Method for producing alcohol having a fluorene skeleton

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]

[0001] The present invention relates to a method for producing an alcohol having a 9,9-bis(fused polycyclic aryl)fluorene skeleton. [Background technology]

[0002] In the field of optical materials, alcohols having a 9,9-bis(fused polycyclic aryl)fluorene skeleton (fluorene-containing alcohols) are attracting attention due to their excellent optical properties such as high refractive index, low Abbe number, low birefringence, and high transparency, as well as heat resistance.

[0003] As a method for producing such a fluorene-containing alcohol, Japanese Patent Laid-Open Publication No. 2009-155253 (Patent Document 1) discloses a method of reacting 9,9-bis(6-hydroxy-2-naphthyl)fluorene with ethylene carbonate in the presence of 1-methylimidazole and diethylene glycol. In the examples of this document, a fluorene-containing alcohol with a purity of 95.7% is produced.

[0004] Furthermore, as a method for industrially suitable production of the fluorene-containing alcohol, Japanese Patent Laid-Open Publication No. 2019-1780 (Patent Document 2) discloses a production method in which 9-fluorenone and naphthol are reacted in the presence of a solid acid and toluene to obtain a bisnaphthol compound, which is then reacted with ethylene carbonate in the presence of potassium carbonate without being separated. In the examples of this document, a fluorene-containing alcohol with a purity of 95.1 to 96.7% is produced. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-155253 [Patent Document 2] JP 2019-1780 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, in recent years, the field of optical materials has required high-performance optical properties, and even the methods of Patent Documents 1 and 2 cannot sufficiently improve the purity of the resulting fluorene-containing alcohol.

[0007] Therefore, an object of the present invention is to provide a method for efficiently producing an alcohol having a 9,9-bis(fused polycyclic aryl)fluorene skeleton with high purity. [Means for solving the problem]

[0008] As a result of intensive research to achieve the above object, the present inventors have found that 9,9-bis(hydroxyalkoxy-fused polycyclic aryl)fluorene can be efficiently produced with high purity by reacting 9,9-bis(hydroxy-fused polycyclic aryl)fluorene with alkylene carbonate in the presence of an inorganic base catalyst and an amide, and have thus completed the present invention.

[0009] That is, the production method of the present invention comprises reacting a compound represented by the following formula (1a) in the presence of an inorganic base catalyst and an amide.

[0010] [ka]

[0011] (In the formula, Z 1 and Z 2 each independently represents a fused polycyclic arene ring; R 1 and R 2 each independently represents 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. and reacting a fluorene compound represented by the formula (I) with an alkylene carbonate, The following formula (1)

[0012] [ka]

[0013] [In the formula, A 1 and A 2 each independently represents a linear or branched alkylene group; 1 , ring Z 2 , R 1 , R 2 , R 3 , m1, m2 and n are the same as in formula (1a). The method for producing the fluorene compound represented by formula (1) includes a reaction step of obtaining a reaction solution containing the fluorene compound represented by formula (1).

[0014] 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.

[0015] The production method includes, as a pre-step of the reaction step, reacting a compound represented by the following formula (2) in the presence of an acid catalyst, a thiol, and an aprotic polar solvent:

[0016] [ka]

[0017] [In the formula, R 3 and n are the same as in formula (1a)]. and fluorenones represented by the following formulae (3a) and (3b):

[0018] [ka]

[0019] [In the formula, ring Z 1 , ring Z 2 , R 1 , R 2 , m1 and m2 are the same as in equation (1a). The method may further include an intermediate reaction step of reacting a compound represented by formula (1a) with a compound represented by formula (1b) to obtain an intermediate reaction solution containing the fluorene compound represented by formula (1a). In the production method, the fluorene compound represented by formula (1a) may be extracted from the intermediate reaction solution and subjected to the reaction step.

[0020] In the formula (1), A 1 and A 2 is an ethylene group, and the ring Z 1 and ring Z 2 may be a naphthalene ring. The inorganic base catalyst may be a metal carbonate and / or a metal hydrogen carbonate. The amides may be alkylamides. The proportion of the inorganic base catalyst may be 1 to 10 parts by mass per 100 parts by mass of the amides.

[0021] In this specification and claims, the number of carbon atoms in a substituent is represented by C1, C6, C 10 For example, "C1 alkyl group" means an alkyl group with 1 carbon atom, and "C 6-10 The term "aryl group" refers to an aryl group having 6 to 10 carbon atoms. [Effects of the Invention]

[0022] In the present invention, 9,9-bis(hydroxy-fused polycyclic aryl)fluorene is reacted with alkylene carbonate in the presence of an inorganic base catalyst and an amide, thereby enabling efficient production of 9,9-bis(hydroxyalkoxy-fused polycyclic aryl)fluorene with high purity. DETAILED DESCRIPTION OF THE INVENTION

[0023] In the present invention, the fluorene compound represented by the formula (1) is produced by a production method including a reaction step of reacting a fluorene compound represented by the formula (1a) [hereinafter also referred to as "fluorene compound (1a)"] with an alkylene carbonate in the presence of an inorganic base catalyst and an amide to obtain a reaction solution containing the fluorene compound represented by the formula (1) [hereinafter also referred to as "fluorene compound (1)"].

[0024] [Fluorene compound represented by formula (1)] In the formula (1), ring Z 1 and ring Z 2 Examples of the fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring) represented by the formula (I) include fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings.

[0025] The fused bicyclic arene rings include fused bicyclic C rings such as naphthalene rings and indene rings. 10-16 Examples of the fused tricyclic arene ring include an anthracene ring and a phenanthrene ring. These fused polycyclic arene rings can be used alone or in combination.

