JP7231389B2 - Method for producing compound having fluorene skeleton and compound having fluorene skeleton with less impurities - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention is suitable as a monomer for forming a thermoplastic resin constituting an optical member represented by an optical lens or an optical film, and is a thermoplastic resin having a high refractive index, low birefringence, and an excellent balance between heat resistance and moldability. The present invention relates to a method for producing a compound having a fluorene skeleton and a compound having a fluorene skeleton containing few impurities.

In recent years, thermoplastic resin materials such as polycarbonates, polyesters, and polyester carbonates made from alcohols having a fluorene skeleton, typified by 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), have been widely used in optical applications. Due to its excellent properties, heat resistance, moldability, etc., it is attracting attention as an optical member such as an optical lens and an optical sheet.

For example, Patent Document 1 discloses a polycarbonate resin made from an alcohol having a BPEF skeleton. However, although there is a description that the refractive index of the polycarbonate resin using the alcohol is 1.64, the rapid technological innovation in recent years requires further improvement of the above properties. Therefore, with the aim of further increasing the refractive index, in Patent Document 2, a thermoplastic resin made from 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPBPEF) has been developed. However, the refractive index of the resin described in the patent document still has room for improvement. In addition, Patent Document 3 describes a high refractive index resin made from 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) as a raw material. Since the birefringence also increases, it becomes a big problem when applied to transparent materials such as optical lenses.

As described above, there is a trade-off between a high refractive index and a low birefringence, and it has been difficult to achieve both properties with conventional polycarbonate and polyester resins.

By the way, as a method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), a method of dehydration condensation of fluorenone and phenoxyethanol using sulfuric acid and thiols as catalysts (Non-Patent Document 1 ) is disclosed. Further, as a method for producing 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF), as in BPEF, sulfuric acid and thiols are used as catalysts to produce fluorenone and 2-naphthyl. A method of dehydrating and condensing xyethanol is disclosed (Patent Document 4). Furthermore, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPBPEF), like BPEF and BNEF, uses sulfuric acid and thiols as catalysts to convert fluorenone and 2-(2-biphenylyl). A method of dehydrating and condensing oxy)ethanol (Patent Document 5) is disclosed, but both methods use a large amount of sulfuric acid, so that complicated purification operations such as neutralization and purification after the reaction are required, and A large amount of neutralized wastewater is generated. In addition, problems such as coloration of the product, deterioration of stability, and deterioration of purity occur due to contamination of the product with the sulfur component derived from the catalyst. Furthermore, in order to obtain a high-purity product such as an optical resin material, it is necessary to repeat the refining operation for removing the sulfur component, which is not an industrially advantageous method.

WO 2007/142149 Pamphlet JP 2015-86265 A JP 2017-171885 A JP 2016-79405 A JP 2009-256342 A

Chemistry Letters, 1998, pp. 1055-1056

The method for producing the compound of the following formula (1) molecularly designed in the present invention mainly consists of two steps. Even if the alcohol of the following formula (7) is synthesized using 5) and the following formula (6), the reaction does not proceed at all, or even if the reaction does proceed, the reaction rate is slow, which is industrially disadvantageous. In addition, when the activity of the catalyst used in step 2 is strong and the amount used increases, a coupling reaction (side reaction) occurs in which the compounds represented by the following formula (8) or (9) react with each other. Not only did the yield of the fluorene compound represented by (1) decrease, the production cost increased, but it also mixed into the fluorene compound represented by the following formula (1), causing a decrease in purity. Furthermore, unless activated carbon treatment or a similar metal removal treatment is performed, the white compound having a fluorene skeleton represented by the following formula (1) is contaminated with black particles derived from the palladium catalyst used in the reaction of step 2. Therefore, the hue of the alcohol compound deteriorated.

Therefore, in the present invention, as a result of studying to solve the problems of the conventional technology, the selectivity from the following formula (5) to the following formula (7) in step 1 is high and the step The coupling reaction (side reaction) between boronic acids in 2 is difficult to occur, and the content of specific metals such as palladium content in the raw material alcohol and the content of specific compounds are low, and the raw materials and resins using the raw materials An object of the present invention is to provide a novel method for producing a compound having a fluorene skeleton which is excellent in hue and various properties (optical properties, heat resistance, moldability, etc.), and to provide a compound having a fluorene skeleton with less impurities.

The present invention has been achieved as a result of studies to solve the problems of the prior art, and has a certain quality, a method for producing a compound having a fluorene skeleton excellent as a polymer raw material, and impurities An object of the present invention is to provide a compound having a small number of fluorene skeletons. Specifically, the present invention relates to a method for producing a compound having a fluorene skeleton and a compound having a fluorene skeleton shown below.

（式中、環Ｚは（同一または異なった）芳香族基、Ｒ^１およびＲ^２はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～１２の芳香族基を含んでいてもよい炭化水素基、Ａｒ^１およびＡｒ^２は炭素数が６～１０の置換基を有してもよい芳香族基、Ｌ^１およびＬ^２はアルキレン基、ｊおよびｋはそれぞれ独立に０以上の整数、ｍおよびｎはそれぞれ独立に０～５の整数を示す。）少なくとも下記の工程１および工程２を含んでなり、
工程１：下記式（５）で示されるフルオレノン類と下記式（６）で示されるアルコール類の化合物とを反応溶媒中、酸触媒を使用して反応させる工程
工程２：工程１で製造した反応物（７）と下記式（８）または（９）で示されるボロン酸類とを反応溶媒中、塩基および下記式（２）で示されるパラジウム触媒の存在下で反応させる工程
Ｐｄ／ＳｉＯ_２ （２）

（式中、Ｘ ^１ は１位、２位、３位または４位の置換基であり、Ｘ ^２ は５位、６位、７位または８位の置換基であり、ハロゲン原子を示す。）

（式中、Ｚは式（１）と同じである。Ｒ ^１２ は水素原子、ハロゲン原子、炭素原子数１～１２の芳香族基を含んでいてもよい炭化水素基、ｓは独立に０以上の整数、Ｒ ^１１ はアルキレン基を示し、ｐは０以上の整数を示す。）

（式中、Ｘ ^１ 、Ｘ ^２ は式（５）と同じである。Ｚ、Ｒ ^１２ 、ｓ、Ｒ ^１１ 、ｐは式（６）と同じである。）

（式中、Ｙは芳香族基、Ｒ ^１３ は水素原子、アルキル基、アルケニル基、アルコキシ基、ハロゲン原子を示す。ｌは１または２であり、ｌ＝２の場合、Ｒ ^１３ は同一でもあるいは異なっていてもよい。）
工程１で使用される酸触媒がリン酸またはケイ酸と、バナジウム、モリブデンおよびタングステンから選ばれる少なくとも一つの元素の酸素酸イオンとから構成されるヘテロポリ酸であり、
かつ得られたフルオレン骨格を有する化合物中のパラジウム元素の含有量が下記式（３）を満たし、
０ ≦ Ｐｄ ≦ １０ｐｐｍ （３）
さらに下記式（４）で表される副生成物が３％以下の範囲内で生成することを特徴とするフルオレン骨格を有する化合物の製造方法。
Ａｒ^１－Ａｒ^１、Ａｒ^１－Ａｒ^２またはＡｒ^２－Ａｒ^２ （４）
（Ａｒ^１およびＡｒ^２は前記式（１）と同じである。） [1] A method for producing a compound having a fluorene skeleton represented by the following formula (1),

(Wherein, ring Z is an aromatic group (same or different); R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon atom optionally containing an aromatic group having 1 to 12 carbon atoms; hydrogen group, Ar ¹ and Ar ² are aromatic groups having 6 to 10 carbon atoms which may have substituents, L ¹ and L ² are alkylene groups, j and k are each independently integers of 0 or more, m and n each independently represent an integer of 0 to 5.) comprising at least steps 1 and 2 below,
Step 1: A step of reacting a fluorenone represented by the following formula (5) with an alcohol compound represented by the following formula (6) in a reaction solvent using an acid catalyst.
Step 2: reactant (7) prepared in step 1 and a boronic acid represented by the following formula (8) or (9) in a reaction solvent in the presence of a base and a palladium catalyst represented by the following formula (2) Process of reacting
Pd/ _SiO2 (2)

(Wherein, X ¹ is a substituent at the 1-, 2-, 3- or 4-position, X ² is a substituent at the 5-, 6-, 7- or 8-position and represents a halogen atom.)

(In the formula, Z is the same as in formula (1). R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms, and s is independently 0 or more. is an integer, R ¹¹ represents an alkylene group, and p represents an integer of 0 or more.)

(In the formula, X ¹ and X ² are the same as in formula (5). Z, R ¹² , s, R ¹¹ and p are the same as in formula (6).)

