WO2020004207A1 - Corps cristallin de 9,9-bis(4-hydroxyphényl)-2,3-benzofluorène - Google Patents

Corps cristallin de 9,9-bis(4-hydroxyphényl)-2,3-benzofluorène Download PDF

Info

Publication number
WO2020004207A1
WO2020004207A1 PCT/JP2019/024412 JP2019024412W WO2020004207A1 WO 2020004207 A1 WO2020004207 A1 WO 2020004207A1 JP 2019024412 W JP2019024412 W JP 2019024412W WO 2020004207 A1 WO2020004207 A1 WO 2020004207A1
Authority
WO
WIPO (PCT)
Prior art keywords
crystal
hydroxyphenyl
bis
benzofluorene
reaction
Prior art date
Application number
PCT/JP2019/024412
Other languages
English (en)
Japanese (ja)
Inventor
中嶋　淳
祐樹 橋本
Original Assignee
本州化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 本州化学工業株式会社 filed Critical 本州化学工業株式会社
Priority to JP2020527451A priority Critical patent/JPWO2020004207A1/ja
Priority to CN201980040423.7A priority patent/CN112334437A/zh
Priority to KR1020207036590A priority patent/KR20210025010A/ko
Publication of WO2020004207A1 publication Critical patent/WO2020004207A1/fr

Links

Images

Classifications

    • 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
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
    • 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
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

