Compound having a fluorene skeleton and method for producing the same

Abstract

To provide a compound having a new fluorene skeleton excellent in various characteristics (such as optical characteristics, heat resistance, and moldability) of a resin obtained by using the compound as a source material, and a production method of the compound.SOLUTION: A compound having a fluorene skeleton represented by formula (1) below is provided. In formula (1), R1 represents a hydrogen atom, a halogen atom or a hydrocarbon group which may contain an aromatic group having 1 to 12 carbon atoms; Ar1 and Ar2 each independently represent an aromatic group which may have a substituent having 6 to 12 carbon atoms; L1 represents an alkylene group having 1 to 12 carbon atoms; m1 and n1 may be the same or different and each represent an integer of 0 to 4; m2 and n2 may be the same or different and each represent an integer of 0 to 3, satisfying m1+m2≥1, however, m1+n1 is an integer of 4 or less, and m2+n2 is an integer of 3 or less; and o1 and o2 each independently represent an integer of 0 to 5.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound having a fluorene skeleton, which is suitable as a monomer for forming a thermoplastic resin constituting an optical member such as an optical lens or an optical film, and is suitable as a raw material for a thermoplastic resin having a high refractive index, low birefringence, and an excellent balance between heat resistance and moldability, and to a method for producing the compound. [Background technology]

[0002] In recent years, thermoplastic resin materials such as polycarbonates, polyesters, and polyester carbonates made from alcohols having a fluorene skeleton, such as 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), have been attracting attention as optical components such as optical lenses and optical sheets due to their excellent optical properties, heat resistance, and moldability.

[0003] For example, Patent Document 1 discloses a polycarbonate resin made from an alcohol having a BPEF skeleton. However, although it is stated that the refractive index of the polycarbonate resin using the alcohol is 1.64, there is a demand for further improvement in the above-mentioned properties due to the rapid technological innovation in recent years. In order to achieve a higher refractive index, Patent Document 2 has developed a thermoplastic resin made from 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPBPEF), but the resin described in the patent document still has room for improvement in refractive index. In addition, Patent Document 3 describes a high refractive index resin made from 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF), but although the refractive index is high, the birefringence is also high, which is a major problem when applied to transparent materials such as optical lenses. Thus, there is a trade-off between a high refractive index and low birefringence, and it has been difficult to achieve both properties with conventional polycarbonate or polyester resins.

[0004] Incidentally, as a method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), a method for dehydrating and condensing 9-fluorenone and 2-phenoxyethanol using sulfuric acid and thiols as catalysts (Non-Patent Document 1) has been disclosed. In addition, as a method for producing 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF), a method for dehydrating and condensing fluorenone and 2-naphthoxyethanol using sulfuric acid and thiols as catalysts, similar to BPEF, has been disclosed (Patent Document 4). Furthermore, as for 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPBPEF), a method for dehydrating and condensing fluorenone and 2-(2-biphenylyloxy)ethanol using sulfuric acid and thiols as catalysts, similar to BPEF and BNEF, has been disclosed (Patent Document 5). In addition, as a method for producing 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF), a method (Patent Document 6) has been disclosed in which 9-fluorenone and 2-naphthol are dehydrated and condensed in toluene and γ-butyrolactone under reduced pressure using phosphotungstic acid and n-dodecyl mercaptan instead of sulfuric acid as acid catalysts, and then ethylene carbonate is added directly without purification. However, both methods use a large amount of sulfuric acid or a small amount of n-dodecyl mercaptan as an acid catalyst, so complicated purification operations such as neutralization and purification after the reaction are required, and a large amount of neutralization wastewater is generated. In addition, problems such as coloration of the product, decreased stability, and decreased purity occur due to the sulfur components derived from the catalyst being mixed into the product. Furthermore, in order to obtain high-purity products such as optical resin materials, it is necessary to repeat purification operations to remove the sulfur components, and this cannot be said to be an industrially advantageous method. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2007 / 142149 Brochure [Patent Document 2] JP 2015-86265 A [Patent Document 3] JP 2017-171885 A [Patent Document 4] JP 2016-79405 A [Patent Document 5] JP 2009-256342 A [Patent Document 6] JP 2019-1780 A [Non-patent literature]

[0006] [Non-Patent Document 1] Chemistry Letters, 1998, pp. 1055-1056 Summary of the Invention [Problem to be solved by the invention]

[0007] The method for producing the compound of the following formula (1) molecularly designed in the present invention consists of two steps, but when the inventors of the present application used the method described in the above patent document in step 1, the reaction did not occur at all, or even if the reaction proceeded, the reaction rate was slow, which was industrially disadvantageous. Furthermore, if a large amount of catalyst was used in step 2, or if activated carbon treatment or a similar metal removal treatment was not performed, black particles derived from the palladium catalyst used in step 2 were mixed into the white compound having a fluorene skeleton represented by the following formula (1), and the hue of the alcohol compound was deteriorated.

[0008] Therefore, the present invention has been achieved as a result of studies to solve the problems of the above-mentioned conventional techniques, and aims to provide a novel compound having a fluorene skeleton, which is excellent in various properties (optical properties, heat resistance, moldability, etc.) of the resin obtained by using the compound as a raw material, and a method for producing the compound. Another aim is to provide a novel compound having a fluorene skeleton, which is preferably low in the content of a specific metal such as palladium, and which is excellent in the hue of the raw material or the resin using the raw material, and a method for producing the compound. [Means for solving the problem]

[0009] The present invention has been achieved as a result of research to solve the problems of the above-mentioned conventional techniques, and aims to provide a compound having a fluorene skeleton and a method for producing the same, which has a certain quality and is excellent as a polymer raw material. Specifically, the present invention relates to the following compound having a fluorene skeleton and a method for producing the same.

[0010] [1] A compound having a fluorene skeleton represented by the following formula (1): [ka]

[0011] (In the formula, R 1 is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; Ar 1 and Ar 2 each independently represents an aromatic group having 6 to 12 carbon atoms which may have a substituent; L 1 is an alkylene group having 1 to 12 carbon atoms, m1 and n1 are the same or different and are an integer of 0 to 4, m2 and n2 are the same or different and are an integer of 0 to 3, and m1+m2≧1, provided that m1+n1 is an integer of 4 or less, and m2+n2 is an integer of 3 or less. о1 and о2 each independently represent an integer of 0 to 5.

[0012] [2] The compound having a fluorene skeleton according to item 1 above, wherein the content of palladium element in the compound having a fluorene skeleton represented by formula (1) satisfies the following formula (2): 0≦Pd≦50ppm (2) [3] The compound having a fluorene skeleton according to the above item 1 or 2, wherein the compound represented by formula (1) has an APHA of 500 or less in a 5% by weight solution dissolved in dimethylformamide.

[0013] [4] The compound having a fluorene skeleton according to any one of items 1 to 3 above, wherein the formula (1) is one of the following formulae (1a) to (1d):

[0014] [ka]

[0015] [ka]

[0016] [ka]

[0017] [ka]

[0018] (In the formula, R 2 ~R 13 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group. 1 , Ar 2 , L 1 and o1 are the same as in formula (1) above.

[0019] [5] The compound having a fluorene skeleton according to item 4 above, wherein the formula (1) is the formula (1b). [6] Ar in the above formula (1) 1 and Ar 2 6. The compound having a fluorene skeleton according to any one of items 1 to 5 above, wherein

[0020] [7] The compound having a fluorene skeleton according to any one of items 1 to 6 above, wherein the formula (1) is a compound represented by formula (1-b): [ka]

[0021] [8] The compound according to item 7 above, wherein the compound represented by formula (1-b) has a diphenylfluorenone content of 0.2% or less. [9] A crystal of the compound according to item 7 above, which has an endothermic peak at 230 to 247°C in differential scanning calorimetry.

