WO2020226126A1 - Composé ayant un squelette fluorène et son procédé de fabrication - Google Patents

Composé ayant un squelette fluorène et son procédé de fabrication Download PDF

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WO2020226126A1
WO2020226126A1 PCT/JP2020/018314 JP2020018314W WO2020226126A1 WO 2020226126 A1 WO2020226126 A1 WO 2020226126A1 JP 2020018314 W JP2020018314 W JP 2020018314W WO 2020226126 A1 WO2020226126 A1 WO 2020226126A1
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compound
formula
acid
reaction
represented
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PCT/JP2020/018314
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Japanese (ja)
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安彦 友成
和徳 布目
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帝人株式会社
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Priority claimed from JP2019132672A external-priority patent/JP7303055B2/ja
Priority claimed from JP2019149641A external-priority patent/JP7303062B2/ja
Application filed by 帝人株式会社 filed Critical 帝人株式会社
Priority to CN202080034248.3A priority Critical patent/CN113795476B/zh
Publication of WO2020226126A1 publication Critical patent/WO2020226126A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/36—Polyhydroxylic alcohols containing six-membered aromatic rings and other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation

Definitions

  • the present invention is suitable as a monomer for forming a thermoplastic resin constituting an optical member represented by an optical lens or an optical film, and has high refractive index, low birefringence, and thermoplasticity having an excellent balance between heat resistance and moldability.
  • the present invention relates to a compound having a thermoplastic skeleton suitable as a raw material for a resin, and a method for producing the same.
  • thermoplastic resin materials such as polycarbonate, polyester, and polyester carbonate made from alcohol having a fluorene skeleton represented by 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF) have been optically used. Since it is excellent in characteristics, heat resistance, moldability, etc., it is attracting attention as an optical member such as an optical lens and an optical sheet.
  • BPEF 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene
  • Patent Document 3 describes a high refractive index resin made from 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (BNEF), it has a high refractive index. Since birefringence is also high, it becomes a big problem when applied to a transparent material such as an optical lens.
  • BNEF 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene
  • the method for producing the compound of the following formula (1) molecularly designed in the present invention consists of two steps, but even if the inventor of the present application uses the method described in the above patent document, the reaction does not occur at all or the reaction proceeds. However, it is industrially disadvantageous because the reaction speed is slow. Further, if the amount of the catalyst used is large, or if the activated carbon treatment or the metal removal treatment similar thereto is not performed, the palladium-based catalyst used in the white compound having a fluorene skeleton represented by the following formula (1) can be used. The derived black particles were mixed in, and the hue of the alcohol compound was deteriorated. In addition, since there are many impurities containing sulfur and bromine, the hue of the alcohol compound may deteriorate, or a reaction failure may occur when the alcohol is used as a raw material for polymerization.
  • the present invention also provides a compound having a novel fluorene skeleton, which preferably has a low specific metal content such as palladium content and is excellent in hue of the raw material and the resin using the raw material, and a method for producing the same.
  • the purpose is to do.
  • the present invention has been achieved as a result of studies for solving the above-mentioned problems of the prior art, and provides a compound having a certain quality and an excellent fluorene skeleton as a polymer raw material, and a method for producing the same. That is. Specifically, the present invention relates to a compound having a fluorene skeleton shown below and a method for producing the same.
  • a compound having a fluorene skeleton represented by the following formula (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 Ar 1 and Ar 2 each independently have 6 to 12 carbon atoms.
  • Indicates an aromatic group which may have a substituent of L 1 represents an alkylene group having 1 to 12 carbon atoms, m1 and n1 represent the same or different integers of 0 to 4, and m2 and n2 are the same. Or differently, it indicates an integer of 0 to 3, and m1 + m2 ⁇ 1. However, m1 + n1 is an integer of 4 or less, and m2 + n2 is an integer of 3 or less.
  • the crystal has a diffraction angle 2 ⁇ of 10.6 ⁇ 0.2 °, 10.8 ⁇ 0.2 °, 17.1 ⁇ 0.2 °, 17 in the powder X-ray diffraction pattern by Cu—K ⁇ rays.
  • the compound according to item 9 above which has peaks at .6 ⁇ 0.2 ° and 18.7 ⁇ 0.2 °.
  • a method for producing a compound having a fluorene skeleton which comprises at least the following steps 1 and 2 in the method for producing a compound having a fluorene skeleton represented by the formula (1).
  • Step 1 A fluorenone represented by the following formula (3) and a boronic acid represented by the following formula (4) or (5) are reacted in a reaction solvent in the presence of a base and a palladium-based catalyst.
  • Step 2 The reaction product (6) produced in step 1 and the alcohols represented by the following formula (7) were reacted in a reaction solvent in the presence of an acid catalyst under reduced pressure, and were obtained after the reaction and neutralization.
  • step 1 Production of the compound having a fluorene skeleton according to item 13 above, wherein the palladium-based catalyst used in step 1 is a palladium-based catalyst represented by tetrakis (triphenylphosphine) palladium and / or Pd / SiO 2. Method.
  • step 1 The method for producing a compound having a fluorene skeleton according to item 13 above, wherein the base used in step 1 is potassium carbonate and / or sodium carbonate.
  • step 2 The above item 13 wherein the acid catalyst used in step 2 is a heteropolyacid 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 fluorene skeleton is a heteropolyacid 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 fluorene skeleton which comprises at least the following steps 1 to 3 in the method for producing a compound having a fluorene skeleton represented by the formula (1).
  • Step 1 The fluorenones represented by the following formula (13) and the alcohols represented by the following formula (14) are reacted in a reaction solvent in the presence of an acid catalyst to obtain a compound represented by the following formula (15).
  • Y represents an aromatic group
  • R 14 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, and a halogen atom.
  • step 3 Production of the compound having a fluorene skeleton according to item 14 above, wherein the palladium-based catalyst used in step 3 is a palladium-based catalyst represented by tetrakis (triphenylphosphine) palladium and / or Pd / SiO 2. Method.
