WO2022097396A1 - Method for producing compound having fluorene skeleton, and compound having fluorene skeleton - Google Patents
Method for producing compound having fluorene skeleton, and compound having fluorene skeleton Download PDFInfo
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- WO2022097396A1 WO2022097396A1 PCT/JP2021/036373 JP2021036373W WO2022097396A1 WO 2022097396 A1 WO2022097396 A1 WO 2022097396A1 JP 2021036373 W JP2021036373 W JP 2021036373W WO 2022097396 A1 WO2022097396 A1 WO 2022097396A1
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- WIPO (PCT)
- Prior art keywords
- compound
- fluorene skeleton
- formula
- acid
- reaction
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 60
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 63
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 13
- 241001550224 Apha Species 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 18
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000005620 boronic acid group Chemical class 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 66
- 238000006243 chemical reaction Methods 0.000 description 33
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 229920005668 polycarbonate resin Polymers 0.000 description 7
- 239000004431 polycarbonate resin Substances 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- GUFIKYXJLDNKON-UHFFFAOYSA-N 2-[6-[9-[6-(2-hydroxyethoxy)naphthalen-2-yl]-2,7-diphenylfluoren-9-yl]naphthalen-2-yl]oxyethanol Chemical compound OCCOC=1C=C2C=CC(=CC2=CC=1)C1(C2=CC(=CC=C2C=2C=CC(=CC1=2)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC2=CC=C(C=C2C=C1)OCCO GUFIKYXJLDNKON-UHFFFAOYSA-N 0.000 description 5
- -1 2-hydroxyethoxy Chemical group 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTPLEVOKSWEYAC-UHFFFAOYSA-N 1,2-diphenyl-9h-fluorene Chemical compound C=1C=CC=CC=1C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 QTPLEVOKSWEYAC-UHFFFAOYSA-N 0.000 description 3
- HXGPBZKGPPZSGX-UHFFFAOYSA-N 2,7-bis[fluoro(dipyridin-2-yl)methyl]-1,8-naphthyridine Chemical compound C=1C=CC=NC=1C(C=1N=C2N=C(C=CC2=CC=1)C(F)(C=1N=CC=CC=1)C=1N=CC=CC=1)(F)C1=CC=CC=N1 HXGPBZKGPPZSGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- ZDJPTLICZYRDQA-UHFFFAOYSA-N 2,3-diphenylfluoren-1-one Chemical compound O=C1C2=CC3=CC=CC=C3C2=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 ZDJPTLICZYRDQA-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 2
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ZYYANAWVBDFAHY-UHFFFAOYSA-N (2,3-dimethylphenyl)boronic acid Chemical compound CC1=CC=CC(B(O)O)=C1C ZYYANAWVBDFAHY-UHFFFAOYSA-N 0.000 description 1
- TYONHSPZXLFWKI-UHFFFAOYSA-N (2,4-dimethylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C(C)=C1 TYONHSPZXLFWKI-UHFFFAOYSA-N 0.000 description 1
- OOMZKLJLVGQZGV-UHFFFAOYSA-N (2,5-dimethylphenyl)boronic acid Chemical compound CC1=CC=C(C)C(B(O)O)=C1 OOMZKLJLVGQZGV-UHFFFAOYSA-N 0.000 description 1
- DGFCTCGCMKEILT-UHFFFAOYSA-N (2-ethoxyphenyl)boronic acid Chemical compound CCOC1=CC=CC=C1B(O)O DGFCTCGCMKEILT-UHFFFAOYSA-N 0.000 description 1
- NSJVYHOPHZMZPN-UHFFFAOYSA-N (2-methylphenyl)boronic acid Chemical compound CC1=CC=CC=C1B(O)O NSJVYHOPHZMZPN-UHFFFAOYSA-N 0.000 description 1