[10] A crystal of the compound according to the preceding paragraph 7, having peaks at diffraction angles 2θ of 10.6±0.2°, 10.8±0.2°, 17.1±0.2°, 17.6±0.2° and 18.7±0.2° in a powder X-ray diffraction pattern using Cu-Kα radiation.

[0022]

[11] A method for producing a compound having a fluorene skeleton represented by the above formula (1), comprising at least the following steps 1 and 2: Step 1: A step of reacting a fluorenone represented by the following formula (3) with a boronic acid represented by the following formula (4) or (5) in a reaction solvent in the presence of a base and a palladium catalyst: Step 2: A step of reacting the reactant (6) produced in step 1 with an alcohol represented by the following formula (7) in a reaction solvent in the presence of an acid catalyst under reduced pressure, and after the reaction, neutralizing the reactant represented by the following formula (8) obtained, without taking it out, reacting it with ethylene carbonate in the presence of a base to produce the target product.

[0023] [ka] (In the formula, 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.

[0024] [ka]

[0025] [ka] (Wherein, Y is an aromatic group, R 14 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a halogen atom. l is 0, 1, or 2. When l=2, R 14may be the same or different.)

[0026] [ka] (In the formula, Ar 1 and Ar 2 is the same as equation (1).

[0027] [ka] In the formula, p1 and p2 are the same or different and each represents an integer of 0 to 4; 1 , n1 and n2 are the same as in formula (1).

[0028] [ka] (In the formula, R 1 , Ar 1 and Ar 2 is the same as in formula (1). p1 and p2 are the same as in formula (7). n1 and n2 are integers from 0 to 3.

[0029]

[12] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein the compound represented by formula (3) is 2,7-dibromofluorenone.

[13] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein the compound represented by formula (4) is phenylboronic acid.

[14] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein the compound represented by formula (5) is an anhydride of phenylboronic acid.

[15] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein the compound represented by formula (6) is 2,7-diphenylfluorenone.

[16] The method for producing a compound having a fluorene skeleton according to item 11 above, wherein the compound represented by formula (7) is 2-naphthol.

[17] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein the compound represented by formula (8) is 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene.

[18] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein the palladium catalyst used in step 1 is a palladium catalyst represented by tetrakis(triphenylphosphine)palladium and / or Pd / SiO2.

[19] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein the base used in step 1 is potassium carbonate and / or sodium carbonate.

[20] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein a mixed solvent of toluene and ethanol is used as the reaction solvent in step 1.

[21] The method for producing a compound having a fluorene skeleton according to item 11 above, wherein the acid catalyst used in step 2 is a heteropolyacid composed of phosphoric acid or silicic acid and an oxyacid ion of at least one element selected from vanadium, molybdenum and tungsten.

[22] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein in step 2, a compound having a thiol group is used in combination with an acid catalyst.

[23] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein a mixed solvent of toluene and γ-butyrolactone is used as a reaction solvent in step 2.

[24] The method for producing a compound having a fluorene skeleton according to the above item 11, wherein a mixed solvent of toluene and ethylene carbonate is used as a reaction solvent in step 2.

[25] A method for using the compound having a fluorene skeleton according to item 1 above as a raw material for a thermoplastic resin. Effect of the Invention

[0030] The fluorene compound of the present invention not only has a ring assembly arene ring substituted at the 9-position of the fluorene ring, but also has a diaryl group (preferably at the 2- and 7-positions), and the thermoplastic resin made from the fluorene compound has excellent optical properties as well as various other properties (heat resistance, transparency, moldability, etc.). In addition, the fluorene compound of the present invention preferably has a low content of specific metals such as palladium and has excellent hue, so that the fluorene compound and the resin using the fluorene compound have excellent hue. Furthermore, in the present invention, a compound having a fluorene skeleton with such excellent properties can be efficiently produced. [Brief description of the drawings]

[0031] [Figure 1] FIG. 1 shows a differential scanning calorimetry (DSC) curve of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylfluorene obtained in Example 6. [Diagram 2] FIG. 1 is a powder X-ray measurement chart of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylfluorene obtained in Example 6. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] The present invention will be described in detail below, but the explanations of the constituent elements described below are representative examples of the embodiment of the present invention, and the present invention is not limited to these contents.

[0033] [Compounds with fluorene skeleton] The compound of the present invention is a compound having a fluorene skeleton represented by the following formula (1), i.e., a compound in which two aromatic hydrocarbons having at least one hydroxyl group are substituted or added to the 9-position of a fluorene.

[0034] [ka]

[0035] (In the formula, R1 is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms which may contain an aromatic group; Ar 1 and Ar 2 each independently represents an aromatic group having 6 to 12 carbon atoms which may have a substituent; L 1 is an alkylene group having 1 to 12 carbon atoms, m1 and n1 are the same or different and are an integer of 0 to 4, m2 and n2 are the same or different and are an integer of 0 to 3, and m1+m2≧1, provided that m1+n1 is an integer of 4 or less, and m2+n2 is an integer of 3 or less. о1 and о2 each independently represent an integer of 0 to 5.

[0036] In the above formula (1), specific examples of the naphthalene ring are preferably a 1,4-naphthalenediyl group or a 2,6-naphthalenediyl group, and more preferably a 2,6-naphthalenediyl group.

[0037] The two naphthalene rings that substitute at the 9th position of the fluorene ring may be the same or different, and are more preferably the same ring.The substituent of the naphthalene ring that substitutes at the 9th position of the fluorene skeleton is not particularly limited.For example, in the case of a naphthalene ring, the group corresponding to the naphthalene ring that substitutes at the 9th position of the fluorene ring may be a 1-naphthyl group, a 2-naphthyl group, etc.

[0038] In the above formula (1), R 1 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.

[0039] In the above formula (1), R 1 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, a naphthyl group, and an aralkyl group. Specific examples of the alkyl group include C 1, C 2, C 3, C 4, C 5, C 6, C 7, C 8, C 9, C 10, C 11, C 12, C 13, C 14, C 15, C 16, C 17, C 18, C 19, C 20, C 21, C 22, C 23, C 24, C 25, C 36, C 26, C 37, C 38, C 41, C 42, C 43, C 44, C 45, C 51, C 52, C 65, C 72, C 73, C 74, C 75, C 76, C 77 1-6 Alkyl group, C 1-4 Alkyl group, C 1-3 Alkyl groups are preferred, C 1-3More preferred are alkyl groups, of which methyl or ethyl groups are even more preferred.

[0040] Specific examples of the cycloalkyl group include cyclopentyl and cyclohexyl groups. 5-8 Cycloalkyl groups, C 5-6 Cycloalkyl groups are preferred, and C 5-6 Cycloalkyl groups are more preferred.

[0041] Specific examples of the aryl group include preferably a phenyl group, an alkylphenyl group (such as a mono- or dimethylphenyl group, a tolyl group, a 2-methylphenyl group, and a xylyl group), and more preferably a phenyl group.

[0042] Specific examples of aralkyl groups include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Preferred examples include alkyl groups. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are preferred.

[0043] In the above formula (1), the substituent R 1 The substitution numbers n1 and n2 can be appropriately selected depending on the number of condensed rings of the condensed hydrocarbon, are not particularly limited, and are preferably each independently an integer of 0 or more, more preferably an integer of 1 or more. Note that the substitution numbers n1 and n2 may be the same or different in the naphthalene ring, and are usually the same in many cases.

[0044] In the above formula (1), L 1 represents a divalent linking group, which is preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an ethylene group. 1 may be the same alkylene group in the same naphthalene ring. 1 may be the same or different in different naphthalene rings, and usually may be the same.

[0045] Oxyalkylene group (OL 1The numbers (number of moles added) o1 and o2 can each be selected from the range of 0 to 5, with the lower limit being preferably 0 or more and the upper limit being preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. Particularly preferred are 0 or 1, and most preferably 1. Note that o1 and o2 may be integers or average values, and may be the same or different in different naphthalene rings. Also, it is preferred that m1 is 1 and m2 is 0.