  • the present invention is characterized in that the melting point is 182 to 187 ° C. by differential scanning calorimetry, and the 9,9-bis (4) is not an inclusion body or has a residual organic solvent content of 1% by weight or less.
  • the present invention relates to a crystal of (-hydroxyphenyl) -2,3-benzofluorene and a method for producing the crystal.
  • thermoplastic synthetic resin raw materials such as polycarbonate resins, epoxy resins, and the like. It is used in applications such as thermosetting resin materials, antioxidant materials, heat-sensitive recording material materials, and photosensitive resist materials.
  • thermosetting resin materials antioxidant materials
  • heat-sensitive recording material materials heat-sensitive resist materials.
  • photosensitive resist materials photosensitive resist materials.
  • a resin produced from 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene having a chemical structure represented by the following formula has attracted attention as having excellent optical properties (eg, Patent Document 1) .
  • acetone is added to a reaction mixture containing 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene to separate crystals precipitated and then recrystallized with acetone.
  • Patent Document 2 the obtained crystal is an inclusion crystal of 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene and acetone.
  • the temperature at which the solvent, which is the guest compound, is released is higher than the melting point of the crystal.
  • the present invention has been made in view of the above-mentioned circumstances, and has a specific melting point, is not an inclusion body, or has a content of a residual organic solvent of 1% by weight or less. It is an object to provide a crystal of (4-hydroxyphenyl) -2,3-benzofluorene and a method for producing the crystal.
  • the present inventors have conducted intensive studies for solving the above-described problems, and as a result, by crystallization using a specific solvent, have a specific melting point, and are not clathrates, or of the remaining organic solvent. It has been found that a crystal of 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene having a content of 1% by weight or less can be obtained, and the present invention has been completed.
  • the present invention is as follows. 1. A crystalline 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene having a melting point of 182 to 187 ° C. as determined by differential scanning calorimetry. 2. It is characterized in that it is not an inclusion body. The crystalline body according to the above. 3. The content of the remaining organic solvent is 1% by weight or less. Or 2. The crystalline body according to the above. 4. The method includes a step of crystallizing using a mixed solvent of methanol and water. ⁇ 3. A method for producing a crystal according to any one of the preceding claims. 5. 3. The method further comprises a step of drying the crystals obtained by crystallization under a temperature condition of 45 ° C. or higher and lower than the melting point. The method according to 1.
  • 9,9-bis (4-hydroxyphenyl) -2,3- which has a specific melting point, is not an inclusion body, or has a residual organic solvent content of 1% by weight or less.
  • a benzofluorene crystal and a method for producing the crystal can be provided.
  • the reaction may be carried out when the inclusion is reacted with, for example, (meth) acrylic acid or the like.
  • the compound such as an organic solvent that is included inhibits the reaction and the reaction does not proceed.
  • FIG. 2 is a view showing a differential scanning calorimetry (DSC) curve of the crystal obtained in Example 1 (crystal of the present invention).
  • FIG. 4 is a view showing a differential scanning calorimetry (DSC) curve of the crystal obtained in Comparative Example 1.
  • FIG. 9 is a diagram showing a differential scanning calorimetry (DSC) curve of the crystal obtained in Comparative Example 2.
  • the 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene of the present invention is a compound represented by the following formula (1).
  • the method for synthesizing 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene of the present invention is not particularly limited, and a fluorene skeleton such as known 9,9-bis (4-hydroxyphenyl) fluorene is used.
  • a fluorene skeleton such as known 9,9-bis (4-hydroxyphenyl) fluorene is used.
  • the reaction of phenol with 2,3-benzo-9-fluorenone shown in the above reaction formula will be described.
  • the charge molar ratio of phenol to 2,3-benzo-9-fluorenone is not particularly limited as long as it is not less than the theoretical value (2.0), but is usually in the range of 2 to 20 times by mole, preferably It is used in an amount of 3 to 10 times the molar amount.