- HYCYKHYFIWHGEX-UHFFFAOYSA-N (2-phenylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C1=CC=CC=C1 HYCYKHYFIWHGEX-UHFFFAOYSA-N 0.000 description 1
- KDVZJKOYSOFXRV-UHFFFAOYSA-N (3,4-dimethylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1C KDVZJKOYSOFXRV-UHFFFAOYSA-N 0.000 description 1
- DJGHSJBYKIQHIK-UHFFFAOYSA-N (3,5-dimethylphenyl)boronic acid Chemical compound CC1=CC(C)=CC(B(O)O)=C1 DJGHSJBYKIQHIK-UHFFFAOYSA-N 0.000 description 1
- CHCWUTJYLUBETR-UHFFFAOYSA-N (3-ethoxyphenyl)boronic acid Chemical compound CCOC1=CC=CC(B(O)O)=C1 CHCWUTJYLUBETR-UHFFFAOYSA-N 0.000 description 1
- BJQCPCFFYBKRLM-UHFFFAOYSA-N (3-methylphenyl)boronic acid Chemical compound CC1=CC=CC(B(O)O)=C1 BJQCPCFFYBKRLM-UHFFFAOYSA-N 0.000 description 1
- GOXICVKOZJFRMB-UHFFFAOYSA-N (3-phenylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=CC=CC=2)=C1 GOXICVKOZJFRMB-UHFFFAOYSA-N 0.000 description 1
- UKZVUHVNTYDSOP-UHFFFAOYSA-N (3-propan-2-yloxyphenyl)boronic acid Chemical compound CC(C)OC1=CC=CC(B(O)O)=C1 UKZVUHVNTYDSOP-UHFFFAOYSA-N 0.000 description 1
- SRSWMXFANVKOFH-UHFFFAOYSA-N (3-propoxyphenyl)boronic acid Chemical compound CCCOC1=CC=CC(B(O)O)=C1 SRSWMXFANVKOFH-UHFFFAOYSA-N 0.000 description 1
- WRQNDLDUNQMTCL-UHFFFAOYSA-N (4-ethoxyphenyl)boronic acid Chemical compound CCOC1=CC=C(B(O)O)C=C1 WRQNDLDUNQMTCL-UHFFFAOYSA-N 0.000 description 1
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 1
- BSKLSKWOKGVQHF-UHFFFAOYSA-N (4-phenylnaphthalen-1-yl)boronic acid Chemical compound C12=CC=CC=C2C(B(O)O)=CC=C1C1=CC=CC=C1 BSKLSKWOKGVQHF-UHFFFAOYSA-N 0.000 description 1
- XPEIJWZLPWNNOK-UHFFFAOYSA-N (4-phenylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=CC=C1 XPEIJWZLPWNNOK-UHFFFAOYSA-N 0.000 description 1
- CJUHQADBFQRIMC-UHFFFAOYSA-N (4-propan-2-yloxyphenyl)boronic acid Chemical compound CC(C)OC1=CC=C(B(O)O)C=C1 CJUHQADBFQRIMC-UHFFFAOYSA-N 0.000 description 1
- IAEUFBDMVKQCLU-UHFFFAOYSA-N (4-propan-2-ylphenyl)boronic acid Chemical compound CC(C)C1=CC=C(B(O)O)C=C1 IAEUFBDMVKQCLU-UHFFFAOYSA-N 0.000 description 1
- WLCGYIWOKVWFLB-UHFFFAOYSA-N (4-propylphenyl)boronic acid Chemical compound CCCC1=CC=C(B(O)O)C=C1 WLCGYIWOKVWFLB-UHFFFAOYSA-N 0.000 description 1
- DEQOVKFWRPOPQP-UHFFFAOYSA-N (5-formylthiophen-2-yl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)S1 DEQOVKFWRPOPQP-UHFFFAOYSA-N 0.000 description 1
- GZFAVYWCPSMLCM-UHFFFAOYSA-N (6-methoxynaphthalen-2-yl)boronic acid Chemical compound C1=C(B(O)O)C=CC2=CC(OC)=CC=C21 GZFAVYWCPSMLCM-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- CVFRBXCMTNBDBI-UHFFFAOYSA-N 1-benzothiophen-4-ylboronic acid Chemical compound OB(O)C1=CC=CC2=C1C=CS2 CVFRBXCMTNBDBI-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- FYEFHYMUEWRCRF-UHFFFAOYSA-N 2,7-dibromofluoren-1-one Chemical compound BrC1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 FYEFHYMUEWRCRF-UHFFFAOYSA-N 0.000 description 1
- JQJYTWHASCGDRQ-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]-2,7-diphenylfluoren-9-yl]phenoxy]ethanol Chemical compound OCCOc1ccc(cc1)C1(c2cc(ccc2-c2ccc(cc12)-c1ccccc1)-c1ccccc1)c1ccc(OCCO)cc1 JQJYTWHASCGDRQ-UHFFFAOYSA-N 0.000 description 1
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 1
