JP2020083813A - Production method of compound having fluorene skeleton and compound having fluorene skeleton of less impurity - Google Patents

Abstract

To provide a production method of a compound having a novel fluorene skeleton excellent in optical characteristics, heat resistance, moldability and the like.SOLUTION: A production method of a compound having a fluorene skeleton is a production method of a compound having a fluorene skeleton shown by the formula (1) (in the formula, a ring Z is (same or different) aromatic group, Rand Reach is independently a hydrogen atom, a halogen atom or the like, Arand Aris an aromatic group that may have a substitution group having 6 to 10 carbon atoms, Land Lis an alkylene group, j and k each is independently an integer of 0 or more, and m and n each is independently an integer of 0 to 5) characterized by using a palladium catalyst represented by a formula (2), a content of palladium element in the compound having a fluorene skeleton obtained from Pd/SiO(2) satisfying the formula (3), and generating a byproduct represented by 0≤Pd≤10 ppm(3) and a formula (4) in the range of 3% or less. Ar-Ar, Ar-Aror Ar-Ar(4).SELECTED DRAWING: None

Description

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

In recent years, thermoplastic resin materials such as polycarbonates, polyesters, and polyester carbonates using alcohols having a fluorene skeleton represented by 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) as raw materials are It is attracting attention as an optical member such as an optical lens and an optical sheet because of its excellent properties, heat resistance, and moldability.

For example, Patent Document 1 discloses a polycarbonate resin using an alcohol having a BPEF skeleton as a raw material. However, although it is described that the polycarbonate resin using the alcohol has a refractive index of 1.64, further improvement of the above characteristics is required due to the recent rapid technological innovation. Therefore, in order to further increase the refractive index, Patent Document 2 has developed a thermoplastic resin using 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPBPEF) as a raw material. However, the resins described in the patent documents still have room for improvement in the refractive index. Further, although Patent Document 3 describes a high refractive index resin using 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) as a raw material, it has a high refractive index. Since the birefringence also becomes high, it becomes a big problem when applied to transparent materials such as optical lenses.

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

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), fluorenone and 2-naphtho are prepared by using sulfuric acid and thiols as catalysts, as in BPEF. A method for dehydration condensation of xyethanol has been disclosed (Patent Document 4). Further, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPBPEF) is also used, like BPEF and BNEF, by using sulfuric acid and thiols as catalysts and fluorenone and 2-(2-biphenylyl). A method for dehydration condensation of (oxy)ethanol (Patent Document 5) is disclosed, but since any method uses a large amount of sulfuric acid, a complicated purification operation such as neutralization and purification after the reaction is required, and A large amount of neutralization drainage is generated. Further, when the sulfur component derived from the catalyst is mixed in the product, problems such as coloring of the product, deterioration of stability, and deterioration of purity occur. Further, in order to obtain a highly pure 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.

International Publication No. 2007/142149 Pamphlet JP, 2005-86265, A JP, 2017-171885, A JP, 2016-79405, A JP, 2009-256342, A

Chemistry Letters, 1998, 1055-1056.

The method for producing a compound of the following formula (1) molecularly designed in the present invention mainly comprises two steps. In the reaction of the step 1, the present inventor used the method described in the above patent document to obtain the following formula ( 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 proceeds, the reaction rate is slow, which is industrially disadvantageous. When the activity of the catalyst used in step 2 is strong and the amount of the catalyst used is increased, a coupling reaction (side reaction) occurs in which the compounds represented by the following formula (8) or (9) react with each other, and Not only did the yield of the fluorene compound represented by (1) decrease, the manufacturing cost also increased, but it was mixed into the fluorene compound represented by the following formula (1), causing a decrease in purity. Furthermore, unless activated carbon treatment or metal removal treatment similar to that is performed, black particles derived from the palladium catalyst used in the reaction of Step 2 are mixed into the white compound having a fluorene skeleton represented by the following formula (1). Therefore, the hue of the alcohol compound has deteriorated.

Therefore, the present invention has been achieved as a result of an examination for solving the above-mentioned problems of the prior art, and the selectivity from the following formula (5) to the following formula (7) in step 1 is high and the step is The coupling reaction (side reaction) between the boronic acids in 2 is unlikely to occur, and the content of a specific metal such as palladium content in the raw material alcohol or the content of a specific compound is small. An object of the present invention is to provide a method for producing a compound having a novel fluorene skeleton, which is excellent in hue and various properties (optical properties, heat resistance, moldability, etc.), and a compound having a fluorene skeleton with few impurities.

The present invention has been achieved as a result of investigations for solving the above-mentioned problems of the prior art, has a certain quality, a method for producing a compound having an excellent fluorene skeleton as a polymer raw material, and impurities. It is intended to provide a compound having a small fluorene skeleton. 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。）
下記式（２）で表されるパラジウム触媒を用い、
Ｐｄ／ＳｉＯ_２ （２）
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):

(In the formula, ring Z is an (identical or different) aromatic group, R ¹ and R ² are each independently a carbon atom which may include a hydrogen atom, a halogen atom and 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 and may have a substituent, L ¹ and L ² are alkylene groups, j and k are each independently an integer of 0 or more, m And n each independently represent an integer of 0 to 5.)
Using a palladium catalyst represented by the following formula (2),
Pd/SiO ₂ (2)
And the content of the palladium element in the obtained compound having a fluorene skeleton satisfies the following formula (3),
0 ≤ Pd ≤ 10ppm (3)
Furthermore, the by-product represented by the following formula (4) is produced within a range of 3% or less, and a method for producing a compound having a fluorene skeleton.
Ar ¹ -Ar ¹ , Ar ¹ -Ar ² or Ar ² -Ar ² (4)
(Ar ¹ and Ar ² are the same as those in the above formula (1).)

[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 formulas (1a) to (1d) below.

(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 the above formula (1).)