[0026] Two Z rings 1 and Z 2 The types of may be the same or different, and are preferably the same. Among these, fused polycyclic C rings such as naphthalene rings and anthracene rings are preferred. 10-16 An arene ring is preferred, and a fused polycyclic C 10-14 An arene ring is more preferred, and a naphthalene ring is most preferred.

[0027] Base A 1 and A 2 Examples of the linear or branched alkylene group represented by the formula (I) include linear or branched C alkylene groups such as ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene. 2-4 These alkylene groups may be used alone or in combination of two or more.

[0028] Two groups A 1 and A 2 The types of may be the same or different, and are preferably the same. 2-3 Alkylene groups are preferred, with ethylene groups being particularly preferred.

[0029] base R 1 and R 2 Examples of the substituent represented by the formula (I) include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, and a cyano group.

[0030] 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, cyano groups, and substituted amino groups. 1 and R 2 Examples of the alkyl group include an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group. The alkyl group may be a straight-chain or branched C 1-6 Examples of the cycloalkyl group include C alkyl groups such as cyclohexyl groups. 5-8 Examples of the aryl group include C aryl groups such as phenyl groups. 6-14 The alkoxy group includes a linear or branched C 1-4 Alkoxy groups and the like are examples of the substituent R 1 and R 2 The types of may be the same or different, but are preferably the same. Among these, alkyl groups are preferred, and linear or branched C groups such as methyl groups are preferred. 1-4 Alkyl groups are particularly preferred.

[0031] R 1 and R 2 The numbers of substitutions m1 and m2 may be integers of 0 or more, and the ring Z 1 and ring Z 2The numbers m1 and m2 can be selected appropriately depending on the type of R and may each be, for example, an integer of 0 to 8. Preferred numbers of substitutions m1 and m2 are, in the following order, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, 0 or 1, with 0 being the most preferred. The numbers of substitutions m1 and m2 may be different, but are preferably the same. When the numbers of substitutions m1 and m2 are 2 or more, 2 or more R 1 or R 2 The types may be the same or different.

[0032] R 3 Examples of the substituent represented by the formula (I) include a hydrocarbon group, a cyano group, and a halogen atom. Examples of the hydrocarbon group include an alkyl group and an aryl group. Examples of the alkyl group include a linear or branched C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. 1-6 Examples of aryl groups include C alkyl groups such as phenyl groups. 6-10 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. These substituents may be used alone or in combination.

[0033] These groups R 3 Among these, alkyl groups, cyano groups, and halogen atoms are preferred, alkyl groups are more preferred, and linear or branched C groups such as methyl groups are preferred. 1-4 Alkyl groups are more preferred, and C 1-2 Alkyl groups are most preferred.

[0034] base R 3 The number of substitutions n may be an integer of 0 to 8, and preferred ranges are, in the following stepwise order, integers of 0 to 6, integers of 0 to 5, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, and 0 or 1, with 0 being the most preferred. Note that the number of substitutions in the two different benzene rings constituting the fluorene ring may be the same or different. In addition, the groups R substituted on the different benzene rings may be 3The types of groups R may be different from each other, but are preferably the same. When n is 2 or more, two or more groups R substituted on the same or different benzene rings may be the same. 3 The types of groups R may be the same or different. 3 The substitution position of is not particularly limited, and may be, for example, the 2- to 7-position of the fluorene ring, with the 2-, 3- and 7-positions being preferred.

[0035] Representative 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, etc. Among these, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene is preferred.

[0036] The fluorene compound (1) obtained by the production method of the present invention 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, further preferably 96 mol % or more, more preferably 98 mol % or more, and most preferably 99 mol % or more.

[0037] The purity of fluorene compound (1) is also high, and the purity (HPLC purity) measured by HPLC (high performance liquid chromatography) can be selected from a range of, for example, about 95% or more, with preferred ranges being 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 a range of about 96 to 100%, preferably 98.5 to 99.99%, and more preferably 98.7 to 99.9%.

[0038] In this specification and claims, the conversion rate (reaction conversion rate) and purity can be measured by the method described in the examples below (method using HPLC), for example.

[0039] [Reaction process] In the reaction step, a fluorene compound represented by the formula (1a) [hereinafter also referred to as "fluorene compound (1a)"] is reacted with an alkylene carbonate in the presence of an inorganic base catalyst and an amide to obtain a reaction solution containing a fluorene compound (1). The fluorene compound (1a), which is one of the raw materials in the reaction step, is represented by the formula (1a), and in the formula (1a), the ring Z 1 , ring Z 2 , R 1 , R 2 , R 3 , m1, m2 and n are the same as those in the formula (1), including preferred embodiments.

[0040] (Alkylene carbonate) The other raw material alkylene carbonate is a group A of the formula (1). 1 and A 2 Specific alkylene carbonates include C alkylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate. 2-4 These alkylene carbonates can be used alone or in combination of two or more. 2-3 Alkylene carbonates are preferred, with ethylene carbonate being particularly preferred.

[0041] The proportion of alkylene carbonate may be 2 moles or more, preferably 2.5 moles or more, per mole of fluorene compound (1a), for example, 2 to 5 moles, preferably 2.5 to 4.5 moles, further preferably 2.8 to 4 moles, and even more preferably 3 to 3.5 moles.

[0042] (catalyst) The catalyst used in the reaction step includes an inorganic base catalyst. In the production method of the present invention, the catalyst includes an inorganic base catalyst, and the solvent described below includes an amide, so that a highly pure fluorene compound (1) can be efficiently produced.

[0043] Inorganic base catalysts include metal carbonates, metal hydrogen carbonates, metal hydroxides, and the like.

[0044] 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.

[0045] 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.

[0046] 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; and thallium(I) hydroxide.

[0047] These inorganic base catalysts can be used alone or in combination. Among these, metal carbonates and / or metal hydrogen carbonates are preferred, alkali metal carbonates and / or alkali metal hydrogen carbonates are more preferred, and alkali metal carbonates such as potassium carbonate are most preferred.