(In the formula, Y is an aromatic group, R ¹³ is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a halogen atom. l is 1 or 2, and when l = 2, R 13 may be the ^same or may be different.)
The acid catalyst used in step 1 is a heteropoly acid composed of phosphoric acid or silicic acid and an oxyacid ion of at least one element selected from vanadium, molybdenum and tungsten,
and the content of the palladium element in the obtained compound having a fluorene skeleton satisfies the following formula (3),
0≦Pd≦10 ppm (3)
Further, a method for producing a compound having a fluorene skeleton, wherein a by-product represented by the following formula (4) is produced within a range of 3% or less.
Ar ¹ -Ar ¹ , Ar ¹ -Ar ² or Ar ² -Ar ² (4)
(Ar ¹ and Ar ² are the same as in formula (1) above.)

[2] The method for producing a compound having a fluorene skeleton according to the above item 1, wherein Z is a phenyl group or a naphthyl group.

[3] The method for producing a compound having a fluorene skeleton according to the above item 1 or 2, wherein the formula (4) is a by-product represented by the following formula (4a), (4b) or (4c).

（式中、Ｒ^３～Ｒ^１０はそれぞれ独立に、水素原子、ハロゲン原子、炭素数１～１２の芳香族基を含んでいてもよい炭化水素基を示す。Ａｒ^１およびＡｒ^２、Ｌ^１およびＬ^２、ｍおよびｎは前記式（１）と同じである。） [4] The method for producing a compound having a fluorene skeleton according to any one of the above items 1 to 3, wherein the formula (1) is one of the following formulas (1a) to (1d).

(In the formula, R ³ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. Ar ¹ and Ar ² , L ¹ and L ² , m and n are the same as in formula (1) above.)

[5] The method for producing a compound having a fluorene skeleton according to [4] above, wherein the formula (1) is the formula (1b).
[6] The method for producing a compound having a fluorene skeleton according to any one of the above items 1 to 5, wherein Ar ¹ and Ar ² in formula (1) are a phenyl group or a naphthyl group.

[ 7 ] The method for producing a compound having a fluorene skeleton according to the above item 1, wherein the compound represented by formula (5) is 2,7-dibromofluorene.

[ 8 ] The method for producing a compound having a fluorene skeleton according to the above item 1 , wherein the compound represented by formula (6) is 2-phenoxyethanol.

[ 9 ] Production of a compound having a fluorene skeleton according to the above item 1 , wherein the compound represented by formula (7) is 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene Method.

[ 10 ] The method for producing a compound having a fluorene skeleton according to the above item 1, wherein the compound represented by formula (8) is 2-naphthaleneboronic acid, 1-naphthaleneboronic acid or phenylboronic acid.

[ 11 ] The compound having a fluorene skeleton according to the preceding item 1 , wherein the compound represented by formula (9) is 2-naphthaleneboronic anhydride, 1-naphthaleneboronic anhydride or phenylboronic anhydride. Production method.

[ 12 ] The method for producing a compound having a fluorene skeleton according to the above item 1 , wherein the heteropolyacid is a previously dehydrated heteropolyacid or an anhydride of the heteropolyacid.

[ 13 ] A method for producing a compound having a fluorene skeleton according to the above item 1, wherein toluene is used as the reaction solvent in step 1 .

[ 14 ] The method for producing a compound having a fluorene skeleton according to the above item 1, wherein the base used in step 2 is potassium carbonate and/or sodium carbonate.

[ 15 ] The method for producing a compound having a fluorene skeleton according to the above item 1 , wherein toluene or a mixed solvent of toluene and ethanol is used as the reaction solvent in step 2.

（式中、環Ｚは（同一または異なった）芳香族基、Ｒ^１およびＲ^２はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～１２の芳香族基を含んでいてもよい炭化水素基、Ａｒ^１およびＡｒ^２は炭素数が６～１０の置換基を有してもよい芳香族基、Ｌ^１およびＬ^２はアルキレン基、ｊおよびｋはそれぞれ独立に０以上の整数、ｍおよびｎはそれぞれ独立に０～５の整数を示す。）
該フルオレン骨格を有する化合物中のパラジウム元素の含有量が下記式（３）を満たし、
０ ≦ Ｐｄ ≦ １０ｐｐｍ （３）
かつ下記式（４）で表される副生成物が３％以下であることを特徴とするフルオレン骨格を有する化合物。
Ａｒ^１－Ａｒ^１、Ａｒ^１－Ａｒ^２またはＡｒ^２－Ａｒ^２ （４）
（Ａｒ^１およびＡｒ^２は前記式（１）と同じである。） [ 16 ] A compound having a fluorene skeleton represented by the following formula (1),

(Wherein, ring Z is an aromatic group (same or different); R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon atom optionally containing an aromatic group having 1 to 12 carbon atoms; hydrogen group, Ar ¹ and Ar ² are aromatic groups having 6 to 10 carbon atoms which may have substituents, L ¹ and L ² are alkylene groups, j and k are each independently integers of 0 or more, m and n each independently represents an integer of 0 to 5.)
The content of the palladium element in the compound having a fluorene skeleton satisfies the following formula (3),
0≦Pd≦10 ppm (3)
A compound having a fluorene skeleton, wherein a by-product represented by the following formula (4) is 3% or less.
Ar ¹ -Ar ¹ , Ar ¹ -Ar ² or Ar ² -Ar ² (4)
(Ar ¹ and Ar ² are the same as in formula (1) above.)

[ 17 ] The compound having a fluorene skeleton according to the above item 16 , which is used as a raw material for a thermoplastic resin.

In the method for producing a fluorene compound of the present invention, a heterogeneous palladium catalyst supported on silica is used to produce the compound, so that the catalytic activity is moderately suppressed and the homocoupling reaction (side reaction) between boronic acids hardly occurs. In addition, since the content of specific metals such as palladium and the content of specific compounds (by-products) are small, the amount of boronic acids used can be suppressed, compared to the manufacturing method using a homogeneous palladium catalyst. Not only is it inexpensive, but the catalyst can be separated only by filtration, and the content of specific metals such as palladium remaining in the fluorene compound and the content of specific compounds are low, so purification is easy. Therefore, the fluorene compound can be produced very efficiently. Furthermore, thermoplastic resins made from the fluorene compound produced according to the present invention are excellent in various properties (heat resistance, hue, moldability, etc.) in addition to optical properties.

DETAILED DESCRIPTION OF THE INVENTION The present invention will now be described in detail, and the descriptions of the constituent elements set forth below are representative of embodiments of the present invention and are not intended to be limiting thereof.
[Method for producing a compound having a fluorene skeleton]
The method for producing the compound having a fluorene skeleton represented by the above formula (1) of the present invention is a production method using a heterogeneous palladium catalyst represented by the following formula (2). and a production method comprising step 2 is preferably mentioned. That is, a first step 1 of reacting a fluorenone represented by the following formula (5) with an alcohol compound represented by the following formula (6), and a reactant (7 ) and a boronic acid represented by the following formula (8) or (9) are reacted in the second step 2. In the above production method, the alcohol represented by the following formula (6) also acts as a reaction solvent and can be easily removed by distillation under reduced pressure, and a heterogeneous palladium catalyst represented by the following formula (2) is used. As a result, the coupling reaction (side reaction) between boronic acids represented by the following formula (8) or (9) is less likely to occur, and the compound having a fluorene skeleton of the present invention can be produced simply and efficiently.

（式中、Ｘ^１は１位、２位、３位または４位の置換基であり、Ｘ^２は５位、６位、７位または８位の置換基であり、ハロゲン原子を示す。）

(Wherein, X ¹ is a substituent at the 1-, 2-, 3- or 4-position, X ² is a substituent at the 5-, 6-, 7- or 8-position and represents a halogen atom.)

（式中、Ｚは式（１）と同じである。Ｒ^１２は水素原子、ハロゲン原子、炭素原子数１～１２の芳香族基を含んでいてもよい炭化水素基、ｓは独立に０以上の整数、Ｒ^１１はアルキレン基を示し、ｐは０以上の整数を示す。）

(In the formula, Z is the same as in formula (1). R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms, and s is independently 0 or more. is an integer, R ¹¹ represents an alkylene group, and p represents an integer of 0 or more.)

（式中、Ｘ^１、Ｘ^２は式（５）と同じである。Ｚ、Ｒ^１２、ｓ、Ｒ^１１、ｐは式（６）と同じである。）

(In the formula, X ¹ and X ² are the same as in formula (5). Z, R ¹² , s, R ¹¹ and p are the same as in formula (6).)

（式中、Ｙは芳香族基、Ｒ^１３は水素原子、アルキル基、アルケニル基、アルコキシ基、ハロゲン原子を示す。ｌは１または２であり、ｌ＝２の場合、Ｒ^１３は同一でもあるいは異なっていてもよい。）
Ｐｄ／ＳｉＯ_２ （２）

(In the formula, Y is an aromatic group, R ¹³ is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a halogen atom. l is 1 or 2, and when l = 2, R ¹³ may be the same or may be different.)
Pd/ _SiO2 (2)

The compound represented by the above formula (5) is a fluorenone compound corresponding to the fluorene skeleton in the above formula (1), X ¹ is a substituent at the 1-, 2-, 3- or 4-position, and X ² is a substituent at the 5-, 6-, 7- or 8-position and represents a halogen atom.