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

（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。）
Ｐｄ／ＳｉＯ_２ （２） [7] A method for producing a compound having a fluorene skeleton according to item 1 above, which comprises at least the following step 1 and step 2 in the method for producing a compound having a fluorene skeleton represented by the above formula (1).
Step 1: a step of reacting a fluorenone represented by the following formula (5) with an alcohol represented by the following formula (6) using an acid catalyst in a reaction solvent Step 2: The reaction product produced in Step 1 ( A step of reacting 7) with 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).

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

(In the formula, Z is the same as the formula (1). R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, and s is independently 0 or more. , And 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 those in the formula (5). Z, R ¹² , s, R ¹¹ and p are the same as those in the formula (6).)

(In the formula, Y represents an aromatic group, R ¹³ represents 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 is the same or It may be different.)
Pd/SiO ₂ (2)

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

[9] The method for producing a compound having a fluorene skeleton according to the above item 7, wherein the compound represented by the formula (6) is 2-phenoxyethanol.

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

[11] The method for producing a compound having a fluorene skeleton according to the above item 7, wherein the compound represented by the formula (8) is 2-naphthaleneboronic acid, 1-naphthaleneboronic acid or phenylboronic acid.

[12] A compound having a fluorene skeleton according to the above item 7, wherein the compound represented by the formula (9) is an anhydride of 2-naphthaleneboronic acid, an anhydride of 1-naphthaleneboronic acid or an anhydride of phenylboronic acid. Production method.

[13] The fluorene according to the above item 7, wherein the acid catalyst used in the step 1 is a heteropoly acid composed of phosphoric acid or silicic acid and an oxygen acid ion of at least one element selected from vanadium, molybdenum and tungsten. A method for producing a compound having a skeleton.

[14] The method for producing a compound having a fluorene skeleton according to the above item 13, wherein the heteropoly acid is a heteropoly acid or an anhydride of a heteropoly acid that has been dehydrated in advance.

[15] The method for producing a compound having a fluorene skeleton according to the above item 7, wherein toluene is used as a reaction solvent used in step 1.

[16] The method for producing a compound having a fluorene skeleton according to the above item 7, wherein the base used in step 2 is potassium carbonate and/or sodium carbonate.

[17] The method for producing a compound having a fluorene skeleton according to the above item 7, wherein toluene or a mixed solvent of toluene and ethanol is used as the reaction solvent used 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。） [18] A compound having a fluorene skeleton represented by the following formula (1),

(In the formula, ring Z is an (identical or different) aromatic group, R ¹ and R ² are each independently a carbon atom which may include a hydrogen atom, a halogen atom and 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 and may have a substituent, L ¹ and L ² are alkylene groups, j and k are each independently an integer of 0 or more, m And n each independently represent 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 ≤ 10ppm (3)
A compound having a fluorene skeleton, characterized in that the 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 those in the above formula (1).)

[19] The compound having a fluorene skeleton according to the above item 18, which is used as a raw material for a thermoplastic resin.

Since the method for producing a fluorene compound of the present invention is produced using a heterogeneous palladium catalyst supported on silica, the catalytic activity is appropriately suppressed, and a homocoupling reaction between boronic acids (a side reaction) is unlikely to occur. In addition, the specific metal content such as palladium content and the specific compound (by-product) content are small, so the amount of boronic acid used is suppressed, so compared to the production method using a homogeneous palladium catalyst. Not only the cost is low, but the catalyst can be separated only by filtration, and the specific metal content such as the palladium content remaining in the fluorene compound and the specific compound content are low, so that the purification is easy. The fluorene compound can be produced very efficiently. Further, the thermoplastic resin produced from the fluorene compound according to the present invention is excellent in various properties (heat resistance, hue, moldability, etc.) in addition to optical properties.

The present invention will be described in detail, but the description of the constituent elements described below is a representative example of the embodiment of the present invention, and is not limited to these contents.
[Method for producing compound having 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 particularly at least the following Step 1 And a production method including the step 2 is preferable. That is, a first step 1 in which a fluorenone represented by the following formula (5) is reacted with an alcohol compound represented by the following formula (6), and a reaction product (7 ) Is reacted with a boronic acid compound represented by the following formula (8) or (9). In the above production method, alcohols represented by the following formula (6) also act as reaction solvents and can be easily removed by distillation under reduced pressure, and a heterogeneous palladium catalyst represented by the following formula (2) is used. Thus, the coupling reaction (side reaction) between the boronic acids represented by the following formula (8) or (9) is unlikely to occur, so that the compound having the fluorene skeleton of the present invention can be simply and efficiently produced.

（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。）

(In the formula, X ¹ is a substituent at the 1-position, 2-position, 3-position or 4-position, X ² is a substituent at the 5-position, 6-position, 7-position 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 the formula (1). R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, and s is independently 0 or more. , And 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 those in the formula (5). Z, R ¹² , s, R ¹¹ and p are the same as those in the 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 represents an aromatic group, R ¹³ represents 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 is the same or It may be different.)
Pd/SiO ₂ (2)

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

Typical examples of the fluorenone compound represented by the above formula (5) are shown below, but the raw materials used in the above formula (1) of the present invention are not limited thereto.

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 Preferred are fluorenone, 3,6-dibromofluorenone, 4,5-dibromofluorenone and the like. Of these, 1,8-dibromofluorenone, 2,7-dibromofluorenone, 3,6-dibromofluorenone and 4,5-dibromofluorenone are preferable, and 2,7-dibromofluorenone is particularly preferable.

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

The purity of the fluorenone represented by the above formula (5) to be used is not particularly limited, but is usually preferably 95% or more, more preferably 99% or more. As the fluorenones, a commercially available product or a synthesized product may be used. For example, as a method for producing dibromofluorenones, a method described in a non-patent document (Journal of American Chemical Society, 2017, Vol. 139, 11073-11080), that is, 9-fluorenone is reacted with bromine in water. Method etc. are mentioned.