[0046] In the above formula (1), Ar 1 and Ar 2 each independently represents an aromatic group having 6 to 10 carbon atoms, and a phenyl group or a naphthyl group is preferable. 1 and Ar 2 They may be different from each other or may be the same, but are usually the same. 1 and Ar 2 The bonding positions of each of the above are preferably the 1-position and the 8-position, the 2-position and the 7-position, the 3-position and the 6-position, or the 4-position and the 5-position, more preferably the 2-position and the 7-position, the 3-position and the 6-position, or the 4-position and the 5-position, and further preferably the 2-position and the 7-position.

[0047] Representative 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.

[0048] The diphenylfluorene type includes 9,9-bis(6-hydroxy-2-naphthyl)-1,8-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-diphenylfluorene, 9,9-bis[6-(2- Preferred examples of the fluorene include 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-1,8-diphenylfluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylfluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-3,6-diphenylfluorene, and 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-4,5-diphenylfluorene. Among these, the following formulas (1-a) to (1-b) are more preferred, including the following formula (1-a): 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene and the following formula (1-b): 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylfluorene, and the following formula (1-b): 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene is particularly preferred.

[0049] [ka]

[0050] [ka]

[0051] Dinaphthylfluorene types include 9,9-bis(6-hydroxy-2-naphthyl)-1,8-di(1-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(1-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-di(1-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-di(1-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-di(1-naphthyl)fluorene, and 9,9-bis(6-hydroxy-2-naphthyl)-1,8-di(1-naphthyl)fluorene. 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-1,8-di(1-naphthyl)fluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-di(1-naphthyl)fluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-3,6-di(1-naphthyl)fluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-4,5-di(1-naphthyl)fluorene fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-1,8-di(2-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-3,6-di(2-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-4,5-di(2-naphthyl)fluorene, 9,9-bis[6-(2-hydroxyethoxy) Preferred examples thereof include 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-1,8-di(2-naphthyl)fluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-di(2-naphthyl)fluorene, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-3,6-di(2-naphthyl)fluorene, and 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-4,5-di(2-naphthyl)fluorene. Among them, the following formulas (2-a) to (2-b) are more preferred, including the following formula (2-a): 9,9-bis(6-hydroxy-2-naphthyl)-2,7-di(2-naphthyl)fluorene and the following formula (2-b): 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-di(2-naphthyl)fluorene, and the following formula (2-b): 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-di(2-naphthyl)fluorene is particularly preferred.

[0052] [ka]

[0053] [ka]

[0054] In the compound having a fluorene skeleton of the present invention, the content of palladium element preferably satisfies the following formula (2). 0≦Pd≦50ppm (2) More preferably, the following formula (2-1) is satisfied. 0 ≦ Pd ≦ 25 ppm (2-1) More preferably, the following formula (2-2) is satisfied. 0 ≦ Pd ≦ 10 ppm (2-2) Even more preferably, the following formula (2-3) is satisfied. 0 ≦ Pd ≦ 5 ppm (2-3) It is particularly preferable that the following formula (2-4) is satisfied. 0 ≦ Pd ≦ 3 ppm (2-4) Most preferably, the following formula (2-5) is satisfied. 0 ≦ Pd ≦ 1 ppm (2-5)

[0055] If the content exceeds the upper limit of the above range, it may have an adverse effect on the color of the resin using the raw material alcohol represented by the formula (1) and on the optical components using the resin. The lower limit of the palladium element content may be 0.01 ppm or more, 0.05 ppm or more, or 0.10 ppm or more.

[0056] The compound having a fluorene skeleton of the present invention preferably has an APHA of 500 or less, more preferably 200 or less, and even more preferably 100 or less, in a 5 wt % solution dissolved in dimethylformamide. If the APHA is more than 500, it may adversely affect the hue of the resin using the raw material alcohol represented by the formula (1) or the optical member using the resin.

[0057] The compound having a fluorene skeleton of the present invention is particularly preferred among the compounds represented by the formula (1-b), and the content of diphenylfluorenone in the compound represented by the formula (1-b) is preferably 0.2% or less, more preferably 0.1% or less, and even more preferably 0.05% or less. If the content of diphenylfluorenone is more than 0.2%, it may have an adverse effect on the hue of the resin using the raw material alcohol represented by the formula (1) and on the optical members using the resin.

[0058] [Polymorphic forms of binaphthalene compounds] The crystal of the compound represented by the formula (1-b) of the present invention preferably has an endothermic peak in the range of 230 to 247°C by differential scanning calorimetry. In addition, the crystal has characteristic peaks at diffraction angles 2θ of 10.6±0.2°, 10.8±0.2°, 17.1±0.2°, 17.6±0.2°, and 18.7±0.2° in a powder X-ray diffraction pattern using Cu-Kα radiation. In addition, the crystal preferably has a maximum peak at a diffraction angle 2θ of 10.8±0.2°. The crystal of the compound represented by the formula (1-b) of the present invention is easy to handle and has good hue and purity.

[0059] [Method of producing a compound having a fluorene skeleton] The method for producing a compound having a fluorene skeleton of the present invention is roughly divided into two steps. The compound can be produced by a first step 1 in which a fluorenone represented by the following formula (3) is reacted with a boronic acid represented by the following formula (4) or (5) in the presence of a palladium catalyst and a base, and a second step 2 in which a reactant (6) produced in the step 1 is reacted with an alcohol compound represented by the following formula (7) in the presence of an acid catalyst (preferably in the presence of an acid catalyst and a thiol compound) under reduced pressure in the reaction system while discharging by-product water out of the system, and then neutralizing the product after completion of the reaction, and reacting the product with ethylene carbonate by adding a basic catalyst without taking out the product (8).

[0060] In the above production method, in step 1, the reactivity of the boronic acids represented by the following formula (4) or (5) is high and side reactions do not occur, and in step 2, the use of a thiol-based compound in combination increases the reaction rate compared to when a thiol-based compound is not used, and by-product water can be efficiently expelled by reducing the pressure in the system. As a result, the reaction is fast, the production of by-products is suppressed, and the reaction can be carried out in the same reaction vessel without removing the reactant (8). As a result, the amount of solvent used is reduced, and the compound having a fluorene skeleton of the present invention can be efficiently produced at low cost.

[0061] Step 1: [ka] (In the formula, 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.

[0062] [ka]

[0063] [ka] (Wherein, Y is an aromatic group, R 14 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, or a halogen atom. l is 0, 1, or 2. When l=2, R 14 may be the same or different.)

[0064] Step 2: [ka] (In the formula, Ar 1 and Ar 2 is the same as equation (1).

[0065] [ka] In the formula, p1 and p2 are the same or different and each represents an integer of 0 to 4; 1 , n1 and n2 are the same as in formula (1).

[0066] [ka] (In the formula, R 1 , Ar 1 and Ar 2 is the same as in formula (1). p1 and p2 are the same as in formula (7). n1 and n2 are integers from 0 to 3.

[0067] The compound represented by the above formula (3) is a fluorenone compound corresponding to the fluorene skeleton in the above formula (1), and 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; X 1 and X 2 Both represent a halogen atom. Representative examples of the fluorenone compound represented by the above formula (3) are shown below, but the raw material used in the above formula (1) of the present invention is not limited thereto.

[0068] Specific examples include 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-dibromofluorenone, 3,6-dibromofluorenone, 4,5-dibromofluorenone, etc. 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 may be arbitrarily selected depending on the purpose. In the present invention, 2,7-dibromofluorenone is preferred.

[0069] The purity of the fluorenones represented by the formula (3) used is not particularly limited, but is usually preferably 95% or more, more preferably 99% or more. The fluorenones may be commercially available or synthesized. For example, a method for producing dibromofluorenones may include the method described in non-patent literature (Journal of American Chemical Society, 2017, Vol. 139, 11073-11080), that is, a method of reacting 9-fluorenone with bromine in water.

