JP2022159074A - Production method of alcohol having fluorene skeleton - Google Patents

Abstract

To efficiently produce an alcohol having a 9,9-bis (condensation polycyclic aryl) fluorene skeleton with high purity.SOLUTION: A 9,9-bis (hydroxy alkoxy condensation polycyclic aryl) fluorene is produced by reacting 9,9-bis (hydroxy condensation polycyclic aryl) fluorene with alkylene carbonate in the presence of an inorganic base catalyst and amides. The inorganic base catalyst may be a metal carbonate and/or a metal hydrogen carbonate. The amides may be alkyl amides. The percentage of the inorganic base catalyst may be 1-10 pts.mass to 100 pts.mass of the amides.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing an alcohol having a 9,9-bis(fused polycyclic aryl)fluorene skeleton.

In the field of optical materials, it has a 9,9-bis (condensed polycyclic aryl) fluorene skeleton because it has excellent optical properties such as high refractive index, low Abbe number, low birefringence and high transparency, and heat resistance. Attention has been focused on alcohols (fluorene-containing alcohols).

As a method for producing such a fluorene-containing alcohol, JP-A-2009-155253 (Patent Document 1) discloses 9,9-bis(6-hydroxy-2-naphthyl) in the presence of 1-methylimidazole and diethylene glycol. ) A method of reacting fluorene with ethylene carbonate is disclosed. In the example of this document, a 95.7% pure fluorene-containing alcohol is produced.

Further, as a method for industrially suitably producing the fluorene-containing alcohol, JP-A-2019-1780 (Patent Document 2) describes a reaction of 9-fluorenone and naphthol in the presence of a solid acid and toluene. A manufacturing method is disclosed in which the resulting bisnaphthol compound is reacted with ethylene carbonate in the presence of potassium carbonate without removal. The examples in this document produce 95.1-96.7% pure fluorene-containing alcohols.

JP 2009-155253 A Japanese Patent Application Laid-Open No. 2019-1780

However, high-performance optical properties are required in the field of optical materials in recent years, and even the methods of Patent Documents 1 and 2 cannot sufficiently improve the purity of the resulting fluorene-containing alcohol.

Accordingly, an object of the present invention is to provide a method for efficiently producing a highly purified alcohol having a 9,9-bis(fused polycyclic aryl)fluorene skeleton.

As a result of intensive studies to achieve the above object, the present inventors have found that 9,9-bis(hydroxy-fused polycyclic aryl)fluorene and alkylene carbonate are reacted in the presence of an inorganic base catalyst and amides. , 9,9-bis(hydroxyalkoxy-fused polycyclic aryl)fluorene can be efficiently produced with high purity, and completed the present invention.

That is, in the production method of the present invention, in the presence of an inorganic base catalyst and amides, the following formula (1a)

(In the formula,
Z ¹ and Z ² independently represent a condensed polycyclic arene ring;
R ¹ and R ² independently represent a substituent, m1 and m2 independently represent an integer of 0 or more,
R ³ represents a substituent and n represents an integer of 0 to 8)
By reacting a fluorene compound and an alkylene carbonate represented by
Formula (1) below

[wherein A ¹ and A ² independently represent a linear or branched alkylene group, ring Z ¹ , ring Z ² , R ¹ , R ² , R ³ , m1, m2 and n are each Same as formula (1a)]
A method for producing a fluorene compound represented by the above formula (1), comprising a reaction step of obtaining a reaction solution containing the fluorene compound represented by.

The production method may further include a purification step of crystallizing the reaction solution obtained in the reaction step using a crystallization solvent containing amides, ketones and aromatic hydrocarbons.

In the production method, as a step before the reaction step, in the presence of an acid catalyst, thiols and an aprotic polar solvent, the following formula (2)

[wherein R ³ and n are the same as in formula (1a)]
and fluorenones represented by the following formulas (3a) and (3b)

[Wherein, ring Z ¹ , ring Z ² , R ¹ , R ² , m1 and m2 are the same as in formula (1a)]
It may further include an intermediate reaction step of obtaining an intermediate reaction liquid containing the fluorene compound represented by the formula (1a) by reacting with a compound represented by the above formula (1a). In the production method, the fluorene compound represented by the formula (1a) may be taken out from the intermediate reaction solution and subjected to the reaction step.

In the above formula (1), A ¹ and A ² may be ethylene groups, and the ring Z ¹ and ring Z ² may be naphthalene rings. The inorganic base catalyst may be a metal carbonate and/or a metal hydrogen carbonate. The amides may be alkylamides. The ratio of the inorganic base catalyst may be 1 to 10 parts by mass with respect to 100 parts by mass of the amides.

In this specification and claims, the number of carbon atoms in a substituent may be indicated by C ₁ , C ₆ , C ₁₀ or the like. For example, a “C ₁ alkyl group” means an alkyl group with 1 carbon number, and a “C _6-10 aryl group” means an aryl group with 6 to 10 carbon atoms.

In the present invention, since 9,9-bis(hydroxy-fused polycyclic aryl)fluorene and alkylene carbonate are reacted in the presence of an inorganic base catalyst and amides, 9,9-bis(hydroxyalkoxy-fused polycyclic Formula aryl)fluorene can be produced efficiently with high purity.

In the present invention, in the presence of an inorganic base catalyst and amides, the fluorene compound represented by the above formula (1a) [hereinafter also referred to as "fluorene compound (1a)"] is reacted with an alkylene carbonate to obtain the above formula (1). A fluorene compound represented by the above formula (1) is produced by a production method including a reaction step of obtaining a reaction solution containing a fluorene compound represented by [hereinafter also referred to as "fluorene compound (1)"].

[Fluorene compound represented by formula (1)]
In the above formula (1), the condensed polycyclic arene ring (condensed polycyclic aromatic hydrocarbon ring) represented by ring Z ¹ and ring Z ² includes condensed bicyclic arene ring and condensed tricyclic arene ring. condensed bi- to tetracyclic arene rings such as rings;

Condensed bicyclic arene rings include condensed bicyclic C _10-16 arene rings such as naphthalene ring and indene ring. Examples of condensed tricyclic arene rings include anthracene ring and phenanthrene ring. These condensed polycyclic arene rings can be used alone or in combination of two or more.