The compound represented by the formula (6) ((poly)hydroxyl group-containing arene ring compound) is a (poly)hydroxyl group-containing arene ring substituted at the 9-position in the fluorene derivative represented by the formula (7). It corresponds. 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 , and s Corresponds to j and k, respectively. Examples of the ring Z include a benzene ring and a naphthalene ring.

The alkylene group represented by R ¹¹ is not particularly limited, and examples thereof include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. It is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms. The substitution position of R ¹¹ is not particularly limited. The number of substituents p is 0 or 1 or more and may be the same or different. It is preferably 0 to 15, more preferably 0 to 5. When p is 2 or more, the polyalkoxy groups may be composed of the same alkoxy group, or may be composed of different kinds of alkoxy groups (for example, an ethoxy group and a propyleneoxy group) mixedly. , Usually composed of the same alkoxy group.

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, and is preferably a hydrogen atom, a methyl group or a phenyl group.

Examples of the hydrocarbon group represented by R ¹² include an alkyl group, a cycloalkyl group, an aryl group, a naphthyl group and an aralkyl group. Specific examples of the alkyl group include a C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group, a C _1-4 alkyl group, and a C _1-3 alkyl group. Preferably, a C _1-3 alkyl group is more preferable, and among them, a methyl group or an ethyl group is even more preferable. As a specific example of the cycloalkyl group, a C _5-8 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a C _5-6 cycloalkyl group and the like are preferable, and a C _5-6 cycloalkyl group is more preferable. Specific examples of the aryl group are preferably 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 a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group and a phenethyl group. As the halogen atom, a fluorine atom, a chlorine atom, a 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. Further, it is preferably an integer of 6 or less, and more preferably an integer of 4 or less.

Specific examples of the compound represented by the formula (6) include, for example, compounds having p=0 such as phenol, 2-methylphenol, alkylphenol such as 3-methylphenol, 2,3-xylenol, and 2,6-. Examples thereof 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. As the compound of p=1, phenoxyalkyl alcohol such as phenoxyethanol, phenoxypropanol, and 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, Dialkylphenoxyalkyl alcohols such as (2,6-dimethylphenoxy)ethanol and (2,6-dibutylphenoxy)ethanol, alkoxyphenoxyalkyl alcohols such as (2-methoxyphenoxy)ethanol, and cyclohexyl such as (2-cyclohexylphenoxy)ethanol. Examples thereof include alkylphenoxyalkyl alcohols and arylphenoxyalkyl alcohols such as biphenylyloxyethanol. Examples of compounds having p of 2 or more include polyoxyalkylene phenyl ethers corresponding to these phenoxyalkyl alcohols. Phenoxy C _2-6 alkyl alcohol or C _1-4 alkylphenoxy C _2-6 alkyl alcohol is preferable, and phenoxyethanol is particularly preferable.

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

As the compound represented by the above formula (6), a commercially available product may be used, or a synthesized product may be used. Examples of the method of producing the compound represented by the formula (6) include a method of reacting the 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 more, preferably 99% or more.

The reaction of step 1 can be usually performed in the presence of an acid catalyst. Examples of the acid catalyst include sulfuric acid, thiol acid, montmorillonite, and heteropoly acid. Among these, particularly, the generation of impurities derived from the acid catalyst is small, and the heteropoly acid having a fluorene skeleton of the present invention is easily obtained. Is preferred.

The heteropolyacid preferably used in the present invention is a general term for compounds formed by condensation of two or more different kinds of inorganic oxygen acids, and generally includes a central oxygen acid and another oxygen acid condensed around it. Various heteropolyacids are possible in combination. An element with a small number of forming the central oxygen acid is called a hetero element, and an element forming an oxygen acid condensed around it is called a poly element. The poly element may be a single kind of element or plural kinds of elements.

The hetero element of the oxygen acid constituting the heteropoly acid is not particularly limited, but for example, copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, phosphorus, Examples include arsenic, antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, ildium and platinum. Phosphorus (phosphoric acid) or silicon (silicic acid) is preferable. Further, the poly element of the oxygen acid that constitutes the heteropoly acid is not particularly limited, and examples thereof include vanadium, molybdenum, tungsten, niobium, and tantalum. It is preferably at least one element selected from vanadium, molybdenum and tungsten.

As the heteropoly acid anion constituting the heteropoly acid skeleton, those having various compositions can be used. For _example, such _{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 hetero element and M is a poly element. Specific examples of the heteropolyacid having these compositions include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid.

The heteropoly acid may be a free heteropoly acid, or may be used as a salt of the heteropoly acid by replacing some or all of the protons with other cations. Therefore, the heteropolyacid referred to in the present invention also includes salts of these heteropolyacids. Examples of the cation capable of substituting for a proton include ammonium, alkali metal, alkaline earth metal and the like.

The heteropolyacid may be an anhydride or a water of crystallization content, but the anhydride is preferred 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 the anhydride can be obtained by previously performing dehydration treatment such as drying under reduced pressure or azeotropic dehydration with a solvent. The heteropolyacid may be used in the form of being supported on a carrier such as activated carbon, alumina, silica-alumina, diatomaceous earth. These heteropolyacids may be used alone or in combination of two or more. Further, if necessary, a catalyst other 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, preferably 0.0001 times by weight or more, more preferably 0.001 to 30 times by weight, and further It is preferably 0.01 to 5 times by weight.

The method for carrying out the reaction of step 1 is not particularly limited, but usually, the compound represented by the formula (5) and the formula (6) and the heteropolyacid are charged in a reaction apparatus, and the reaction is performed in air or nitrogen. It can be carried out by heating and stirring under an atmosphere of an inert gas such as argon, in the presence or absence of an inert solvent such as toluene and xylene. At this time, by removing water 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 in the case without dehydration, the production of by-products is suppressed, The target product can be obtained in a higher yield. The dehydration method is not particularly limited, and examples thereof include dehydration by adding a dehydrating agent, dehydration under reduced pressure, dehydration by azeotropic distillation with a solvent under normal pressure or reduced pressure, and the like.