  • the acid catalyst to be used is not particularly limited, and a known acid catalyst can be used.
  • Specific acid catalysts include, for example, hydrochloric acid, hydrogen chloride gas, inorganic acids such as 60 to 98% sulfuric acid and 85% phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid or trichloroacetic acid.
  • Organic acids such as fluoroacetic acid and solid acids such as heteropolyacid can be exemplified.
  • Preferred is hydrogen chloride gas.
  • the preferred amount of such an acid catalyst varies depending on the reaction conditions.For example, in the case of hydrogen chloride gas, after replacing the air in the reaction system with an inert gas such as nitrogen gas, hydrogen chloride gas is blown thereinto.
  • the concentration of hydrogen chloride gas in the gas phase in the reaction vessel is 75 to 100% by volume, and the concentration of hydrogen chloride in the reaction solution is a saturated concentration.
  • 35% hydrochloric acid it is used in an amount of 5 to 70 parts by weight, preferably 10 to 40 parts by weight, more preferably 20 to 30 parts by weight based on 100 parts by weight of phenol.
  • a co-catalyst may be used together with the acid catalyst, if necessary. For example, when using hydrogen chloride gas as a catalyst, the reaction rate can be accelerated by using thiols as a cocatalyst.
  • thiols examples include alkyl mercaptans and mercaptocarboxylic acids, preferably alkylmercaptans having 1 to 12 carbon atoms and mercaptocarboxylic acids having 1 to 12 carbon atoms, for example, methyl mercaptan, ethyl Examples thereof include alkali metal salts such as mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and sodium salts thereof, thioacetic acid, ⁇ -mercaptopropionic acid and the like. These can be used alone or in combination of two or more.
  • the amount of thiols used as a cocatalyst is usually in the range of 1 to 30 mol%, preferably 2 to 10 mol%, based on 2,3-benzo-9-fluorenone as a raw material.
  • the reaction solvent may not be used during the reaction, but may be used for reasons such as improvement in operability during industrial production and improvement in the reaction rate.
  • the reaction solvent is not particularly limited as long as it does not distill out of the reactor at the reaction temperature and is inert to the reaction. Examples thereof include aromatic hydrocarbons such as toluene and xylene, methanol, ethanol, 1-propanol, 2-propanol and the like. Organic solvents such as lower aliphatic alcohols such as propanol, saturated aliphatic hydrocarbons such as hexane, heptane and cyclohexane, water, and mixtures thereof. Of these, aromatic hydrocarbons are preferably used.
  • the reaction temperature varies depending on the type of phenol or acid catalyst used as a raw material.
  • the reaction temperature is usually in the range of 10 to 60 ° C, preferably 25 to 50 ° C.
  • the reaction is usually carried out under normal pressure, but depending on the boiling point of the organic solvent that may be used, the reaction may be carried out under increased or reduced pressure so that the reaction temperature falls within the above range.
  • the reaction time varies depending on the reaction conditions such as the type of the raw material phenol and acid catalyst and the reaction temperature, but is usually completed in about 1 to 30 hours. The end point of the reaction can be confirmed by liquid chromatography or gas chromatography analysis.
  • the time when the unreacted 2,3-benzo-9-fluorenone disappears and the increase in the target substance is not observed is determined as the end point of the reaction.
  • the method of adding the reaction raw materials is not particularly limited, but it can be carried out according to a known method for producing a compound having a fluorene skeleton such as 9,9-bis (4-hydroxyphenyl) fluorene.
  • a reaction vessel is charged with a predetermined amount of phenol, an acid catalyst and, if necessary, a co-catalyst and a reaction solvent, and while stirring under a nitrogen stream, the temperature is raised to a predetermined reaction temperature.
  • a known post-treatment method can be applied.
  • an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous ammonia solution is added to the reaction termination solution to neutralize the acid catalyst.
  • the neutralized reaction mixture is allowed to stand, and if necessary, a solvent that separates from water is added, and the aqueous layer is separated and removed. Distilled water is added to the obtained oil layer as needed, and after stirring and washing, the operation of separating and removing the aqueous layer is repeated once or more times to remove the neutralized salt, and excess oil is obtained from the obtained oil layer.