  • step 3 The method for producing a compound having a fluorene skeleton according to item 14 above, wherein the base used in step 3 is potassium carbonate and / or sodium carbonate.
  • step 14 The above item 14 wherein the acid catalyst used in step 1 is a heteropolyacid 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 fluorene skeleton is a heteropolyacid composed of phosphoric acid or silicic acid and an oxygen acid ion of at least one element selected from vanadium, molybdenum and tungsten.
  • thermoplastic resin made from the fluorene compound is excellent in various properties (heat resistance, transparency, hue, moldability, etc.) in addition to optical properties. Further, in the present invention, a compound having a fluorene skeleton excellent in such properties can be efficiently produced.
  • the compound having a fluorene skeleton according to the aspect I of the present invention includes a compound having a fluorene skeleton represented by the following formula (1), that is, an aromatic hydrocarbon having at least one hydroxy group at the 9-position of fluorenes. It is a compound substituted or added.
  • 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
  • Ar 1 and Ar 2 each independently have 6 to 12 carbon atoms.
  • Indicates an aromatic group which may have a substituent of L 1 represents an alkylene group having 1 to 12 carbon atoms
  • m1 and n1 represent the same or different integers of 0 to 4, and m2 and n2 are the same. Or differently, it indicates an integer of 0 to 3, and m1 + m2 ⁇ 1.
  • m1 + n1 is an integer of 4 or less
  • m2 + n2 is an integer of 3 or less.
  • naphthalene ring a 1,4-naphthalenediyl group or a 2,6-naphthalenediyl group is preferable, and a 2,6-naphthalenediyl group is more preferable.
  • examples of the hydrocarbon group represented by R 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 C 1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group, C 1-4 alkyl group and C 1-3 alkyl group.
  • a C 1-3 alkyl group is even more preferred, of which a methyl or ethyl group is even more preferred.
  • cycloalkyl group a C 5-8 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a C 5-6 cycloalkyl group and the like are preferable, and a C 5-6 cycloalkyl group is more preferable.
  • aryl group a phenyl group, an alkylphenyl group (mono or dimethylphenyl group, tolyl group, 2-methylphenyl group, xsilyl group, etc.) and the like are preferable, and a phenyl group is more preferable.
  • a C 6-10 aryl-C 1-4 alkyl group such as a benzyl group and a phenethyl group can be preferably exemplified.
  • n1 and n2 are the substitution number of the substituents R 1 may be selected as appropriate depending on the condensed ring number of condensed hydrocarbons are not particularly limited, preferably each independently 0 or greater, and more It is preferably an integer of 1 or more.
  • the substitution numbers n1 and n2 may be the same or different in the naphthalene ring, and are usually the same in many cases.
  • the number of oxyalkylene groups (OL 1 ) (number of added moles) schreib1 and schreib2 can be selected from the range of 0 to 5, respectively, the lower limit is preferably 0 or more, and the upper limit is preferably 4 or less, more preferably. It is 3 or less, more preferably 2 or less. It is particularly preferably 0 or 1, and most preferably 1.
  • Ar 1 and Ar 2 each independently represent an aromatic group having 6 to 10 carbon atoms, and a phenyl group or a naphthyl group is preferable.
  • the groups Ar 1 and Ar 2 may be different or the same, but are usually the same.
  • the bonding positions of Ar 1 and Ar 2 are preferably 1st and 8th positions, 2nd and 7th positions, 3rd and 6th positions, or 4th and 5th positions of the fluorene skeleton, respectively, and 2nd and 7th positions.
  • the 3rd and 6th positions or the 4th and 5th positions are more preferable, and the 2nd and 7th positions are even more preferable.
  • diphenylfluorene type examples include 9,9-bis (6-hydroxy-2-naphthyl) -1,8-diphenylfluorene, 9,9-bis (6-hydroxy-2-naphthyl) -2,7-diphenylfluorene, and the like.
  • the compound having a fluorene skeleton of the present invention preferably has a palladium element content that satisfies the following formula (2). 0 ⁇ Pd ⁇ 50 ppm (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) Particularly preferably, 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)
  • the lower limit of the content of the palladium element may be 0.01 ppm or more, 0.05 ppm or more, or 0.10 ppm or more.
  • the compound having a fluorene skeleton of the present invention preferably has an APHA of 500% by weight or less, more preferably 200 or less, and further preferably 100 or less in a 5% by weight solution dissolved in dimethylformamide. If APHA is larger than 500, the hue of the resin using the raw material alcohol represented by the above formula (1) and the optical member using the same may be adversely affected.
  • the compound having a fluorene skeleton of the present invention preferably contains diphenylfluorenone in the compound represented by the above formula (1-b) in an amount of 0.2% or less, more preferably 0.1% or less. , 0.05% or less is even more preferable. If the content of diphenylfluorenone is larger than 0.2%, it may adversely affect the hue of the resin using the raw material alcohol represented by the above formula (1) and the optical member using the same.
  • 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. Further, the diffraction angles 2 ⁇ in the powder X-ray diffraction pattern by Cu—K ⁇ rays are 10.6 ⁇ 0.2 °, 10.8 ⁇ 0.2 °, 17.1 ⁇ 0.2 °, 17.6 ⁇ 0. It has characteristic peaks at 2 ° and 18.7 ⁇ 0.2 °. Further, it is preferable that the diffraction angle 2 ⁇ has a maximum peak at 10.8 ⁇ 0.2 °.
  • the crystal of the compound represented by the formula (1-b) of the present invention is a crystal having excellent handleability and good hue and purity.
  • the method for producing a compound having a fluorene skeleton according to the aspect I of the present invention is roughly divided into two steps, and is represented by fluorenones represented by the following formula (3) and the following formula (4) or (5).