[0070] The ring Y of the compound represented by the above formula (4) or (5) is a group Ar 1 and Ar 2 In addition, in the formulas (4) and (5), the group R 14 A preferred embodiment of the R 1 The preferred embodiments of l are the same as the preferred embodiments of n1 and n2.

[0071] The purity of the boronic acids used is not particularly limited, but is usually preferably 95% or more, more preferably 99% or more. The boronic acids may be commercially available or synthesized. Examples of methods for producing boronic acids include the method described in Patent Document (JP Patent Publication 2002-47292 A), that is, a method of reacting a phenyl Grignard reagent with a boric acid ester dissolved in a non-ether aromatic solvent.

[0072] The boronic acids used in the present invention include alkylboronic acids, alkenylboronic acids, arylboronic acids, and heteroarylboronic acids represented by the above formulas (4) and (5), and their anhydrides. Examples of alkylboronic acids include 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, pentylboronic acid, 2-phenylethylboronic acid, and their anhydrides. Rarely, alkenylboronic acids include 1-cyclopentenylboronic acid, ferroceneboronic acid, 1,1'-ferrocenediboronic acid and their anhydrides, while arylboronic acids include 2-anthraceneboronic acid, 9-anthraceneboronic acid, benzylboronic acid, 2-biphenylboronic acid, 3-biphenylboronic acid, 4-biphenylboronic acid, 2,3-dimethylphenylboronic acid, 2,4-dimethylphenylboronic acid, 2,5-dimethylphenylboronic acid, 2,6-dimethylphenylboronic acid, 3,4-dimethylphenylboronic acid, 3,5-Dimethylphenylboronic acid, 2-ethoxyphenylboronic 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-(naphthalene-1- Examples of boronic acids include 10-(naphthalene-2-yl)-9-anthraceneboronic acid, 10-(naphthalene-2-yl)-9-anthraceneboronic acid, and their anhydrides, and examples of heteroarylboronic acids include benzofuran-2-boronic acid, 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-boronic 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-thiopheneboronic acid, 3-thiopheneboronic acid, 5-pyrimidineboronic acid, and their anhydrides.

[0073] These may be used alone or in combination of two or more, and may be selected arbitrarily depending on the purpose. In the present invention, preferred are phenylboronic acid, 2-naphthaleneboronic acid or anhydride thereof, and particularly preferred is phenylboronic acid or anhydride thereof.

[0074] The ratio of the compound represented by the formula (4) used as a raw material may be preferably 2 to 5 moles, more preferably 2.05 to 3.0 moles, and even more preferably about 2.1 to 2.5 moles, relative to 1 mole of the compound represented by the formula (3) (halogenated fluorenone compound). If the boronic acid is less than 2 moles, the yield of the product represented by the formula (6) may be low. If it exceeds 5 moles, the reaction rate is high and the yield is high, but the production cost of the compound having the fluorene skeleton may increase.

[0075] The ratio of the compound represented by the formula (5) to be used may be preferably 0.7 to 5 moles, more preferably 0.8 to 3 moles, and even more preferably about 1 to 2 moles, relative to 1 mole of the compound represented by the formula (3) (halogenated fluorenone compound). If the boronic acid is less than 0.7 moles, the yield of the product represented by the formula (6) may be low. If it exceeds 5 moles, the reaction rate is high and the yield is high, but the production cost of the compound having the fluorene skeleton may increase. The reaction (dehalogenation reaction) of the compound represented by the formula (3) with the compound represented by the formula (4) and / or (5) in step 1 can be carried out in a reaction solvent in the presence of a base and a catalyst.

[0076] Examples of the base used in the reaction of step 1 include hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate (Na2CO3), potassium carbonate (K2CO3), and cesium carbonate (Cs2CO3), acetates such as sodium acetate and potassium acetate, phosphates such as sodium phosphate (Na3PO4) and potassium phosphate (K3PO4), and other inorganic salts, as well as organic salts such as triethylamines, pyridine, morpholine, quinoline, piperidine, anilines, and ammonium salts such as tetra-n-butylammonium acetate. Among these, carbonates are preferably used, and potassium carbonate and / or sodium carbonate are preferred. Such bases may be used alone or in combination of two or more. In the reaction of step 1, the amount of the base used is not particularly limited, but is preferably 1 to 30 equivalents, more preferably 1 to 10 equivalents, per mole of the boronic acid.

[0077] The palladium catalyst used in the reaction of step 1 is preferably a palladium compound used in Suzuki coupling, such as tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, palladium acetate, tris(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, and palladium catalysts represented by Pd / SiO2. Among these, tetrakis(triphenylphosphine)palladium and / or palladium catalysts represented by Pd / SiO2 are preferred. Such palladium catalysts may be used alone or in combination of two or more.

[0078] In the reaction of step 1, the amount of the catalyst used is not particularly limited, but is preferably 0.1 to 10 mmol, more preferably 0.5 to 5 mmol, in terms of palladium metal atom, relative to 1 mole of the fluorenone compound represented by the formula (3). 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. In addition, when the amount of the palladium catalyst used is more than 10 mmol in terms of palladium metal atom, the reaction is completed, but it is difficult to make the palladium element content in the compound having a fluorene skeleton within the range of formula (2), which may deteriorate the hue of the thermoplastic resin produced using the alcohol raw material, and may also increase the production cost of the compound having a fluorene skeleton.

[0079] The reaction solvent used in step 1 is not particularly limited, and may be, for example, an aromatic hydrocarbon solvent such as toluene or xylene, or an alcohol such as methanol, ethanol, isopropyl alcohol, or n-butanol, used alone or in combination. Aromatic hydrocarbon solvents are high-boiling point solvents, so the reaction temperature can be set high, and alcohols have good affinity with water and good reactivity, so they are preferably used. Such solvents may be used alone or in combination of two or more. Furthermore, aprotic solvents such as N,N-dimethylformamide or N,N-dimethylacetamide, and halobenzenes such as o-dichlorobenzene may also be used. Such solvents may be used alone or in combination of two or more. In the present invention, a mixed solvent of toluene and ethanol is more preferable.

[0080] The amount of the reaction solvent (mixed solvent of toluene and ethanol in the present invention) is not particularly limited, but the amount of toluene is preferably 0.1 times by weight or more, more preferably 0.5 to 100 times by weight, and even more preferably 1 to 50 times by weight, relative to the fluorenones represented by the formula (3). If the amount of toluene used is less than 0.1 times by weight, the product may precipitate and stirring may become difficult. If the amount of toluene used exceeds 100 times by weight, there may be no effect commensurate with the amount used, the volumetric efficiency may deteriorate, and the production cost of the compound having the fluorene skeleton may increase. The amount of ethanol used is also not particularly limited, but it is preferably 0.1 to 50 times by weight, and more preferably 1 to 20 times by weight, relative to the fluorenones represented by the formula (3). If the amount of ethanol used is less than 0.1 times by weight, there may be a possibility that the reaction rate is slow and the yield may decrease. If the amount of ethanol used exceeds 50 times by weight, there may be no effect commensurate with the amount used, similar to toluene, and the volumetric efficiency may deteriorate, and the production cost of the compound having the fluorene skeleton may increase.

[0081] The reaction temperature varies depending on the types of raw materials and 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 monitored by an analytical means such as liquid chromatography.

[0082] The reaction mixture after the reaction is completed usually contains unreacted fluorenones, unreacted boronic acids, bases, catalysts, by-products, etc., in addition to the compound represented by the formula (6) produced. Therefore, it can be separated and purified by a conventional method, such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or a similar metal removal treatment, column chromatography, or a combination of these. For example, it may be purified by removing boronic acids by a conventional method (such as a method of adding an alkaline aqueous solution to form a water-soluble complex), removing palladium compounds by activated carbon treatment or a similar metal removal treatment, adding a recrystallization solvent, cooling, and recrystallizing, and then filtering and separating.