  • Phenol is removed by vacuum distillation.
  • a solvent such as an aromatic hydrocarbon is added to the obtained residue to form a uniform solution, and the solution is cooled to separate the precipitated crystal to obtain a crude crystal.
  • the crude crystals and the residue have a specific melting point, are not clathrates, or have a residual organic solvent content of 1% by weight or less.
  • the production method of the present invention is characterized by including a step of crystallization using a mixed solvent of methanol and water.
  • usable methanol is not particularly limited, and generally commercially available methanol can be used, and any of special grade, primary grade, and industrial grade may be used.
  • usable water is not particularly limited, and for example, tap water, distilled water, ion-exchanged water, natural water, and the like can be appropriately used.
  • the amount of residual methanol in the target 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene is reduced.
  • the content of water is determined based on the mixing ratio (weight ratio) of methanol and water.
  • the solvent used for the reaction or the post-treatment of the reaction for example, 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene, which includes an aromatic hydrocarbon solvent such as toluene, is added.
  • the mixing ratio (weight ratio) of methanol and water is more preferably from 1.0 to 1.8: 1.0, and even more preferably from 1.4 to 1.6: 1.0.
  • the amount of the mixed solvent used with methanol and water is determined by the amount of 9,9-bis (4-hydroxyphenyl) -2,3 contained in the residue obtained in the post-treatment step of the reaction used in the crystallization step or in the crude crystals. 250 to 1000 parts by weight, preferably 300 to 700 parts by weight, more preferably 400 to 600 parts by weight, and most preferably 450 to 550 parts by weight, based on 100 parts by weight of benzofluorene.
  • the amount of the mixed solvent used with methanol and water is large, the amount of crystals obtained is reduced, and if it is small, the purity of the target product is undesirably reduced. Furthermore, in the crystallization step of the present invention, when a solvent other than methanol and water is used, it has a specific melting point, is not an inclusion body, or has a residual organic solvent content of 1% by weight or less. , 9-Bis (4-hydroxyphenyl) -2,3-benzofluorene is not preferred because it cannot be obtained.
  • a mixed solvent of methanol and water having the above-mentioned mixing ratio (weight ratio) with methanol and water is added to the residue or crude crystals after the post-treatment of the reaction to be used.
  • cooling after heating to obtain a uniform solution at 5 to 15 ° C./hour, preferably 8 to 12 ° C./hour, 0 to 40 ° C., preferably 10 to 35 ° C., more preferably 20 to 35 ° C.
  • the solvent (methanol or water) used in the crystallization step of the present invention can be removed.
  • the drying step of the present invention can be carried out under the temperature condition of 45 ° C. or higher and lower than the melting point of the crystal obtained by the crystallization step, preferably 70 ° C. or higher, more preferably 90 ° C. or higher. Preferably, 120 ° C. or higher is particularly preferred. Further, the hue of the crystal may be deteriorated by heat depending on other conditions and the like. Therefore, the temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower.
  • the drying step may be carried out at normal pressure or under reduced pressure. However, when the drying step is carried out industrially, it is more efficient to carry out under reduced pressure, and the solvent used in the crystallization step (methanol or water) is more efficiently used. ) Can also be removed. In addition, the drying step is more preferably performed in an atmosphere of an inert gas such as nitrogen.
  • the crystalline form of 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene according to the present invention has a melting point of 182 ° C. or more as measured by differential scanning calorimetry and is in a range of 187 ° C. or less. I do.
  • the lower limit of the melting point determined by differential scanning calorimetry is preferably 183 ° C or higher, and particularly preferably 184 ° C or higher.
  • the upper limit may be 186 ° C. or less.
  • the crystal of 9,9-bis (4-hydroxyphenyl) -2,3-benzofluorene of the present invention is not an inclusion, that is, a crystal that does not include a compound such as an organic solvent.