The azeotropic dehydration solvent is not particularly limited, but it is an aromatic hydrocarbon solvent such as toluene or xylene, a halogenated aromatic hydrocarbon solvent such as chlorobenzene or dichlorobenzene, an aliphatic solvent such as pentane, hexane or heptane. Hydrocarbon solvents, halogenated aliphatic hydrocarbon solvents such as dichloromethane and 1,2-dichloroethane, aliphatic and cyclic ether solvents such as diethyl ether, di-iso-propyl ether, methyl-t-butyl ether, diphenyl ether, tetrahydrofuran and 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 A solvent, etc. are mentioned. Preferred are aromatic hydrocarbon solvents and halogenated aromatic hydrocarbon solvents, more preferred are toluene, xylene, chlorobenzene and dichlorobenzene, and further preferred is toluene. The amount used is not particularly limited, but from the viewpoint of economy, it is preferably 0.1 times by weight or more, more preferably 0.5 to 100 times by weight, further preferably 1 to 20 times by weight, relative to fluorenone. Double.

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

Further, after the reaction, the compound represented by the above formula (7) may be precipitated from the obtained reaction mixture, and further, after subjected to post-treatments such as washing, concentration, dilution and activated carbon treatment, the temperature is lower than 50°C. Then, the compound represented by the above formula (7) can be precipitated. The operation of precipitating the compound represented by the above formula (7) from the reaction mixture which has been subjected to the above-mentioned post-treatment, if necessary, is such that the reaction mixture optionally mixed with a solvent is at least 50° C. and below the boiling point of the solvent (preferably 70 to 110° C.), and cooling this to less than 50° C. When crystals of the compound represented by the above formula (7) precipitate from the reaction mixture at 50° C. or higher, it was obtained after mixing the reaction mixture with an amount of the diluent solvent at which crystals did not precipitate at 50° C. or higher. It may be carried out by setting the mixture to 50° C. or higher and not higher than the boiling point of the solvent (preferably 70 to 110° C.), and cooling this to below 50° C. Examples of the diluent solvent include those exemplified as the solvent 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 preferable, and methanol is particularly preferable.

Such a crystallization operation may be performed once or may be repeated a plurality of times. In particular, in the reaction of the step 1, when the acid catalyst is phosphotungstic acid, use of an alcohol such as methanol is simple and efficient, and even if the crystallization operation is performed once, the content of phosphorus or tungsten can be increased. A small amount of the compound represented by the formula (7) can be obtained.

The 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 product of the compound represented by the formula (7) thus obtained is preferably 95% or more.

Further, after the reaction, the obtained reaction mixture can be directly used as a raw material in 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 formulas (8) and (9), preferred embodiments of the group R ¹³ are the same as the preferred embodiments of R ¹ and R ² described later, and a preferred embodiment of l is the same as the preferred embodiments of j and k described later. Is.

The purity of the boronic acid to be used is not particularly limited, but is usually preferably 95% or higher, more preferably 99% or higher. In addition, as the boronic acids, a commercially available product or a synthesized product may be used. As a method for producing a boronic acid, 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. Method etc. are mentioned.

The boronic acid used in the present invention includes alkylboronic acid, alkenylboronic acid, arylboronic acid, heteroarylboronic acid and their anhydrides represented by the above 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-phenylethylboronic acid and their anhydrides are included, and as alkenylboronic acid, 1-cyclopentenylboronic acid, ferroceneboronic acid, 1,1′-ferrocenediboronic acid and their anhydrides are included. Examples of the arylboronic acid include 2-anthraceneboronic acid, 9-anthraceneboronic acid, benzylboronic acid, 2-biphenylboronic acid, 3-biphenylboronic acid, 4-biphenylboronic acid and 2,3-dimethylphenylboron. 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(naphthalen-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 their anhydrides are included, and as heteroarylboronic acid, benzofuran-2-boronic acid and dibenzofuran-4-boronic acid can be used. , 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-thiopheneboronic acid, 5-pyrimidineboronic acid and their anhydrides are included.

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

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

In addition, the use ratio of the compound represented by the formula (9) is preferably 1 to 5 mol, and more preferably 0.1% with respect to 1 mol of the compound (halogenated fluorene compound) represented by the formula (7). It may be 8 to 3 mol, and more preferably about 0.7 to 1 mol. If the amount of the boronic acid is less than 0.7 mol, the yield of the product represented by the formula (1) may be low. On the other hand, if it exceeds 1 mol, the reaction rate is high and the yield is high, but the production cost of the compound having the fluorene skeleton may be increased.

The reaction (dehalogenation reaction) of the formula (7) with the compound represented by the formula (8) and/or (9) in step 2 may be performed in a reaction solvent in the presence of a base and a catalyst. it 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 ). ₃ ) and other carbonates, sodium acetate, potassium acetate and other acetates, sodium phosphate (Na ₃ PO ₄ ), potassium phosphate (K ₃ PO ₄ ), and other inorganic salts such as phosphates, triethylamines, pyridine , Organic salts such as morpholine, quinoline, piperidine, anilines, and ammonium salts such as tetra-n-butylammonium acetate. Among them, carbonate is preferably used, and potassium carbonate and/or sodium carbonate is preferable. Such bases may be used alone or in combination of two or more.

In the reaction of step 2, the amount of the above-mentioned base used is not particularly limited, but is preferably added in an amount of 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, and examples thereof include tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, palladium acetate, tris( Dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, bis[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine palladium 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 above-mentioned catalyst used is not particularly limited, but is preferably 0.1 to 10 in terms of palladium metal atom based on 1 mol of the compound represented by the formula (7) (halogenated fluorene compound). It is 2 millimole, and more preferably 0.15 to 1 millimole. When the amount of the palladium catalyst used is less than 0.1 mmol in terms of palladium metal atom, the reaction may be difficult to complete. Further, when the amount of the palladium catalyst used exceeds 2 mmol in terms of palladium metal atom, not only a homocoupling reaction (side reaction) between boronic acids occurs but also the palladium element content in the compound having the fluorene skeleton is increased. It may be difficult to set it within the range of the formula (3), which may deteriorate the hue of the thermoplastic resin produced by using the alcohol raw material, and may increase the production cost of the compound having the fluorene skeleton. is there.