  • the first step 1 in which boronic acids are reacted in the presence of a palladium-based catalyst and a base, and the reaction product (6) produced in step 1 and an alcohol compound represented by the following formula (7) are used as an acid catalyst.
  • the reaction is carried out while discharging water produced as a by-product in the reaction system under reduced pressure to the outside of the system, and then the product is neutralized as it is after the reaction is completed. It can be produced by the second step 2 in which a basic catalyst is added and reacted with ethylene carbonate without taking out (8).
  • step 1 the boronic acids represented by the following formulas (4) or (5) are highly reactive and no side reaction occurs, and in step 2, when a thiol compound is used in combination and not used in combination.
  • the reaction rate is faster than that of the above, and by reducing the pressure in the system, the by-produced water can be efficiently expelled, so that the reaction is fast, the production of by-products is suppressed, and the reactant (8) is taken out. Since it can be produced in the same reaction vessel without any need, the amount of solvent used is reduced, and the compound having the fluorene skeleton of the present invention can be efficiently produced at low cost.
  • Step 1 (In the formula, X 1 is a substituent at the 1-position, 2-position, 3-position or 4-position and indicates a halogen atom, and X 2 is a substituent at the 5-position, 6-position, 7-position or 8-position and is a halogen. Indicates an atom.)
  • Y represents an aromatic group
  • R 14 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, and a halogen atom.
  • Step 2 (In the equation, Ar 1 and Ar 2 are the same as in equation (1).) (Wherein, the p1 and p2 is an integer of the same or different 0 ⁇ 4, R 1, n1 and n2 are the same as the formula (1).) (In the equation, R 1 , Ar 1 and Ar 2 are the same as in equation (1). P1 and p2 are the same as in equation (7). N1 and n2 are integers of 0 to 3.)
  • the compound represented by the above formula (3) is a fluorenone compound corresponding to the fluorene skeleton in the above 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 both X 1 and X 2 indicate a halogen atom.
  • fluorenone compound represented by the above formula (3) Representative examples of the fluorenone compound represented by the above formula (3) are shown below, but the raw materials used in the above formula (1) of the present invention are not limited thereto.
  • 1,8-dibromofluorenone, 2,7-dibromofluorenone, 3,6-dibromofluorenone, and 4,5-dibromofluorenone are preferable, and 2,7-dibromofluorenone is particularly preferable.
  • the amount of the reaction solvent (in the case of the present invention, a mixed solvent of toluene and ethanol) used is not particularly limited, but toluene is preferably 0.1% by weight or more with respect to the fluorenones represented by the formula (3). It is more preferably 0.5 to 100 times by weight, and even more preferably 1 to 50 times by weight. If the amount of toluene used is less than 0.1 times by weight, the product may precipitate and stirring may become difficult. Further, when the amount of toluene used exceeds 100 times by weight, the effect corresponding to the amount used is not obtained, the volumetric efficiency is deteriorated, and the production cost of the compound having the fluorene skeleton may increase.
  • It is preferably an aromatic hydrocarbon solvent and an ester solvent, more preferably a mixed solvent of toluene, xylene, chlorobenzene or dichlorobenzene and ethyl acetate, butyl acetate, ⁇ -butyrolactone or ethylene carbonate, and further preferably with toluene. It is a mixed solvent with ⁇ -butyrolactone or ethylene carbonate. These reaction solvents may be used alone, or two or more of them may be used in combination.
  • step 2 when carrying out the reaction between the fluorene compound represented by the above formula (8) and ethylene carbonate, the reaction may be carried out in the presence of a basic compound, if necessary.
  • the reaction when carried out in the presence of a basic compound, the solid acid used in step 1 is preferably separated or neutralized by filtration before carrying out step 2.
  • the compound having a fluorene skeleton according to the second aspect of the present invention has a sulfur element content of 200 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less, and further preferably 30 ppm or less. If the content of the sulfur element is larger than 200 ppm, the hue of the resin using the raw material alcohol represented by the above formula (1) and the optical member using the same are adversely affected. Further, when the raw material alcohol represented by the above formula (1) is used to obtain a resin, a reaction failure occurs.
  • Step 1 The fluorenones represented by the following formula (13) and the alcohols represented by the following formula (14) are reacted in a reaction solvent in the presence of an acid catalyst to obtain a compound represented by the following formula (15).
  • Step Step 2 The compound represented by the following formula (15) and ethylene carbonate are reacted in the reaction solvent in the presence of a base to obtain the compound represented by the following formula (16).
  • the compound represented by the above formula (13) is a fluorenone compound corresponding to the fluorene skeleton in the above 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 both X 1 and X 2 indicate a halogen atom.
  • 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 and the like are preferably mentioned.
  • the alcohols represented by the formula (14) correspond to the (poly) hydroxyl group-containing arene ring substituted at the 9-position in the fluorene derivative represented by the formula (13). That is, the formula naphthalene ring in (14) to the naphthalene ring in the formula (1), R 1, n1 and n2 correspond to R 1, n1 and n2 in the formula (1).
  • Alkylnaphthols such as butylnaphthol (C 1-4 alkylnaphthols), alkoxynaphthols (C 1-4 alkoxynaphthols such as ethoxynaphthols), halonaphthols (chloronaphthols, bromonaphthols), these naphthols (or mono).
  • Polyhydroxynaphthalene eg, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1, Di or trihydroxynaphthalene such as 8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,2,4-trihydroxynaphthalene, 1,3,8-trihydroxynaphthalene) and the like. Be done. Of these, 1-naphthol and 2-naphthol are preferable, and 2-naphthol is particularly preferable. These alcohols may be used alone, or two or more of them may be mixed and reacted with fluorenones, and may be arbitrarily selected depending on the purpose. In the present invention, it is preferably 2-naphthol.
  • the alcohols represented by the above formula (14) commercially available products may be used, or synthetic ones may be used.