[0048] The total proportion of the metal carbonate and metal hydrogencarbonate preferably accounts for the major component of the inorganic base catalyst, and 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 of the total inorganic base catalyst. Furthermore, the proportion of the metal carbonate more preferably accounts for the major component of the inorganic base catalyst, and 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 of the total inorganic base catalyst.

[0049] The proportion of the inorganic base catalyst is 0.1 part by mass or more (for example, about 0.1 to 10,000 parts by mass) relative to 100 parts by mass of the amides, and preferred ranges are 0.1 to 1,000 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, and most preferably 2 to 4 parts by mass. If the proportion of the inorganic base catalyst is too low, the yield may decrease, and conversely, if it is too high, the purity may decrease.

[0050] The proportion 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, even more preferably 1.5 to 5 parts by mass, and most preferably 2 to 4 parts by mass, relative to 100 parts by mass of the fluorene compound (1a). If the proportion 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. Conversely, if the proportion is too high, the inorganic base catalyst may remain as an impurity.

[0051] The catalyst may further include other catalysts such as an organic base catalyst, an acid catalyst, etc., in addition to the inorganic base catalyst. The other catalyst may be an acid catalyst, but an organic base catalyst is preferred.

[0052] Examples of the organic base catalyst include amines such as triethylamine, N,N-dimethylaniline, and 1-methylimidazole; metal carboxylates such as sodium acetate and calcium acetate; and the like. These organic base catalysts can be used alone or in combination.

[0053] The proportion of the other catalysts is 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on the total amount of the catalysts. If the proportion of the other catalysts is too high, it may be difficult to produce the fluorene compound (1) with high purity.

[0054] The proportion of the inorganic base catalyst in the total catalyst is 50 mass % or more, preferably 70 mass % or more, further preferably 90 mass % or more, further preferably 95 mass % or more, and most preferably 100 mass %. If the proportion of the inorganic base catalyst is too small, it may be difficult to efficiently produce a highly pure fluorene compound (1).

[0055] The proportion 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, even more preferably 1.5 to 5 parts by mass, and most preferably 2 to 4 parts by mass, relative to 100 parts by mass of the fluorene compound (1a). If the proportion 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. Conversely, if the proportion is too large, the catalyst may remain as an impurity.

[0056] (Reaction solvent) The reaction solvent (solvent inert to the reaction) used in the reaction step includes amides. When the amount of amides in the reaction solvent is small, the amides may function as an additive. The amides include alkylamides (alkylacylamines), cyclic amides, etc. The amides may be cyclic amides such as N-methyl-2-pyrrolidone (NMP), but alkylamides are preferred.

[0057] Alkylamides include N,N-diC alkylamides such as N,N-dimethylformamide (DMF) and N,N-diethylformamide. 1-4 Alkylformamides; N,N-di-C such as N,N-dimethylacetamide (DMAc) and N,N-diethylacetamide 1-4 These amides can be used alone or in combination of two or more. Among these, N,N-diC 1-4 Alkylformamide, N,N-diC 1-4 Alkylacetamides are preferred, and N,N-diC 1-3 Alkylformamide, N,N-diC 1-3 Alkylacetamides are more preferred, and N,N-diC 1-2Alkylformamide, N,N-diC 1-2 Alkylacetamides are more preferred, and DMF is most preferred.

[0058] The proportion of the amides can be selected from a range of about 0.1 to 3,000 parts by mass (particularly 1 to 3,000 parts by mass) relative to 100 parts by mass of the fluorene compound (1a), and is, for example, 10 to 3,000 parts by mass, preferably 20 to 1,000 parts by mass, further preferably 30 to 300 parts by mass, more preferably 50 to 150 parts by mass, and most preferably 80 to 130 parts by mass. If the proportion of the amides is too low, there is a risk of reduced handleability, and conversely, if it is too high, there is a risk of reduced reactivity.

[0059] The reaction solvent may further contain other solvents in addition to the amides. Examples of 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; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane; alcohols such as methanol, ethanol, isopropanol, and ethylene glycol; linear ethers such as diethyl ether and diisopropyl ether; glycol ethers such as methyl cellosolve, methyl carbitol, and dimethoxyethane; 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; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as dimethyl sulfoxide. These other solvents can be used alone or in combination.

[0060] 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 preferred, aromatic hydrocarbons and / or ketones, and aromatic hydrocarbons and / or cyclic ethers are more preferred, and a combination of aromatic hydrocarbons and ketones is even more preferred.

[0061] When aromatic hydrocarbons and ketones are combined, the proportion of the aromatic hydrocarbons relative to 100 parts by mass of the ketones is, for example, 1 to 100 parts by mass, preferably 5 to 80 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 20 to 30 parts by mass.

[0062] The proportion of the other solvent is 99.9% by mass or less (particularly 99% by mass or less) of the total reaction solvent, and preferred ranges are 90% by mass or less, 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, and most preferably 5% by mass or less. If the proportion of the other solvent is too high, it may be difficult to produce fluorene compound (1) with high purity.

[0063] When the amides are combined with other solvents and used as additives, the proportion of the amides is, for example, 1 to 50 parts by mass, preferably 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 10 to 20 parts by mass, per 100 parts by mass of the other solvent.

[0064] The proportion of the amides is 0.1% by mass or more (particularly 1% by mass or more) in the total reaction solvent, and preferred ranges are 10% by mass or more, 30% by mass or more, 50% by mass or more, 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 the amides is too low, it may be difficult to produce fluorene compound (1) with high purity.

[0065] The proportion of the reaction solvent is, for example, 10 to 3000 parts by mass, preferably 30 to 1000 parts by mass, further preferably 50 to 300 parts by mass, further preferably 80 to 200 parts by mass, and most preferably 100 to 150 parts by mass, relative to 100 parts by mass of the fluorene compound (1a).