[0083] The alcohols represented by the formula (7) correspond to the (poly)hydroxyl group-containing arene ring substituted at the 9-position in the diarylfluorene derivative represented by the formula (6). That is, the naphthalene ring in the formula (7) is the naphthalene ring in the formula (1) with R 1 , n1 and n2 are R in the formula (1) 1 , n1 and n2.

[0084] Specific examples of the compound represented by the formula (7) include naphthols (e.g., naphthol (1-naphthol, 2-naphthol), naphthols having a hydrocarbon group (methyl naphthol, ethyl naphthol, dimethyl naphthol, propyl naphthol, butyl naphthol (C 1-4 Alkyl naphthols (such as alkyl naphthols), alkoxynaphthols (such as ethoxynaphthols), 1-4Alkoxynaphthols), halonaphthols (chloronaphthols, bromonaphthols), polyhydroxynaphthalenes corresponding to these naphthols (or monohydroxynaphthalenes) (for example, di- or trihydroxynaphthalenes such as 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,2,4-trihydroxynaphthalene, and 1,3,8-trihydroxynaphthalene) can be mentioned. Among them, 1-naphthol and 2-naphthol are preferred, and 2-naphthol is particularly preferred.

[0085] These alcohols may be used alone or in combination with the fluorenones, and may be selected arbitrarily depending on the purpose. In the present invention, 2-naphthol is preferred.

[0086] In the reaction of step 2, the amount of the alcohol represented by the above formula (7) used is not particularly limited, but from the viewpoints of suppressing side reactions and economic efficiency, it is preferably 2 to 20 mol, more preferably 2.1 to 10 mol, and even more preferably 2.3 to 5 mol per mol of the fluorenones.

[0087] The alcohols represented by the above formula (7) may be commercially available products or may be synthesized. For example, a method for producing naphthols includes a method described in a patent document (JP Patent Publication 61-115039 A), that is, a method in which 2-naphthalenesulfonic acid obtained by sulfonating naphthalene is neutralized with an alkali to obtain sodium 2-naphthalenesulfonate, and the product is dissolved in an alkali to obtain an alkali salt, which is then hydrolyzed to produce 2-naphthol.

[0088] The purity of the alcohols represented by the above formula (7) (eg, naphthols) used as raw materials is not particularly limited, but is usually preferably 95% or more, more preferably 99% or more.

[0089] The reaction in step 2 can usually be carried out in the presence of an acid catalyst. Examples of the acid catalyst include sulfuric acid, thiolic acid, montmorillonite, and heteropolyacid. Among these, heteropolyacid is particularly preferred because it generates less impurities derived from the acid catalyst and is easy to obtain the compound having a fluorene skeleton of the present invention.

[0090] 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, and various heteropolyacids are possible by combining a central oxyacid with another oxyacid that condenses around it. The elements that form the central oxyacid in small numbers are called heteroelements, and the elements that form the oxyacids that condense around it are called polyelements. The polyelements may be a single type of element or multiple types of elements.

[0091] The hetero element of the oxygen acid constituting the heteropoly acid is not particularly limited, and examples thereof 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, irodium, and platinum. Phosphorus (phosphoric acid) or silicon (silicic acid) is preferred. The poly element of the oxygen acid constituting the heteropoly acid is not particularly limited, and examples thereof include vanadium, molybdenum, tungsten, niobium, and tantalum. At least one element selected from vanadium, molybdenum, and tungsten is preferred.

[0092] The heteropolyacid anion constituting the heteropolyacid skeleton may have a variety of compositions. For example, XM 12 O 40 , X.M. 12 O 42 , X.M. 18 O 62 , XM6O 24The preferred composition of the heteropoly acid anion is XM 12 O 40 In each formula, X is a hetero element and M is a poly element. Specific examples of heteropolyacids having these compositions include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid.

[0093] 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. Therefore, the heteropolyacid referred to in the present invention also includes the salts of these heteropolyacids. Examples of the cations that can replace the protons include ammonium, alkali metals, and alkaline earth metals.

[0094] The heteropolyacid may be an anhydride or may contain water of crystallization, but an anhydride is preferred because it reacts faster and suppresses the generation of by-products. In the case of a compound containing water of crystallization, the same effect as that of an anhydride can be obtained by previously carrying out a dehydration treatment such as drying under reduced pressure or azeotropic dehydration with a solvent. The heteropolyacid may be used in a form supported on a carrier such as activated carbon, alumina, silica-alumina, or diatomaceous earth.

[0095] These heteropolyacids may be used alone or in combination of two or more kinds. If necessary, a catalyst other than the heteropolyacid may be used in combination within a range that does not impair the object of the present invention.

[0096] 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 by weight or more, more preferably 0.001 to 30 times by weight, and even more preferably 0.01 to 5 times by weight relative to the amount of fluorenone.

[0097] When carrying out the present invention, the reaction rate can be improved and the generation of impurities can be suppressed by using a compound having a thiol group (hereinafter sometimes abbreviated as SH group) together with the heteropolyacid in the reaction of step 2. Examples of thiol compounds that can be used in combination in the present invention include mercaptocarboxylic acids, alkanethiols, and salts thereof.

[0098] Examples of mercaptocarboxylic acids include α-mercaptopropionic acid, β-mercaptopropionic acid, thioacetic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, and mercaptobenzoic acid. Examples of alkanethiols include C thiol, methanethiol, ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-butanethiol, 1-pentanethiol, 2-pentanethiol, 1-hexanethiol, 1-heptanethiol, 2-heptanethiol, 1-octanethiol, 2-octanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol, and 1-dodecanethiol. 1-16 Among such compounds having an SH group, β-mercaptopropionic acid and 1-dodecanethiol are preferred, and 1-dodecanethiol is particularly preferred, since they are inexpensively available. Such compounds having an SH group may be used alone or in combination of two or more kinds.

[0099] The method for carrying out the reaction in step 2 is not particularly limited, but can usually be carried out by charging the compounds represented by the formulas (6) and (7) and the heteropolyacid and / or thiol compound into a reaction apparatus, and heating and stirring in the presence of aromatic hydrocarbons such as toluene and xylene and inert solvents such as ethyl acetate and γ-butyrolactone in air or in an inert gas atmosphere such as nitrogen or argon. In this case, by carrying out the reaction under dehydration conditions that remove water in the reaction system, such as catalyst-containing water and reaction product water, the reaction proceeds faster than in the absence of dehydration, the production of by-products is suppressed, and the target product can be obtained in a higher yield. The dehydration method is not particularly limited, but examples thereof include dehydration by adding a dehydrating agent, dehydration by reduced pressure, and dehydration by azeotropy with a solvent under normal pressure or reduced pressure.

[0100] The reaction solvent used in step 2 is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene, aliphatic hydrocarbon solvents such as pentane, hexane and heptane, 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, butyl acetate, γ-butyrolactone and ethylene carbonate, nitrile solvents such as acetonitrile, propionitrile, butyronitrile and benzonitrile, and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and 1-methyl-2-pyrrolidinone. Preferred are aromatic hydrocarbon solvents and ester solvents, more preferred are mixed solvents of toluene, xylene, chlorobenzene or dichlorobenzene with ethyl acetate, butyl acetate, γ-butyrolactone or ethylene carbonate, and further preferred are mixed solvents of toluene with γ-butyrolactone or ethylene carbonate. These reaction solvents may be used alone or in combination of two or more.

[0101] The amount used is not particularly limited, but from the economical point of view, it is preferably 0.1 times by weight or more, more preferably 0.5 to 100 times by weight, and even more preferably 1 to 20 times by weight relative to the diphenylfluorenone represented by the above formula (6).

[0102] The reaction temperature in step 2 varies depending on the types of raw materials and solvent used, but is preferably 50 to 300° C., more preferably 80 to 250° C., and even more preferably 100 to 180° C. The reaction can be monitored by an analytical means such as liquid chromatography.