The types of the two rings Z ¹ and Z ² may be the same or different, preferably the same. Among these, a condensed polycyclic C _10-16 arene ring such as a naphthalene ring or anthracene ring is preferred, a condensed polycyclic C _10-14 arene ring is more preferred, and a naphthalene ring is most preferred.

Linear or branched alkylene groups represented by groups A ¹ and A ² include ethylene group, propylene group (1,2-propanediyl group), trimethylene group, 1,2-butanediyl group and tetramethylene group. linear or branched C _2-4 alkylene groups such as and the like. These alkylene groups can be used alone or in combination of two or more.

The types of the two groups A ¹ and A ² may be identical or different from each other, identical being preferred. Of these, linear or branched C _2-3 alkylene groups are preferred, and ethylene groups are particularly preferred.

Substituents represented by groups R ¹ and R ² include halogen atoms, hydrocarbon groups, alkoxy groups, cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, cycloalkylthio groups, arylthio groups, aralkylthio groups, acyl groups, nitro groups, cyano groups, and the like.

Representative examples of these substituents include halogen atoms; hydrocarbon groups such as alkyl groups, cycloalkyl groups and aralkyl groups; alkoxy groups; acyl groups; nitro groups; Preferred R ¹ and R ² include an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and the like, and examples of the alkyl group include linear or branched C _1-6 alkyl groups such as a methyl group. Examples of cycloalkyl groups include C _5-8 cycloalkyl groups such as cyclohexyl group, examples of aryl groups include C _6-14 aryl groups such as phenyl group, and examples of alkoxy groups include Linear or branched C _1-4 alkoxy groups such as a methoxy group, and the like. The types of substituents R ¹ and R ² may be the same or different from each other, but are preferably the same. Among these, an alkyl group is preferred, and a linear or branched C _1-4 alkyl group such as a methyl group is particularly preferred.

The substitution numbers m1 and m2 of R ¹ and R ² may be integers of 0 or more, and can be appropriately selected depending on the type of ring Z ¹ and ring Z ^2. For example, each may be an integer of 0 to 8. Preferred substitution numbers m1 and m2 are, step by step, integers from 0 to 4, integers from 0 to 3, integers from 0 to 2, 0 or 1, with 0 being most preferred. Although the number of substitutions m1 and the number of substitutions m2 may be different numbers of substitutions, the same number of substitutions is preferable. Moreover, when the substitution numbers m1 and m2 are 2 or more, the types of the 2 or more R ¹ or R ² may be the same or different.

Examples of substituents represented by R ³ include hydrocarbon groups, cyano groups and halogen atoms. Examples of hydrocarbon groups include alkyl groups and aryl groups. Alkyl groups include linear or branched C _1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and t-butyl group. Aryl groups include C _6-10 aryl groups such as phenyl groups. Halogen atoms include, for example, fluorine, chlorine, and bromine atoms. These substituents can be used alone or in combination of two or more.

Of these groups R ³ , alkyl groups, cyano groups and halogen atoms are preferred, alkyl groups are more preferred, linear or branched C _1-4 alkyl groups such as methyl groups are more preferred, C _1-2 Alkyl groups are most preferred.

The substitution number n of the group R ³ may be an integer of 0 to 8, and the preferable range is an integer of 0 to 6, an integer of 0 to 5, an integer of 0 to 4, 0 to An integer of 3, an integer of 0-2, 0 or 1, with 0 being most preferred. In addition, in two different benzene rings constituting the fluorene ring, the number of substitutions may be the same or different. Also, the types of the groups R ³ substituting the different benzene rings may be different from each other, but are preferably the same. When n is 2 or more, the types of the ^two or more groups R3 substituted on the same or different benzene rings may be the same or different. The substitution position of the group R3 is not particularly limited ^, and may be, for example, the 2- to 7-positions of the fluorene ring, preferably the 2-, 3- and 7-positions.

Typical examples of the fluorene compound (1) include 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene, 9,9-bis[6-(2-hydroxypropoxy)-2 -naphthyl]fluorene, 9,9-bis[5-(2-hydroxyethoxy)-1-naphthyl]fluorene and the like. Among these, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene is preferred.

The fluorene compound (1) obtained by the production method of the present invention, which will be described later, is obtained with a high reaction conversion rate. The reaction conversion rate of the fluorene compound (1a) is usually 90 mol% or more, for example 93 mol% or more, preferably 95 mol% or more, more preferably 96 mol% or more, more preferably 98 mol% or more, most preferably 98 mol% or more. is 99 mol % or more.

In addition, the fluorene compound (1) has high purity, and the purity (HPLC purity) measured by HPLC (high performance or high performance liquid chromatograph) can be selected, for example, from a range of about 95% or more. It is 96% or more, 97% or more, 97.5% or more, 98% or more, and most preferably 98.5% or more. The HPLC purity can usually be selected from the range of about 96-100%, preferably 98.5-99.99%, more preferably 98.7-99.9%.

In the present specification and claims, the conversion rate (reaction conversion rate) and purity can be measured by the method described in Examples below (method using HPLC).

[Reaction step]
In the reaction step, in the presence of an inorganic base catalyst and an amide, the fluorene compound represented by the formula (1a) [hereinafter also referred to as "fluorene compound (1a)"] is reacted with an alkylene carbonate to obtain fluorene compound (1). Obtain a reaction solution containing ^{The fluorene} compound ⁽ 1a) ^, which is ^one of the raw materials in the reaction step, is represented by the above formula (1a). and n are the same as in the above formula (1), including preferred embodiments.

(alkylene carbonate)
As the alkylene carbonate that is the other raw material, alkylene carbonates corresponding to the groups A ¹ and A ² of the formula (1) can be used. Specific alkylene carbonates include C _2-4 alkylene-carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and the like. These alkylene carbonates can be used alone or in combination of two or more. Of these, C _2-3 alkylene-carbonates are preferred, and ethylene carbonate (ethylene carbonate) is particularly preferred.

The ratio of the alkylene carbonate may be 2 mol or more, preferably 2.5 mol or more, relative to 1 mol of the fluorene compound (1a), for example 2 to 5 mol, preferably 2.5 to 4.5 mol, More preferably 2.8 to 4 mol, more preferably 3 to 3.5 mol.