Further, the addition method of the palladium catalyst may be added all at once at the time of charging the reaction, or in some cases, during the reaction, it may be added in divided portions so that the total amount used is the same as when added all at once. Good. In that case, confirmation of the reaction rate can be followed by an analysis means such as liquid chromatography.

As the reaction solvent used in step 2, for example, an aromatic hydrocarbon solvent such as toluene or xylene and an alcohol such as methanol, ethanol, isopropyl alcohol, or n-butanol can be used alone or in combination. Since the aromatic hydrocarbon solvent is a high boiling point solvent, the reaction temperature can be set high, and the alcohol is preferably used because it has good affinity with water and good reactivity. Such a solvent may be used alone or in combination of two or more kinds. Furthermore, aprotic solvents such as N,N-dimethylformamide or N,N-dimethylacetamide, and halobenzenes such as o-dichlorobenzene can also be used. These solvents may be used alone or in combination of two or more. 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 (in the present invention, toluene or a mixed solvent of toluene and ethanol) used is not particularly limited, but toluene is preferably used with respect to the compound (halogenated fluorene compound) represented by the formula (7). The amount is 0.1 times by weight or more, more preferably 0.5 to 100 times by weight, and further 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, if the amount of toluene used exceeds 100 times by weight, there is no effect commensurate with the amount used and the volume efficiency deteriorates, and the production cost of the compound having the fluorene skeleton may increase. The amount of ethanol used is also not particularly limited, but is preferably 0.1 to 50 times by weight, more preferably 1 to 20 times by weight that of the compound represented by the formula (7) (halogenated fluorene compound). 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 be reduced. Further, when the amount of ethanol used exceeds 50 times by weight, there is a case where the amount of ethanol is not equal to the amount used and the volume efficiency is deteriorated, and the production cost of the compound having the fluorene skeleton may be increased.

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

The reaction mixture after the reaction usually contains unreacted fluorenes, unreacted boronic acids, a base, a catalyst, a side reaction product, etc., in addition to the produced compound represented by the formula (1). ing. Therefore, by a conventional method, for example, filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or a metal removal treatment that is very similar thereto, separation means such as column chromatography, or a separation means combining these. Can be separated and purified. For example, boronic acids are removed by a conventional method (a method of forming a water-soluble complex by adding an alkaline aqueous solution), a palladium compound is removed by filtration, and then a recrystallization solvent is added to cool and recrystallize. You may refine|purify by making it convert 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 more, more preferably 80% or more, still more preferably 90% or more.

[Compound having 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 in which two aromatic hydrocarbons having at least one hydroxy group at the 9-position of fluorene are substituted or added. ..

（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。）

(In the formula, ring Z is an (identical or different) aromatic group, R ¹ and R ² are each independently a carbon atom which may include a hydrogen atom, a halogen atom and 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 and may have a substituent, L ¹ and L ² are alkylene groups, j and k are each independently an integer of 0 or more, m And n each independently represent an integer of 0 to 5.)

In the above formula (1), examples of the aromatic group represented by ring Z include a condensed polycyclic aromatic hydrocarbon having at least a benzene ring skeleton in addition to a benzene ring, and examples thereof include a condensed bicyclic hydrocarbon. Preferred are condensed bicyclic to tetracyclic hydrocarbon rings such as condensed tricyclic hydrocarbons.

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

Among ring Z, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.

As a specific example of the aromatic hydrocarbon ring represented by ring Z in the above formula (1), a 1,4-phenylene group, a 1,4-naphthalenediyl group or a 2,6-naphthalenediyl group is preferable, and A 4-phenylene group is more preferred.

The two rings Z substituting at the 9-position of the fluorene ring may be the same or different from each other, and the same ring is more preferable. In addition, the substituent of the ring Z that substitutes 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 substituting at the 9-position of the fluorene ring may be a 1-naphthyl group, a 2-naphthyl group or the like.

In the above formula (1), R ¹ and R ² 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, and a hydrogen atom or a methyl group. Alternatively, a phenyl group is preferable.

Examples of the hydrocarbon group represented by R ¹ and R ² in the above formula (1) include an alkyl group, a cycloalkyl group, an aryl group, a naphthyl group, and an aralkyl group. Specific examples of the alkyl group include a C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group, a C _1-4 alkyl group, and a C _1-3 alkyl group. Preferably, a C _1-3 alkyl group is more preferable, and among them, a methyl group or an ethyl group is even more preferable.

As specific examples of the cycloalkyl group, a C _5-8 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a C _5-6 cycloalkyl group and the like are preferable, and a C _5-6 cycloalkyl group is more preferable.

As specific examples of the aryl group, a phenyl group, an alkylphenyl group (mono- or dimethylphenyl group, a tolyl group, a 2-methylphenyl group, a xylyl group, etc.) and the like are preferable, and a phenyl group is more preferable.

As specific examples of the aralkyl group, a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group and a phenethyl group can be preferably exemplified.

Further, as the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and the like are preferable.

In the above formula (1), the number of substitutions 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 and the like, and is not particularly limited, and preferably 0 or more independently. More preferably, it is an integer of 1 or more. Further, it is preferably an integer of 6 or less, and more preferably an integer of 4 or less. The substitution numbers j and k may be the same or different in the ring Z, and are usually the same in many cases.

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

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

In the above formula (1), 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 from each other and may be the same, but they are usually the same. Further, the respective bonding 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. The third and sixth positions or the fourth and fifth positions are more preferable, and the second and seventh positions are further preferable.