[0066] (Other additives) In the reaction step, conventional additives used in reactions may be further used. Examples of conventional additives include a co-catalyst (phase transfer catalyst). Examples of the co-catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and trioctylmethylammonium chloride. These co-catalysts can be used alone or in combination. Among these co-catalysts, TBAB is often used.

[0067] The proportion of the co-catalyst 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, and even more preferably 2 to 4 parts by mass, relative to 100 parts by mass of the fluorene compound (1a).

[0068] (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., and even more preferably 90 to 120° C. The reaction time is not particularly limited, but can be selected from the range of about 30 minutes to 24 hours, for example, 0.5 to 12 hours, preferably 1 to 6 hours, and more preferably 1.5 to 3 hours.

[0069] The reaction may be carried out with stirring, in air, or in an inert atmosphere such as nitrogen or a rare gas such as helium or argon, under normal pressure or pressure, and may also be carried out while dehydrating.

[0070] [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. The fluorene compound (1) obtained in the reaction step can be prepared into a fluorene compound (1) with a higher purity by crystallization using a mixed solvent containing amides, ketones, and aromatic hydrocarbons as a crystallization solvent in the purification step.

[0071] The amides, including preferred embodiments thereof, are the same as those exemplified in the section on reaction solvents.

[0072] Ketones include chain ketones, cyclic ketones, etc. Chain ketones include C ketones such as acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone (MIBK), diisopropyl ketone, and butyl propyl ketone. 3-8 Examples of cyclic ketones include C ketones such as cyclohexanone. 5-10 These ketones can be used alone or in combination. Among these, chain ketones are preferred, and C ketones such as MIBK are preferred. 4-7 Acyclic ketones are particularly preferred.

[0073] Aromatic hydrocarbons include benzene, alkylbenzenes, etc. Examples of alkylbenzenes include mono- and tetra-C alkylbenzenes such as toluene, xylene, ethylbenzene, trimethylbenzene, ethyltoluene, propylbenzene, and cumene. 1-4 These aromatic hydrocarbons can be used alone or in combination. Among these, mono- or di-C hydrocarbons such as toluene, xylene, and ethylbenzene are preferred. 1-2 Alkyl-benzenes are preferred, with toluene being especially preferred.

[0074] 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 the crystallization solvent as is, or a crystallization solvent identical to or different from the crystallization solvent used as the reaction solvent may be added.

[0075] In the purification step of the reaction, the proportion 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, and most preferably 80 to 120 parts by mass, relative to 100 parts by mass of amides.

[0076] The proportion of the aromatic hydrocarbons relative to 100 parts by mass of the amides 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.

[0077] The crystallization solvent may further contain other solvents in addition to amides, ketones, and aromatic hydrocarbons. Examples of the other solvents include the solvents exemplified as the reaction solvents in the reaction step and water. Examples of the other solvents include C 10 solvents such as methanol. 1-4 Alkanols are preferred.

[0078] The proportion of the other solvent may be 30% by mass or less, for example, about 0 to 20% by mass, based on the total crystallization solvent. From the viewpoint of efficiently producing a highly pure fluorene compound (1), the preferred ranges are 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, i.e., substantially no other solvent is contained.

[0079] When the amides function as an additive to the reaction solvent, it is preferable to contain another solvent, and the proportion of the other solvent is, for example, 1 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass relative to 100 parts by mass of the amides.

[0080] The proportion of the crystallization solvent may be, for example, about 10 to 2000 parts by mass relative to 100 parts by mass of the fluorene compound (1), and preferred ranges are 50 to 1500 parts by mass, 100 to 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 following stepwise manner.

[0081] In the purification step, fluorene compound (1) can be dissolved in the crystallization solvent and cooled to precipitate a fluorene compound (1) with a higher purity. In particular, fluorene compound (1) can be precipitated or crystallized with a higher purity by heating and dissolving the fluorene compound (1) in the crystallization solvent, followed by 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 to fall within the above-mentioned ratio range. The crystallization solvent may be added (or mixed) in its entirety before heating, or may be added stepwise, e.g., by adding a portion of the solvent, raising the temperature to a predetermined level, and then adding the remaining solvent.

[0082] 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, and preferred ranges are 50 to 150°C, 60 to 130°C, 70 to 120°C, and 75 to 100°C in the following stepwise order.

[0083] The solution obtained by dissolving fluorene compound (1) in a crystallization solvent is cooled to crystallize fluorene compound (1) with higher purity. Crystallization can be performed by rapid cooling, natural cooling, or slow cooling. Rapid cooling appears to be relatively easy to obtain fluorene compound (1) with higher purity. Typical cooling rates can be selected, for example, from a range of about 0.1 to 100°C / min. Preferred ranges are the following stepwise: 1°C / min or more, 1 to 50°C / min, 3 to 30°C / min, 5 to 20°C / min, 7 to 15°C / min, 8 to 12°C / min, and 9 to 11°C / min. The precipitation temperature (the temperature at which precipitation or crystallization begins) can be 80°C or lower, for example, 30 to 80°C, preferably 40 to 75°C, more preferably 50 to 70°C, and even more preferably 55 to 65°C. The ultimate cooling temperature is, for example, −10° C. to 30° C., preferably −5° C. to 20° C., and more preferably 0 to 10° C. The retention time at the ultimate cooling temperature is not particularly limited and may be, for example, about 1 minute to 12 hours, preferably 0.5 to 6 hours, and more preferably 1 to 3 hours.

[0084] In the crystallization procedure, seed crystals may be added if necessary, and the crystallization procedure may be carried out once or repeatedly. The crystals produced by the crystallization are usually filtered by a separation means such as filtration (e.g., suction filtration) or centrifugation, and then dried to obtain a highly pure fluorene compound (1).