  • a method for producing naphthols the method described in Patent Document (Japanese Unexamined Patent Publication No. 61-115039), that is, 2-naphthalene sulfonic acid obtained by sulfonated naphthalene is neutralized with alkali to 2-naphthalene sulfone.
  • Examples thereof include a method in which sodium acid is obtained, the product is alkali-melted to form an alkali salt, and then hydrolyzed to produce 2-naphthol.
  • the purity of alcohols (for example, naphthols) represented by the above formula (14) used as a raw material is not particularly limited, but is usually preferably 95% or more, and more preferably 99% or more.
  • the heteroelement of the oxygen acid constituting the heteropolyacid is not particularly limited, but for example, copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, tellurium, nitrogen, phosphorus, Examples include arsenic, antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, yldium and platinum. It is preferably phosphorus (phosphoric acid) or silicon (silicic acid).
  • heteropolyacid anion constituting the heteropolyacid skeleton those having various compositions can be used.
  • XM 12 O 40 , XM 12 O 42 , XM 18 O 62 , XM 6 O 24 and the like can be mentioned.
  • a preferred heteropolyacid anion composition is XM 12 O 40 .
  • X is a hetero element and M is a poly element.
  • Specific examples of the heteropolyacid having these compositions include phosphomolybdic acid, phosphotungstic acid, silicate molybdic acid, silicate tungstic acid, and limbanado molybdic acid.
  • the heteropolyacid may be a free heteropolyacid, and some or all of the protons may be replaced with other cations to be used as a salt of the heteropolyacid. Therefore, the heteropolyacid referred to in the present invention also includes salts of these heteropolyacids. Examples of cations that can be replaced with protons include ammonium, alkali metals, and alkaline earth metals.
  • Examples of the mercaptocarboxylic acid include ⁇ -mercaptopropionic acid, ⁇ -mercaptopropionic acid, thioacetic acid, thioglycolic acid, thiosuccinic acid, mercaptosuccinic acid, and mercaptobenzoic acid.
  • the alkanethiols include methanethiol, ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-butanethiol, 1-pentanethiol, 2-pentanethiol, 1-hexanethiol, 1-.
  • Such a compound having an SH group may be used alone, or may be used in combination of two or more.
  • the method for carrying out the reaction in step 1 is not particularly limited, but usually, the compound represented by the above formula (13) and the above formula (14) and the heteropolyacid and / or thiol compound are used in the reaction apparatus.
  • the method of dehydration is not particularly limited, and examples thereof include dehydration by adding a dehydrating agent, dehydration by reduced pressure, and dehydration by azeotropic boiling with a solvent under normal pressure or reduced pressure.
  • the reaction solvent used in the step 1 is not particularly limited, but for example, an aromatic hydrocarbon solvent such as toluene and xylene, a halogenated aromatic hydrocarbon solvent such as chlorobenzene and dichlorobenzene, pentane, hexane, heptane and the like.
  • Aliphatic hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, aliphatics such as diethyl ether, di-iso-propyl ether, methyl-t-butyl ether, diphenyl ether, tetrahydrofuran, dioxane and Cyclic ether solvent, ester solvent such as ethyl acetate, butyl acetate, ⁇ -butyrolactone, ethylene carbonate, nitrile solvent such as acetonitrile, propionitrile, butyronitrile, benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, Examples thereof include an amide solvent such as 1-methyl-2-pyrrolidinone.
  • It is preferably an aromatic hydrocarbon solvent and an ester solvent, more preferably a mixed solvent of toluene, xylene, chlorobenzene or dichlorobenzene and ethyl acetate, butyl acetate, ⁇ -butyrolactone or ethylene carbonate, and further preferably with toluene. It is a mixed solvent with ethylene carbonate. These reaction solvents may be used alone, or two or more of them may be used in combination.
  • the amount used is not particularly limited, but from the viewpoint of economy, it is preferably 0.1% by weight or more, more preferably 0.5 to 100 times by weight, still more preferably 1 with respect to fluorenones. It is up to 20 times by weight.
  • the reaction temperature in step 1 varies depending on the type of raw material 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 followed by analytical means such as liquid chromatography.
  • the internal pressure during the reaction in step 1 is preferably 101.3 kPa or less, more preferably 60.0 kPa or less. It is preferable to react the by-produced water while discharging it from the system at this internal pressure because the reaction proceeds more efficiently and the amount of by-products produced is reduced.
  • the solid acid used may be removed by filtration or neutralized, if necessary.
  • the base used for neutralization include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide, potassium carbonate, calcium carbonate, sodium carbonate and sodium carbonate.
  • alkali metal or alkaline earth metal carbonate (hydrogen carbonate) salts, amines and the like can be mentioned.
  • separation and purification may be performed by a separation means such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or a metal removal treatment very similar thereto, column chromatography, or a separation means combining these. ..
  • the reaction solution after neutralization can be used for the reaction with ethylene carbonate without removing the salt generated by the neutralization.
  • the salt generated by neutralization can be separated by filtration, or water can be added, stirred, and then separated to remove the aqueous layer (sometimes called a water washing process).
  • the salt produced by the sum may be separated from the reaction system. This washing step may be repeated as needed.
  • step 1 After the reaction in step 1, it can be reacted with ethylene carbonate without taking out the fluorene compound represented by the above formula (15). That is, step 1 and step 2 can be performed in one pot. If the fluorene compound represented by the above formula (15) is taken out by a method such as concentration or crystallization, the yield may decrease and the cost may increase.
  • ethylene carbonate is usually used in an amount of 2 to 10 mol, preferably 2 to 8 mol, and more preferably 2 to 6 mol with respect to 1 mol of fluorenone.
  • step 2 when carrying out the reaction between the fluorene compound represented by the above formula (15) and ethylene carbonate, the reaction may be carried out in the presence of a basic compound, if necessary.
  • the reaction when carried out in the presence of a basic compound, the solid acid used in step 1 is preferably separated or neutralized by filtration before carrying out step 2.