Typical examples of the diol component represented by the above formula (1) are shown below, but the raw materials used in the above formula (1) of the present invention are not limited thereto.

The diphenylfluorene type includes 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- Preferred are hydroxy-2-naphthyl)-4,5-diphenylfluorene and the like.

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, Formula (1-b): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene, 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, Formula (1-g): 9,9-bis(4-hydroxyphenyl)-3,6-diphenylfluorene, Formula (1-h): 9,9-bis(4-hydroxyphenyl)-4,5 -Diphenylfluorene is more preferable, and in particular, 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.

Examples of the dinaphthylfluorene type include 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-dinaphthylfluorene and 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) Preferable examples include 4,5-dinaphthylfluorene and 9,9-bis(6-hydroxy-2-naphthyl)-4,5-dinaphthylfluorene.

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): 9,9-bis(4-hydroxyphenyl)-1,8-dinaphthylfluorene, Formula (2-f): 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 preferable, and in particular, the following formula (2-b): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene, The following formula (2-f): 9,9-bis(4-hydroxyphenyl)-2,7-dinaphthylfluorene is preferable.

The content of the palladium element in the compound having a fluorene skeleton of the present invention satisfies the following formula (3).
0 ≤ Pd ≤ 10ppm (3)
Preferably, the following expression (3-1) is satisfied.
0 ≤ Pd ≤ 5 ppm (3-1)
More preferably, the following expression (3-2) is satisfied.
0 ≤ Pd ≤ 3 ppm (3-2)
More preferably, the following expression (3-3) is satisfied.
0 ≤ Pd ≤ 1 ppm (3-3)
Exceeding the upper limit of the above range is not preferable because it adversely affects the hue of the resin using the raw material alcohol represented by the formula (1) and the optical member using the same.

Furthermore, in the compound having a fluorene skeleton of the present invention, in the compound represented by the above formula (1), the by-product represented by the following formula (4) is 3% or less, preferably 1% or less, 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 those in the above formula (1).)
The by-product represented by the following formula (4) is preferably a by-product represented by the following formula (4a), (4b) or (4c).

If the upper limit of the above range is exceeded, the productivity (or reactivity) of the resin using the raw material alcohol represented by the above formula (1) and various characteristics of the produced resin (heat resistance, moldability, dimensional stability, etc.) ) May be adversely affected, which is not preferable.

[Characteristics and applications of compounds having fluorene skeleton]
The compound having a fluorene skeleton of the present invention is preferably a combination of a diphenylfluorene skeleton or a dinaphthylfluorene skeleton and an arene ring, and thus not only has high refractive index and high heat resistance but also reduces birefringence when formed into a polymer. be able to. Up to now, a fluorene compound in which a ring-assembled arene ring is substituted at the 9-position of the fluorene skeleton has been used to improve the refractive index, but this has a high refractive index and high heat resistance, but the birefringence decreases. .. On the other hand, the compound having a fluorene skeleton of the present invention may have a diphenylfluorene skeleton, so that the birefringence becomes small despite the high refractive index. Furthermore, since the arene ring has one or more hydroxyl groups, and the entire fluorene compound has a plurality of hydroxyl groups, the reactivity is high. Therefore, the compound having a fluorene skeleton of the present invention can be used as a raw material (monomer) of various resins. For example, thermoplastic resin (eg, polyester resin, polycarbonate resin, polyester carbonate resin, polyurethane resin, etc.) or thermosetting resin (eg, epoxy resin, phenol resin, thermosetting polyurethane resin, (meth)acrylate ((meth)) Acrylic ester) and the like). When the compound having a fluorene skeleton of the present invention is used as a polyol component, the resulting resin has a high refractive index and a low refractive index, probably because the benzene ring is substituted at the 9-position of the fluorene skeleton and the fluorene skeleton has a diaryl group. It has an advantage that birefringence can be compatible with a high level.

Further, 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, further preferably 140 to 240°C, particularly preferably 150. ~ 210°C.

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 with the following devices and conditions.
Equipment used: Waters column: ACQUITY UPLC@BEH C18 2.1 x 150 mm
Eluent (volume): dimethylformamide: ultrapure water (0.1% by weight trifluoroacetic acid)=70/30
(2) NMR measurement The compounds and resins obtained in the examples were measured with the following devices and solvents.
Device: JEM-AL400 (400MHz) manufactured by JEOL Ltd.
Solvent: CDCl ₃
(3) ICP measurement The compounds obtained in the examples were measured by the following device.
Equipment used: Agilent Technologies
Device: Agilent 5100 ICP-OES
(4) Measurement of glass transition temperature (Tg) The resins obtained in the examples were measured with the following devices and conditions.
Device: Shimadzu Corporation DSC-60A
Conditions: temperature rising rate 20°C/min
(5) Measurement of pellet b* value The resin obtained in the example was measured by the following device.
Device: X-Rite integrating sphere spectrophotometer CE-7000A
(6) Refractive index (nD) and Abbe number measurement The resin obtained in the examples was measured by the following device and method.
Apparatus: ATAGO DR-M2 Abbe refractometer Method: Resin pellets obtained after completion of polymerization were 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 the Abbe number (calculated from the refractive index at wavelengths: 486 nm, 589 nm and 656 nm using the following formula) were measured.
ν=(nD-1)/(nF-nC)
In the present invention,
nD: refractive index at a wavelength of 589 nm,
nC: refractive index at a wavelength of 656 nm,
nF: means the refractive index at a wavelength of 486 nm.
(7) PL catalyst A palladium compound manufactured by NE Chemcat, which is abbreviated as Pd/SiO _2, and is a powdery solid catalyst in which palladium is supported on silica. This catalyst is specialized for the Suzuki coupling reaction, and when bromoaryls are used as substrates, the reaction proceeds in a ligand-free manner compared to the homogeneous palladium catalyst. Further, since it is supported on silica, it is a feature that Pd is little eluted in the product after the reaction.

