g of 1-butanol was distilled off under normal pressure, and then cooled to 30 ° C to precipitate the precipitated crystals. The obtained crystal was reduced to 80 ° C under reduced pressure. Drying, thereby obtaining 48.5 g of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one.

Proton nuclear magnetic resonance spectroscopy (400MHz, solvent DMSO-D ₆ , standard TMS) chemical shift (signal shape, number of protons): 3.7ppm (m, 4H), 4.0ppm (t, 4H), 4.9ppm (t, 2H), 6.7 ppm (d, 1H), 6.9 ppm (d, 4H), 7.1 to 7.2 ppm (m, 5H), 7.3 ppm (t, 1H), 7.4 ppm (d, 1H), 7.5 ppm (m, 3H), 7.6 ppm (t, 2H).

<Example 2>

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

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

1-phenyl-1H-indole-2,3-dione conversion after completion of the reaction is 100%, 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl -1H-indol-2-one The reaction yield (relative to 1-phenyl-1H-indole-2,3-dione) is 85.3%, the 1EO body represented by the formula (7) and the 3EO body represented by the formula (9) are To detect the limit below.

As is clear from the results of the first and second examples, it was confirmed that the production method of the present invention can obtain a high-purity dihydroxy group containing almost no impurities of the 1EO body represented by the formula (7) or the 3EO body represented by the formula (9). A method of compound and can be utilized as an industrial manufacturing method.

Moreover, the N-phenyl ruthenium compound represented by the formula (2) and a phenol compound are reacted with reference to the production method described in JP-A-2010-505011, and the resulting porphyrin skeleton is obtained. The phenol compound is reacted with an alkylene carbonate or the like to carry out hydroxyalkylation, and the method for producing the dihydroxy compound represented by the general formula (1) cannot suppress the 1EO body represented by the general formula (7) or the general formula (9). The formation of impurities of the 3EO body shown was not able to obtain a high-purity dihydroxy compound. This is specifically described in the following "Comparative Example 1".

<Comparative Example 1>

Manufacture of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one (Step 1) Manufacture of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one

In a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, 225.9 g (2.40 mol) of phenol and 44.6 g (0.20 mol) of 1-phenyl-1H-indole-2,3-dione were added and replaced with nitrogen. After the reaction vessel, hydrogen chloride gas was blown at 40 ° C to adjust the concentration of hydrogen chloride gas in the gas phase portion to 95% or more. Thereafter, the mixture was stirred at 30 ° C for 22 hours. 1-phenyl-1H-indole-2,3-dione conversion after completion of the reaction Reaction yield of 100%, 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one (relative to 1-phenyl-1H-indole-2,3) - Diketone) is 88.8%.

After completion of the reaction, 57.4 g of a 16% aqueous sodium hydroxide solution (0.23 mol of 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. Thereafter, the mixture was cooled to 30 ° C, and the precipitated crystals were filtered, whereby 86.8 g of a crude crystal was obtained.

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 after dissolving at 70 ° C, the aqueous layer was allowed to stand and the aqueous layer was removed. Further, a water washing operation was carried out in which water was added and stirred at 70 ° C, and the aqueous layer was allowed to stand and removed. After washing with water, the obtained oil layer was heated to 110 ° C, and the solvent was distilled off, toluene was added, the mixture was cooled to 30 ° C, and the precipitated crystals were filtered. The obtained crystal was dried under reduced pressure at 60 ° C, whereby 56.1 g of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indole-2-one was obtained.

(Step 2)

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

Add 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one 40.0 g (0.10 mol) obtained in step 1 to a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube. ), 1-butanol 60.0g, ethyl carbonate ethyl ester 26.0g (0.30 moles), 48% potassium hydroxide aqueous solution 0.60g (potassium hydroxide is 0.0051 moles), tetrabutylammonium bromide 0.33g (0.0010 moles) Ear), after replacing the reaction vessel with nitrogen, stirring was carried out for 12 hours while maintaining the temperature at 118 to 120 ° C, and then 5.1 g of water was added thereto. The mixture was further stirred for 4 hours while maintaining the temperature at 105 to 107 °C.