Representative examples of the fluorenone compound represented by the above formula (5) are shown below, but the raw material used in the above formula (1) of the present invention is not limited to them.

1,8-difluorofluorenone, 2,7-difluorofluorenone, 3,6-difluorofluorenone, 4,5-difluorofluorenone, 1,8-dichlorofluorenone, 2,7-dichlorofluorenone, 3,6-dichlorofluorenone, 4 ,5-dichlorofluorenone, 1,8-diiodofluorenone, 2,7-diiodofluorenone, 3,6-diiodofluorenone, 4,5-diiodofluorenone, 1,8-dibromofluorenone, 2,7-dibromo Fluorenone, 3,6-dibromofluorenone, 4,5-dibromofluorenone and the like are preferred. Among them, 1,8-dibromofluorenone, 2,7-dibromofluorenone, 3,6-dibromofluorenone and 4,5-dibromofluorenone are preferred, and 2,7-dibromofluorenone is particularly preferred.

These may be used alone or in combination of two or more, and can be arbitrarily selected depending on the purpose. In the present invention, 2,7-dibromofluorenone is preferred.

The purity of the fluorenone represented by the formula (5) to be used is not particularly limited, but is usually preferably 95% or higher, more preferably 99% or higher. As for the fluorenones, commercially available products or synthesized products may be used. For example, dibromofluorenone can be produced by the method described in Non-Patent Document (Journal of American Chemical Society, 2017, Vol. 139, 11073-11080), that is, reacting 9-fluorenone and bromine in water. methods and the like.

The compound ((poly)hydroxyl group-containing arene ring compound) represented by the formula (6) is a (poly)hydroxyl group-containing arene ring substituted at the 9-position in the fluorene derivative represented by the formula (7). Yes. That is, in the formula (6), the ring Z is the ring Z in the formula (1), R ¹¹ is L ¹ and L ² , p is m and n, R ¹² is R ¹ and R ² , s correspond to j and k, respectively. Ring Z can be exemplified by a benzene ring and a naphthalene ring.

Examples of the alkylene group represented by R ¹¹ include, but are not limited to, ethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group and the like. An alkylene group having 1 to 6 carbon atoms is preferred, and an alkylene group having 2 to 3 carbon atoms is more preferred. The substitution position of R ¹¹ is not particularly limited. The number p of substituents is 0 or 1 or more, and may be the same or different. Preferably 0-15, more preferably 0-5. When p is 2 or more, the polyalkoxy group may be composed of the same alkoxy group, or may be composed of a mixture of different alkoxy groups (for example, an ethoxy group and a propyleneoxy group). , usually composed of identical alkoxy groups.

R ¹² represents a hydrogen atom, a halogen atom or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, preferably a hydrogen atom, a methyl group or a phenyl group.

Examples of hydrocarbon groups represented by R ¹² include alkyl groups, cycloalkyl groups, aryl groups, naphthyl groups and aralkyl groups. Specific examples of alkyl groups include C _1-6 alkyl groups, C _1-4 alkyl groups and C _1-3 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group. Preferred are C _1-3 alkyl groups, of which methyl or ethyl groups are even more preferred. Specific examples of the cycloalkyl group are preferably C _5-8 cycloalkyl groups such as cyclopentyl group and cyclohexyl group, C _5-6 cycloalkyl groups, and more preferably C _5-6 cycloalkyl groups. Specific examples of the aryl group are preferably a phenyl group, an alkylphenyl group (mono- or dimethylphenyl group, tolyl group, 2-methylphenyl group, xylyl group, etc.), and more preferably a phenyl group. Preferable examples of the aralkyl group include C _6-10 aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group. As the halogen atom, fluorine atom, chlorine atom, bromine atom and the like are preferable.

The substitution number s of the substituent R ¹² can be appropriately selected according to the number of condensed rings of the condensed hydrocarbon, and is not particularly limited, and is preferably an integer of 0 or more, more preferably an integer of 1 or more. Also, it is preferably an integer of 6 or less, more preferably an integer of 4 or less.

Specific examples of the compound represented by the formula (6) include, for example, compounds where p=0, phenol, alkylphenols such as 2-methylphenol and 3-methylphenol, 2,3-xylenol, 2,6- Examples include dialkylphenols such as xylenol and 3,5-xylenol, alkoxyphenols such as 2-methoxyphenol and 2-ethoxyphenol, and phenylphenols such as 2-phenylphenol and 3-phenylphenol. Examples of compounds where p = 1 include phenoxyalkyl alcohols such as phenoxyethanol, phenoxypropanol, phenoxybutanol, (2-methyl-phenoxy)ethanol, (3-methyl-phenoxy)ethanol, (3-ethyl-phenoxy)ethanol, (3- butyl-phenoxy)ethanol, (2-methyl-phenoxy)propanol, alkylphenoxyalkyl alcohols such as (3-methyl-phenoxy)propanol, (2,3-dimethylphenoxy)ethanol, (2,5-dimethylphenoxy)ethanol, (2,6-dimethylphenoxy)ethanol, dialkylphenoxyalkyl alcohols such as (2,6-dibutylphenoxy)ethanol, alkoxyphenoxyalkyl alcohols such as (2-methoxyphenoxy)ethanol, cyclohexylphenoxy)ethanol such as (2-cyclohexylphenoxy)ethanol and arylphenoxyalkyl alcohols such as alkylphenoxyalkyl alcohols and biphenylyloxyethanol. Compounds in which p is 2 or more include polyoxyalkylene phenyl ethers corresponding to these phenoxyalkyl alcohols. Preferred are phenoxy C _2-6 alkyl alcohols and C _1-4 alkylphenoxy C _2-6 alkyl alcohols, and particularly preferred is phenoxyethanol.

In the reaction of step 1, the amount of the compound represented by the formula (6) is not particularly limited, but from the viewpoint of side reaction suppression and economic efficiency, it is preferably It is 2 to 50 mol, more preferably 2.5 to 20 mol, still more preferably 3 to 10 mol. Moreover, these compounds can also be used as a reaction solvent.

These compounds represented by formula (6) may be commercially available products or synthesized products. Examples of the method for producing the compound represented by the formula (6) include a method of reacting a hydroxyl group of phenol with ethylene oxide or ethylene carbonate in the presence of an alkali catalyst.

The purity of the compound represented by the formula (6) used as a raw material is not particularly limited, but is usually 95% or higher, preferably 99% or higher.

The reaction of step 1 can be generally carried out in the presence of an acid catalyst. Acid catalysts include, for example, sulfuric acid, thiolic acid, montmorillonite, heteropolyacids, etc. Among these, heteropolyacids are particularly preferred because they produce less impurities derived from acid catalysts and facilitate the production of the compound having a fluorene skeleton of the present invention. is preferred.

The heteropolyacid preferably used in the present invention is generally a general term for compounds produced by condensation of two or more different inorganic oxyacids. Various heteropolyacids are possible by combination. Elements that form a central oxyacid in small numbers are called heteroelements, and elements that form condensed oxyacids around them are called polyelements. The poly element may be a single type of element or multiple types of elements.

The heteroelement of the oxyacid constituting the heteropolyacid is not particularly limited, but examples include copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, phosphorus, Arsenic, antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, irdium, platinum. Phosphorus (phosphoric acid) or silicon (silicic acid) is preferred. In addition, although the polyelement of the oxyacid constituting the heteropolyacid is not particularly limited, examples thereof include vanadium, molybdenum, tungsten, niobium, and tantalum. At least one element selected from vanadium, molybdenum and tungsten is preferred.

Various compositions can be used as the heteropolyacid anion constituting the heteropolyacid skeleton. Examples include XM ₁₂ O ₄₀ , XM ₁₂ O ₄₂ , XM ₁₈ O ₆₂ , XM ₆ O ₂₄ and the like. A preferred heteropolyacid anion composition is XM ₁₂ O ₄₀ . In each formula, X is a heteroelement and M is a polyelement. Specific examples of heteropolyacids having these compositions include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid.

The heteropolyacid may be a free heteropolyacid, or may be used as a salt of the heteropolyacid by replacing some or all of the protons with other cations. Accordingly, the heteropolyacids referred to in the present invention also include salts of these heteropolyacids. Examples of proton-substitutable cations include ammonium, alkali metals, alkaline earth metals, and the like.

The heteropolyacid may be an anhydride or a material containing water of crystallization, but the anhydride is preferable because the reaction is faster and the production of by-products is suppressed. In the case of a substance containing water of crystallization, the same effect as that of an anhydride can be obtained by previously performing a dehydration treatment such as drying under reduced pressure or azeotropic dehydration with a solvent. The heteropolyacid may be used in the form supported on a carrier such as activated carbon, alumina, silica-alumina, or diatomaceous earth. These heteropolyacids may be used alone or in combination of two or more. Moreover, if necessary, other catalysts than the heteropolyacid may be used in combination as long as the object of the present invention is not impaired.