[Example 1]
<Step 1>
A 500 mL flask equipped with a stirrer, a cooler, and a thermometer was charged with 150 g of toluene as a solvent, 12 tungst (VI) phosphoric acid nhydrate H ₃ [PW ₁₂ O ₄₀ ].nH ₂ O 2.19 g. Was azeotropically dehydrated under toluene reflux. After cooling the content, 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. The water produced by the reaction was stirred for 13 hours while being discharged out of the system. The progress of the reaction was appropriately confirmed by HPLC, and it was confirmed that the residual amount of DBFN was 0.1% by weight or less, and the reaction was terminated. Toluene 150g was added to the obtained reaction mixture, and it wash|cleaned 3 times with 300g of water. After washing, the organic layer was treated with activated carbon and then concentrated under reduced pressure to remove the solvent toluene and a large excess of 2-phenoxyethanol. The obtained mixture was recrystallized with methanol, and the precipitated crystals were collected by filtration and dried to obtain the desired product 9,9-bis(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene (hereinafter referred to as "target compound"). , BPDB) was obtained as a pale yellow crystal (36 g, yield 61%, purity 98%).

<Step 2>
In a 500 mL flask equipped with a stirrer, a condenser, and a thermometer, 17.9 g (0.03 mol) of BPDB obtained in Step 1, 11.4 g (0.066 mol) of 2-naphthaleneboronic acid, and further A PL catalyst 0.2 g (Pd conversion value: 200 ppm equivalent) manufactured by NE Chemcat Corporation, 150 g of toluene, and 35 mL of a 2M 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 it was confirmed that the residual amount of BPDB was 0.1% by weight or less, and 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 to each other was produced, and the selectivity for the target product was 98%. Next, the obtained reaction solution was cooled to room temperature, chloroform was added to completely dissolve the reaction product, and the solid derived from the palladium compound was collected by filtration. The recovered filtrate was washed 3 times with water, concentrated, and recrystallized from ethyl acetate/hexane to give the desired product 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-di 18.9 g (yield 91%, purity 98.7%) of white crystals of naphthylfluorene (hereinafter sometimes abbreviated as BPDN2) were obtained. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, when the HPLC of the final product was measured, the obtained white crystals did not contain the compound represented by the 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 sodium hydrogen carbonate 42. 0.0×10 ⁻⁵ parts by mass was placed in a reaction kettle equipped with a stirrer and a distillation device, and after nitrogen replacement was performed 3 times, the jacket was heated to 180° C. to melt the raw materials. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the jacket was heated to 260° C. at a rate of 60° C./hr to carry out a transesterification reaction. Then, while maintaining the jacket at 260° C., the pressure was reduced to 0.13 kPa over 50 minutes, and a polymerization reaction was performed under the conditions of 260° C. and 0.13 kPa or less until a predetermined torque was reached. After the completion of the reaction, the produced resin was pelletized and extracted to obtain polycarbonate resin pellets. The obtained polycarbonate resin was analyzed by ¹ H NMR, and it was confirmed that 50 mol% of the BPDN2 component was introduced with respect to all the monomer components. The obtained 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 was prepared in the same manner as in Example 1 except that 2-naphthaleneboronic acid in Step 2 was changed to 1-naphthaleneboronic acid. A white solid (hereinafter sometimes abbreviated as BPDN1) was obtained (yield 91%, purity 99.0%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4b) was 2%, and the selectivity for the target product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, when the HPLC of the final product was measured, the obtained white crystals did not contain the compound represented by the formula (4b).

[Example 3]
9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene (hereinafter, referred to as in Example 1) except that 2-naphthaleneboronic acid in step 2 was changed to phenylboronic acid. A white solid (sometimes abbreviated as BPDP) was obtained (yield 91%, purity 99.0%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4c) was 2% and the selectivity for the target product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, when the HPLC of the final product was measured, the obtained white crystals did not contain the compound represented by the formula (4c).

[Example 4]
A BPDP white solid 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%). .. By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4a) was 2% and the selectivity for the target product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, when the HPLC of the final product was measured, the obtained white crystals did not contain the compound represented by the 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%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4a) was 2% and the selectivity for the target product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, when the HPLC of the final product was measured, the obtained white crystals did not contain the compound represented by the formula (4a).

[Example 6]
A white solid of BPDN2 was obtained in the same manner as in Example 1 except that the acid catalyst used in Step 1 was previously dried under reduced pressure to remove water of crystallization, and a white solid was obtained (yield 89%, purity 99.0%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4a) was 2% and the selectivity for the target product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, when the HPLC of the final product was measured, the obtained white crystals did not contain the compound represented by the 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). 89%, purity 99.0%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4a) was 2% and the selectivity for the target product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, when the HPLC of the final product was measured, the obtained white crystals did not contain the compound represented by the 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 ]) obtained by previously drying the acid catalyst in step 1 under reduced pressure to remove water of crystallization was used. Rate 89%, purity 99.0%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4a) was 2% and the selectivity for the target product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, when the HPLC of the final product was measured, the obtained white crystals did not contain the compound represented by the 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%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4a) was 2% and the selectivity for the target product was 98%. When the amount of residual metal was measured by ICP, Pd was 3.0 ppm. Furthermore, when the HPLC of the final product was measured, the obtained white crystals did not contain the compound represented by the 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 activated carbon treatment was performed as Pd removal treatment ( Yield 88%, purity 97.9%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4a) was 16%, and the selectivity for the target product was 91%. When the amount of residual metal was measured by ICP, Pd was 30 ppm. Furthermore, when the HPLC of the final product was measured, the obtained pale yellow crystals contained 1% of the compound represented by the formula (4a).