(catalyst)
Catalysts used in the reaction step include inorganic base catalysts. In the production method of the present invention, the catalyst contains an inorganic base catalyst and the solvent, which will be described later, contains an amide, so that a highly pure fluorene compound (1) can be efficiently produced.

Inorganic base catalysts include metal carbonates, metal bicarbonates, metal hydroxides, and the like.

Examples of metal carbonates include alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; and thallium (I) carbonate.

Examples of metal hydrogen carbonates include alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate.

Examples of metal hydroxides include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metal hydroxides such as barium hydroxide; thallium (I) hydroxide; are mentioned.

These inorganic base catalysts can be used alone or in combination of two or more. Of these, metal carbonates and/or metal hydrogencarbonates are preferred, alkali metal carbonates and/or alkali metal hydrogencarbonates are more preferred, and alkali metal carbonates such as potassium carbonate are most preferred.

The total proportion of metal carbonate and metal hydrogencarbonate preferably accounts for the main component in the inorganic base catalyst, and is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass in the total inorganic base catalyst. % or more, more preferably 95 mass % or more, most preferably 100 mass %. Furthermore, the ratio of the metal carbonate is more preferably the main component in the inorganic base catalyst, and is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more in the total inorganic base catalyst, More preferably 95% by mass or more, most preferably 100% by mass.

The ratio of the inorganic base catalyst is 0.1 parts by mass or more (for example, about 0.1 to 10000 parts by mass) relative to 100 parts by mass of the amides, and the preferred range is 0.1 to 1000 parts in stages below. Parts by mass, 0.1 to 100 parts by mass, 0.1 to 50 parts by mass, 0.1 to 20 parts by mass, 0.5 to 15 parts by mass, 1 to 10 parts by mass, and 1.5 to 5 parts by mass , most preferably 2 to 4 parts by weight. If the ratio of the inorganic base catalyst is too small, the yield may decrease, and if it is too large, the purity may decrease.

The ratio of the inorganic base catalyst is, for example, 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass, more preferably 100 parts by mass of the fluorene compound (1a). 1.5 to 5 parts by weight, most preferably 2 to 4 parts by weight. If the ratio of the inorganic base catalyst is too low, not only may the reaction conversion rate decrease, but also the purity may decrease due to impurities such as unreacted components. There is a risk that it will remain.

The catalyst may further contain other catalysts such as organic base catalysts and acid catalysts in addition to inorganic base catalysts. Other catalysts may be acid catalysts, but organic base catalysts are preferred.

Examples of organic base catalysts include amines such as triethylamine, N,N-dimethylaniline and 1-methylimidazole; metal carboxylates such as sodium acetate and calcium acetate. These organic base catalysts can be used alone or in combination of two or more.

The ratio of other catalysts is 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less in the total catalyst. If the ratio of other catalysts is too high, it may become difficult to produce fluorene compound (1) with high purity.

The proportion of the inorganic base catalyst is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 100% by mass in the total catalyst. If the proportion of the inorganic base catalyst is too small, it may become difficult to efficiently produce a highly pure fluorene compound (1).

The ratio of the catalyst is, for example, 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass, more preferably 1.5 parts by mass, with respect to 100 parts by mass of the fluorene compound (1a). 5 to 5 parts by weight, most preferably 2 to 4 parts by weight. If the ratio of the catalyst is too small, not only may the reaction conversion rate decrease, but also the purity may decrease due to impurities such as unreacted components. be.

(reaction solvent)
The reaction solvent (solvent inert to the reaction) used in the reaction step contains amides. When the amount of amides in the reaction solvent is small, the amides may function as additives. Amides include alkylamides (alkylacylamines), cyclic amides, and the like. Amides may be cyclic amides such as N-methyl-2-pyrrolidone (NMP), but alkylamides are preferred.

Examples of alkylamides include N,N-dimethylformamide (DMF), N,N-diC _1-4 alkylformamide such as N,N-diethylformamide; N,N-dimethylacetamide (DMAc), N,N- Examples include N,N-diC _1-4 alkylacetamides such as diethylacetamide. These amides can be used alone or in combination of two or more. Among these, N,N-di-C _1-4 alkylformamide and N,N-di-C _1-4 alkylacetamide are preferred, N,N-di-C _1-3 alkylformamide, N,N-di-C _{1- 3} -alkylacetamides are more preferred, N,N-di-C _1-2 alkylformamides, N,N-di-C _1-2 alkylacetamides are more preferred, and DMF is most preferred.

The ratio of the amides can be selected from a range of about 0.1 to 3000 parts by mass (especially 1 to 3000 parts by mass) relative to 100 parts by mass of the fluorene compound (1a), for example 10 to 3000 parts by mass, preferably 20 to 3000 parts by mass. 1000 parts by mass, more preferably 30 to 300 parts by mass, more preferably 50 to 150 parts by mass, most preferably 80 to 130 parts by mass. If the proportion of amides is too low, the handleability may be lowered, and if it is too high, the reactivity may be lowered.

The reaction solvent may further contain other solvents in addition to the amides. Other solvents include water; aliphatic hydrocarbons such as hexane, heptane, octane, decane and dodecane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; , chloroform, carbon tetrachloride, 1,2-dichloroethane and other halogenated hydrocarbons; methanol, ethanol, isopropanol, ethylene glycol and other alcohols; diethyl ether, diisopropyl ether and other chain ethers; cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone (MIBK); esters such as ethyl acetate; acetonitrile, nitriles such as benzonitrile; sulfoxides such as dimethylsulfoxide; These other solvents can be used alone or in combination of two or more.

Among these, at least one selected from the group consisting of aromatic hydrocarbons such as toluene, ketones such as MIBK, and cyclic ethers such as 1,4-dioxane is preferable, aromatic hydrocarbons and / or ketones, Aromatic hydrocarbons and/or cyclic ethers are more preferred, and combinations of aromatic hydrocarbons and ketones are more preferred.

When an aromatic hydrocarbon and ketones are combined, the proportion of the aromatic hydrocarbon is, for example, 1 to 100 parts by mass, preferably 5 to 80 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the ketones. parts by mass, more preferably 20 to 30 parts by mass.

