WO2021187075A1 - Composé d'hydrocarbure aromatique polycyclique, son cristal et son procédé de production - Google Patents

Composé d'hydrocarbure aromatique polycyclique, son cristal et son procédé de production Download PDF

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Publication number
WO2021187075A1
WO2021187075A1 PCT/JP2021/007767 JP2021007767W WO2021187075A1 WO 2021187075 A1 WO2021187075 A1 WO 2021187075A1 JP 2021007767 W JP2021007767 W JP 2021007767W WO 2021187075 A1 WO2021187075 A1 WO 2021187075A1
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polycyclic aromatic
aromatic hydrocarbon
hydrocarbon compound
formula
group
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PCT/JP2021/007767
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English (en)
Japanese (ja)
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和徳 布目
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帝人株式会社
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Priority to JP2022508182A priority Critical patent/JP7455190B2/ja
Priority to CN202180013854.1A priority patent/CN115135631B/zh
Publication of WO2021187075A1 publication Critical patent/WO2021187075A1/fr

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    • 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

Definitions

  • the present invention relates to a polycyclic aromatic hydrocarbon compound, a crystal thereof, and a method for producing the same.
  • Patent Document 1 discloses that the refractive index of a polycarbonate resin made of BN2EO is 1.668.
  • Patent Document 2 discloses that the refractive index of a polycarbonate resin composed of 6,6'-diphenyl-2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene is 1.679. Has been done. However, with the rapid technological innovation in recent years, further improvement of the refractive index is required.
  • An object of the present invention is to provide a novel polycyclic aromatic hydrocarbon compound having a high refractive index, a crystal thereof, and a method for producing the same.
  • a polycyclic aromatic hydrocarbon compound represented by the following formula (1) A polycyclic aromatic hydrocarbon compound represented by the following formula (1).
  • Z is a polycyclic aromatic hydrocarbon in which three benzene rings are bonded
  • L 1 is an alkylene group having 1 to 15 carbon atoms
  • R 1 is a hydrocarbon group having 1 to 12 carbon atoms.
  • M 1 is an integer of 1 to 5
  • n 1 is an integer of 0 to 8.
  • ⁇ Aspect 2 The polycyclic aromatic hydrocarbon compound according to embodiment 1, wherein Z in the formula (1) is phenanthrene.
  • ⁇ Aspect 3 The polycyclic aromatic hydrocarbon compound according to Aspect 1 or 2, wherein the polycyclic aromatic hydrocarbon compound represented by the formula (1) is a polycyclic aromatic hydrocarbon compound represented by the following formula (2). ..
  • R 2 and R 3 are hydrocarbon groups having 1 to 12 carbon atoms, n 2 and n 3 are integers of 0 to 4, and L 1 and m 1 are the same as in the above formula (1). Is.
  • Aspect 4 Aspect in which the polycyclic aromatic hydrocarbon compound represented by the formula (1) is 10,10'-bis (2-hydroxyethoxy) -9,9'-biphenanthrene represented by the following formula (3).
  • ⁇ Aspect 5 The polycyclic aromatic hydrocarbon compound according to any one of aspects 1 to 4, wherein the HPLC purity is 95 area% or more.
  • ⁇ Aspect 6 The polycyclic aromatic compound according to any one of aspects 1 to 5, wherein the Hazen unit color number (hereinafter, also referred to as APHA) of a 5% by weight solution in which a polycyclic aromatic hydrocarbon compound is dissolved in dimethylformamide is 100 or less. Hydrocarbon compounds.
  • ⁇ Aspect 7 The crystal of the polycyclic aromatic hydrocarbon compound according to aspect 4, which has an endothermic peak by differential scanning calorimetry in the range of 230 to 250 ° C.
  • a method for producing a polycyclic aromatic hydrocarbon compound represented by the formula (1) by reacting a polycyclic aromatic hydrocarbon compound represented by the following formula (4) with an ethylene carbonate in the presence of a base The method for producing a polycyclic aromatic hydrocarbon compound according to Aspect 1, wherein an aprotonic polar solvent is used as a reaction solvent.
  • Z is a polycyclic aromatic hydrocarbon in which three benzene rings are bonded, R 1 is a hydrocarbon group having 1 to 12 carbon atoms, and n 1 is an integer of 0 to 8.
  • Aspect 9 The method for producing a polycyclic aromatic hydrocarbon compound according to Aspect 8, which uses dimethylformamide as a reaction solvent.
  • Z is a polycyclic aromatic hydrocarbon in which three benzene rings are bonded
  • L 1 is an alkylene group having 1 to 15 carbon atoms
  • R 1 is a hydrocarbon group having 1 to 12 carbon atoms.
  • M 1 is an integer of 1 to 5
  • n 1 is an integer of 0 to 8.
  • Z in the formula (1) is a polycyclic aromatic hydrocarbon in which three benzene rings are bonded, and anthracene, phenanthrene, and phenanthrene are preferable, and phenanthrene is more preferable.