The amount of the heteropolyacid used is not particularly limited, but in order to obtain a sufficient reaction rate, it is preferably 0.0001 times or more by weight, more preferably 0.001 to 30 times by weight, more preferably 0.001 to 30 times by weight, and further It is preferably 0.01 to 5 times the weight.

The method for carrying out the reaction in step 1 is not particularly limited, but usually, the compounds represented by the above formulas (5) and (6) and the heteropolyacid are charged into a reactor, and the reaction is carried out in air or nitrogen. , under an atmosphere of an inert gas such as argon, in the presence or absence of an inert solvent such as toluene or xylene, and heating with stirring. At this time, by removing moisture in the reaction system, such as catalyst-containing water and reaction product water, by performing the reaction under dehydration conditions, the reaction proceeds faster than when not dehydrated, and the generation of by-products is suppressed. The desired product can be obtained with a higher yield. The dehydration method is not particularly limited, but includes, for example, dehydration by addition of a dehydrating agent, dehydration by reduced pressure, and dehydration by azeotropy with a solvent under normal pressure or reduced pressure.

The azeotropic dehydration solvent is not particularly limited, but aromatic hydrocarbon solvents such as toluene and xylene; halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene; and aliphatic solvents such as pentane, hexane and heptane. hydrocarbon solvents, halogenated aliphatic hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, aliphatic and cyclic ether solvents such as diethyl ether, di-iso-propyl ether, methyl-t-butyl ether, diphenyl ether, tetrahydrofuran, dioxane , ester solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile, propionitrile, butyronitrile and benzonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and 1-methyl-2-pyrrolidinone. solvent, and the like. Preferred are aromatic hydrocarbon solvents and halogenated aromatic hydrocarbon solvents, more preferred are toluene, xylene, chlorobenzene and dichlorobenzene, and even more preferred is toluene. The amount used is not particularly limited, but from the viewpoint of economy, it is preferably 0.1 times or more by weight, more preferably 0.5 to 100 times by weight, still more preferably 1 to 20 times by weight the weight of fluorenone. Double.

The reaction temperature varies depending on the raw material and solvent used, but is preferably 50 to 300°C, more preferably 80 to 250°C, still more preferably 120 to 180°C. The reaction can be followed by analytical means such as liquid chromatography.

In addition, after the reaction, the compound represented by the formula (7) may be precipitated from the resulting reaction mixture, and further subjected to post-treatment such as washing, concentration, dilution, activated carbon treatment, etc. It is also possible to precipitate the compound represented by the formula (7). The operation of precipitating the compound represented by the above formula (7) from the reaction mixture that has been subjected to the post-treatment as described above, if necessary, is performed by heating the reaction mixture mixed with a solvent to 50 ° C. or more and the boiling point of the solvent or less (preferably 70-110°C) and cooled to less than 50°C. When crystals of the compound represented by the formula (7) are precipitated from the reaction mixture at 50°C or higher, after mixing the reaction mixture with an amount of diluent solvent that does not precipitate crystals at 50°C or higher, the obtained It may be carried out by bringing the mixture to 50°C or higher and not higher than the boiling point of the solvent (preferably 70 to 110°C) and cooling it to below 50°C. Examples of the diluting solvent include those exemplified as the solvents used in the above reaction, alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, isobutanol and pentanol, and carbonate solvents such as dimethyl carbonate and diethyl carbonate. etc., but methanol or dimethyl carbonate is preferred, and methanol is particularly preferred.

Such a crystallization operation may be performed once or may be repeated multiple times. In particular, in the reaction of step 1, when the acid catalyst is phosphotungstic acid, alcohol such as methanol can be used simply and efficiently. A small amount of the compound represented by the formula (7) can be obtained.

Precipitated crystals are collected by filtration or the like. The obtained crystals may be washed with the solvent or the like used in the above reaction, or may be dried. The purity of the purified compound represented by the formula (7) thus obtained is preferably 95% or higher.

After the reaction, the reaction mixture obtained can be used as a starting material for the next step 2 without isolation or purification.
The ring Y of the compound represented by the above formula (8) or (9) corresponds to the groups Ar ¹ and Ar ² in the above formula (1), and the corresponding boronic acids can be exemplified. In the above formulas (8) and (9), the preferred embodiment of the group R ¹³ is the same as the preferred embodiment of R ¹ and R ² described later, and the preferred embodiment of l is the same as the preferred embodiment of j and k described later. is.

Although the purity of the boronic acid used is not particularly limited, it is usually preferably 95% or higher, more preferably 99% or higher. In addition, boronic acids may be commercially available or may be synthesized. As a method for producing boronic acids, for example, a method described in Patent Document (JP-A-2002-47292), that is, a phenyl Grignard reagent and a boric acid ester dissolved in a non-ether aromatic solvent are reacted. methods and the like.

Boronic acids used in the present invention include alkylboronic acids, alkenylboronic acids, arylboronic acids, heteroarylboronic acids and anhydrides thereof represented by the formulas (8) and (9). is butylboronic acid, cyclohexylboronic acid, cyclopentylboronic acid, 2-ethylboronic acid, 4-ethylboronic acid, hexylboronic acid, isobutylboronic acid, isopropylboronic acid, methylboronic acid, n-octylboronic acid, propylboronic acid, pentyl Boronic acid, 2-phenylethyl boronic acid and their anhydrides are included, and alkenyl boronic acids include 1-cyclopentenyl boronic acid, ferrocene boronic acid, 1,1′-ferrocene diboronic acid and their anhydrides. 2-anthracene boronic acid, 9-anthracene boronic acid, benzyl boronic acid, 2-biphenyl boronic acid, 3-biphenyl boronic acid, 4-biphenyl boronic acid, 2,3-dimethylphenyl boron acid, 2,4-dimethylphenylboronic acid, 2,5-dimethylphenylboronic acid, 2,6-dimethylphenylboronic acid, 3,4-dimethylphenylboronic acid, 3,5-dimethylphenylboronic acid, 2-ethoxy phenylboronic acid, 3-ethoxyphenylboronic acid, 4-ethoxyphenylboronic acid, 6-methoxy-2-naphthaleneboronic acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 1 -naphthaleneboronic acid, 2-naphthaleneboronic acid, 9-phenanthreneboronic acid, 10-phenyl-9-anthraceneboronic acid, phenylboronic acid, phenylethaneboronic acid, 4-phenyl(naphthalene-1-yl)boronic acid, 3 -propoxyphenylboronic acid, 3-iso-propoxyphenylboronic acid, 4-iso-propoxyphenylboronic acid, 4-propylphenylboronic acid, 4-iso-propylphenylboronic acid, 10-(naphthalen-1-yl)- 9-anthraceneboronic acid, 10-(naphthalen-2-yl)-9-anthraceneboronic acid and anhydrides thereof are included, and heteroarylboronic acids include benzofuran-2-boronic acid and dibenzofuran-4-boronic acid. , 5-formyl-2-furanboronic acid, 5-formylthiophene-2-boronic acid, furan-2-boronic acid, furan-3-boronic acid, pyridine-3-boronic acid, pyridine-4-boronic acid, quinoline -2-boro acid, quinoline-3-boronic acid, quinoline-4-boronic acid, quinoline-5-boronic acid, quinoline-6-boronic acid, quinoline-8-boronic acid, iso-quinoline-4-boronic acid, 2-thiophene Boronic acid, 3-thiophene boronic acid, 5-pyrimidine boronic acid and their anhydrides are included.

These may be used alone or in combination of two or more, and can be arbitrarily selected depending on the purpose. In the present invention, 2-naphthaleneboronic acid or its anhydride is preferred.

The use ratio of the compound represented by the formula (8) used as a raw material is preferably 2 to 5 mol per 1 mol of the compound (halogenated fluorene compound) represented by the formula (7), and more preferably, It may be about 2.05 to 3.0 mol, more preferably about 2.00 to 2.5 mol. If the boronic acid is less than 2 mol, the yield of the product represented by the formula (1) may be low. On the other hand, when the amount exceeds 2.5 mol, although the reaction rate is high and the yield is high, the production cost of the compound having the fluorene skeleton may increase.

The ratio of the compound represented by the formula (9) to be used is preferably 1 to 5 mol, more preferably 0.5 mol, per 1 mol of the compound (halogenated fluorene compound) represented by the formula (7). It may be about 8 to 3 mol, more preferably about 0.7 to 1 mol. If the amount of boronic acids is less than 0.7 mol, the yield of the product represented by formula (1) may be low. On the other hand, when the amount exceeds 1 mol, the reaction rate is fast and the yield is high, but the production cost of the compound having the fluorene skeleton may increase.

The reaction (dehalogenation reaction) between the compound represented by the above formula (7) and the above formula (8) and/or (9) in step 2 can be carried out in a reaction solvent in the presence of a base and a catalyst. can.