The ratio of the other solvent is 99.9% by mass or less (especially 99% by mass or less) in the total reaction solvent, and the preferred range is 90% by mass or less, 50% by mass or less, and 30% by mass in a stepwise manner. 20% by mass or less, 10% by mass or less, and most preferably 5% by mass or less. If the ratio of the other solvent is too high, it may become difficult to produce fluorene compound (1) with high purity.

When amides and other solvents are combined and the amides function as additives, the ratio of the amides is, for example, 1 to 50 parts by weight, preferably 3 to 40 parts by weight, with respect to 100 parts by weight of the other solvent. , more preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass.

The ratio of amides is 0.1% by mass or more (especially 1% by mass or more) in the total reaction solvent, and the preferred range is 10% by mass or more, 30% by mass or more, and 50% by mass or more in a stepwise manner. , 80% by mass or more, 90% by mass or more, 95% by mass or more, and most preferably 100% by mass. If the proportion of amides is too low, it may become difficult to produce fluorene compound (1) with high purity.

The proportion of the reaction solvent is, for example, 10 to 3000 parts by mass, preferably 30 to 1000 parts by mass, more preferably 50 to 300 parts by mass, more preferably 80 to 200 parts by mass, relative to 100 parts by mass of the fluorene compound (1a). , and most preferably 100 to 150 parts by weight.

(other additives)
In the reaction step, conventional additives used in the reaction may be further used. Commonly used additives include promoters (phase transfer catalysts) and the like. Examples of co-catalysts include tetrabutylammonium bromide (TBAB) and tetraalkylammonium halides such as trioctylmethylammonium chloride. These co-catalysts may be used alone or in combination of two or more. Among these promoters, TBAB and the like are often used.

The proportion of the promoter is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass, more preferably 1 to 5 parts by mass, more preferably 2 parts by mass, relative to 100 parts by mass of the fluorene compound (1a). ~4 parts by mass.

(Reaction conditions)
The reaction temperature is not particularly limited, but can be selected from the range of about 0 to 200°C, for example, 30 to 180°C, preferably 50 to 150°C, more preferably 70 to 130°C, more preferably 90 to 120°C. . The reaction time is not particularly limited and can be selected in the range of about 30 minutes to 24 hours, for example 0.5 to 12 hours, preferably 1 to 6 hours, more preferably 1.5 to 3 hours.

The reaction may be carried out while stirring, in the air, in an inert atmosphere such as nitrogen; a rare gas such as helium or argon, or under normal pressure or increased pressure. Also, the reaction may be carried out while dehydrating.

[Reaction solution purification process]
In the purification step of the reaction solution (reaction mixture), the reaction solution obtained in the reaction step may be purified by crystallization using a crystallization solvent containing ketones and aromatic hydrocarbons. In the purification step, the fluorene compound (1) obtained in the reaction step is crystallized using a mixed solvent containing amides, ketones and aromatic hydrocarbons as a crystallization solvent to obtain a fluorene compound of higher purity. Compound (1) can be prepared.

The amides, including preferred embodiments, are the same as the amides exemplified in the section on the reaction solvent.

Ketones include chain ketones, cyclic ketones, and the like. Chain ketones include _C3-8 chain ketones such as acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone (MIBK), diisopropyl ketone, butyl propyl ketone, etc. . Cyclic ketones include C _5-10 cycloalkanones such as cyclohexanone. These ketones can be used alone or in combination of two or more. Of these, linear ketones are preferred, and _C4-7 linear ketones such as MIBK are particularly preferred.

Aromatic hydrocarbons include benzene, alkylbenzene and the like. Alkylbenzenes include mono- to tetra-C _1-4 alkyl-benzenes such as toluene, xylene, ethylbenzene, trimethylbenzene, ethyltoluene, propylbenzene, and cumene. These aromatic hydrocarbons can be used alone or in combination of two or more. Among these, mono- or di-C _1-2 alkyl-benzenes such as toluene, xylene and ethylbenzene are preferred, with toluene being particularly preferred.

When at least one selected from the group consisting of amides, ketones and aromatic hydrocarbons is used as the reaction solvent, the reaction solvent may be used as it is as a crystallization solvent, or the crystallization used as the reaction solvent may be The same or a different crystallization solvent may additionally be added to the solvent.

In the purification step of the reaction, the ratio of ketones is, for example, 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, more preferably 50 to 200 parts by mass, most preferably 80 to 100 parts by mass, with respect to 100 parts by mass of amides. 120 parts by mass.

The proportion of aromatic hydrocarbons is, for example, 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, more preferably 50 to 200 parts by mass, and most preferably 80 to 120 parts by mass with respect to 100 parts by mass of amides. is.

The crystallization solvent may further contain other solvents in addition to amides, ketones and aromatic hydrocarbons. Other solvents include the solvents exemplified as the reaction solvent in the reaction step, water, and the like. Other solvents are preferably C _1-4 alkanols such as methanol.

The ratio of the other solvent may be 30% by mass or less, for example, about 0 to 20% by mass in the total crystallization solvent. , 10% by mass or less, 5% by mass or less, 1% by mass or less, 0.1% by mass or less, and more preferably 0% by mass, that is, substantially free of other solvents preferable.

As the reaction solvent, when amides function as additives, it is preferable to contain another solvent, and the ratio of the other solvent is, for example, 1 to 100 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass.

The ratio of the crystallization solvent may be, for example, about 10 to 2,000 parts by mass with respect to 100 parts by mass of the fluorene compound (1). 1000 parts by mass, 200 to 700 parts by mass, 300 to 500 parts by mass, and 350 to 450 parts by mass.

In the purification step, the fluorene compound (1) is dissolved in the crystallization solvent and cooled to precipitate the fluorene compound (1) with higher purity. In particular, fluorene compound (1) of higher purity can be precipitated or crystallized by dissolving fluorene compound (1) in the crystallization solvent by heating and cooling. After dissolution, if necessary, a predetermined amount of the solvent may be distilled off under reduced pressure to adjust the amount of the crystallization solvent within the range of the ratio. In addition, the crystallization solvent may be added (or mixed) with all the solvents in advance before heating, or added stepwise. may be added.

The temperature at which the fluorene compound (1) is dissolved in the crystallization solvent is a temperature below the boiling point of the solvent, for example, 30 to 200°C. , 70-120°C, and 75-100°C.