In step 3, pellets of a polycarbonate resin were obtained in the same manner as in Example 1 except that BPDN2 synthesized by the above method was used. The obtained polycarbonate resin was analyzed by ¹ H NMR, and it was confirmed that 50 mol% of the BPDN2 component was introduced with respect to all the monomer components. The obtained 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 light yellow solid of BPDN2 was obtained in the same manner as in Comparative Example 1 except that the amount of tetrakis(triphenylphosphine)palladium was changed to 0.01 g (Pd conversion value: 40 ppm) (yield 85%, purity 98.5%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4a) was 5%, and the selectivity for the target product was 95%. When the amount of residual metal was measured by ICP, Pd was 12 ppm. Furthermore, when the HPLC of the final product was measured, the obtained light yellow crystals contained 0.5% of the compound represented by the formula (4a).

[Comparative Example 3]
A light 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%). By HPLC immediately after the completion of the coupling reaction, it was confirmed that the production rate of the compound (4a) was 16%, and the selectivity for the target product was 91%. When the amount of residual metal was measured by ICP, Pd was 600 ppm. Furthermore, when HPLC of the final product was measured, the obtained pale yellow solid contained 1% of the compound represented by the formula (4a).

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

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

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

Therefore, a compound having a fluorene skeleton or a derivative thereof of the present invention or a resin using a compound having a novel fluorene skeleton as a raw material (monomer) is, for example, a film, a lens, a prism, an optical disk, a transparent conductive substrate, an optical card, a sheet. It can be used as an optical member such as an optical fiber, an optical film, an optical filter, and a hard coat film, and is particularly useful for a lens.

Claims (19)

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

(In the formula, ring Z is an (identical or different) aromatic group, R ¹ and R ² are each independently a carbon atom which may include a hydrogen atom, a halogen atom and 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 and may have a substituent, L ¹ and L ² are alkylene groups, j and k are each independently an integer of 0 or more, m And n each independently represent an integer of 0 to 5.)
Using a palladium catalyst represented by the following formula (2),
Pd/SiO ₂ (2)
And the content of the palladium element in the obtained compound having a fluorene skeleton satisfies the following formula (3),
0 ≤ Pd ≤ 10ppm (3)
Furthermore, the by-product represented by the following formula (4) is produced within a range of 3% or less, and a method for producing a compound having a fluorene skeleton.
Ar ¹ -Ar ¹ , Ar ¹ -Ar ² or Ar ² -Ar ² (4)
(Ar ¹ and Ar ² are the same as those in the above formula (1).) 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 claim 1, 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 claim 1, wherein the formula (1) is one of formulas (1a) to (1d) below.

(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 the above formula (1).) The method for producing a compound having a fluorene skeleton according to claim 4, wherein the formula (1) is the formula (1b). The method for producing a compound having a fluorene skeleton according to claim 1, wherein Ar ¹ and Ar ² in the formula (1) are phenyl groups or naphthyl groups. The method for producing a compound having a fluorene skeleton according to claim 1, comprising at least the following step 1 and step 2 in the method for producing a compound having a fluorene skeleton represented by the formula (1).
Step 1: a step of reacting a fluorenone represented by the following formula (5) with a compound of an alcohol represented by the following formula (6) in a reaction solvent using an acid catalyst Step 2: the reaction produced in the step 1 A step of reacting the compound (7) with a boronic acid represented by the following formula (8) or (9) in a reaction solvent in the presence of a base and the palladium catalyst represented by the above formula (2).

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

(In the formula, Z is the same as the formula (1). R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms, and s is independently 0 or more. , And 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 those in the formula (5). Z, R ¹² , s, R ¹¹ and p are the same as those in the formula (6).)

(In the formula, Y represents an aromatic group, R ¹³ represents 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 is the same or It may be different.) The method for producing a compound having a fluorene skeleton according to claim 7, wherein the compound represented by the formula (5) is 2,7-dibromofluorenone. The method for producing a compound having a fluorene skeleton according to claim 7, wherein the compound represented by the formula (6) is 2-phenoxyethanol. The method for producing a compound having a fluorene skeleton according to claim 7, wherein the compound represented by the formula (7) is 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dibromofluorene). .. The method for producing a compound having a fluorene skeleton according to claim 7, wherein the compound represented by the formula (8) is 2-naphthaleneboronic acid, 1-naphthaleneboronic acid or phenylboronic acid. The method for producing a compound having a fluorene skeleton according to claim 7, wherein the compound represented by the formula (9) is an anhydride of 2-naphthaleneboronic acid, an anhydride of 1-naphthaleneboronic acid or an anhydride of phenylboronic acid. .. The fluorene skeleton according to claim 7, wherein the acid catalyst used in step 1 is a heteropoly acid composed of phosphoric acid or silicic acid and an oxygen acid ion of at least one element selected from vanadium, molybdenum and tungsten. A method for producing a compound having. The method for producing a compound having a fluorene skeleton according to claim 13, wherein the heteropolyacid is a heteropolyacid that has been dehydrated in advance or an anhydride of the heteropolyacid. The method for producing a compound having a fluorene skeleton according to claim 7, wherein toluene is used as a reaction solvent used in step 1. The method for producing a compound having a fluorene skeleton according to claim 7, wherein the base used in step 2 is potassium carbonate and/or sodium carbonate. The method for producing a compound having a fluorene skeleton according to claim 7, wherein toluene or a mixed solvent of toluene and ethanol is used as the reaction solvent used in step 2. A compound having a fluorene skeleton represented by the following formula (1),

(In the formula, ring Z is an (identical or different) aromatic group, R ¹ and R ² are each independently a carbon atom which may include a hydrogen atom, a halogen atom and 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 and may have a substituent, L ¹ and L ² are alkylene groups, j and k are each independently an integer of 0 or more, m And n each independently represent 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 ≤ 10ppm (3)
A compound having a fluorene skeleton, characterized in that the 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 those in the above formula (1).) The compound having a fluorene skeleton according to claim 18, which is used as a raw material for a thermoplastic resin.