  • a crystal not including a compound such as an organic solvent a crystal having a residual organic solvent content of 1% by weight or less is preferable, and a crystal having a content of 0.5% by weight or less is more preferable. Crystals having a content of not more than 0.3% by weight are more preferred, and those having a content of not more than 0.1% by weight are particularly preferred.
  • ⁇ Analysis method> Powder X-ray diffraction (XRD) About 100 mg of the crystal was filled in a sample filling portion of a glass test plate, and measured using a powder X-ray diffractometer (SmartLab, manufactured by Rigaku Corporation) under the following conditions.
  • Differential scanning calorimetry 5 mg of the crystal was weighed into an aluminum pan, and measured using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation) with aluminum oxide as a control under the following operating conditions. (Operating conditions) Heating rate: 10 ° C / min Measurement temperature range: 30 to 260 ° C Measurement atmosphere: open, nitrogen 50 mL / min 3.
  • Heating rate 10 ° C / min Measurement temperature range: 30 to 300 ° C Measurement atmosphere: open, nitrogen 50 mL / min 4.
  • Hue APHA
  • the crystals were dissolved in methanol to obtain a 10% by weight solution, and the following measurement equipment was calibrated with methanol, and then the dissolved color of the 10% by weight solution was measured.
  • Measuring equipment TZ 6000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • FIG. 1 shows a differential scanning calorimetry (DSC) curve of the obtained crystal.
  • Example 1 Of the white crystals obtained in the above “Synthesis Example”, a solution prepared by heating and dissolving 70 g of the white crystals in 210 g of methanol was maintained at a temperature of not lower than 60 ° C. and not higher than the boiling point (64.7 ° C.). Dropped over minutes. Immediately after completion of the dropping, precipitation of crystals was confirmed. Thereafter, the temperature was maintained for 1 hour, and then cooled to 25 ° C at a rate of 10 ° C per hour, and the precipitated crystals were separated by filtration. The obtained white crystals were gradually heated to 120 ° C. under a reduced pressure of 1.2 kPa, and dried under reduced pressure at 120 ° C. for 3 hours.
  • FIG. 2 shows a differential scanning calorimetry (DSC) curve of the obtained crystal.
  • the precipitated crystals were filtered, and the obtained white crystals were gradually heated to 120 ° C. under a reduced pressure of 1.2 kPa, dried under reduced pressure at 120 ° C. for 1 hour, and the amount of the remaining organic solvent was determined by 1 H-NMR analysis. It was measured. Furthermore, drying was continued at 120 ° C. for 3 hours under a reduced pressure of 1.2 kPa, but there was no change in the amount of organic solvent contained in the crystals.
  • FIG. 3 shows a differential scanning calorimetry (DSC) curve of the obtained crystal.
  • FIG. 4 shows a differential scanning calorimetry (DSC) curve of the obtained crystal.
  • the reaction was carried out at a temperature of 1 hour. Thereafter, 69.9 g of toluene and 43.7 g of water were added to the reaction solution, and the mixture was stirred and allowed to stand. Then, the aqueous layer was separated and removed. Further, a washing operation of adding 43.7 g of a saturated saline solution to the obtained organic layer, stirring, and allowing to stand, separating and removing the aqueous layer was repeated three times. Thereafter, the organic layer was gradually cooled to 5 ° C., and stirring was continued for another 5 hours, but no crystals were precipitated. Stirring was further continued at room temperature for 15 hours, but no crystals were precipitated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un corps cristallin de 9,9-bis(4-hydroxyphényl)-2,3-benzofluorène, qui a un point de fusion spécifique, et qui n'est pas un corps d'inclusion ou a une teneur en solvant organique restant inférieure ou égale à 1 % en poids. L'invention concerne un 9,9-bis(4-hydroxyphényl)-2,3-benzofluorène ayant une structure chimique représentée par la formule (1) qui est cristallisé à l'aide d'un solvant spécifique, permet de produire un corps cristallin qui n'est pas un corps d'inclusion et qui a une teneur en solvant organique restant de 1 % en poids ou moins.
PCT/JP2019/024412 2018-06-27 2019-06-20 Corps cristallin de 9,9-bis(4-hydroxyphényl)-2,3-benzofluorène WO2020004207A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2020527451A JPWO2020004207A1 (ja) 2018-06-27 2019-06-20 ９，９−ビス（４−ヒドロキシフェニル）−２，３−ベンゾフルオレンの結晶体
CN201980040423.7A CN112334437A (zh) 2018-06-27 2019-06-20 9,9-双(4-羟基苯基)-2,3-苯并芴的结晶体
KR1020207036590A KR20210025010A (ko) 2018-06-27 2019-06-20 9,9－비스(4－히드록시페닐)－2,3－벤조플루오렌의 결정체