A solution obtained by dissolving fluorene compound (1) in a crystallization solvent is cooled to crystallize fluorene compound (1) with higher purity. Crystallization may be performed by quenching, standing to cool, or slow cooling, and it seems that fluorene compound (1) with high purity can be obtained relatively easily by quenching. A typical cooling rate can be selected, for example, from a range of about 0.1 to 100° C./min. °C/min, 5-20 °C/min, 7-15 °C/min, 8-12 °C/min, 9-11 °C/min. In addition, the precipitation temperature (the temperature at which precipitation or crystallization begins) may be 80° C. or lower, for example, 30 to 80° C., preferably 40 to 75° C., more preferably 50 to 70° C., more preferably 55 to 65° C. °C. The ultimate cooling temperature is, for example, -10°C to 30°C, preferably -5°C to 20°C, more preferably 0°C to 10°C. The retention time at the aforementioned cooling temperature is not particularly limited, and may be, for example, about 1 minute to 12 hours, preferably 0.5 to 6 hours, more preferably 1 to 3 hours.

In the crystallization operation, if necessary, seed crystals may be added, and the crystallization operation may be performed only once or may be repeated multiple times. The fluorene compound (1) of high purity can be obtained by filtering the crystals produced by the crystallization, usually by filtration such as suction filtration, separation means such as centrifugation, and drying the crystals.

Drying after crystallization may be drying under reduced pressure, and the drying temperature may be, for example, about 50 to 200°C. , 80 to 100° C., and 85 to 95° C., and the temperature may be raised at once for drying, or the temperature may be raised stepwise for drying. The drying time may be, for example, about 1 hour to 1 week, preferably 1 to 3 days.

In the purification step, the reaction liquid (reaction mixture) before being subjected to crystallization is neutralized and washed as necessary, impurities are removed from the reaction liquid mixture, and the residue is added to the crystallization solvent as the fluorene compound (1 ) may be dissolved to crystallize a higher purity fluorene compound.

[Intermediate reaction step]
In the intermediate reaction step, as a step preceding the reaction step, the fluorenone represented by the formula (2) and the formulas (3a) and (3b) are reacted in the presence of an acid catalyst, thiols, and an aprotic polar solvent. An intermediate reaction liquid (intermediate reaction mixture) containing the fluorene compound (1a) is obtained by reacting the represented compound.

(Fluorenones Represented by Formula (2))
In formula (2) above, R ³ and n are the same as in formula (1) above, including preferred embodiments. Examples of the fluorenone represented by the formula (2) include fluorenone (or 9-fluorenone); alkylfluorenone such as methylfluorenone. Among these, fluorenone is preferred.

(Compounds represented by formulas (3a) and (3b))
In formulas (3a) and (3b), ring Z ¹ , ring Z ² , R ¹ , R ² , m1 and m2 are the same as in formula (1) above, including preferred embodiments. Examples of the compounds represented by formulas (3a) and (3b) include naphthols such as 1-naphthol and 2-naphthol; C _1-4 alkylnaphthols such as methylnaphthol. Of these, 2-naphthol is preferred.

The ratio of the compounds represented by the formulas (3a) and (3b) is, for example, 2 to 5 mol, preferably 2.3 to 4 mol, per 1 mol of the fluorenone represented by the formula (2). More preferably, it is 2.5 to 3.5 mol.

(acid catalyst)
Examples of acid catalysts used in the intermediate reaction step include inorganic acids, organic acids and solid acids. Among these, inorganic acids are preferred. Inorganic acids include sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid and the like. These inorganic acids can be used alone or in combination of two or more. Among these inorganic acids, sulfuric acid is more preferable, and concentrated sulfuric acid is more preferable, since it also acts as a dehydrating agent for water generated as the reaction progresses.

The sulfuric acid includes dilute sulfuric acid having a concentration of about 30 to 90% by mass, concentrated sulfuric acid having a concentration of 90% by mass or more, fuming sulfuric acid, and the like. Sulfur may be used. Sulfuric acid may be selected from a range having a concentration of about 80 to 99% by mass in terms of H ₂ SO ₄ . Concentrated sulfuric acid of 96 to 99% by mass, 97 to 98.5% by mass, and particularly preferably 98% by mass of concentrated sulfuric acid.

The ratio of the acid catalyst can be selected, for example, from a range of about 10 to 1,000 parts by mass, for example, 30 to 500 parts by mass, preferably 50 to 300 parts by mass, more preferably 80 to 200 parts by mass, based on 100 parts by mass of the fluorenones. parts by mass, more preferably 100 to 150 parts by mass. If the proportion of the acid catalyst is too low, the reaction may not proceed efficiently (or the reaction rate may be significantly reduced), while if it is too high, the purity may decrease.

(thiols)
Thiols include mercaptocarboxylic acids such as mercaptoacetic acid (thioglycolic acid), β-mercaptopropionic acid, α-mercaptopropionic acid, thiooxalic acid, mercaptosuccinic acid, and mercaptobenzoic acid; thiocarboxylic acids such as thioacetic acid and thiopropionic acid; Acids; thioglycols such as mercaptoethanol; alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, 1-octyl mercaptan and t-dodecyl mercaptan; aralkyl mercaptans such as benzyl mercaptan; ethanethiol (also known as cysteamine), 2-aminopropanethiol, 3-aminopropanethiol, 2-aminobutanethiol, 3-aminobutanethiol, 4-aminobutanethiol, 6-aminohexanethiol, 8-aminooctanethiol, Amino C _2-20 alkanethiols such as 11-aminoundecanethiol, 16-aminohexadecanethiol, and the like. These thiols can be used alone or in combination of two or more.

Thiols may be in the form of salts. Representative salts include inorganic acid salts such as hydrochlorides and sulfates; organic acid salts such as acetates; alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; tetraalkylammonium salts such as ammonium salts and tetramethylammonium salts; or double salts thereof.

Among these thiols, mercapto C _2-4 carboxylic acids are preferred, and mercapto C _2-3 carboxylic acids such as β-mercaptopropionic acid are particularly preferred.

The proportion of thiols is, for example, 0.1 to 50 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, more preferably 1.5 parts by mass, relative to 100 parts by mass of the fluorenones. ~3 parts by mass. If the ratio of thiols is too low, the reaction conversion rate may decrease, and impurities such as unreacted components may lower the purity. There is fear.