[0103] The internal pressure during the reaction in step 2 is preferably 101.3 kPa or less, more preferably 60.0 kPa or less. It is preferable to carry out the reaction while discharging the by-produced water from the system at this internal pressure, because this makes the reaction proceed more efficiently and reduces the amount of by-products produced.

[0104] After the reaction in step 2, the solid acid used may be removed by filtration or neutralized as necessary. Examples of bases used in neutralization include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, alkali metal or alkaline earth metal carbonates (hydrogen carbonates) such as potassium carbonate, calcium carbonate, sodium carbonate, and sodium carbonate, and amines.

[0105] In the reaction of step 2, the reaction solution after neutralization can be used for the reaction with ethylene carbonate without removing the salt generated by neutralization. If necessary, the salt generated by neutralization may be separated from the reaction system by filtering, or by adding water, stirring, leaving to stand, and then separating and removing the water layer (sometimes referred to as a water-washing step). This water-washing step may be carried out repeatedly as necessary.

[0106] In step 2, after reacting the reactant (6) produced in step 1 with the alcohol represented by the above formula (7), it can be reacted with ethylene carbonate without isolating the fluorene compound represented by the above formula (8). If the fluorene compound represented by the above formula (8) is isolated by a method such as concentration or crystallization, the yield may decrease, resulting in an increase in costs.

[0107] In step 2, ethylene carbonate is usually used in an amount of 2 to 10 mol, more preferably 2 to 5 mol, per mol of diphenylfluorenone represented by the above formula (6) used in step 1.

[0108] In step 2, when the fluorene compound represented by the above formula (8) is reacted with ethylene carbonate, the reaction may be carried out in the presence of a basic compound as necessary. When the reaction is carried out in the presence of a basic compound, it is preferable that the solid acid used in step 1 is separated by filtration or neutralized before carrying out step 2.

[0109] Examples of the basic compound that can be used in step 2 include carbonates, hydrogen carbonates, hydroxides, organic bases, etc. Examples of carbonates include potassium carbonate, sodium carbonate, cesium carbonate, lithium carbonate, etc. Examples of hydrogen carbonates include potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, etc. Examples of hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. Examples of organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride, etc.

[0110] Among the above basic compounds, potassium carbonate and sodium carbonate are preferably used from the viewpoints of ease of handling and safety. These basic compounds may be used alone or in combination of two or more kinds.

[0111] When a basic compound is used in step 2, the amount used is usually 0.01 to 1.0 mol, and preferably 0.03 to 0.5 mol, per 1 mol of diphenylfluorenone represented by the above formula (6) used in step 1.

[0112] After the reaction of step 2 is completed, the reaction mixture obtained may be added with a dilution solvent to precipitate the compound represented by the formula (1) as it is, or may be subjected to post-treatment such as washing, concentration, dilution, activated carbon treatment, etc., and then the compound represented by the formula (1) may be precipitated at less than 50 ° C. The operation of precipitating the compound represented by the formula (1) from the reaction mixture that has been subjected to the above-mentioned post-treatment as necessary is carried out by heating the reaction mixture, which has been mixed with a solvent as necessary, to 50 ° C. or higher and the boiling point of the solvent or lower (preferably 70 to 110 ° C.), and cooling it to less than 50 ° C. If crystals of the compound represented by the formula (1) precipitate from the reaction mixture at 50 ° C. or higher, the reaction mixture may be mixed with a dilution solvent in an amount that does not precipitate crystals at 50 ° C. or higher, and then the resulting mixture may be heated to 50 ° C. or higher and the boiling point of the solvent or lower (preferably 70 to 110 ° C.), and cooled to less than 50 ° C. Examples of the dilution solvent include those exemplified as the solvent used in the above reaction, alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, isobutanol, and pentanol, carbonate solvents such as dimethyl carbonate, diethyl carbonate, ester solvents such as ethyl acetate, butyl acetate, γ-butyrolactone, butyl benzoate, methyl benzoate, and phenyl acetate, ether solvents such as diethyl ether, di-iso-propyl ether, methyl-tert-butyl ether, diphenyl ether, and tetrahydrofuran, and aliphatic hydrocarbon solvents such as hexane, heptane, octane, and pentane, with methanol, ethanol, or dimethyl carbonate being preferred, and methanol and ethanol being more preferred.

[0113] Such a crystallization procedure may be carried out once or may be repeated several times. In particular, if an alcohol such as methanol or ethanol is used in the reaction of the step 2, impurities such as unreacted 2-naphthol and by-produced ethylene glycol mono(2-naphthyl) ether can be easily and efficiently removed, so that the compound represented by the formula (1) that satisfies the formula (2) can be obtained even by a single crystallization procedure.

[0114] The precipitated crystals are collected by filtration, etc. The obtained crystals may be washed with the solvent used in the above reaction, etc., or may be dried. The purity of the purified product of the compound represented by the formula (1) thus obtained is preferably 95% or more.

[0115] 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%, and is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.

[0116] [Characteristics and uses of compounds with fluorene skeleton] The compound having a fluorene skeleton of the present invention preferably combines a diphenylfluorene skeleton and a dinaphthylfluorene skeleton with an arene ring, and therefore not only has a high refractive index and heat resistance, but also reduces birefringence when made into a polymer. In the past, in order to improve the refractive index, a fluorene compound in which a ring-assembly arene ring is substituted at the 9th position of the fluorene skeleton has been used, but this has a high refractive index and heat resistance but a low birefringence. In contrast, the compound having a fluorene skeleton of the present invention has a low birefringence despite its high refractive index, probably because it has a diphenylfluorene skeleton and a dinaphthylfluorene skeleton. Furthermore, the arene ring has one or more hydroxyl groups, and the fluorene compound as a whole has multiple hydroxyl groups, so it is highly reactive. Therefore, the compound having a fluorene skeleton of the present invention can be used as a raw material (monomer) for various resins. For example, it can be used as a polyol component of a thermoplastic resin (e.g., polyester resin, polycarbonate resin, polyester carbonate resin, polyurethane resin, etc.) or a thermosetting resin (e.g., epoxy resin, phenol resin, thermosetting polyurethane resin, (meth)acrylate ((meth)acrylic acid ester), etc.). When the compound having a fluorene skeleton of the present invention is used as a polyol component, the resulting resin has an advantage of being able to achieve both a high refractive index and low birefringence at a high level, probably because a naphthalene ring is substituted at the 9-position of the fluorene skeleton and the fluorene skeleton has a diaryl group.

[0117] In addition, the compound having a fluorene skeleton of the present invention can be efficiently used to prepare derivatives in a commonly used 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, and is preferably 120 to 280°C, more preferably 130 to 260°C, further preferably 140 to 240°C, and particularly preferably 150 to 230°C. EXAMPLES

[0118] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention. In the examples, various measurements were carried out as follows.

[0119] (1) High performance liquid chromatography (HPLC) measurement The compounds obtained in the examples were measured using a Hitachi high performance liquid chromatograph L-2350 under the measurement conditions in the following Table 1. In the examples, unless otherwise specified, % is an area percentage value corrected excluding the solvent in HPLC.

[0120] [Table 1]

[0121] (2)NMR measurement The compounds and resins obtained in the examples were measured using the following devices and solvents. Equipment: JNM-AL400 (400MHz) manufactured by JEOL Ltd. Solvent: CDCl3

[0122] (3)ICP measurement The compounds obtained in the examples were measured using the following apparatus. Equipment used: Agilent Technologies Equipment: Agilent5100 ICP-OES

[0123] (4) Glass transition temperature (Tg) measurement, differential scanning calorimetry (DSC) The compounds and resins obtained in the examples were measured using the following apparatus and conditions. Equipment: TA Instruments Discovery DSC25 Conditions: Heating rate 20℃ / min

[0124] (5) Pellet b* value measurement The resins obtained in the examples were measured using the following devices. Equipment: X-Rite integrating sphere spectrophotometer CE-7000A

[0125] (6) Refractive index (nD) and Abbe number measurement The resins obtained in the examples were measured using the following devices and methods. Equipment: ATAGO DR-M2 Abbe refractometer Method: After the polymerization was completed, the resin pellets obtained were dissolved in methylene chloride, cast onto a glass petri dish, and dried. The refractive index (wavelength: 589 nm) and Abbe number (calculated using the following formula from the refractive indexes at wavelengths of 486 nm, 589 nm, and 656 nm) of the film produced were measured at 25°C. 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: Refractive index at a wavelength of 486 nm.