- FHZQOYSKWUJKDZ-UHFFFAOYSA-N 2-[6-[9-[6-(2-hydroxyethoxy)naphthalen-2-yl]fluoren-9-yl]naphthalen-2-yl]oxyethanol Chemical compound C1=C(OCCO)C=CC2=CC(C3(C4=CC=CC=C4C4=CC=CC=C43)C3=CC4=CC=C(C=C4C=C3)OCCO)=CC=C21 FHZQOYSKWUJKDZ-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- KIHCSOMVJQDKCN-UHFFFAOYSA-N 4-[2-tert-butylphosphanyl-1-[4-(dimethylamino)phenyl]-2-methylpropyl]-N,N-dimethylaniline Chemical compound CN(C)C1=CC=C(C=C1)C(C(C)(C)PC(C)(C)C)C1=CC=C(C=C1)N(C)C KIHCSOMVJQDKCN-UHFFFAOYSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- KPLUSVABVWBMFT-UHFFFAOYSA-N 6-(2,7-dibromo-9H-fluoren-1-yl)naphthalen-2-ol Chemical compound OC=1C=C2C=CC(=CC2=CC1)C1=C(C=CC=2C3=CC=C(C=C3CC12)Br)Br KPLUSVABVWBMFT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BFSLSOIBLFRLDV-UHFFFAOYSA-N OCCOC=1C=C2C=CC(=CC2=CC1)C1(C2=CC(=CC=C2C=2C=CC(=CC12)Br)Br)C1=CC2=CC=C(C=C2C=C1)OCCO Chemical compound OCCOC=1C=C2C=CC(=CC2=CC1)C1(C2=CC(=CC=C2C=2C=CC(=CC12)Br)Br)C1=CC2=CC=C(C=C2C=C1)OCCO BFSLSOIBLFRLDV-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- LXGQHDUCNDGTDB-PAMNCVQHSA-N [2-[(8s,9r,10s,13s,14s,16s,17r)-9-fluoro-11,17-dihydroxy-10,13,16-trimethyl-3-oxo-6,7,8,11,12,14,15,16-octahydrocyclopenta[a]phenanthren-17-yl]-2-oxoethyl] acetate;[2-[(8s,9r,10s,13s,14s,16s,17r)-9-fluoro-11,17-dihydroxy-10,13,16-trimethyl-3-oxo-6,7,8,11, Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)COC(C)=O)(O)[C@@]1(C)CC2O.C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)COP(O)(O)=O)(O)[C@@]1(C)CC2O LXGQHDUCNDGTDB-PAMNCVQHSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- YNCYPMUJDDXIRH-UHFFFAOYSA-N benzo[b]thiophene-2-boronic acid Chemical compound C1=CC=C2SC(B(O)O)=CC2=C1 YNCYPMUJDDXIRH-UHFFFAOYSA-N 0.000 description 1
- HBWDWGMBZIFBQE-UHFFFAOYSA-N benzylboronic acid Chemical compound OB(O)CC1=CC=CC=C1 HBWDWGMBZIFBQE-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZXHUJRZYLRVVNP-UHFFFAOYSA-N dibenzofuran-4-ylboronic acid Chemical compound C12=CC=CC=C2OC2=C1C=CC=C2B(O)O ZXHUJRZYLRVVNP-UHFFFAOYSA-N 0.000 description 1
- CSLSCVHILGCSTE-UHFFFAOYSA-N dibenzothiophen-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3SC2=C1 CSLSCVHILGCSTE-UHFFFAOYSA-N 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- YAWFNMSUKBTQIT-UHFFFAOYSA-N ditert-butyl(3-methylbut-2-enyl)phosphane Chemical compound CC(C)=CCP(C(C)(C)C)C(C)(C)C YAWFNMSUKBTQIT-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- PZJSZBJLOWMDRG-UHFFFAOYSA-N furan-2-ylboronic acid Chemical compound OB(O)C1=CC=CO1 PZJSZBJLOWMDRG-UHFFFAOYSA-N 0.000 description 1
- CYEFKCRAAGLNHW-UHFFFAOYSA-N furan-3-ylboronic acid Chemical compound OB(O)C=1C=COC=1 CYEFKCRAAGLNHW-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920002100 high-refractive-index polymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JCDAUYWOHOLVMH-UHFFFAOYSA-N phenanthren-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC3=CC=CC=C3C2=C1 JCDAUYWOHOLVMH-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000013308 plastic optical fiber Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 1
- QLULGIRFKAWHOJ-UHFFFAOYSA-N pyridin-4-ylboronic acid Chemical compound OB(O)C1=CC=NC=C1 QLULGIRFKAWHOJ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HZFPPBMKGYINDF-UHFFFAOYSA-N pyrimidin-5-ylboronic acid Chemical compound OB(O)C1=CN=CN=C1 HZFPPBMKGYINDF-UHFFFAOYSA-N 0.000 description 1