(solvent)
The solvent used in the intermediate reaction step includes an aprotic polar solvent from the viewpoint of efficiently producing a highly pure fluorene compound (1a).

Aprotic polar solvents include ethers, ketones, esters, carbonates, amides, ureas, nitriles, nitrated hydrocarbons, phosphoramides, sulfones, sulfoxides and the like. These aprotic polar solvents can be used alone or in combination of two or more.

Among the aprotic polar solvents, at least one selected from ethers, sulfones, sulfoxides, ureas and amides is preferable, and at least one selected from ethers, sulfones, ureas and amides More preferably, it contains at least a cyclic compound having a cyclic structure in its molecule (an aprotic polar solvent having a cyclic structure), such as cyclic ethers, cyclic sulfones, cyclic ureas and cyclic Most preferably, it contains at least one selected from amides.

The cyclic ethers include tetrahydrofuran (THF), tetrahydrofuran optionally having a C _1-4 alkyl group or dioxane such as 1,4-dioxane, and among them, a C _1-3 alkyl group is preferred, 1,4-dioxane optionally having a C _1-2 alkyl group such as 1,4-dioxane is more preferred, and 1,4-dioxane is most preferred. .

Examples of the cyclic sulfones include tetra- to pentamethylene sulfones optionally having a C _1-4 alkyl group such as sulfolane, and sulfolane optionally having a C _1-3 alkyl group are preferred. , sulfolanes optionally having a C _1-2 alkyl group are more preferred, and sulfolane is most preferred.

As the cyclic ureas, N optionally having a C _1-4 alkyl group such as 1,3-dimethyl-2-imidazole (DMI), N,N'-dimethyl-N,N'-trimethylene urea ,N'-diC _1-6 alkyl-N,N'-di to trimethylene ureas, and N,N'-diC _1-4 alkyl- optionally having a C _1-3 alkyl group. Ethylene ureas are preferred, N,N'-diC _1-3 alkyl-ethylene ureas optionally having a C _1-2 alkyl group are more preferred, and DMI is most preferred.

Examples of the cyclic amides include 5- to 7-membered lactams optionally having a C _1-4 alkyl group such as NMP, and 5- to 6-membered lactams optionally having a C _1-3 alkyl group. Ring lactams are preferred, 5-membered ring lactams optionally having a C _1-2 alkyl group are more preferred, and NMP is most preferred.

Among these aprotic polar solvents, dioxanes optionally having a C _1-3 alkyl group are preferred, and optionally having a C _1-2 alkyl group such as 1,4-dioxane 1, 4-dioxane is more preferred and 1,4-dioxane is most preferred.

The proportion of the aprotic polar solvent may be selected from a range of, for example, about 10 to 1,000 parts by weight, for example, 30 to 500 parts by weight, preferably 50 to 300 parts by weight, with respect to 100 parts by weight of the fluorenones. More preferably 80 to 200 parts by mass, more preferably 100 to 150 parts by mass. If the proportion of the aprotic polar solvent is too high, the concentration of the raw materials may be too low, resulting in reduced reactivity. If the proportion of the aprotic polar solvent is too low, the viscosity will be too high, reducing reactivity There is fear.

The solvent may further contain other solvents in addition to the aprotic polar solvent. Other solvents are preferably hydrocarbons and/or halogenated hydrocarbons. Examples of hydrocarbons and halogenated hydrocarbons include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons exemplified as solvents used in the reaction step. be done. Other solvents can be used alone or in combination of two or more. Among other solvents, aromatic hydrocarbons are preferred, mono- to tri-C _1-4 alkyl-benzenes are more preferred, and mono- or di-C _1-2 alkyl-benzenes such as toluene, xylene, ethylbenzene are more preferred.

The ratio of the other solvent is 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less in the total solvent. If the ratio of the other solvent is too high, it may become difficult to produce the fluorene compound (1a) with high purity.

The proportion of the aprotic polar solvent in the total solvent is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 100% by mass. .

The proportion of the solvent may be selected from a range of, for example, about 10 to 1,000 parts by weight, for example, 30 to 500 parts by weight, preferably 50 to 300 parts by weight, more preferably 80 parts by weight, based on 100 parts by weight of the fluorenones. to 200 parts by mass, more preferably 100 to 150 parts by mass. If the proportion of the solvent is too high, the concentration of the raw material may be too low and reactivity may be lowered.

(Reaction conditions)
The reaction temperature is not particularly limited, but can be selected, for example, from the range of about 0 to 200°C, for example, 10 to 150°C, preferably 30 to 100°C, more preferably 40 to 80°C, more preferably 50 to 70°C. be. The reaction time is not particularly limited and can be selected in the range of about 0.1 to 24 hours, for example 0.5 to 12 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours.

The reaction may be carried out while stirring, in the air or in an inert atmosphere such as nitrogen gas or rare gas, and may be carried out under normal pressure or increased pressure. Also, the reaction may be carried out while dehydrating.

In the intermediate reaction step, the fluorenone compound can be reacted at a high reaction conversion rate by performing the reaction under specific conditions using the raw material composition. Therefore, the reaction conversion rate of the fluorenone is usually 90 mol% or more, for example 93 mol% or more, preferably 95 mol% or more, more preferably 96 mol% or more, more preferably 98 mol% or more, most preferably 98 mol% or more. is 99 mol % or more.

[Purification step of intermediate reaction solution]
The obtained intermediate reaction solution may be subjected to the reaction step as it is, but from the point of view of efficiently producing a highly pure fluorene compound (1), the intermediate reaction solution is subjected to a purification step to obtain fluorene compound (1a) from the intermediate reaction solution. It is preferably taken out and subjected to the reaction step.

The intermediate reaction solution contains, in addition to the fluorene compound (1a), unreacted compounds represented by the formulas (3a) and (3b), an acid catalyst, thiols, a solvent, water, and the like. Separation (or purification) of the fluorene compound (1a) from such an intermediate reaction solution includes conventional methods such as filtration, concentration, extraction, neutralization, washing, crystallization, recrystallization, column chromatography, and the like. A purification or separation means or a combination of these purification or separation means can be used. In the step of purifying the intermediate reaction solution, for example, after removing the acid catalyst (and thiols) by a method of neutralizing by adding an aqueous alkali solution such as an aqueous solution of sodium hydrogencarbonate, the fluorene compound (1a) is crystallized. , may be separated (purified).