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-122163 2018-06-27
JP2018122163 2018-06-27

Publications (1)

Publication Number Publication Date
WO2020004207A1 true WO2020004207A1 (fr) 2020-01-02

Family

ID=68985034

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/024412 WO2020004207A1 (fr) 2018-06-27 2019-06-20 Corps cristallin de 9,9-bis(4-hydroxyphényl)-2,3-benzofluorène

Country Status (5)

Country Link
JP (1) JPWO2020004207A1 (fr)
KR (1) KR20210025010A (fr)
CN (1) CN112334437A (fr)
TW (1) TWI820160B (fr)
WO (1) WO2020004207A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0441450A (ja) * 1990-06-06 1992-02-12 Nippon Steel Chem Co Ltd ビス（４―ヒドロキシフェニル）フルオレン類の製造方法
JP2009234998A (ja) * 2008-03-27 2009-10-15 Osaka Gas Co Ltd フルオレン骨格を含有する化合物を用いた包接化合物
JP2017036249A (ja) * 2015-08-12 2017-02-16 富士フイルム株式会社 化合物の製造方法及び混晶
JP2018024611A (ja) * 2016-08-10 2018-02-15 大神薬化株式会社 ９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレン結晶の製造方法
JP2018048086A (ja) * 2016-09-21 2018-03-29 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化合物の結晶およびその製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3521242B2 (ja) 1997-03-05 2004-04-19 大阪瓦斯株式会社 ビスクレゾール類の精製方法
CN101657406B (zh) * 2007-02-15 2014-04-02 田冈化学工业株式会社 芴衍生物的结晶多形体及其制造方法
WO2013133106A1 (fr) * 2012-03-09 2013-09-12 本州化学工業株式会社 Procédé de production de 9,9-bis(4-(2-hydroxyéthoxy)phényl)fluorène, cristal dudit composé et son procédé de production
WO2015147115A1 (fr) 2014-03-28 2015-10-01 富士フイルム株式会社 Composition de résine (méth)acrylique, film, film de protection pour plaque de polarisation, plaque de polarisation, et affichage à cristaux liquides
JP6241977B2 (ja) * 2016-05-19 2017-12-06 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化合物の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0441450A (ja) * 1990-06-06 1992-02-12 Nippon Steel Chem Co Ltd ビス（４―ヒドロキシフェニル）フルオレン類の製造方法
JP2009234998A (ja) * 2008-03-27 2009-10-15 Osaka Gas Co Ltd フルオレン骨格を含有する化合物を用いた包接化合物
JP2017036249A (ja) * 2015-08-12 2017-02-16 富士フイルム株式会社 化合物の製造方法及び混晶
JP2018024611A (ja) * 2016-08-10 2018-02-15 大神薬化株式会社 ９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレン結晶の製造方法
JP2018048086A (ja) * 2016-09-21 2018-03-29 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化合物の結晶およびその製造方法

Also Published As

Publication number Publication date
TW202012349A (zh) 2020-04-01
TWI820160B (zh) 2023-11-01
JPWO2020004207A1 (ja) 2021-07-08
CN112334437A (zh) 2021-02-05
KR20210025010A (ko) 2021-03-08

Similar Documents

Publication Publication Date Title
KR102564609B1 (ko) 플루오렌 골격을 갖는 알코올의 결정 및 그 제조 방법
WO2013133106A1 (fr) Procédé de production de 9,9-bis(4-(2-hydroxyéthoxy)phényl)fluorène, cristal dudit composé et son procédé de production
TWI658034B (zh) 具有茀骨架之醇之結晶及其製造方法
WO2021015083A1 (fr) Cristal de 2, 2'-bis(éthoxycarbonylméthoxy)-1, 1'-binaphtyle
WO2020004207A1 (fr) Corps cristallin de 9,9-bis(4-hydroxyphényl)-2,3-benzofluorène
WO2020059710A1 (fr) Cristal d'un composé bifluorène
WO2022138178A1 (fr) Cristal de 1,1,1-tris(4-hydroxy-3,5-diméthylphényl)éthane et son procédé de production
WO2022075120A1 (fr) Procédé de production d'un composé de tétrakisphénol ayant un squelette biphényle
WO2020256045A1 (fr) Cristal de 4,4'-bis(2-propène-1-yloxy)-1,1'-biphényle à substitution hexaméthyle/à substitution diméthyle
TWI826527B (zh) 雙茀化合物的結晶混合體
JP6250453B2 (ja) トリスフェノール化合物
JP2009107991A (ja) 新規なヒドロキシメチル置換又はアルコキシメチル置換ビスフェノール化合物
TW202344494A (zh) 聯菲化合物或其鹼金屬鹽
JP4336501B2 (ja) 新規な４，４”−ジアルコキシターフェニル類
JP2019026627A (ja) 新規なビスフェノール化合物
JP2005220300A (ja) エポキシ樹脂の製造法
JP2005029507A (ja) 新規な４、４”−ジ（ヒドロキシアルコキシ）ターフェニル類
JP2005272375A (ja) ４，４’’’−ジアルコキシ−ｐ−クォーターフェニル類及びその製造方法
JP2010024247A (ja) １，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサンの製造方法
JP2005179192A (ja) カルボラクトン環を有する３級アルコール化合物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19827456

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020527451

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19827456

Country of ref document: EP

Kind code of ref document: A1