Examples of the base used in the reaction of step 2 include hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), cesium carbonate (Cs ₂ CO ₃ ) carbonates, acetates such as sodium acetate and potassium acetate, inorganic salts such as phosphates such as sodium phosphate (Na ₃ PO ₄ ) and potassium phosphate (K ₃ PO ₄ ), triethylamines, pyridine , morpholine, quinoline, piperidine, anilines, and organic salts such as ammonium salts such as tetra-n-butylammonium acetate. Among them, carbonate is preferably used, and potassium carbonate and/or sodium carbonate are preferred. Such bases may be used alone, or two or more of them may be used in combination.

In the reaction of step 2, the amount of the base used is not particularly limited, but is preferably 1 to 30 equivalents, more preferably 1 to 10 equivalents, relative to 1 mol of the boronic acid.

The catalyst used in the reaction of step 2 is preferably a palladium compound used in the Suzuki coupling reaction. Dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, bis[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphinepalladium dichloride, bis(di-tert-butylprenylphosphine)palladium dichloride , bis(di-tert-crotylphosphine)palladium dichloride, Pd/SiO ₂ , Pd/C and the like. Among them, Pd/SiO ₂ is preferably used. Such catalysts may be used alone or in combination of two or more.

In the reaction of step 2, the amount of the catalyst used is not particularly limited, but is preferably 0.1 to 0.1 in terms of palladium metal atom per 1 mol of the compound (halogenated fluorene compound) represented by the formula (7). 2 millimoles, more preferably 0.15 to 1 millimoles. If the amount of the palladium catalyst used is less than 0.1 mmol in terms of palladium metal atoms, the reaction may be difficult to complete. In addition, when the amount of the palladium catalyst used exceeds 2 millimoles in terms of palladium metal atoms, not only does a homocoupling reaction (side reaction) between boronic acids occur, but the palladium element content in the compound having a fluorene skeleton increases. It becomes difficult to keep the range of formula (3) within the range, and not only the hue of the thermoplastic resin produced using the alcohol raw material may be deteriorated, but also the production cost of the compound having the fluorene skeleton may increase. be.

In addition, the palladium catalyst may be added all at once at the time of reaction preparation, or depending on the case, it may be added in portions during the reaction as appropriate so that the total amount used is the same as when it is added at once. good. In that case, confirmation of the reaction rate can be followed by analytical means such as liquid chromatography.

As the reaction solvent used in step 2, aromatic hydrocarbon solvents such as toluene and xylene and alcohols such as methanol, ethanol, isopropyl alcohol and n-butanol can be used alone or in combination. Since the aromatic hydrocarbon solvent is a solvent with a high boiling point, the reaction temperature can be set high, and by using an alcohol, it has good affinity with water and good reactivity, so that it is preferably used. Such solvents may be used alone, or two or more of them may be used in combination. Furthermore, aprotic solvents such as N,N-dimethylformamide or N,N-dimethylacetamide and halobenzenes such as o-dichlorobenzene can also be used. Such solvents may be used alone, or two or more of them may be used in combination. In the present invention, it is more preferable to use toluene or a mixed solvent of toluene and ethanol.

The amount of the reaction solvent (toluene or a mixed solvent of toluene and ethanol in the present invention) used is not particularly limited, but toluene is preferably used for the compound represented by the formula (7) (halogenated fluorene compound) It is 0.1 times or more by weight, more preferably 0.5 to 100 times by weight, still more preferably 1 to 50 times by weight. If the amount of toluene used is less than 0.1 times by weight, the product may precipitate and stirring may become difficult. Further, when the amount of toluene used exceeds 100 times the weight, the effect is not commensurate with the amount used, and the volumetric efficiency deteriorates, which may increase the production cost of the compound having the fluorene skeleton. The amount of ethanol used is also not particularly limited, but is preferably 0.1 to 50 times the weight of the compound (halogenated fluorene compound) represented by the formula (7), more preferably 1 to 20 times the weight. is. If the amount of ethanol used is less than 0.1 times by weight, the reaction rate may be slow and the yield may decrease. Moreover, when the amount of ethanol used exceeds 50 times the weight, the volumetric efficiency is deteriorated and the production cost of the compound having the fluorene skeleton increases, as is the case with toluene.

The reaction temperature varies depending on the raw material and solvent used, but is preferably 50 to 150°C, more preferably 60 to 130°C, still more preferably 70 to 120°C. The reaction can be followed by analytical means such as liquid chromatography.

The reaction mixture after completion of the reaction usually contains unreacted fluorenes, unreacted boronic acids, bases, catalysts, side reaction products, etc., in addition to the produced compound represented by the formula (1). ing. Therefore, conventional methods such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or similar metal removal treatment, column chromatography, or a combination of these separation means It can be separated and purified. For example, boronic acids are removed by a conventional method (such as a method of forming a water-soluble complex by adding an alkaline aqueous solution), the palladium compound is removed by filtration, and then a recrystallization solvent is added and cooled to recrystallize. It may be purified by lysing and then separating by filtration.

The purity of the compound having a fluorene skeleton obtained by the production method of the present invention can be selected from a wide range of 60 to 100%, preferably 70% or higher, more preferably 80% or higher, and still more preferably 90% or higher.

[Compound having a fluorene skeleton]
The compound of the present invention is a compound having a fluorene skeleton represented by the following formula (1), that is, a compound obtained by substituting or adding two aromatic hydrocarbons having at least one hydroxy group at the 9-position of a fluorene. .

（式中、環Ｚは（同一または異なった）芳香族基、Ｒ^１およびＲ^２はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～１２の芳香族基を含んでいてもよい炭化水素基、Ａｒ^１およびＡｒ^２は炭素数が６～１０の置換基を有してもよい芳香族基、Ｌ^１およびＬ^２はアルキレン基、ｊおよびｋはそれぞれ独立に０以上の整数、ｍおよびｎはそれぞれ独立に０～５の整数を示す。）

(Wherein, ring Z is an aromatic group (same or different); R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon atom optionally containing an aromatic group having 1 to 12 carbon atoms; hydrogen group, Ar ¹ and Ar ² are aromatic groups having 6 to 10 carbon atoms which may have substituents, L ¹ and L ² are alkylene groups, j and k are each independently integers of 0 or more, m and n each independently represents an integer of 0 to 5.)

In the above formula (1), examples of the aromatic group represented by ring Z include benzene rings and condensed polycyclic aromatic hydrocarbons having at least a benzene ring skeleton, such as condensed bicyclic hydrocarbons. , condensed bi- to tetra-cyclic hydrocarbon rings such as condensed tricyclic hydrocarbons are preferred.

The condensed bicyclic hydrocarbon ring preferably has 8 to 20 carbon atoms (hereinafter sometimes referred to as C _8-20 ) such as an indene ring and a naphthalene ring, and a C _10-16 condensed bicyclic hydrocarbon ring. A hydrogen ring is more preferred. Moreover, as the condensed tricyclic hydrocarbon ring, an anthracene ring, a phenanthrene ring, and the like are preferable.

Of ring Z, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

Specific examples of the aromatic hydrocarbon ring represented by the ring Z in the above formula (1) are preferably a 1,4-phenylene group, a 1,4-naphthalenediyl group or a 2,6-naphthalenediyl group. A 4-phenylene group is more preferred.

The two rings Z substituted at the 9-position of the fluorene ring may be the same or different, and are more preferably the same ring. In addition, the substituent of the ring Z substituted at the 9-position of the fluorene skeleton is not particularly limited. For example, when the ring Z is naphthalene, the group corresponding to the ring Z substituted at the 9-position of the fluorene ring may be a 1-naphthyl group, a 2-naphthyl group, and the like.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, a hydrogen atom, a methyl group, Alternatively, a phenyl group is preferred.

In formula (1) above, examples of hydrocarbon groups represented by R ¹ and R ² include alkyl groups, cycloalkyl groups, aryl groups, naphthyl groups, and aralkyl groups. Specific examples of alkyl groups include C _1-6 alkyl groups, C _1-4 alkyl groups and C _1-3 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group. Preferred are C _1-3 alkyl groups, of which methyl or ethyl groups are even more preferred.

Further, specific examples of the cycloalkyl group are preferably a C _5-8 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a C _5-6 cycloalkyl group, more preferably a C _5-6 cycloalkyl group.

Preferable examples of the aryl group include a phenyl group and an alkylphenyl group (mono- or dimethylphenyl group, tolyl group, 2-methylphenyl group, xylyl group, etc.), and more preferably a phenyl group.

Preferable examples of the aralkyl group include C _6-10 aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group.

Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are preferable.

In the above formula (1), the substitution numbers j and k of the substituents R ¹ and R ² can be appropriately selected according to the number of condensed rings of the condensed hydrocarbon, etc., and are not particularly limited. More preferably, it is an integer of 1 or more. Also, it is preferably an integer of 6 or less, more preferably an integer of 4 or less. Incidentally, the substitution numbers j and k in the ring Z may be the same or different, and are usually the same in many cases.