  • L 1 in the formula (1) is an alkylene group having 1 to 15 carbon atoms, preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. It is preferably an ethylene group, and particularly preferably an ethylene group.
  • R 1 in the formula (1) is a hydrocarbon group having 1 to 12 carbon atoms
  • the hydrocarbon group 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, more preferably C 1-4 alkyl group, and C 1 A -3 alkyl group is more preferable, and a methyl group and an ethyl group are particularly preferable.
  • cycloalkyl group a C 5-8 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferable, and a C 5-6 cycloalkyl group is more preferable.
  • a phenyl group an alkylphenyl group (mono or dimethylphenyl group, tolyl group, 2-methylphenyl group, xsilyl group, etc.) and a naphthyl group 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.
  • M 1 in Formula (1) is an integer of 1 to 5, preferably an integer of 1 or 2, and more preferably 1.
  • N 1 in the formula (1) is an integer of 0 to 8, preferably an integer of 0 to 4, and more preferably 0.
  • the biphenanthrene compound represented by the following formula (2) is preferable.
  • R 2 and R 3 are hydrocarbon groups having 1 to 12 carbon atoms, n 2 and n 3 are integers of 0 to 4, and L 1 and m 1 are the same as in the above formula (1). Is.
  • R 2 and R 3 in the formula (2) are hydrocarbon groups having 1 to 12 carbon atoms, and are specifically the same as R 1 in the above formula (1).
  • N 2 and n 3 in the formula (2) are integers of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
  • L 1, m 1 in formula (2) is the same as L 1, m 1 in Formula (1) described above.
  • biphenanthrene compound represented by the formula (2) examples include 2,2'-bis (2-hydroxyethoxy) -1,1'-biphenanthrene and 3,3'-bis (2-hydroxyethoxy)-.
  • 4,4'-biphenanthrene, 10,10'-bis (2-hydroxyethoxy) -9,9'-biphenanthrene is preferable, and 10,10'-bis (2-hydroxy) represented by the following formula (3) is preferable.
  • Ethoxy) -9,9'-biphenanthrene is particularly preferred.
  • the polycyclic aromatic hydrocarbon compound of the present invention preferably has an HPLC purity measured by HPLC of 95 area% or more, more preferably 97 area% or more, and further preferably 98 area% or more. ..
  • the polycyclic aromatic hydrocarbon compound of the present invention preferably has an APHA of 100 or less, more preferably 70 or less, and 50 or less in a 5% by weight solution in which the compound is dissolved in dimethylformamide. Is even more preferable.
  • APHA is 100 or less, the hue of the compound becomes good, which is preferable.
  • Crystals of polycyclic aromatic hydrocarbon compounds preferably has an endothermic peak in the range of 230 to 250 ° C. by differential scanning calorimetry, and more preferably in the range of 235 to 250 ° C. It is more preferable to have it in the range of 240 to 248 ° C, and particularly preferably to have it in the range of 243 to 246 ° C.
  • the crystal of the compound represented by the above formula (3) obtained in the present invention is excellent in processability, productivity and handleability, and also has good hue and purity.
  • the polycyclic aromatic hydrocarbon compound of the present invention is produced by reacting a polycyclic aromatic hydrocarbon compound represented by the following formula (4) with ethylene carbonate in the presence of an aprotonic polar solvent and a base. be able to.
  • Z is a polycyclic aromatic hydrocarbon in which three benzene rings are bonded, R 1 is a hydrocarbon group having 1 to 12 carbon atoms, and n 1 is an integer of 0 to 8.
  • Examples of the aprotonic polar solvent used in the production method of the present invention include N-methylpyrrolidone, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, ethylene carbonate, propylene carbonate and the like, and dimethylformamide is used. preferable.
  • the amount of the aprotic polar solvent used in the production method of the present invention is preferably 0.1 to 10 times by weight, preferably 0.3 to 10 times the weight of the polycyclic aromatic hydrocarbon compound represented by the formula (4). 7 times by weight is more preferable, and 0.5 to 5 times by weight is even more preferable. If the amount of the solvent used is less than 0.1 times by weight, the polycyclic aromatic hydrocarbon compound represented by the formula (4) and the produced polycyclic aromatic hydrocarbon compound represented by the formula (1) are difficult to stir. May become. If the amount of solvent used is more than 10 times by weight, the reaction time may be delayed and the volumetric efficiency may decrease, resulting in deterioration of production efficiency and economic disadvantage. In addition, long-term heating operations may increase side reactants. May cause coloring.