After adding 12.7 g of a 10% aqueous acetic acid solution to the obtained reaction liquid at 70 ° C, 20.0 g of methyl isobutyl ketone and 40.0 g of water were added, and after dissolving at 80 ° C, the aqueous layer was allowed to stand and the aqueous layer was removed. Further, a water washing operation was carried out, which was carried out by adding water and stirring, and then standing and removing the water layer. After washing with water, the obtained oil layer was heated to 126 ° C to distill off the solvent, and then toluene and water were added. After cooling to 25 ° C, the precipitated crystals were filtered, whereby 75.1 g of a crude crystal was obtained.

To the obtained crude crystal, 300.4 g of 1-butanol was added, and after dissolving at 75 ° C, the temperature was raised to 120 ° C, and the solvent was distilled off, and then cooled to 25 ° C to precipitate the precipitated crystal. The resulting crystals were taken to 80 under reduced pressure. Drying at ° C, whereby 31.5 g of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-one was obtained.

<Comparative Example 2>

Manufacture of 9,9-((4-hydroxyethoxy)phenyl)anthracene

78.3 g (0.57 mol) of 2-phenoxyethanol was placed in a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and the reaction vessel was replaced with nitrogen, and then hydrogen chloride gas was blown at 40 ° C to cause hydrogen chloride gas in the gas phase portion. The concentration is 98% the above. Then, after adding 11.3 g of a 21% sodium methyl mercaptanate aqueous solution (0.034 mol of sodium methyl mercaptan), 90.0 g (0.28) of 9-fluorenone which had been dissolved in 75 g (0.54 mol) of 2-phenoxyethanol. Mohr) takes 2 hours to drip. After stirring at 40 ° C for 30 hours, the conversion of 9-fluorenone was 27%, and the reaction yield of 9,9-((4-hydroxyethoxy)phenyl)fluorene was 15%.

<Comparative Example 3>

Manufacture of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-2-phenylbenzylcarfenamide

In a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, 331.6 g (2.40 mol) of 2-phenoxyethanol and 44.8 g (0.20 mol) of N-phenylphthalimide were added and replaced with nitrogen. After the reaction vessel, hydrogen chloride gas was blown at 40 ° C to adjust the concentration of hydrogen chloride gas in the gas phase portion to 95% or more. Thereafter, 4.2 g of a sodium 15% methylthiolate aqueous solution (0.009 mol of sodium methyl mercaptan) was added, and the mixture was stirred at 40 ° C for 22 hours.

No formation of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-2-phenylbenzylcarfenamide was observed in the reaction mixture after 22 hours of reaction.

From the results of Comparative Examples 2 and 3, it was confirmed that the reaction was compared with 9-fluorenone and 2-phenoxyethanol (Comparative Example 2), or N-phenylphthalimide and 2-phenoxyl The reaction of the basal ethanol (Comparative Example 3), the reactivity of the N-phenyl ruthenium compound represented by the formula (2) and the phenoxyethanol compound represented by the formula (3) in the production method of the present invention is particularly high.

That is, the method for producing the dihydroxy compound represented by the formula (1) of the present invention is N-phenyl ruthenium compared to the reactivity of the ketones of the conventionally known cardo structure with the phenoxy alcohol compound. A process in which the reactivity of the compound with the phenoxy alcohol compound is particularly high is an advantageous manufacturing method.

The production method of the present invention is high in reactivity, and can be reacted at a high yield and/or high conversion rate as compared with a conventionally known production method, or the reaction time can be shortened, and the reaction can be carried out under mild conditions. It has become an industrially advantageous manufacturing method.

Further, the production method of the present invention can obtain a high-purity dihydroxy compound which contains almost no impurities, and is therefore used as an industrial production method.

Claims (1)

A method for producing a dihydroxy compound represented by the formula (1), which is an N-phenylisatin compound represented by the following formula (2) and a phenoxy alcohol compound represented by the following formula (3) reaction; In the formula, R represents an alkylene group having 2 to 6 carbon atoms, and R ₁ and R ₂ each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m system represents an integer of 0 to 3, n-system represents an integer of 0 to 2, but, m is 2 or more, R ₁ may be the same or different, n R ₂ may be the same or different when is 2; Wherein R ₂ and n are the same as those of the formula (1); In the formula, R, R ₁ and m are the same as those of the formula (1).