[0126] (7) Powder X-ray diffraction measurement Measurements were performed using a RIGAKU RINT TTR III under the following measurement conditions. X-ray source: Cu-Kα, output: 50kV-300mA (15kW) DS:1 / 2°, HS:10mm, SS:1 / 2°, RS:0.15°, Step: 0.01°, Scan speed: 1.0° / min

[0127] [Example 1] <Process 1> In a flask equipped with a stirrer, a cooler, and a thermometer, 101.4 g (0.30 mol) of 2,7-dibromofluorenone (hereinafter sometimes abbreviated as DBFN) and 76.8 g (0.63 mmol) of phenylboronic acid were dissolved in a mixed solvent of 1 L of toluene and 200 mL of ethanol, and then 1.7 g (1.45 mmol) of tetrakis(triphenylphosphine)palladium and 347 mL of 2 M potassium carbonate aqueous solution were added, and the reaction was carried out by stirring at 80 ° C for 6 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the remaining amount of DBFN was 0.1% or less. The obtained reaction solution was concentrated under reduced pressure to distill off toluene and ethanol, and then 1 M aqueous sodium hydroxide solution was added to the residue and extracted with chloroform. The chloroform layer was treated with activated carbon to remove the palladium catalyst remaining in the system, and the chloroform was concentrated, and the concentration was stopped when yellow crystals began to precipitate, and the mixture was recrystallized as it was. The precipitated yellow solid crystals were collected by filtration and dried at 85°C for 24 hours to obtain 80.5 g of the target yellow crystals of 2,7-diphenylfluorenone (hereinafter sometimes abbreviated as DPFN) in a yield of 81%. The purity of the obtained yellow crystals was 99.8% when measured by HPLC.

[0128] <Process 2> In a flask equipped with a stirrer, a condenser, a water separator, and a thermometer, 56.5 g (0.17 mol) of DPFN prepared in step 1, 58.8 g (0.41 mol) of 2-naphthol, and 12-tungsto(VI)phosphate n-hydrate (H3[PW 12 O 40 After adding 0.8 g (0.24 mmol) of n-dodecanethiol, 1.8 g (0.01 mmol), 53 mL of toluene, and 13 mL of γ-butyrolactone, the pressure was reduced to 55 kPa, the temperature was raised to 100°C, and the mixture was stirred at the same temperature for 10 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the remaining amount of DPFN was 0.3% or less.

[0129] After the reaction, 25% by weight of sodium hydroxide solution was added to obtain 12-tungsto(VI)phosphate n-hydrate (H3[PW 12 O40 After neutralizing the 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene shown below in (8-1), the water in the system was distilled off at 120°C (referred to as the water washing step). After completing the water washing step, 1.2g (8.87mmol) of potassium carbonate and 37.4g (0.42mol) of ethylene carbonate were added and the reaction was carried out with stirring for 15 hours at 110°C. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the remaining amount of 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene shown in (8-1) below was 0.2% or less.

[0130] After the reaction was completed, water and 25% by weight aqueous sodium hydroxide solution were added to the reaction solution obtained and stirred at 85°C for 5 hours, and then the aqueous layer was separated. The reaction solution obtained was cooled to 20°C and crystallized as it was to obtain the target pale yellow solid of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylfluorene (hereinafter sometimes abbreviated as BNDP). The obtained BNDP was treated with activated carbon and washed with water, and then dried overnight under reduced pressure to obtain a pale yellow solid with a yield of 78% and a purity of 98.8%. The amount of residual metals was measured by ICP, and Pd was less than 1 ppm. DPFN was 0.2% and APHA was 500.

[0131] [ka]

[0132] <Process 3> 25.91 parts by mass of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylfluorene synthesized in step 2, 16.44 parts by mass of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 16.23 parts by mass of diphenyl carbonate, and 3.15×10 sodium hydrogen carbonate were added. -3Parts by weight were placed in a reactor equipped with a stirrer and a distillation device, and after three nitrogen substitutions, the jacket was heated to 200°C to melt the raw materials. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and the jacket was heated to 260°C at a rate of 60°C / hr to carry out an ester exchange reaction. Thereafter, while maintaining the jacket at 260°C, the pressure was reduced to 0.13 kPa over 50 minutes, and a polymerization reaction was carried out until a predetermined torque was reached under conditions of 260°C and 0.13 kPa or less. After completion of the reaction, the produced resin was pelletized and extracted to obtain pellets of polycarbonate resin. The obtained polycarbonate resin was 1 Analysis by H NMR confirmed that 50 mol% of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylfluorene was introduced into the polymer. The refractive index of the resulting polycarbonate resin was 1.682, the Abbe number was 17.1, the Tg was 177°C, and the pellet b* value was 13.5.

[0133] [Example 2] The target fluorene compound was obtained (yield 78%, purity 98.8%) in the same manner as in Example 1, except that phenylboronic acid was changed to phenylboronic anhydride in step 1. The amount of remaining metal was measured by ICP, and the amount of Pd was 1 ppm or less.

[0134] [Example 3] A fluorene compound was obtained (yield 78%, purity 98.8%) in the same manner as in Example 1, except that the base in step 1 was changed to sodium carbonate. The amount of remaining metal was measured by ICP, and the amount of Pd was 1 ppm or less.

[0135] [Example 4] A fluorene compound was obtained in the same manner as in Example 1, except that the palladium catalyst in step 1 was changed to a PL catalyst represented by Pd / SiO2 (yield 78%, purity 98.9%). The amount of remaining metal was measured by ICP, and Pd was found to be 1 ppm or less.

[0136] [Example 5] The acid catalyst in step 2 is silicotungstic acid n-hydrate (H4[SiW 12 O 40 A fluorene compound was obtained in the same manner as in Example 1, except that the solvent used was changed to 0.01% by weight, and the solvent was changed to 0.01% by weight. The same procedure was followed as in Example 1, except that the solvent used was changed to 0.01% by weight, and the solvent used was changed to 0.01% by weight.

[0137] [Example 6] In a flask equipped with a stirrer, a cooler, a water separator, and a thermometer, 28.1 g (0.08 mol) of DPFN produced in step 1 of Example 1, 29.3 g (0.20 mol) of 2-naphthol, 0.4 g (0.12 mmol) of 12-tungsto(VI)phosphate n-hydrate (H3[PW12O40]·nH2O), 1.8 g (0.01 mol) of n-dodecanethiol, 30 mL of toluene, and 7.8 g (0.09 mol) of ethylene carbonate were added, and the pressure was reduced to 55 kPa, and the temperature was raised to 100°C and the mixture was stirred at the same temperature for 3 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the remaining amount of DPFN was 0.0%.

[0138] After the reaction, 25% by weight of sodium hydroxide solution was added to neutralize the 12-tungsto(VI)phosphate n-hydrate (H3[PW12O40]·nH2O), and the water in the system was distilled off at 120°C (referred to as the water washing process). After the water washing process was completed, 0.6g (4.41 mmol) of potassium carbonate, 29.4g (0.33 mol) of ethylene carbonate, and 100mL of dimethylformamide were added and the reaction was carried out by stirring at 110°C for 4 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the remaining amount of 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene was 0.0%.