[0085] Drying after crystallization may be performed under reduced pressure, and the drying temperature may be, for example, about 50 to 200°C, with preferred ranges being 60 to 150°C, 70 to 120°C, 80 to 100°C, and 85 to 95°C in the following stepwise manner. Drying may be performed by raising the temperature all at once or by raising the temperature stepwise. Drying time may be, for example, about 1 hour to 1 week, and is preferably 1 to 3 days.

[0086] In the purification step, the reaction liquid (reaction mixture) before being subjected to crystallization may be neutralized and washed as necessary, impurities may be removed from the reaction liquid mixture, and the residue may be dissolved in the crystallization solvent to crystallize the fluorene compound (1) with a higher purity.

[0087] [Intermediate reaction process] In the intermediate reaction step, as a pre-step of the reaction step, the fluorenones represented by the formula (2) are reacted with the compounds represented by the formulas (3a) and (3b) in the presence of an acid catalyst, thiols, and an aprotic polar solvent to obtain an intermediate reaction liquid (intermediate reaction mixture) containing the fluorene compound (1a).

[0088] (Fluorenones represented by formula (2)) In the formula (2), R 3 and n are the same as those in the formula (1), including preferred embodiments. Fluorenones represented by the formula (2) include fluorenone (or 9-fluorenone); alkyl fluorenones such as methyl fluorenone, etc. Among these, fluorenone is preferred.

[0089] (Compounds represented by formulas (3a) and (3b)) In the formulas (3a) and (3b), the ring Z 1 , ring Z 2 , R 1 , R 2 The compounds represented by the formulas (3a) and (3b) include naphthols such as 1-naphthol and 2-naphthol; C naphthols such as methylnaphthol; 1-4 Among these, 2-naphthol is preferred.

[0090] The proportion of the compounds represented by the formulas (3a) and (3b) is, for example, 2 to 5 moles, preferably 2.3 to 4 moles, and more preferably 2.5 to 3.5 moles, relative to 1 mole of the fluorenone represented by the formula (2).

[0091] (acid catalyst) Examples of the acid catalyst used in the intermediate reaction step include inorganic acids, organic acids, and solid acids. Among these, inorganic acids are preferred. Examples of inorganic acids include sulfuric acid, hydrogen chloride, hydrochloric acid, and phosphoric acid. These inorganic acids can be used alone or in combination of two or more. Among these inorganic acids, sulfuric acid is more preferred, and concentrated sulfuric acid is even more preferred, as it also acts as a dehydrating agent for water produced as the reaction proceeds.

[0092] The sulfuric acid includes dilute sulfuric acid with a concentration of about 30 to 90% by mass, concentrated sulfuric acid with a concentration of 90% by mass or more, fuming sulfuric acid, etc., and sulfur trioxide may be used as a sulfuric acid precursor as long as it can be converted to sulfuric acid in the reaction system. The sulfuric acid may be selected from a range of about 80 to 99% by mass in terms of H2SO4, with preferred ranges being 90 to 99% by mass, 93 to 99% by mass, 96 to 99% by mass, and 97 to 98.5% by mass of concentrated sulfuric acid, with 98% by mass being particularly preferred.

[0093] The proportion of the acid catalyst can be selected from the range of, for example, about 10 to 1000 parts by mass relative to 100 parts by mass of the fluorenones, and is, for example, 30 to 500 parts by mass, preferably 50 to 300 parts by mass, further preferably 80 to 200 parts by mass, and even 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 decrease significantly), and conversely, if it is too high, the purity may decrease.

[0094] (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; thioglycols such as mercaptoethanol; methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, and 1-octyl mercaptan. alkyl mercaptans such as t-dodecyl mercaptan; aralkyl mercaptans such as benzyl mercaptan; amino C such as 2-aminoethanethiol (also known as cysteamine), 2-aminopropanethiol, 3-aminopropanethiol, 2-aminobutanethiol, 3-aminobutanethiol, 4-aminobutanethiol, 6-aminohexanethiol, 8-aminooctanethiol, 11-aminoundecanethiol, and 16-aminohexadecanethiol 2-20 Alkanethiol, etc. These thiols can be used alone or in combination of two or more.

[0095] The thiols may be in the form of a salt. Typical salts include inorganic acid salts such as hydrochloride and sulfate, organic acid salts such as acetate, alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, ammonium salt, tetraalkylammonium salts such as tetramethylammonium salt, and double salts thereof.

[0096] Among these thiols, mercapto C 2-4Carboxylic acids are preferred, and mercapto C such as β-mercaptopropionic acid 2-3 Carboxylic acids are particularly preferred.

[0097] The proportion of the thiols relative to 100 parts by mass of the fluorenones 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, and even more preferably 1.5 to 3 parts by mass. If the proportion of the thiols is too low, not only may the reaction conversion rate decrease, but also there is a risk of the purity decreasing due to impurities such as unreacted components, while conversely, if it is too high, there is a risk of the thiols remaining as impurities.

[0098] (solvent) The solvent used in the intermediate reaction step includes an aprotic polar solvent, which allows for efficient production of a highly pure fluorene compound (1a).

[0099] Examples of aprotic polar solvents include ethers, ketones, esters, carbonates, amides, ureas, nitriles, nitrated hydrocarbons, phosphoramides, sulfones, sulfoxides, etc. These aprotic polar solvents can be used alone or in combination of two or more.

[0100] Of the aprotic polar solvents, at least one selected from ethers, sulfones, sulfoxides, ureas, and amides is preferred, at least one selected from ethers, sulfones, ureas, and amides is more preferred, at least one cyclic compound having a cyclic structure in the molecule (aprotic polar solvent having a cyclic structure) is even more preferred, and at least one selected from cyclic ethers, cyclic sulfones, cyclic ureas, and cyclic amides is most preferred.