  • the amount (molar ratio) of the polycyclic aromatic hydrocarbon compound represented by the formula (4) and ethylene carbonate used is preferably 1: 1.9 to 1: 2.9, and 1: 1. 2 to 1: 2.7 is more preferable, and 1: 2.1 to 1: 2.5 is even more preferable. If the amount of ethylene carbonate used is less than 1: 1.9, the reaction time may be long. Further, the polycyclic aromatic hydrocarbon compound represented by the formula (4) remains unreacted, and 1 mol of the polycyclic aromatic hydrocarbon compound represented by the formula (4) reacts with 1 mol of ethylene carbonate. Yield and purity may decrease due to the increase in the amount of by-products.
  • the amount of ethylene carbonate used is more than 1: 2.9, the amount of by-products obtained by reacting 1 mol of the polycyclic aromatic hydrocarbon compound represented by the formula (4) with 3 mol or more of ethylene carbonate increases. The rate and purity may decrease.
  • the reaction temperature is not particularly limited, but is preferably 150 ° C. or lower, more preferably 140 to 40 ° C., and even more preferably 130 to 70 ° C. If the reaction temperature is too high, it may cause a decrease in yield or a deterioration in hue due to an increase in side reactants. If the reaction temperature is too low, the reaction may not proceed rapidly.
  • Examples of the base used in the production method of the present invention include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate and the like, and potassium hydroxide, sodium hydroxide and potassium carbonate are preferable, and carbonic acid is preferable. Potassium is more preferred.
  • the amount of the base used in the production method of the present invention is not particularly limited, but is 0.01 to 0.5 mol with respect to 1 mol of the polycyclic aromatic hydrocarbon compound represented by the formula (4). Is preferable, and 0.05 to 0.3 mol is more preferable. If the amount of base used is small, the reaction may not proceed or the reaction may be delayed. If the amount used is large, the yield and purity may decrease due to the increase in by-products, which may cause coloring.
  • Refractive index (nD) The compound obtained in the example was dissolved in dimethyl sulfoxide to prepare a solution having a predetermined concentration, and the refractive index of each concentration solution was measured using a DR-M2 Abbe refractometer manufactured by ATAGO to determine the D-line refractive index at 25 ° C. It was measured. The value extrapolated to a concentration of 100% from the measurement results of each concentration was taken as the refractive index (nD) of the compound obtained in the example.
  • APHA measurement A solution prepared by dissolving 0.5 g of a measurement sample in 10 ml of dimethylformamide was placed in a test tube having a diameter of 25 mm and measured using TZ6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
  • Example 1 In a nitrogen atmosphere, in a flask equipped with a stirrer, a cooler, and a thermometer, 10.00 g of 10,10'-dihydroxy-9,9'-biphenanthrene, 5.24 g of ethylene carbonate, 0.36 g of potassium carbonate, and 20 ml of dimethylformamide. was added, and the mixture was reacted at 120 ° C. for 5 hours. After cooling the reaction solution, 15 ml of dimethylformamide and 2 ml of a 10% NaOH aqueous solution were added, and alkali treatment was carried out at 110 ° C. for 3 hours. After cooling the reaction solution, the reaction solution was added dropwise to the distilled water with stirring, and the obtained crystals were recovered.
  • the recovered crystals were washed with distilled water in a slurry, and then the crystals were recovered and dried to obtain 10.3 g of white crystals of 10,10'-bis (2-hydroxyethoxy) -9,9'-biphenanthrene (yield). Rate 84%).
  • the purity of the obtained crystals was 97.27%, APHA was 70, the endothermic peak by differential scanning calorimetry was 237 ° C, and the refractive index was 1.713.
  • the NMR chart of the obtained 10,10'-bis (2-hydroxyethoxy) -9,9'-biphenanthrene is shown in FIG. 1, and the differential scanning calorimetry result is shown in FIG.
  • Example 2 After dissolving 10.3 g of the crystal obtained in Example 1 in 10 ml of chloroform, 100 ml of hexane was added and recrystallized. The crystals were recovered and dried to obtain 8.4 g of white crystals of 10,10'-bis (2-hydroxyethoxy) -9,9'-biphenanthrene. The purity of the obtained crystals was 98.96%, APHA was 50, and the endothermic peak by differential scanning calorimetry was 245 ° C. The results of differential scanning calorimetry analysis of the obtained crystals are shown in FIG.
  • Example 1 The reaction was carried out in the same manner as in Example 1 except that 20 ml of dimethylformamide in Example 1 was changed to 70 ml of toluene and the reaction temperature was changed from 120 ° C. to 110 ° C.
  • the target product of 10,10'-bis (2-hydroxyethoxy) -9,9'-biphenanthrene was about 4%, and the raw material of 10,10'-dihydroxy.
  • novel polycyclic aromatic hydrocarbon compound obtained in the present invention has a high refractive index, it is suitable as a monomer for forming a resin constituting an optical member represented by an optical lens or an optical film.