[0139] After the reaction was completed, water and 25% by weight aqueous sodium hydroxide solution were added to the reaction solution obtained, and the mixture was stirred at 85°C for 1.5 hours, after which the aqueous layer was separated. The reaction solution obtained was cooled to 20°C and crystallized as it was to obtain BNDP. The obtained BNDP was treated with activated carbon and washed with water, and then dried overnight under reduced pressure to obtain white crystals with a yield of 78% and a purity of 98.8%. In addition, Pd was less than 1 ppm, DPFN was 0.0%, APHA was 80, and the endothermic peak by DSC was 237°C. The DSC chart is shown in Figure 1, the powder X-ray measurement chart is shown in Figure 2, and the main peaks of the powder X-ray measurement are shown in Table 2.

[0140] [Table 2]

[0141] [Example 7] In a flask equipped with a stirrer, a cooler, a water separator, and a thermometer, 28.1 g (0.08 mol) of DPFN produced in step 1, 29.3 g (0.20 mol) of 2-naphthol, 0.8 g (0.23 mmol) of 12-tungsto(VI) phosphate n-hydrate (H3[PW12O40]·nH2O), 1.8 g (0.01 mol) of n-dodecanethiol, 45 mL of toluene, and 37.20 g (0.42 mol) of ethylene carbonate were added, and the pressure was reduced to 55 kPa, and the mixture was heated to 100°C and stirred at the same temperature for 9 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the remaining amount of DPFN was 0.0%.

[0142] After the reaction, 25% by weight aqueous sodium hydroxide solution was added to neutralize the 12-tungsto(VI)phosphate n-hydrate (H3[PW12O40]·nH2O), and the water in the system was distilled off at 120°C (referred to as the water washing process). After the water washing process was completed, 0.6g (4.41 mmol) of potassium carbonate and 100mL of dimethylformamide were added, and the reaction was carried out by stirring at 110°C for 4 hours. The progress of the reaction was confirmed by HPLC, and the reaction was terminated when it was confirmed that the remaining amount of 9,9'-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene was 0.0% or less.

[0143] After the reaction was completed, water and 25% by weight aqueous sodium hydroxide solution were added to the reaction solution obtained, and the mixture was stirred at 85°C for 1.5 hours, after which the aqueous layer was separated. The reaction solution obtained was cooled to 20°C and crystallized as it was to obtain BNDP. The obtained BNDP was treated with activated carbon and washed with water, and then dried overnight under reduced pressure to obtain white crystals with a yield of 78% and a purity of 98.8%. In addition, Pd was less than 1 ppm, DPFN was 0.0%, and APHA was 90.

[0144] [Comparative Example 1] A fluorenone compound was synthesized in the same manner as in Example 1 except that the reaction solvent was changed to toluene in step 1. However, the reaction did not proceed and the target fluorenone compound could not be obtained.

[0145] [Comparative Example 2] A fluorene compound was synthesized in the same manner as in Example 1, except that the amount of tetrakis(triphenylphosphine)palladium used in step 1 was changed to 0.56 g (0.48 mmol). Although the reaction proceeded, the diphenyl and monophenyl compounds were mixed in a ratio of 95:5 (weight ratio), and the desired fluorenone compound could not be obtained in high purity.

[0146] [Comparative Example 3] A fluorene compound was synthesized in the same manner as in Example 1 except that in step 2, the acid catalyst was changed to sulfuric acid and 3-mercaptopropionic acid. However, the reaction did not proceed and the target fluorene compound could not be obtained.

[0147] [Reference example 1] A yellow solid of a fluorene compound (BNDP) was obtained in the same manner as in Example 1, except that the activated carbon treatment was not performed in steps 1 and 2 (yield 78%, purity 98.1%). The amount of remaining metal was measured by ICP, and Pd was 70 ppm. APHA was over 500.

[0148] A polycarbonate resin pellet was obtained in the same manner as in Example 1, except that 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylfluorene synthesized by the above method was used in step 3. The obtained polycarbonate resin was analyzed by 1H NMR, and it was confirmed that 50 mol% of the 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]-2,7-diphenylfluorene component was introduced with respect to the total monomer components. The refractive index of the obtained polycarbonate resin was 1.682, the Abbe number was 17.1, the Tg was 177°C, and the pellet b* value was 32.3.

[0149] [Reference example 2] In step 2, the synthesis of a fluorene compound was carried out in the same manner as in Example 1 except that the reaction pressure was 101.3 kPa (normal pressure), but the reaction was not completed, and 5 wt% of DPFN remained, causing a decrease in the purity of BNDP. Furthermore, the pellet b* value of the polycarbonate resin obtained using the monomer in the same manner as in step 3 of Example 1 was 105.

[0150] [Reference example 3] In step 2, the synthesis of a fluorene compound was carried out in the same manner as in Example 1, except that the reaction solvent was changed to toluene, but the reaction was not completed, and 10% by weight of DPFN remained, causing a decrease in the purity of the target BNDP. The obtained yellow solid had a yield of 50% and a purity of 88.7%. The pellet b* value of the polycarbonate resin obtained using the monomer in the same manner as in step 3 of Example 1 was 200. [Industrial Applicability]

[0151] According to the compound having a fluorene skeleton and the method for producing the same of the present invention, a resin raw material (monomer) having excellent properties such as a high refractive index, heat resistance, and low birefringence can be efficiently produced, and therefore the compound can be suitably used as a resin raw material (monomer), a reaction component of a derivative, etc.

[0152] Therefore, the compound having a fluorene skeleton of the present invention or a derivative thereof, or a resin made from a compound having a novel fluorene skeleton as a raw material (monomer) can be used for optical components such as films, lenses, prisms, optical disks, transparent conductive substrates, optical cards, sheets, optical fibers, optical membranes, optical filters, and hard coat films, and is particularly useful for lenses.

Claims

1. A compound having a fluorene skeleton represented by one of the following formulas (1a) to (1d), wherein the content of palladium element in the compound having the fluorene skeleton satisfies the following formula (2), and the APHA of a 5 wt % solution obtained by dissolving the compound having the fluorene skeleton in dimethylformamide is 500 or less. 0.01≦Pd≦50ppm (2) 【Chemistry 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 (In the formula, R 2 to R 13 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 each independently represent an aromatic group having 6 to 12 carbon atoms which may have a substituent. L 1 represents an alkylene group having 1 to 12 carbon atoms. o1 represents an integer of 0 to 5.)

2. The compound having a fluorene skeleton according to claim 1, wherein the content of palladium element in the compound having a fluorene skeleton represented by any one of the formulas (1a) to (1d) satisfies the following formula (2-1): 0.05≦Pd≦25ppm (2-1)

3. 3. The compound having a fluorene skeleton according to claim 1, wherein the APHA of a 5% by weight solution of the compound represented by any one of formulas (1a) to (1d) in dimethylformamide is 200 or less.

4. The compound having a fluorene skeleton according to claim 1, wherein the formulas (1a) to (1d) are the formula (1b).

5. Ar in the formulas (1a) to (1d) １ and Ar ２ 5. The compound having a fluorene skeleton according to claim 1, wherein is a phenyl group or a naphthyl group.

6. The compound having a fluorene skeleton according to any one of claims 1 to 5, wherein the formulas (1a) to (1d) are compounds represented by formula (1-b): 【Chemistry 5】

7. The compound according to claim 6, wherein the content of diphenylfluorenone in the compound represented by formula (1-b) is 0.2% or less.

8. The compound according to claim 6, which has an endothermic peak at 230 to 247° C. in differential scanning calorimetry.

9. 7. A crystal of the compound according to claim 6, which has peaks at diffraction angles 2θ of 10.6±0.2°, 10.8±0.2°, 17.1±0.2°, 17.6±0.2° and 18.7±0.2° in a powder X-ray diffraction pattern using Cu-Kα radiation.

10. 10. A method for using the compound having a fluorene skeleton according to claim 1 as a raw material for a thermoplastic resin.

11. A method for using the compound having a fluorene skeleton according to claim 10 as a thermoplastic resin for lenses.

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