[0101] Examples of the cyclic ethers include C cyclic ethers such as tetrahydrofuran (THF) and 1,4-dioxane. 1-4 Examples thereof include tetrahydrofurans or dioxanes which may have an alkyl group, and among these, C 1-3Dioxanes which may have an alkyl group are preferred, and C 1-2 1,4-dioxanes which may have an alkyl group are more preferred, and 1,4-dioxane is most preferred.

[0102] Examples of the cyclic sulfones include C 1-4 tetra- or pentamethylene sulfones which may have an alkyl group; C 1-3 Sulfolanes which may have an alkyl group are preferred, and C 1-2 Sulfolanes which may have an alkyl group are more preferred, and sulfolane is most preferred.

[0103] Examples of the cyclic ureas include C ureas such as 1,3-dimethyl-2-imidazole (DMI) and N,N'-dimethyl-N,N'-trimethylene urea. 1-4 N,N'-diC optionally having an alkyl group 1-6 Alkyl-N,N'-di- to trimethylene ureas are included, and C 1-3 N,N'-diC optionally having an alkyl group 1-4 Alkyl-ethylene ureas are preferred, C 1-2 N,N'-diC optionally having an alkyl group 1-3 Alkyl-ethylene ureas are more preferred, with DMI being most preferred.

[0104] Examples of the cyclic amides include C 1-4 5- to 7-membered lactams which may have an alkyl group, and C 1-3 5- to 6-membered lactams which may have an alkyl group are preferred, and C 1-2 A 5-membered lactam which may have an alkyl group is more preferred, and NMP is most preferred.

[0105] Among these aprotic polar solvents, C 1-3 Dioxanes which may have an alkyl group are preferred, and C 1-21,4-dioxanes which may have an alkyl group are more preferred, and 1,4-dioxane is most preferred.

[0106] The proportion of the aprotic polar solvent may be selected from the range of, for example, about 10 to 1000 parts by mass relative to 100 parts by mass of the fluorenones, and is, for example, 30 to 500 parts by mass, preferably 50 to 300 parts by mass, further preferably 80 to 200 parts by mass, and even 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 a decrease in reactivity, whereas if the proportion of the aprotic polar solvent is too low, the viscosity may be too high, resulting in a decrease in reactivity.

[0107] The solvent may further contain other solvents in addition to the aprotic polar solvent. The other solvents are preferably hydrocarbons and / or halogenated hydrocarbons. Examples of the hydrocarbons and halogenated hydrocarbons include the aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons exemplified as solvents used in the reaction step. The other solvents can be used alone or in combination of two or more. Among the other solvents, aromatic hydrocarbons are preferred, and mono- to tri-C 1-4 Alkyl-benzenes are more preferred, and mono- or di-C alkyl-benzenes such as toluene, xylene, and ethylbenzene are preferred. 1-2 Alkyl-benzenes are more preferred.

[0108] The proportion 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, based on the total amount of the solvent. If the proportion of the other solvent is too high, it may be difficult to produce the fluorene compound (1a) with high purity.

[0109] The proportion of the aprotic polar solvent in the total solvent is 50% by mass or more, preferably 80% by mass or more, further preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass.

[0110] The proportion of the solvent may be selected from the range of, for example, about 10 to 1000 parts by mass relative to 100 parts by mass of the fluorenones, and is, for example, 30 to 500 parts by mass, preferably 50 to 300 parts by mass, further preferably 80 to 200 parts by mass, and even more preferably 100 to 150 parts by mass. If the proportion of the solvent is too high, the concentration of the raw materials may be too low, which may result in a decrease in reactivity, and if the proportion of the solvent is too low, the viscosity may be too high, which may result in a decrease in reactivity.

[0111] (Reaction conditions) The reaction temperature is not particularly limited, but can be selected, for example, from a range of about 0 to 200° C., such as 10 to 150° C., preferably 30 to 100° C., more preferably 40 to 80° C., and even more preferably 50 to 70° C. The reaction time is not particularly limited, but can be selected from a range of about 0.1 to 24 hours, for example, 0.5 to 12 hours, preferably 1 to 8 hours, and even more preferably 2 to 5 hours.

[0112] The reaction may be carried out with stirring, in air or in an inert atmosphere such as nitrogen gas or a rare gas, under normal pressure or pressure, and may also be carried out while dehydrating.

[0113] In the intermediate reaction step, the raw material composition is used to carry out the reaction under specific conditions, so that the fluorenones can be reacted with a high conversion rate.Therefore, the conversion rate of the fluorenones 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, and most preferably 99 mol% or more.

[0114] [Purification process of intermediate reaction solution] The intermediate reaction solution obtained may be subjected to the reaction step as it is. However, in order to efficiently produce a highly pure fluorene compound (1), it is preferable to subject the intermediate reaction solution to a purification step to extract a fluorene compound (1a) from the intermediate reaction solution and then subject the fluorene compound (1a) to the reaction step.

[0115] In addition to the fluorene compound (1a), the intermediate reaction solution contains unreacted compounds represented by the formulas (3a) and (3b), an acid catalyst, thiols, a solvent, water, etc. The fluorene compound (1a) can be separated (or purified) from the intermediate reaction solution by conventional methods, such as filtration, concentration, extraction, neutralization, washing, crystallization, recrystallization, column chromatography, or a combination thereof. The intermediate reaction solution can be purified by, for example, neutralizing the solution with an aqueous alkali solution such as sodium bicarbonate to remove the acid catalyst (and thiols), followed by crystallizing the fluorene compound (1a) to separate (purify). [Example]

[0116] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In addition, the analytical methods for 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]fluorene (hereinafter referred to as "BNEF") are shown below.