  • Examples of the basic compound that can be used in step 2 include carbonates, bicarbonates, hydroxides, organic bases and the like.
  • Examples of carbonates include potassium carbonate, sodium carbonate, cesium carbonate, lithium carbonate and the like.
  • Examples of hydrogen carbonates include potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate and the like.
  • Examples of hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.
  • Examples of the organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride and the like.
  • potassium carbonate and sodium carbonate are preferably used from the viewpoint of handleability and safety. These basic compounds may be used alone, or may be used in combination of two or more.
  • the amount used is usually 0.01 to 1.0 mol, preferably 0.03 to 0.5 mol, based on 1 mol of fluorenones.
  • an alkaline aqueous solution having a concentration of 3% by weight or more to the obtained reaction mixture and heat and stir at a temperature of 50 ° C. or higher (hereinafter, referred to as an alkali purification step).
  • the concentration of the alkaline aqueous solution added to the reaction mixture solution is preferably 3% by weight or more, more preferably 6% by weight, still more preferably 8% by weight or more.
  • the alkali concentration is not particularly limited as long as it is 3% by weight or more, but is preferably 50% by weight or less, more preferably 30% by weight or less, still more preferably 15% by weight or less, from the viewpoint of alkali solubility and ease of handling. Concentration is preferred.
  • the temperature for heating and stirring the alkaline aqueous solution is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 80 ° C. or higher. Further, the temperature is lower than the boiling point of the solvent used, more preferably 130 ° C. or lower. If the temperature is lower than 50 ° C., by-products cannot be removed or efficiently removed, which is not preferable. Further, if the temperature is higher than 130 ° C., impurities increase, the purity decreases, and the hue deteriorates, which is not preferable.
  • the stirring time is not particularly limited, but is preferably 0.5 to 10 hours, more preferably 1 to 9 hours, and even more preferably 2 to 8 hours.
  • the alkali used in the alkaline aqueous solution of the present invention is not particularly limited, but is limited to lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, calcium hydroxide, and barium hydroxide. , Sodium carbonate, potassium carbonate and the like. Sodium hydroxide and potassium hydroxide are preferable.
  • the amount of alkali used is not particularly limited, but in order to efficiently remove by-products and coloring components, it is usually 0 to 1 mol of the compound represented by the formula (16). It is preferably 1 to 20 mol, more preferably 0.2 to 10 mol, and even more preferably 0.3 to 5 mol.
  • the amount of alkali is less than 0.1 mol, by-products may not be removed efficiently. In addition, it may not be possible to efficiently remove the coloring component, which is not preferable. If the amount of alkali is more than 20 mol, the purity may be lowered and the hue may be deteriorated, which is not preferable.
  • the alkali purification step may be carried out by adding an alkaline aqueous solution to the reaction mixture solution containing the compound represented by the formula (16) and heating and stirring, or by diluting the reaction mixture solution with an organic solvent and then adding the alkaline aqueous solution. It may be heated and stirred. Usually, the alkali purification step is carried out after diluting the organic solvent.
  • the organic solvent to be diluted is not particularly limited, but is limited to aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, aliphatic hydrocarbons such as pentane, hexane and heptane, and halogenated aromatics such as chlorobenzene and dichlorobenzene. Examples thereof include group hydrocarbons, dimethylformamide, dimethylsulfoxide and the like.
  • the obtained reaction mixture is subjected to separation means such as washing, filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or similar metal removal treatment, column chromatography and the like. , These may be separated and purified by a separation means in combination.
  • separation means such as washing, filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or similar metal removal treatment, column chromatography and the like. , These may be separated and purified by a separation means in combination.
  • the operation of precipitating the compound represented by the above formula (16) from the reaction mixture subjected to the above post-treatment is such that the reaction mixture mixed with the solvent is, if necessary, 50 ° C. or higher and below the boiling point of the solvent (preferably). 70-110 ° C.), and this is carried out by cooling this to less than 50 ° C.
  • crystallization solvent examples include those exemplified as the solvent used in the above reaction, alcohol solvents such as methanol, ethanol, propanol, isopurpanol, butanol, tert-butanol, isobutanol and pentanol, and carbonic acid such as dimethyl carbonate and diethyl carbonate.
  • alcohol solvents such as methanol, ethanol, propanol, isopurpanol, butanol, tert-butanol, isobutanol and pentanol
  • carbonic acid such as dimethyl carbonate and diethyl carbonate.
  • Ester solvent such as ethyl acetate, butyl acetate, ⁇ -butyrolactone, butyl benzoate, methyl benzoate, phenyl acetate, ether solvent such as diethyl ether, di-is GmbH-propyl ether, methyl-tert-butyl ether, diphenyl ether, tetrahydrofuran etc. , Hexane, heptane, octane, pentane and other aliphatic hydrocarbon solvents, etc., but methanol, ethanol, toluene or dimethyl carbonate are preferable.
  • Such a crystallization operation may be performed once or may be repeated a plurality of times.
  • impurities such as unreacted 2-naphthol and by-produced ethylene glycol mono (2-naphthyl) ether can be easily and efficiently removed.
  • step 3 may be carried out in one pot without taking out the compound represented by the above formula (16). Further, steps 1 to 3 may all be performed in one pot. Yield and productivity can be improved by performing in one pot.
  • the ring Y of the compound represented by the above formula (17) or (18) corresponds to the groups Ar 1 and Ar 2 in the above formula (1). Further, in the above formulas (17) and (18), the preferred embodiment of the group R 14 is the same as the preferred embodiment of the above R 1 , and the preferred embodiment of l is the same as the preferred embodiment of the n1 and n2.
  • the purity of the boronic acids used is not particularly limited, but is usually preferably 95% or more, more preferably 99% or more.
  • a commercially available product may be used, or a synthesized product may be used.