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples. In addition, the reaction products 9,9-bis(6-hydroxy-2-naphthyl)fluorene (hereinafter referred to as "BNF") and 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl] A method for analyzing fluorene (hereinafter referred to as "BNEF") is shown below.

(HPLC: Analysis of BNF)
Using "LC-2010C HT" manufactured by Shimadzu Corporation as a HPLC (high performance or high performance liquid chromatograph) device and "ODS-80TM" manufactured by Tosoh Corporation as a column, the sample was dissolved in acetonitrile and acetonitrile and HPLC purity [area %] was measured using water as an eluent.

(HPLC: Analysis of BNEF)
HPLC (high-performance or high-performance liquid chromatograph) device manufactured by Shimadzu Corporation "Nexera-iLC-2040C Plus", column manufactured by Shimadzu GLC Co., Ltd. "Luna PFP (2)" was used, and the sample was added to acetonitrile. was dissolved, and acetonitrile and 0.1 mass % phosphoric acid aqueous solution were used as eluents to measure the HPLC purity [area %].

Example 1
In a 1 L separable flask, fluorenone (hereinafter referred to as "FLN") 40.0 g (0.22 mol), β-naphthol 96.0 g (0.67 mol), 1,4-dioxane 55.5 g, β- 0.7 g of mercaptopropionic acid was added and dissolved at 60°C. After dissolution, 57.2 g of concentrated sulfuric acid was added dropwise in the temperature range of 55 to 65° C., and the mixture was stirred at 60° C. for 4 hours. 18.5 g of 1,4-dioxane, 255.1 g of o-xylene and 74.0 g of water were added to the obtained reaction solution, and the mixture was sufficiently stirred at 80° C., and the water layer was removed. After that, 74.0 g of a 5% by mass sodium hydrogencarbonate aqueous solution was added and sufficiently stirred, and the water layer was removed. Further, 74.0 g of 1% by mass hydrochloric acid was added and sufficiently stirred, and after removing the aqueous layer, the organic layer was washed with water several times. After removing o-xylene by concentrating the obtained organic layer under reduced pressure, 249.8 g of toluene heated to 70° C. was added to carry out cooling crystallization. In the cooling crystallization, after confirming the precipitation of crystals at 50°C, 36.7 g of heptane was added and then cooled to 10°C or less at a rate of 10°C/hour. After reaching 10 ° C. or less, it is aged for 2 hours in the temperature range of 0 to 10 ° C. and filtered, then rinsed with cold toluene adjusted to 0 to 10 ° C., filtered, and dried under reduced pressure at 85 ° C. , 66.8 g of BNF (66.8% converted yield from FLN, HPLC purity 98.4%) were obtained.

Subsequently, in a 500 mL separable flask, 56.3 g (0.13 mol) of BNF, 38.5 g (0.44 mol) of ethylene carbonate, 1.7 g of potassium carbonate, 62.6 g of DMF, tetrabutylammonium bromide (hereinafter , TBAB) was added and reacted at 110°C for 2 hours, and HPLC confirmed that the conversion of BNF was 99% or more.

After that, 50.0 g of a 3% by mass sodium hydroxide aqueous solution was added to the obtained reaction solution, and the mixture was stirred at 90° C. for 8 hours. After that, 62.6 g of methyl isobutyl ketone (hereinafter referred to as "MIBK") and 62.6 g of toluene were added and thoroughly stirred at 80°C, and the water layer was removed. Subsequently, 38.0 g of 3% by mass hydrochloric acid was added, sufficiently stirred, and the aqueous layer was removed. After that, the organic layer was washed with water several times, and cooled and crystallized. In cooling crystallization, after confirming the precipitation of crystals at 60°C, the mixture was cooled to 10°C or less at a rate of 10°C/hour. After reaching 10°C or less, it is aged for 2 hours in the temperature range of 0 to 10°C, filtered, then rinsed in order with cold toluene and cold methanol adjusted to 0 to 10°C, filtered, and decompressed at 90°C. By drying, 57.4 g of BNEF (converted yield from BNF: 85.3%, converted yield from FLN: 57.0%, HPLC purity: 98.8%) was obtained.

Example 2
80.0 g (0.44 mol) of FLN, 192.0 g (1.33 mol) of β-naphthol, 111.1 g of 1,4-dioxane, and 1.4 g of β-mercaptopropionic acid were added to a 1 L separable flask. and dissolved at 60°C. After dissolution, 114.4 g of concentrated sulfuric acid was added dropwise in the temperature range of 55 to 65° C., and the mixture was stirred at 60° C. for 4 hours. 37.0 g of 1,4-dioxane, 510.2 g of o-xylene and 148.0 g of water were added to the obtained reaction solution, and the mixture was sufficiently stirred at 80° C., and the water layer was removed. After that, 148.0 g of a 5% by mass sodium bicarbonate aqueous solution was added and sufficiently stirred, and the water layer was removed. Further, 148.0 g of 1% by mass hydrochloric acid was added, and the mixture was sufficiently stirred. After removing the aqueous layer, the organic layer was washed with water several times. After removing o-xylene by concentrating the obtained organic layer under reduced pressure, 499.6 g of toluene heated to 70° C. was added to carry out cooling crystallization. In the cooling crystallization, after confirming the precipitation of crystals at 50°C, 73.4 g of heptane was added, and the mixture was cooled to 10°C or less at a rate of 10°C/hour. After reaching 10 ° C. or less, it is aged for 2 hours in the temperature range of 0 to 10 ° C. and filtered, then rinsed with cold toluene adjusted to 0 to 10 ° C., filtered, and dried under reduced pressure at 85 ° C. , 133.6 g of BNF (calculated yield from FLN 66.8%, HPLC purity 98.4%).

Subsequently, 67.6 g (0.15 mol) of BNF, 31.7 g (0.36 mol) of ethylene carbonate, 2.1 g of potassium carbonate, 75.1 g of MIBK, 19.1 g of toluene, and DMF were added to a 500 mL separable flask. 15.0 g of TBAB and 2.4 g of TBAB were added and reacted at 110° C. for 6 hours. HPLC confirmed that the conversion of BNF was 99% or more.