[0117] (HPLC: Analysis of BNF) The HPLC (high performance or high performance liquid chromatograph) was measured using an LC-2010C HT manufactured by Shimadzu Corporation as the apparatus and an ODS-80™ manufactured by Tosoh Corporation as the column. The sample was dissolved in acetonitrile, and acetonitrile and water were used as the eluent to measure the HPLC purity [area %].

[0118] (HPLC: Analysis of BNEF) The HPLC (high performance or high performance liquid chromatograph) was performed using a Shimadzu Corporation "Nexera-iLC-2040C Plus" system and a Shimadzu GLC Corporation "Luna PFP(2)" column. The sample was dissolved in acetonitrile, and the HPLC purity [area %] was measured using acetonitrile and 0.1% by mass phosphoric acid aqueous solution as the eluent.

[0119] Example 1 A 1-L separable flask was charged with 40.0 g (0.22 mol) of fluorenone (hereinafter referred to as "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, and the mixture was dissolved at 60°C. After dissolution, 57.2 g of concentrated sulfuric acid was added dropwise at a temperature range of 55 to 65°C, and the mixture was stirred at 60°C for 4 hours. HPLC confirmed that the conversion of FLN was 99% or higher. To the resulting reaction solution, 18.5 g of 1,4-dioxane, 255.1 g of o-xylene, and 74.0 g of water were added, and the mixture was thoroughly stirred at 80°C. The aqueous layer was then removed. 74.0 g of a 5% by mass aqueous solution of sodium bicarbonate was then added, and the mixture was thoroughly stirred. The aqueous layer was then removed. 74.0 g of 1% by mass hydrochloric acid was then added, and the mixture was thoroughly stirred. The aqueous layer was then removed, and the organic layer was washed multiple times with water. The resulting organic layer was concentrated under reduced pressure to remove o-xylene, and then 249.8 g of toluene heated to 70°C was added to perform cooling crystallization. After confirming crystal precipitation at 50°C, 36.7 g of heptane was added and the mixture was cooled to 10°C or below at a rate of 10°C / hour. After reaching 10°C or below, the mixture was aged for an additional 2 hours in the temperature range of 0 to 10°C and filtered. It was then rinsed with cold toluene adjusted to 0 to 10°C, filtered, and dried under reduced pressure at 85°C to obtain 66.8 g of BNF (66.8% yield converted from FLN, 98.4% HPLC purity).

[0120] Next, 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, and 2.0 g of tetrabutylammonium bromide (hereinafter also referred to as TBAB) were added to a 500 mL separable flask and reacted at 110°C for 2 hours, and it was confirmed by HPLC that the conversion rate of BNF was 99% or more.

[0121] Next, 50.0 g of 3% by weight aqueous sodium hydroxide solution was added to the resulting reaction solution and stirred at 90°C for 8 hours. Then, 62.6 g of methyl isobutyl ketone (hereinafter referred to as "MIBK") and 62.6 g of toluene were added, and the mixture was thoroughly stirred at 80°C, and the aqueous layer was removed. Subsequently, 38.0 g of 3% by weight hydrochloric acid was added, and the mixture was thoroughly stirred, and the aqueous layer was removed. The organic layer was then washed multiple times with water and subjected to cooling crystallization. After confirming crystal precipitation at 60°C, the mixture was cooled to below 10°C at a rate of 10°C / hour. After reaching below 10°C, the mixture was aged for an additional 2 hours at a temperature range of 0 to 10°C, filtered, rinsed sequentially with cold toluene and cold methanol adjusted to 0 to 10°C, filtered, and dried under reduced pressure at 90°C to obtain 57.4 g of BNEF (85.3% yield converted from BNF, 57.0% yield converted from FLN, 98.8% HPLC purity).

[0122] Example 2 A 1-L separable flask was charged with 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, and the mixture was dissolved at 60°C. After dissolution, 114.4 g of concentrated sulfuric acid was added dropwise at a temperature range of 55–65°C, followed by stirring at 60°C for 4 hours. HPLC confirmed that the conversion of FLN was 99% or higher. To the resulting reaction solution, 37.0 g of 1,4-dioxane, 510.2 g of o-xylene, and 148.0 g of water were added, and the mixture was thoroughly stirred at 80°C. The aqueous layer was then removed. Next, 148.0 g of a 5% by weight aqueous solution of sodium bicarbonate was added, thoroughly stirred, and the aqueous layer was removed. Furthermore, 148.0 g of 1% by weight hydrochloric acid was added, thoroughly stirred, and the aqueous layer was removed. The organic layer was then washed multiple times with water. The resulting organic layer was concentrated under reduced pressure to remove o-xylene, and then 499.6 g of toluene heated to 70°C was added to perform cooling crystallization. After confirming crystal precipitation at 50°C, 73.4 g of heptane was added and the mixture was cooled to 10°C or below at a rate of 10°C / hour. After reaching 10°C or below, the mixture was aged for an additional 2 hours in the temperature range of 0 to 10°C and filtered. It was then rinsed with cold toluene adjusted to 0 to 10°C, filtered, and dried under reduced pressure at 85°C to obtain 133.6 g of BNF (66.8% yield converted from FLN, 98.4% HPLC purity).

[0123] Next, 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, 15.0 g of DMF, and 2.4 g of TBAB were added to a 500 mL separable flask and reacted at 110°C for 6 hours, and it was confirmed by HPLC that the conversion rate of BNF was 99% or more.