  • a method for producing boronic acids for example, the method described in Patent Document (Japanese Unexamined Patent Publication No. 2002-47292), that is, the phenyl Grignard reagent is reacted with boric acid esters dissolved in a non-ether aromatic solvent. The method etc. can be mentioned.
  • the boronic acid used in the present invention includes alkylboronic acid represented by the above formulas (14) and (15), alkenylboronic acid, arylboronic acid, heteroarylboronic acid and its anhydride as alkylboronic acid.
  • alkylboronic acid represented by the above formulas (14) and (15)
  • alkenylboronic acid alkenylboronic acid, arylboronic acid, heteroarylboronic acid and its anhydride
  • alkylboronic acid represented by the above formulas (14) and (15)
  • alkenylboronic acid alkenylboronic acid, arylboronic acid, heteroarylboronic acid and its anhydride as alkylboronic acid.
  • arylboronic acid 2-anthracemboronic acid, 9-anthracemboronic acid, benzylboronic acid, 2-biphenylboronic acid, 3-biphenylboronic acid, 4-biphenylboronic acid, 2,3-dimethylphenylboronic acid are included.
  • phenylboronic acid, 2-naphthaleneboronic acid or an anhydride thereof is preferable, and phenylboronic acid or an anhydride thereof is particularly preferable.
  • the ratio of the compound represented by the formula (17) used as a raw material is preferably 2 to 5 mol, more preferably 2.05 to 3. To 1 mol of the compound represented by the formula (16). It may be about 0 mol, more preferably about 2.1 to 2.5 mol. If the amount of boronic acids is less than 2 mol, the yield of the product represented by the above formula (1) may be low. On the other hand, if it exceeds 5 mol, the reaction rate is high and the yield is high, but the production cost of the compound having the fluorene skeleton may increase.
  • the ratio of the compound represented by the formula (18) to be used is preferably 0.7 to 5 mol, more preferably 0.8 to 3 mol, based on 1 mol of the compound represented by the formula (16). , More preferably about 1 to 2 mol. If the amount of boronic acids is less than 0.7 mol, the yield of the product represented by the above formula (1) may be low. On the other hand, if it exceeds 5 mol, 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) between the formula (16) of step 3 and the compound represented by the formulas (17) and / or (18) can be carried out in the reaction solvent in the presence of a base and a catalyst. it can.
  • Examples of the base used in the reaction of step 3 include hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), and cesium carbonate (Cs 2 CO).
  • carbonates are preferably used, with potassium carbonate and / or sodium carbonate being preferred.
  • Such bases may be used alone or in combination of two or more.
  • the amount of the above-mentioned base used is not particularly limited, but is preferably 1 to 30 equivalents, more preferably 1 to 10 equivalents, added to 1 mol of boronic acids.
  • the reaction solvent used in step 3 is not particularly limited, but for example, an aromatic hydrocarbon solvent such as toluene and xylene and alcohols such as methanol, ethanol, isopropyl alcohol and n-butanol are used alone or in combination. Can be used. Since the aromatic hydrocarbon solvent is a high boiling point solvent, the reaction temperature can be set high, and by using an alcohol, the affinity with water is good and the reactivity is good, so that it is preferably used. Such a solvent may be used alone, or two or more kinds may be used in combination.
  • aprotonic solvents such as N, N-dimethylformamide or N, N-dimethylacetamide, and halobenzenes such as o-dichlorobenzene can also be used.
  • a solvent may be used alone, or two or more kinds may be used in combination.
  • a mixed solvent of toluene and ethanol is more preferable.
  • the amount of the reaction solvent (in the case of the present invention, a mixed solvent of toluene and ethanol) used is not particularly limited, but toluene is preferably 0.1% by weight or more with respect to 1 mol of the compound represented by the formula (16). , More preferably 0.5 to 100 times by weight, and even more preferably 1 to 50 times by weight. If the amount of toluene used is less than 0.1 times by weight, the product may precipitate and stirring may become difficult. Further, when the amount of toluene used exceeds 100 times by weight, the effect corresponding to the amount used is not obtained, the volumetric efficiency is deteriorated, 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, based on 1 mol of the compound represented by the formula (16). If the amount of ethanol used is less than 0.1 times by weight, the reaction rate may be slow and the yield may decrease. Further, when the amount of ethanol used exceeds 50 times by weight, the effect corresponding to the amount used is not as good as that of toluene, the volumetric efficiency is deteriorated, and the production cost of the compound having the fluorene skeleton may increase.
  • the reaction temperature varies depending on the type of raw material and solvent used, but is preferably 50 to 150 ° C, more preferably 60 to 130 ° C, and even more preferably 70 to 120 ° C.
  • the reaction can be followed by analytical means such as liquid chromatography.
  • the reaction mixture after completion of the reaction usually contains unreacted boronic acids, bases, catalysts, side reaction products, etc., in addition to the produced compound represented by the formula (1). Therefore, by conventional methods such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or similar metal removal treatment, column chromatography and other separation means, or a separation means combining these. Can be separated and purified.
  • boronic acids are removed by a conventional method (such as adding an alkaline aqueous solution to form a water-soluble complex), activated carbon treatment or a metal removal treatment similar to that is performed to remove the palladium compound, and then recrystallization. It is preferable to add a crystal solvent, cool the mixture to recrystallize it, and then filter and separate it for purification.
  • the method of recrystallization is the same as the method described in step 2.
  • the purity of the compound represented by the formula (1) 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, more preferably 95% or more.
  • the compound having a fluorene skeleton of the present invention preferably combines a diphenylfluorene skeleton and a dinaphthylfluorene skeleton with an allene ring, it not only has high refractive index and heat resistance, but also reduces birefringence when made into a polymer. Can be done. So far, in order to improve the refractive index, a fluorene compound in which a ring-assembled array ring is substituted at the 9-position of the fluorene skeleton has been used, but this has high refractive index and heat resistance, but lowers birefringence. ..