After that, 60.0 g of DMF and 30.0 g of 6% by mass sodium hydroxide aqueous solution were added to the obtained reaction solution, and the mixture was stirred at 90° C. for 2 hours. After that, 56.1 g of toluene and 30.0 g of water were added and thoroughly stirred at 80° C., and the water layer was removed. Subsequently, 112.5 g of 3% by mass oxalic acid water was added and sufficiently stirred, and the water layer was removed. After adding 61.4 g of 2.4% by mass saline and sufficiently stirring and removing the aqueous layer, 37.8 g of DMF and 37.6 g of MIBK were added. After that, the organic layer was washed with water several times, and then 25.0 g of methanol was added to carry out cooling crystallization. In cooling crystallization, after confirming crystal precipitation at 50°C, the mixture was cooled to 20°C or lower at a rate of 10°C/hour, aged at 20°C for 9 hours, and cooled to 10°C or lower at a rate of 10°C/hour. . After reaching a temperature of 10°C or less, it is aged for another hour at a temperature range of 0 to 10°C and filtered, then rinsed in order with cold toluene and cold methanol adjusted to 0 to 10°C, filtered, and decompressed at 120°C. By drying, 58.5 g of BNEF (72.4% converted yield from BNF, 48.4% converted yield from FLN, HPLC purity 98.2%) was obtained.

Example 3
40.0 g (0.22 mol) of FLN, 96.0 g (0.67 mol) of β-naphthol, 55.5 g of 1,4-dioxane, and 0.7 g of β-mercaptopropionic acid were added to a 1 L separable flask. and dissolved at 60°C. After dissolution, 57.2 g of concentrated sulfuric acid was added dropwise in the temperature range of 55 to 65° C., and the mixture was stirred at 60° C. for 4 hours. 255.1 g of toluene and 74.0 g of water were added to the obtained reaction liquid, and the mixture was sufficiently stirred at 80° C., and the water layer was removed. After that, 74.0 g of a 5% by mass sodium hydrogencarbonate aqueous solution was added and sufficiently stirred, and the water layer was removed. Furthermore, 74.0 g of 1% by mass hydrochloric acid was added, and the mixture was sufficiently stirred. After the aqueous layer was removed, the organic layer was washed with water several times, followed by cooling and crystallization. Cooling crystallization was performed by adding 27.6 g of heptane at 60°C and then cooling to 10°C or less at a rate of 10°C/hour. After reaching 10°C or less, the toluene and 1,4-dioxane are filtered by rinsing with cold toluene adjusted to 0 to 10°C and filtering for an additional 2 hours at a temperature range of 0 to 10°C. 97.3 g of crude BNF containing about 20% by mass (HPLC purity 96.9%) was obtained.

Subsequently, 68.6 g of crude BNF, 38.5 g (0.44 mol) of ethylene carbonate, 1.7 g of potassium carbonate, 62.6 g of DMF, and 2.0 g of TBAB were added to a 500 mL separable flask and It was confirmed by HPLC that the conversion rate of BNF was 99% or more when reacted for time. 50.0 g of a 3% by mass sodium hydroxide aqueous solution was added to the obtained reaction solution, and the mixture was stirred at 90° C. for 8 hours. After that, 62.6 g of MIBK and 62.6 g of toluene were added and thoroughly stirred at 80° C., and the water layer was removed. Subsequently, 38.0 g of 3% by mass hydrochloric acid was added, sufficiently stirred, and the aqueous layer was removed. After that, the organic layer was washed with water several times, and cooled and crystallized. In cooling crystallization, after confirming the precipitation of crystals at 60°C, the mixture was cooled to 10°C or less at a rate of 10°C/hour. After reaching 10°C or less, it is aged for 2 hours in the temperature range of 0 to 10°C, filtered, then rinsed in order with cold toluene and cold methanol adjusted to 0 to 10°C, filtered, and decompressed at 90°C. By drying, 52.5 g of BNEF (62.3% converted yield from FLN, HPLC purity 98.3%) was obtained.

The fluorene-containing alcohol obtained by the production method of the present invention has excellent heat resistance and can suppress coloring, so it can be used as a resin raw material, as an additive (or resin additive) such as a heat resistance improver and a refractive index improver. can be used effectively.

Claims (5)

In the presence of an inorganic base catalyst and amides, the following formula (1a)

(In the formula,
Z ¹ and Z ² independently represent a condensed polycyclic arene ring;
R ¹ and R ² independently represent a substituent, m1 and m2 independently represent an integer of 0 or more,
R ³ represents a substituent and n represents an integer of 0 to 8)
By reacting a fluorene compound and an alkylene carbonate represented by
Formula (1) below

[In the formula, A ¹ and A ² independently represent a linear or branched alkylene group, and ring Z ¹ , ring Z ² , R ¹ , R ² , R ³ , m1, m2 and n are each Same as formula (1a)]
A method for producing a fluorene compound represented by the above formula (1), comprising a reaction step of obtaining a reaction solution containing the fluorene compound represented by. 2. The production method according to claim 1, further comprising a purification step of crystallizing the reaction solution obtained in the reaction step using a crystallization solvent containing amides, ketones and aromatic hydrocarbons. As a step before the reaction step, in the presence of an acid catalyst, thiols and an aprotic polar solvent, the following formula (2)

[wherein R ³ and n are the same as in formula (1a)]
and fluorenones represented by the following formulas (3a) and (3b)

[Wherein, ring Z ¹ , ring Z ² , R ¹ , R ² , m1 and m2 are the same as in formula (1a)]
to obtain an intermediate reaction liquid containing the fluorene compound represented by the formula (1a), and from the intermediate reaction liquid represented by the formula (1a) 3. The production method according to claim 1 or 2, wherein the fluorene compound is taken out and supplied to the reaction step. 4. The production method according to any one of claims 1 to 3, wherein in the formula (1), A ¹ and A ² are ethylene groups, and the ring Z ¹ and ring Z ² are naphthalene rings. The inorganic base catalyst is a metal carbonate and/or a metal hydrogen carbonate, the amides are alkylamides, and the proportion of the inorganic base catalyst is 1 to 10 parts by mass with respect to 100 parts by mass of the amides. The production method according to any one of claims 1 to 4.