[0124] Then, 60.0 g of DMF and 30.0 g of 6% by weight sodium hydroxide aqueous solution were added to the resulting reaction solution and stirred at 90 ° C for 2 hours. Then, 56.1 g of toluene and 30.0 g of water were added, and the mixture was thoroughly stirred at 80 ° C, and the aqueous layer was removed. Subsequently, 112.5 g of 3% by weight oxalic acid aqueous solution was added, and the mixture was thoroughly stirred, and the aqueous layer was removed. 61.4 g of 2.4% by weight saline solution was added, and the mixture was thoroughly stirred, and the aqueous layer was removed. Then, 37.8 g of DMF and 37.6 g of MIBK were added. The organic layer was then washed multiple times with water, and 25.0 g of methanol was added to perform cooling crystallization. For cooling crystallization, after confirming crystal precipitation at 50 ° C, the mixture was cooled to 20 ° C or below at a rate of 10 ° C / hour, aged at 20 ° C for 9 hours, and then cooled to 10 ° C or below at a rate of 10 ° C / hour. After the temperature reached 10°C or below, the mixture was aged for another hour at a temperature range of 0 to 10°C and then filtered. The mixture was then rinsed in turn with cold toluene and cold methanol adjusted to 0 to 10°C, filtered, and then dried under reduced pressure at 120°C to obtain 58.5 g of BNEF (72.4% yield converted from BNF, 48.4% yield converted from FLN, 98.2% HPLC purity).

[0125] Example 3 A 1-L separable flask was charged with 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, and the mixture was dissolved at 60°C. After dissolution, 57.2 g of concentrated sulfuric acid was added dropwise at a temperature range of 55 to 65°C, and the mixture was stirred at 60°C for 4 hours. HPLC confirmed that the conversion of FLN was 99% or higher. To the resulting reaction solution, 255.1 g of toluene and 74.0 g of water were added, and the mixture was thoroughly stirred at 80°C. The aqueous layer was then removed. 74.0 g of a 5% by weight aqueous solution of sodium bicarbonate was then added, and the mixture was thoroughly stirred. The aqueous layer was then removed. 74.0 g of 1% by weight hydrochloric acid was then added, and the mixture was thoroughly stirred. The aqueous layer was then removed. The organic layer was washed multiple times with water and subjected to cooling crystallization. For cooling crystallization, 27.6 g of heptane was added at 60°C, followed by cooling to 10°C or below at a rate of 10°C / hour. After the temperature reached 10°C or below, the mixture was aged for an additional 2 hours in the temperature range of 0 to 10°C and then filtered. Subsequently, the mixture was rinsed with cold toluene adjusted to 0 to 10°C and filtered, yielding 97.3 g of crude BNF (HPLC purity 96.9%) containing approximately 20% by mass of toluene and 1,4-dioxane.

[0126] Next, 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 reacted at 110 °C for 2 hours. A BNF conversion of 99% or more was confirmed by HPLC. 50.0 g of a 3% by mass aqueous sodium hydroxide solution was added to the resulting reaction solution and stirred at 90 °C for 8 hours. Then, 62.6 g of MIBK and 62.6 g of toluene were added and thoroughly stirred at 80 °C, and the aqueous layer was removed. Next, 38.0 g of 3% by mass hydrochloric acid was added and thoroughly stirred, and the aqueous layer was removed. The organic layer was then washed multiple times with water and subjected to cooling crystallization. After confirming crystal precipitation at 60 °C, the mixture was cooled to 10 °C or below at a rate of 10 °C / hour. After the temperature reached 10°C or below, the mixture was aged for another 2 hours at a temperature range of 0 to 10°C and then filtered. The mixture was then rinsed in turn with cold toluene and cold methanol adjusted to 0 to 10°C, filtered, and then dried under reduced pressure at 90°C to obtain 52.5 g of BNEF (62.3% yield converted from FLN, 98.3% HPLC purity). [Industrial Applicability]

[0127] The fluorene-containing alcohol obtained by the production method of the present invention has excellent heat resistance and can suppress coloration, and therefore can be effectively used as a resin raw material or an additive (or resin additive) such as a heat resistance improver or a refractive index improver.

Claims

1. In the presence of an inorganic base catalyst and an amide, a compound represented by the following formula (1a) 【Chemical 1】 (In the formula, Z １ and Z ２ each independently represents a fused polycyclic C 10-14 arene ring; R １ and R ２ each independently represents a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, or a cyano group; m1 and m2 each independently represent an integer of 0 or more; R ３ represents a hydrocarbon group, a cyano group or a halogen atom, and n represents an integer of 0 to 8. and reacting a fluorene compound represented by the formula (I) with an alkylene carbonate, The following formula (1) 【Chemistry 2】 [In the formula, A １ and A ２ each independently represents a linear or branched alkylene group; １ , ring Z ２ , R １ , R ２ , R ３ , m1, m2 and n are the same as in formula (1a). A reaction step of obtaining a reaction solution containing a fluorene compound represented by the formula: A method for producing a fluorene compound represented by formula (1), comprising a purification step of crystallizing the reaction solution obtained in the reaction step using a crystallization solvent containing alkylamides, ketones, and aromatic hydrocarbons.

2. As a pre-step of the reaction step, a reaction of a compound represented by the following formula (2) is carried out in the presence of an acid catalyst, a thiol, and an aprotic polar solvent. 【Chemistry 3】 [In the formula, R ３ and n are the same as in formula (1a). and fluorenones represented by the following formulae (3a) and (3b): 【Chemistry 4】 [In the formula, ring Z １ , ring Z ２ , R １ , R ２ , m1 and m2 are the same as those in formula (1a)] to obtain an intermediate reaction solution containing the fluorene compound represented by formula (1a), and the fluorene compound represented by formula (1a) is extracted from the intermediate reaction solution and subjected to the reaction step.

3. In the formula (1), A １ and A ２ is an ethylene group, and the ring Z １ and ring Z ２ 3. The method according to claim 1, wherein is a naphthalene ring.

4. The production method according to any one of claims 1 to 3, wherein 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 per 100 parts by mass of the amides.

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