  • the compound having a fluorene skeleton of the present invention has a diphenylfluorene skeleton and a dinaphthylfluorene skeleton, so that the birefringence is small even though the refractive index is high. Further, since the allene 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) for various resins.
  • thermoplastic resins eg, polyester resins, polycarbonate resins, polyester carbonate resins, polyurethane resins, etc.
  • thermosetting resins eg, epoxy resins, phenolic resins, thermosetting polyurethane resins, (meth) acrylates ((meth)).
  • It can be used as a polyol component of) such as acrylic acid ester).
  • the compound having a fluorene skeleton of the present invention is used as a polyol component, the obtained resin has a high refractive index and low refractive index, probably because the naphthalene ring is substituted at the 9-position of the fluorene skeleton and the fluorene skeleton has a diaryl group. It has the advantage of being able to achieve both birefringence at a high level.
  • the compound having a fluorene skeleton of the present invention can efficiently prepare 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., and further preferably 140 to 240 ° C.
  • nD Refractive index at wavelength 589 nm
  • nC Refractive index at wavelength 656 nm
  • nF means the refractive index at a wavelength of 486 nm.
  • Powder X-ray diffraction measurement Using RIGAKU RINT TTR III, measurement was performed under the following measurement conditions.
  • X-ray source Cu-K ⁇ , output: 50kV-300mA (15kW)
  • DS 1/2 °
  • HS 10 mm
  • SS 1/2 °
  • RS 0.15 °
  • Step 0.01 °
  • scan speed 1.0 ° / min
  • Example I-1 ⁇ Step 1> In a flask equipped with a stirrer, a cooler, and a thermometer, 101.4 g (0.30 mol) of 2,7-dibromofluorenone (hereinafter, may be abbreviated as DBFN) and 76.8 g of phenylboronic acid (0). .63 mmol) is dissolved in a mixed solvent of 1 L of toluene and 200 mL of ethanol, 1.7 g (1.45 mmol) of tetrakis (triphenylphosphine) palladium is added, and 347 mL of a 2M potassium carbonate aqueous solution is added, followed by stirring at 80 ° C.
  • DBFN 2,7-dibromofluorenone
  • reaction was carried out by doing so. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of DBFN was 0.1% or less, and the reaction was terminated.
  • the obtained reaction solution was concentrated under reduced pressure to distill off toluene and ethanol, and then a 1 M aqueous sodium hydroxide solution was added to the residue and the mixture was extracted with chloroform.
  • the chloroform layer was depalladium-catalyzed with activated carbon to remove the palladium catalyst remaining in the system, and then chloroform was concentrated. When yellow crystals were precipitated, the concentration was stopped and recrystallized as it was. The precipitated yellow solid crystals are collected by filtration and dried at 85 ° C.
  • DPFN 2,7-diphenylfluorenone
  • BNDP 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene
  • BNDP was treated with activated carbon, washed with water, and dried under reduced pressure overnight to obtain a pale yellow solid with a yield of 78% and a purity of 98.8%.
  • Pd was 1 ppm or less.
  • the DPFN was 0.2% and the APHA was 500.
  • 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, and a transesterification reaction was carried out. Then, while keeping the jacket at 260 ° C., the pressure was reduced to 0.13 kPa over 50 minutes, and the polymerization reaction was carried out under the conditions of 260 ° C. and 0.13 kPa or less until a predetermined torque was reached. After completion of the reaction, the produced resin was extracted while pelletizing to obtain pellets of polycarbonate resin.
  • Example I-2 The desired fluorene compound was obtained in the same manner as in Example I-1 except that the phenylboronic acid in step 1 was changed to an anhydride of phenylboronic acid (yield 78%, purity 98.8%). When the amount of residual metal was measured by ICP, Pd was 1 ppm or less.
  • Example I-3 A fluorene compound was obtained in the same manner as in Example I-1 except that the base in step 1 was changed to sodium carbonate (yield 78%, purity 98.8%). When the amount of residual metal was measured by ICP, Pd was 1 ppm or less.
  • Example I-4 A fluorene compound was obtained in the same manner as in Example I-1 except that the palladium-based catalyst in step 1 was changed to a PL catalyst represented by Pd / SiO 2 (yield 78%, purity 98.9%). When the amount of residual metal was measured by ICP, Pd was 1 ppm or less.
  • Example I-5 A fluorene compound was obtained in the same manner as in Example I-1 except that the acid catalyst in step 2 was changed to n-hydrate of silicotungstic acid (H 4 [SiW 12 O 40 ], nH 2 O) (yield). 78%, purity 98.8%). When the amount of residual metal was measured by ICP, Pd was 1 ppm or less.
  • Example I-6 28.1 g (0.08 mol) of DPFN and 29.3 g (0.) of 2-naphthol produced in step 1 of Example I-1 were placed in a flask equipped with a stirrer, a cooler, a water separator, and a thermometer.
  • DPFN 2,7-diphenylfluorenone
  • a raw material (monomer) of a resin having excellent properties such as high refractive index, heat resistance, and low birefringence can be efficiently produced. It can be suitably used as a raw material (monomer) for a resin, a reaction component of a derivative, or the like.
  • the resin using the compound having a fluorene skeleton or a derivative thereof of the present invention or the compound having a novel fluorene skeleton as a raw material (monomer) is, for example, a film, a lens, a prism, an optical fiber, a transparent conductive substrate, an optical card, a sheet. It can be used for optical members such as optical fibers, optical films, optical filters, and hard coat films, and is particularly useful for lenses.