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

Abstract

La présente invention concerne un composé d'hydrocarbure aromatique polycyclique représenté par la formule (1). (Dans la formule, Z est un hydrocarbure aromatique polycyclique ayant trois cycles benzène liés, L1 est un groupe alkylène ayant de 1 à 15 atomes de carbone, R1 est un groupe hydrocarboné ayant de 1 à 12 atomes de carbone, m1 est un nombre entier de 1 à 5 et n1 est un nombre entier de 0 à 8.)
PCT/JP2021/007767 2020-03-19 2021-03-01 Composé d'hydrocarbure aromatique polycyclique, son cristal et son procédé de production WO2021187075A1 (fr)

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JP2022508182A JP7455190B2 (ja) 2020-03-19 2021-03-01 多環芳香族炭化水素化合物、その結晶およびその製造方法
CN202180013854.1A CN115135631B (zh) 2020-03-19 2021-03-01 多环芳烃化合物、其晶体及其制造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023195505A1 (fr) * 2022-04-07 2023-10-12 三菱瓦斯化学株式会社 Résine thermoplastique et lentille optique la comprenant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001072872A (ja) * 1999-07-02 2001-03-21 Konica Corp 樹脂組成物および光学用レンズ
WO2010027676A2 (fr) * 2008-09-04 2010-03-11 3M Innovative Properties Company Composition dentaire comprenant un monomère de di(méth)acrylate de biphényle
JP2015193548A (ja) * 2014-03-31 2015-11-05 大阪ガスケミカル株式会社 新規ジオール化合物及びポリエステル
JP2017179323A (ja) * 2016-03-28 2017-10-05 大阪ガスケミカル株式会社 高屈折率ポリカーボネート系樹脂及び成形体
WO2020175353A1 (fr) * 2019-02-27 2020-09-03 帝人株式会社 Composé comprenant un squelette binaphtalène et procédé de production d'un composé comprenant un squelette binaphtalène

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001072872A (ja) * 1999-07-02 2001-03-21 Konica Corp 樹脂組成物および光学用レンズ
WO2010027676A2 (fr) * 2008-09-04 2010-03-11 3M Innovative Properties Company Composition dentaire comprenant un monomère de di(méth)acrylate de biphényle
JP2015193548A (ja) * 2014-03-31 2015-11-05 大阪ガスケミカル株式会社 新規ジオール化合物及びポリエステル
JP2017179323A (ja) * 2016-03-28 2017-10-05 大阪ガスケミカル株式会社 高屈折率ポリカーボネート系樹脂及び成形体
WO2020175353A1 (fr) * 2019-02-27 2020-09-03 帝人株式会社 Composé comprenant un squelette binaphtalène et procédé de production d'un composé comprenant un squelette binaphtalène

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
REINELT, S ET AL.: "Synthesis and Photopolymerization of Thiol-Modified Triazine- Based Monomers and Oligomers for the Use in Thiol- Ene-Based Dental Composites", MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 215, no. 14, 2014, pages 1415 - 1425, XP055763368, DOI: 10.1002/macp.201400174 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023195505A1 (fr) * 2022-04-07 2023-10-12 三菱瓦斯化学株式会社 Résine thermoplastique et lentille optique la comprenant

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TW202140412A (zh) 2021-11-01
JP7455190B2 (ja) 2024-03-25
CN115135631A (zh) 2022-09-30

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