In formula (1), L ¹ and L ² each independently represent a divalent linking group, preferably an alkylene group having 1 to 12 carbon atoms, more preferably an ethylene group. Generally, L ¹ and L ² may be the same alkylene group on the same ring Z. In addition, L ¹ and L ² may be the same or different, and usually the same, in different rings Z.

The number of oxyalkylene groups (OL ¹ ) and (OL ² ) (addition mole number) m and n can be selected from the range of 0 to 5, respectively, the lower limit is preferably 0 or more, the upper limit is preferably 4 or less, It is more preferably 3 or less, still more preferably 2 or less. 0 or 1 is particularly preferred, and 1 is most preferred. Note that m and n may be integers or average values, and different rings Z may be the same or different.

In formula (1) above, Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 10 carbon atoms, preferably a phenyl group or a naphthyl group. The groups Ar ¹ and Ar ² may be different or the same, but are usually the same. Further, the binding positions of Ar ¹ and Ar ² are preferably 1-position and 8-position, 2-position and 7-position, 3-position and 6-position, or 4-position and 5-position of the fluorene skeleton, and 2-position and 7-position. , 3 and 6 or 4 and 5, more preferably 2 and 7.

Representative examples of the diol component represented by the formula (1) are shown below, but the raw material used in the formula (1) of the present invention is not limited to them.

Diphenylfluorene types include 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-diphenylfluorene and 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl) -1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy) -1-naphthyl)-1,8-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxyphenyl )-1,8-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-1, 8-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-1,8-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-diphenylfluorene, 9 ,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-2,7-diphenylfluorene , 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-2 ,7-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-2,7-diphenyl fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-2,7-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-2,7-diphenylfluorene, 9, 9-bis(4-hydroxy-1-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(4- (2-hydroxyethoxy)phenyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-3,6-diphenylfluorene, 9,9-bis( 4-(2-hydroxyethoxy)-3-phenylphenyl) -3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-3,6-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)- 2-naphthyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-3,6 -diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-3,6-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-3,6-diphenylfluorene, 9 ,9-bis(6-hydroxy-2-naphthyl)-3,6-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5-diphenylfluorene, 9,9-bis (4-(2-hydroxyethoxy)-3-methylphenyl)-4,5-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-4,5-diphenylfluorene , 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-4,5-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-4, 5-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-4,5-diphenylfluorene, 9,9 -bis(4-hydroxy-3-phenylphenyl)-4,5-diphenylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-4,5-diphenylfluorene, 9,9-bis(6- Hydroxy-2-naphthyl)-4,5-diphenylfluorene and the like are preferred.

Among them, the following formula (1-a) represented by the following formulas (1-a) to (1-h): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-diphenylfluorene, The following formula (1-b): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene, the following formula (1-c): 9,9-bis(4-(2 -hydroxyethoxy)phenyl)-3,6-diphenylfluorene, the following formula (1-d): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5-diphenylfluorene, the following formula (1 -e): 9,9-bis(4-hydroxyphenyl)-1,8-diphenylfluorene, the following formula (1-f): 9,9-bis(4-hydroxyphenyl)-2,7-diphenylfluorene, The following formula (1-g): 9,9-bis(4-hydroxyphenyl)-3,6-diphenylfluorene, the following formula (1-h): 9,9-bis(4-hydroxyphenyl)-4,5 -diphenylfluorene is more preferred, especially the following formula (1-b): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene, the following formula (1-f): 9 ,9-bis(4-hydroxyphenyl)-2,7-diphenylfluorene, is preferred.

Dinaphthylfluorene types include 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methyl Phenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-(2 -hydroxyethoxy)-1-naphthyl)-1,8-dinaphthylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-dinaphthylfluorene, 9,9- Bis(4-hydroxyphenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-hydroxy- 3-phenylphenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-1,8-dinaphthylfluorene, 9,9-bis(6-hydroxy-2-naphthyl )-1,8-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)- 3-methylphenyl)-2,7-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-2,7-dinaphthylfluorene, 9,9-bis(4 -(2-hydroxyethoxy)-1-naphthyl)-2,7-dinaphthylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-dinaphthylfluorene, 9 ,9-bis(4-hydroxyphenyl)-2,7-dinaphthylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-2,7-dinaphthylfluorene, 9,9-bis(4 -hydroxy-3-phenylphenyl)-2,7-dinaphthylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-2,7-dinaphthylfluorene, 9,9-bis(6-hydroxy- 2-naphthyl)-2,7-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-3,6-dinaphthylfluorene, 9,9-bis(4-(2-hydroxy ethoxy)-3-methylphenyl)-3,6-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl) -3,6-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-3,6-dinaphthylfluorene, 9,9-bis(6-(2-hydroxyethoxy) )-2-naphthyl)-3,6-dinaphthylfluorene, 9,9-bis(4-hydroxyphenyl)-3,6-dinaphthylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl) -3,6-dinaphthylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-3,6-dinaphthylfluorene, 9,9-bis(4-hydroxy-1-naphthyl)-3, 6-dinaphthylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5- Dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-4,5-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3- phenylphenyl)-4,5-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-4,5-dinaphthylfluorene, 9,9-bis(6-(2 -hydroxyethoxy)-2-naphthyl)-4,5-dinaphthylfluorene, 9,9-bis(4-hydroxyphenyl)-4,5-dinaphthylfluorene, 9,9-bis(4-hydroxy-3- methylphenyl)-4,5-dinaphthylfluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)-4,5-dinaphthylfluorene, 9,9-bis(4-hydroxy-1-naphthyl) -4,5-dinaphthylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-dinaphthylfluorene and the like are preferred.

Among them, the following formula (2-a) represented by the following formulas (2-a) to (2-h): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-dinaphthylfluorene , the following formula (2-b): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene, the following formula (2-c): 9,9-bis(4- (2-hydroxyethoxy)phenyl)-3,6-dinaphthylfluorene, the following formula (2-d): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-4,5-dinaphthylfluorene, Formula (2-e) below: 9,9-bis(4-hydroxyphenyl)-1,8-dinaphthylfluorene, formula (2-f) below: 9,9-bis(4-hydroxyphenyl)-2, 7-dinaphthylfluorene, the following formula (2-g): 9,9-bis(4-hydroxyphenyl)-3,6-dinaphthylfluorene, the following formula (2-h): 9,9-bis(4- hydroxyphenyl)-4,5-dinaphthylfluorene is more preferred, and in particular, formula (2-b) below: 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene, The following formula (2-f): 9,9-bis(4-hydroxyphenyl)-2,7-dinaphthylfluorene is preferred.

In the compound having a fluorene skeleton of the present invention, the content of palladium element satisfies the following formula (3).
0≦Pd≦10 ppm (3)
Preferably, the following formula (3-1) is satisfied.
0 ≤ Pd ≤ 5 ppm (3-1)
More preferably, the following formula (3-2) is satisfied.
0 ≤ Pd ≤ 3 ppm (3-2)
More preferably, the following formula (3-3) is satisfied.
0 ≤ Pd ≤ 1 ppm (3-3)
If the upper limit of the above range is exceeded, the hue of the resin using the raw material alcohol represented by the formula (1) and the optical member using the resin are adversely affected, which is not preferable.

Furthermore, in the compound having a fluorene skeleton of the present invention, the by-product represented by the following formula (4) is 3% or less, preferably 1% or less, in the compound represented by the above formula (1), It is more preferably 0.5% or less, still more preferably 0.3% or less, and particularly preferably 0.1% or less.
Ar ¹ -Ar ¹ , Ar ¹ -Ar ² or Ar ² -Ar ² (4)
(Ar ¹ and Ar ² are the same as in formula (1) above.)
Also, the by-product represented by the following formula (4) is preferably a by-product represented by the following formula (4a), (4b) or (4c).

When the upper limit of the above range is exceeded, the productivity (or reactivity) of the resin using the raw material alcohol represented by the formula (1) and various properties of the produced resin (heat resistance, moldability, dimensional stability, etc.) ) and is not preferred.

[Features and Uses of Compound Having Fluorene Skeleton]
The compound having a fluorene skeleton of the present invention preferably has a combination of a diphenylfluorene skeleton or a dinaphthylfluorene skeleton and an arene ring, and thus not only has a high refractive index and high heat resistance, but also reduces birefringence when polymerized. be able to. In order to improve the refractive index, fluorene compounds in which a ring-aggregated arene ring is substituted at the 9-position of the fluorene skeleton have been used. . On the other hand, the compound having a fluorene skeleton of the present invention has a small birefringence, although it has a high refractive index, probably because it has a diphenylfluorene skeleton. Furthermore, the arene ring has one or more hydroxyl groups, and the entire fluorene compound has a plurality of hydroxyl groups, so the reactivity is high. Therefore, the compound having a fluorene skeleton of the present invention can be used as a raw material (monomer) for various resins. For example, thermoplastic resins (e.g., polyester resins, polycarbonate resins, polyester carbonate resins, polyurethane resins, etc.) and thermosetting resins (e.g., epoxy resins, phenolic resins, thermosetting polyurethane resins, (meth) acrylate ((meth) acrylic acid ester), etc.) can be used as a polyol component. When the compound having a fluorene skeleton of the present invention is used as a polyol component, the obtained resin has a high refractive index and a low It has the advantage of being compatible with birefringence at a high level.