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Abstract

L'invention concerne un composé ayant un squelette fluorène représenté par la formule (1), qui est caractérisé en ce qu'une résine obtenue par utilisation, en tant que matière de départ, de ce composé ayant un squelette fluorène, est excellente en termes de différentes caractéristiques (telles que des caractéristiques optiques, la résistance à la chaleur et l'aptitude au moulage). (Dans la formule, R1 représente un atome d'hydrogène, un atome d'halogène ou un groupe hydrocarboné qui peut contenir un groupe aromatique ayant 1 à 12 atomes de carbone ; chacun de Ar1 et Ar2 représente indépendamment un groupe aromatique qui peut avoir un substituant ayant 6 à 12 atomes de carbone ; L1 représente un groupe alkylène ayant 1 à 12 atomes de carbone ; m1 et n1 peuvent être identiques ou différents, et chacun représente un entier de 0 à 4 ; m2 et n2 peuvent être identiques ou différents, et chacun représente un entier de 0 à 3 ; la condition (m1 + m2) ≥ 1 est satisfaite. En outre, (m1 + n1) est un entier valant 4 ou moins, et (m2 + n2) est un entier valant 3 ou moins. Chacun de o1 et o2 représente indépendamment un entier de 0 à 5).
PCT/JP2020/018314 2019-05-09 2020-04-30 Composé ayant un squelette fluorène et son procédé de fabrication WO2020226126A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022190800A1 (fr) * 2021-03-09 2022-09-15 帝人株式会社 Résine thermoplastique et élément optique

Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
CN114409493B (zh) * 2022-01-14 2024-02-23 浙江工业大学 一种合成9-芳基芴类化合物的方法
CN114702655B (zh) * 2022-04-06 2023-06-27 华为技术有限公司 聚碳酸酯及其制备方法和应用

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005104935A (ja) * 2003-10-01 2005-04-21 Osaka Gas Co Ltd フルオレン骨格を有する多価アルコールおよびその製造方法
JP2008222708A (ja) * 2007-02-15 2008-09-25 Taoka Chem Co Ltd フルオレン誘導体の結晶多形体およびその製造方法
JP2010248095A (ja) * 2009-04-13 2010-11-04 Taoka Chem Co Ltd ９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレンの製造法
CN104263287A (zh) * 2014-09-19 2015-01-07 华烁科技股份有限公司 一种刚挠结合印制电路板用高耐热低流动度胶粘剂、胶膜及其制备方法
JP2016079405A (ja) * 2014-10-20 2016-05-16 大阪ガスケミカル株式会社 フルオレン骨格を有するポリエステルポリ（メタ）アクリレート、その硬化性組成物及び硬化物、並びにその製造方法
JP2017114947A (ja) * 2015-12-21 2017-06-29 Ｊｆｅケミカル株式会社 フルオレン縮合体組成物およびエポキシ化組成物ならびにこれらの製造方法
WO2018025799A1 (fr) * 2016-08-04 2018-02-08 大阪ガスケミカル株式会社 Composé de clathrate et son procédé de production, et son utilisation
JP2019001780A (ja) * 2017-06-15 2019-01-10 田岡化学工業株式会社 フルオレン骨格を有するアルコール類の製造方法
WO2019044214A1 (fr) * 2017-08-30 2019-03-07 帝人株式会社 Résine thermoplastique et élément optique
CN109722198A (zh) * 2018-11-27 2019-05-07 张家港康得新光电材料有限公司 增亮膜用胶水
WO2019131841A1 (fr) * 2017-12-28 2019-07-04 帝人株式会社 Poly(ester) carbonate, et procédé de fabrication de celui-ci
WO2019151264A1 (fr) * 2018-01-31 2019-08-08 帝人株式会社 Composé ayant un squelette fluorène et procédé de fabrication associé
JP2020083813A (ja) * 2018-11-26 2020-06-04 帝人株式会社 フルオレン骨格を有する化合物の製造方法および不純物の少ないフルオレン骨格を有する化合物

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005104935A (ja) * 2003-10-01 2005-04-21 Osaka Gas Co Ltd フルオレン骨格を有する多価アルコールおよびその製造方法
JP2008222708A (ja) * 2007-02-15 2008-09-25 Taoka Chem Co Ltd フルオレン誘導体の結晶多形体およびその製造方法
JP2010248095A (ja) * 2009-04-13 2010-11-04 Taoka Chem Co Ltd ９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレンの製造法
CN104263287A (zh) * 2014-09-19 2015-01-07 华烁科技股份有限公司 一种刚挠结合印制电路板用高耐热低流动度胶粘剂、胶膜及其制备方法
JP2016079405A (ja) * 2014-10-20 2016-05-16 大阪ガスケミカル株式会社 フルオレン骨格を有するポリエステルポリ（メタ）アクリレート、その硬化性組成物及び硬化物、並びにその製造方法
JP2017114947A (ja) * 2015-12-21 2017-06-29 Ｊｆｅケミカル株式会社 フルオレン縮合体組成物およびエポキシ化組成物ならびにこれらの製造方法
WO2018025799A1 (fr) * 2016-08-04 2018-02-08 大阪ガスケミカル株式会社 Composé de clathrate et son procédé de production, et son utilisation
JP2019001780A (ja) * 2017-06-15 2019-01-10 田岡化学工業株式会社 フルオレン骨格を有するアルコール類の製造方法
WO2019044214A1 (fr) * 2017-08-30 2019-03-07 帝人株式会社 Résine thermoplastique et élément optique
WO2019131841A1 (fr) * 2017-12-28 2019-07-04 帝人株式会社 Poly(ester) carbonate, et procédé de fabrication de celui-ci
WO2019151264A1 (fr) * 2018-01-31 2019-08-08 帝人株式会社 Composé ayant un squelette fluorène et procédé de fabrication associé
JP2020083813A (ja) * 2018-11-26 2020-06-04 帝人株式会社 フルオレン骨格を有する化合物の製造方法および不純物の少ないフルオレン骨格を有する化合物
CN109722198A (zh) * 2018-11-27 2019-05-07 张家港康得新光电材料有限公司 增亮膜用胶水

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022190800A1 (fr) * 2021-03-09 2022-09-15 帝人株式会社 Résine thermoplastique et élément optique

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