Moreover, the compound having a fluorene skeleton of the present invention can be efficiently prepared as a derivative in a general-purpose solvent.

The melting point of the compound having a fluorene skeleton of the present invention can be selected from a wide range of 100 to 300°C, preferably 120 to 280°C, more preferably 130 to 260°C, still more preferably 140 to 240°C, particularly preferably 150°C. ~210°C.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In the examples, various measurements were performed as follows.

(1) HPLC measurement The compounds obtained in the examples were measured using the following equipment and conditions.
Equipment used: Waters column: ACQUITY UPLC @ BEH C18 2.1 x 150 mm
Eluent (volume): dimethylformamide: ultrapure water (0.1 wt% trifluoroacetic acid) = 70/30
(2) NMR measurement The compounds and resins obtained in Examples were measured using the following apparatus and solvent.
Device: JNM-AL400 (400 MHz) manufactured by JEOL Ltd.
Solvent: _CDCl3
(3) ICP measurement The compounds obtained in the examples were measured with the following equipment.
Equipment used: Agilent Technologies
Apparatus: Agilent 5100 ICP-OES
(4) Measurement of glass transition temperature (Tg) The resins obtained in the examples were measured using the following equipment and conditions.
Apparatus: DSC-60A manufactured by Shimadzu Corporation
Conditions: Heating rate 20°C/min
(5) Pellet b* value measurement The resins obtained in the examples were measured using the following equipment.
Apparatus: Integrating sphere spectrophotometer CE-7000A manufactured by X-Rite
(6) Measurement of refractive index (nD) and Abbe's number The resins obtained in the examples were measured using the following apparatus and method.
Apparatus: ATAGO DR-M2 Abbe refractometer Method: The resin pellets obtained after the completion of polymerization are dissolved in methylene chloride, cast on a glass petri dish, dried, and the refractive index of the prepared film at 25 ° C. (wavelength: 589 nm ) and Abbe number (calculated from refractive indices at wavelengths of 486 nm, 589 nm and 656 nm using the following formula) were measured.
ν=(nD−1)/(nF−nC)
In addition, in the present invention,
nD: refractive index at a wavelength of 589 nm;
nC: refractive index at a wavelength of 656 nm;
nF: Refractive index at a wavelength of 486 nm.
(7) PL catalyst This is a palladium compound manufactured by N E Chemcat Company, abbreviated as Pd/SiO ₂ , and is a powdery solid catalyst in which palladium is supported on silica. This catalyst is specialized for Suzuki coupling reactions, and when bromoaryls are used as substrates, the reaction proceeds in a ligand-free manner compared to homogeneous palladium catalysts. Furthermore, it is characterized by little Pd elution in the product after the reaction, partly because it is supported on silica.

[Example 1]
<Step 1>
A 500 mL flask equipped with stirrer, condenser and thermometer was charged with 150 g of toluene as solvent and _{2.19 g} of 12-tungsto(VI) phosphate n-hydrate _H3 [ _PW12O40 ].nH2O. was azeotropically dehydrated under reflux of toluene. After cooling the contents, 33.8 g (0.10 mol) of 2,7-dibromofluorenone (hereinafter sometimes abbreviated as DBFN) and 138.2 g (1.0 mol) of 2-phenoxyethanol were added, and the mixture was refluxed with toluene. Then, the mixture was stirred for 13 hours while discharging water produced by the reaction out of the system. The progress of the reaction was appropriately checked by HPLC, and after confirming that the residual amount of DBFN was 0.1% by weight or less, the reaction was terminated. 150 g of toluene was added to the obtained reaction mixture, and the mixture was washed with 300 g of water three times. After washing, the organic layer was treated with activated charcoal and then concentrated under reduced pressure to remove the toluene solvent and a large excess of 2-phenoxyethanol. The resulting mixture is recrystallized with methanol, the precipitated crystals are collected by filtration, and the crystals are dried to obtain the desired product, 9,9-bis(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene (hereinafter referred to as , sometimes abbreviated as BPDB), 36 g of pale yellow crystals (yield 61%, purity 98%) were obtained.

<Step 2>
17.9 g (0.03 mol) of BPDB obtained in Step 1, 11.4 g (0.066 mol) of 2-naphthaleneboronic acid, and 0.2 g of PL catalyst manufactured by NE Chemcat (Pd conversion value: equivalent to 200 ppm), 150 g of toluene, and 35 mL of 2 M potassium carbonate aqueous solution were charged, and the reaction was carried out by stirring at 80° C. for 17 hours. The progress of the reaction was confirmed by HPLC, and after confirming that the residual amount of BPDB was 0.1% by weight or less, the reaction was terminated. At the end of the reaction, it was confirmed by HPLC measurement that 2% of the compound (4a) in which 2-naphthaleneboronic acids were coupled together was produced, and the selectivity to the desired product was 98%. Next, after cooling the obtained reaction solution to room temperature, chloroform was added to completely dissolve the reactant, and the solid derived from the palladium compound was collected by filtration. The collected filtrate was washed with water three times, concentrated and recrystallized from ethyl acetate/hexane to obtain the desired product, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di 18.9 g of white crystals of naphthylfluorene (hereinafter sometimes abbreviated as BPDN2) were obtained (yield 91%, purity 98.7%). When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Further, HPLC measurement of the final product revealed that the obtained white crystals did not contain the compound represented by formula (4a) (detection limit 0.1%).

<Step 3>
29.51 parts by mass of BPDN2 synthesized in step 2, 21.93 parts by mass of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 21.64 parts by mass of diphenyl carbonate, and 42 parts by mass of sodium hydrogen carbonate 0×10 ⁻⁵ parts by mass was placed in a reactor equipped with a stirrer and a distiller, and after purging with nitrogen three times, the jacket was heated to 180° C. to melt the starting material. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the temperature of the jacket was increased to 260°C at a rate of 60°C/hr to carry out the transesterification reaction. Thereafter, while the jacket was kept at 260° C., the pressure was reduced to 0.13 kPa over 50 minutes, and the polymerization reaction was carried out under conditions of 260° C. and 0.13 kPa or less until a predetermined torque was reached. After completion of the reaction, the produced resin was extracted while being pelletized to obtain pellets of polycarbonate resin. The obtained polycarbonate resin was analyzed by ¹ H NMR, and it was confirmed that the BPDN2 component was introduced in an amount of 50 mol % with respect to the total monomer components. The resulting polycarbonate resin had a refractive index of 1.664, an Abbe number of 18, a Tg of 161° C. and a pellet b* value of 8.0.

[Example 2]
9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene in the same manner as in Example 1 except that 2-naphthaleneboronic acid in step 2 was changed to 1-naphthaleneboronic acid (hereinafter sometimes abbreviated as BPDN1) was obtained as a white solid (yield 91%, purity 99.0%). HPLC immediately after the completion of the coupling reaction confirmed that the yield of compound (4b) was 2% and the selectivity to the desired product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, HPLC measurement of the final product revealed that the resulting white crystals did not contain the compound represented by formula (4b).

[Example 3]
9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene (hereinafter referred to as (Sometimes abbreviated as BPDP) was obtained as a white solid (yield 91%, purity 99.0%). HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4c) was 2% and the selectivity to the desired product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Further, HPLC measurement of the final product revealed that the resulting white crystals did not contain the compound represented by formula (4c).

[Example 4]
A white solid of BPDP was obtained in the same manner as in Example 1, except that phenylboronic acid in step 2 was changed to phenylboronic acid anhydride (triphenylboroxine) (yield 91%, purity 99.0%). . HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4a) was 2% and the selectivity to the desired product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Further, HPLC measurement of the final product revealed that the obtained white crystals did not contain the compound represented by formula (4a).

[Example 5]
A white solid of BPDN2 was obtained in the same manner as in Example 1 except that the base in step 1 was changed to sodium carbonate (yield 90%, purity 98.9%). HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4a) was 2% and the selectivity to the desired product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Further, HPLC measurement of the final product revealed that the obtained white crystals did not contain the compound represented by formula (4a).

[Example 6]
A white solid of BPDN2 was obtained in the same manner as in Example 1 (yield 89%, purity 99.0%) except that the acid catalyst in step 1 was previously dried under reduced pressure to remove water of crystallization. HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4a) was 2% and the selectivity to the desired product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Further, HPLC measurement of the final product revealed that the obtained white crystals did not contain the compound represented by formula (4a).

[Example 7]
A white solid of BPDN2 was obtained in the same manner as in Example 1 except that the acid catalyst in step 1 was changed to n-hydrate of silicotungstic acid (H ₄ [SiW ₁₂ O ₄₀ ].nH ₂ O) (yield: 89%, purity 99.0%). HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4a) was 2% and the selectivity to the desired product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Further, HPLC measurement of the final product revealed that the obtained white crystals did not contain the compound represented by formula (4a).

[Example 8]
A white solid of BPDN2 was obtained in the same manner as in Example 6 except that silicotungstic acid (H ₄ [SiW ₁₂ O ₄₀ ]) from which water of crystallization had been removed by previously drying the acid catalyst in step 1 under reduced pressure was used. yield 89%, purity 99.0%). HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4a) was 2% and the selectivity to the desired product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Further, HPLC measurement of the final product revealed that the obtained white crystals did not contain the compound represented by formula (4a).

[Example 9]
A white solid of BPDN2 was obtained in the same manner as in Example 1 except that the solvent in step 2 was changed to a mixed solvent of toluene and ethanol (yield 88%, purity 99.0%). HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4a) was 2% and the selectivity to the desired product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Further, HPLC measurement of the final product revealed that the obtained white crystals did not contain the compound represented by formula (4a).

[Comparative Example 1]
A pale yellow solid of BPDN2 was obtained in the same manner as in Example 1 except that the palladium catalyst in step 2 was changed to 0.35 g of tetrakistriphenylphosphine palladium (Pd conversion value: 740 ppm) and the activated carbon treatment was performed as the Pd removal treatment ( Yield 88%, Purity 97.9%). HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4a) was 16% and the selectivity to the desired product was 91%. When the amount of residual metal was measured by ICP, Pd was 30 ppm. Furthermore, HPLC measurement of the final product revealed that the pale yellow crystals obtained contained 1% of the compound represented by formula (4a).

Polycarbonate resin pellets were obtained in the same manner as in Example 1, except that BPDN2 synthesized by the above method was used in step 3. The obtained polycarbonate resin was analyzed by ¹ H NMR, and it was confirmed that the BPDN2 component was introduced in an amount of 50 mol % with respect to the total monomer components. The resulting polycarbonate resin had a refractive index of 1.664, an Abbe number of 18, a Tg of 161° C. and a pellet b* value of 8.0.

[Comparative Example 2]
A pale yellow solid of BPDN2 was obtained in the same manner as in Comparative Example 1 except that 0.01 g of tetrakis(triphenylphosphine)palladium (Pd conversion value: 40 ppm) was used (yield 85%, purity 98.5%). HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4a) was 5% and the selectivity to the desired product was 95%. When the amount of residual metal was measured by ICP, Pd was 12 ppm. Further, HPLC measurement of the final product revealed that the pale yellow crystals obtained contained 0.5% of the compound represented by formula (4a).

[Comparative Example 3]
A pale yellow solid of BPDN2 was obtained in the same manner as in Comparative Example 1 except that the Pd removal treatment in step 2 was not performed (yield 84%, purity 97.9%). HPLC immediately after the completion of the coupling reaction confirmed that the production rate of compound (4a) was 16% and the selectivity to the desired product was 91%. When the amount of residual metal was measured by ICP, Pd was 600 ppm. Furthermore, HPLC measurement of the final product showed that the resulting pale yellow solid contained 1% of the compound represented by formula (4a).

[Comparative Example 4]
A pale yellow solid of BPDN2 was obtained in the same manner as in Comparative Example 2 except that the Pd removal treatment in step 2 was not performed (yield 84%, purity 98.5%). HPLC immediately after the coupling reaction confirmed that the production rate of compound (4a) was 5% and the selectivity to the desired product was 95%. When the amount of residual metal was measured by ICP, Pd was 25 ppm. Furthermore, HPLC measurement of the final product showed that the resulting pale yellow solid contained 0.5% of the compound represented by formula (4a).

[Comparative Example 5]
A fluorene compound was synthesized in the same manner as in Example 1, except that the acid catalyst in step 1 was changed to sulfuric acid and 3-mercaptopropionic acid, but the reaction did not proceed and the target fluorene compound could not be obtained. rice field.

According to the compound having a fluorene skeleton produced by the production method of the present invention, it is possible to efficiently produce raw materials (monomers) for resins having excellent properties such as high refractive index, heat resistance, and low birefringence. Therefore, it can be suitably used as a raw material (monomer) for resins, a reaction component for derivatives, and the like.

Therefore, resins made from the compound having a fluorene skeleton of the present invention or a derivative thereof, or the compound having a novel fluorene skeleton as a raw material (monomer) can be used, for example, in films, lenses, prisms, optical discs, transparent conductive substrates, optical cards, and sheets. , optical fibers, optical films, optical filters, hard coat films, etc., and is particularly useful for lenses.

Claims (15)

A method for producing a compound having a fluorene skeleton represented by the following formula (1),

(Wherein, ring Z is an aromatic group (same or different); R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a carbon atom optionally containing an aromatic group having 1 to 12 carbon atoms; hydrogen group, Ar ¹ and Ar ² are aromatic groups having 6 to 10 carbon atoms which may have substituents, L ¹ and L ² are alkylene groups, j and k are each independently integers of 0 or more, m and n each independently represents an integer of 0 to 5.)
comprising at least steps 1 and 2 of the following;
Step 1: Reacting a fluorenone compound represented by the following formula (5) with an alcohol compound represented by the following formula (6) in a reaction solvent using an acid catalyst Step 2: Reaction produced in step 1 (7) and a boronic acid represented by the following formula (8) or (9) in a reaction solvent in the presence of a base and a palladium catalyst represented by the following formula ( ₂ ): )

(Wherein, X ¹ is a substituent at the 1-, 2-, 3- or 4-position, X ² is a substituent at the 5-, 6-, 7- or 8-position and represents a halogen atom.)

(In the formula, Z is the same as in formula (1). R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group that may contain an aromatic group having 1 to 12 carbon atoms, and s is independently 0 or more. is an integer, R ¹¹ represents an alkylene group, and p represents an integer of 0 or more.)

(In the formula, X ¹ and X ² are the same as in formula (5). Z, R ¹² , s, R ¹¹ and p are the same as in formula (6).)

(In the formula, Y is an aromatic group, R ¹³ is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a halogen atom. l is 1 or 2, and when l = 2, R ¹³ may be the same or may be different.)
The acid catalyst used in step 1 is a heteropoly acid composed of phosphoric acid or silicic acid and an oxyacid ion of at least one element selected from vanadium, molybdenum and tungsten,
and the content of the palladium element in the obtained compound having a fluorene skeleton satisfies the following formula (3),
0≦Pd≦10 ppm (3)
Further, a method for producing a compound having a fluorene skeleton, wherein a by-product represented by the following formula (4) is produced within a range of 3% or less.
Ar ¹ -Ar ¹ , Ar ¹ -Ar ² or Ar ² -Ar ² (4)
(Ar ¹ and Ar ² are the same as in formula (1) above.) 2. The method for producing a compound having a fluorene skeleton according to claim 1, wherein Z is a phenyl group or a naphthyl group. The method for producing a compound having a fluorene skeleton according to any one of claims 1 and 2, wherein the formula (4) is a by-product represented by the following formula (4a), (4b) or (4c).

The method for producing a compound having a fluorene skeleton according to any one of claims 1 to 3, wherein the formula (1) is one of the following formulas (1a) to (1d).

(In the formula, R ³ to R ¹⁰ each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms. Ar ¹ and Ar ² , L ¹ and L ² , m and n are the same as in formula (1) above.) 5. The method for producing a compound having a fluorene skeleton according to claim 4, wherein said formula (1) is said formula (1b). 6. The method for producing a compound having a fluorene skeleton according to any one of claims 1 to 5, wherein Ar ¹ and Ar ² in formula (1) are a phenyl group or a naphthyl group. 2. The method for producing a compound having a fluorene skeleton according to claim 1, wherein the compound represented by formula (5) is 2,7-dibromofluorenone. 2. The method for producing a compound having a fluorene skeleton according to claim 1, wherein the compound represented by formula (6) is 2-phenoxyethanol. The method for producing a compound having a fluorene skeleton according to claim 1, wherein the compound represented by formula (7) is 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene). . 2. The method for producing a compound having a fluorene skeleton according to claim 1, wherein the compound represented by formula (8) is 2-naphthaleneboronic acid, 1-naphthaleneboronic acid or phenylboronic acid. 2. The method for producing a compound having a fluorene skeleton according to claim 1, wherein the compound represented by formula (9) is 2-naphthaleneboronic anhydride, 1-naphthaleneboronic anhydride or phenylboronic anhydride. . 2. The method for producing a compound having a fluorene skeleton according to claim 1, wherein the heteropolyacid is a previously dehydrated heteropolyacid or a heteropolyacid anhydride. 2. The method for producing a compound having a fluorene skeleton according to claim 1, wherein toluene is used as the reaction solvent in step 1. 2. The method for producing a compound having a fluorene skeleton according to claim 1, wherein the base used in step 2 is potassium carbonate and/or sodium carbonate. 2. The method for producing a compound having a fluorene skeleton according to claim 1, wherein toluene or a mixed solvent of toluene and ethanol is used as the reaction solvent in step 2.