- DWHCQRBWSBKHMI-UHFFFAOYSA-N quinolin-2-ylboronic acid Chemical compound C1=CC=CC2=NC(B(O)O)=CC=C21 DWHCQRBWSBKHMI-UHFFFAOYSA-N 0.000 description 1
- YGDICLRMNDWZAK-UHFFFAOYSA-N quinolin-3-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CN=C21 YGDICLRMNDWZAK-UHFFFAOYSA-N 0.000 description 1
- KATIRQRAVXTBNY-UHFFFAOYSA-N quinolin-4-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=NC2=C1 KATIRQRAVXTBNY-UHFFFAOYSA-N 0.000 description 1
- NWIJBOCPTGHGIK-UHFFFAOYSA-N quinolin-5-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=N1 NWIJBOCPTGHGIK-UHFFFAOYSA-N 0.000 description 1
- JLOLSBLXNMVKGY-UHFFFAOYSA-N quinolin-6-ylboronic acid Chemical compound N1=CC=CC2=CC(B(O)O)=CC=C21 JLOLSBLXNMVKGY-UHFFFAOYSA-N 0.000 description 1
- KXJJSKYICDAICD-UHFFFAOYSA-N quinolin-8-ylboronic acid Chemical compound C1=CN=C2C(B(O)O)=CC=CC2=C1 KXJJSKYICDAICD-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- QNMBSXGYAQZCTN-UHFFFAOYSA-N thiophen-3-ylboronic acid Chemical compound OB(O)C=1C=CSC=1 QNMBSXGYAQZCTN-UHFFFAOYSA-N 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
- C08G63/197—Hydroxy compounds containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Definitions
- the present invention relates to a method for producing a compound having a fluorene skeleton and a compound having a fluorene skeleton.
- Patent Document 2 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene
- Patent Document 3 9,9-bis [4- (2-hydroxyethoxy) phenyl] -2,7-diphenyl
- fluorene 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene
- Patent Document 3 9,9-bis [4- (2-hydroxyethoxy) phenyl] -2,7-diphenyl
- fluorene Patent Document 3
- Aspect 1 The compound represented by the following formula (1) and the boronic acid represented by the following formula (2) or (3) are reacted in a reaction solvent in the presence of a base and a palladium-based catalyst, and the following formula (4) is used.
- a method for producing a compound having a fluorene skeleton which comprises using at least dimethylformamide as a reaction solvent in the step of obtaining the compound having the fluorene skeleton represented.
- X 1 and X 2 each independently indicate a halogen atom.
- Z indicates an aromatic group which may independently have a substituent having 6 to 20 carbon atoms.
- ⁇ Aspect 2 The method for producing a compound having a fluorene skeleton according to the first aspect, wherein at least dimethylformamide and an aromatic hydrocarbon solvent are used as the reaction solvent.
- ⁇ Aspect 3 A compound having a fluorene skeleton represented by the following formula (4) in which the Hazen unit color number (APHA) of a 5% by weight solution dissolved in dimethylformamide is 50 or less.
- APHA Hazen unit color number
- ⁇ Aspect 4 The method for using a compound having a fluorene skeleton according to Aspect 3 as a raw material for a thermoplastic resin.
- ⁇ Aspect 5 A thermoplastic resin obtained by polymerizing the compound having the fluorene skeleton according to the third aspect.
- a compound having a fluorene skeleton having an excellent hue can be obtained.
- the yield and productivity of producing a compound having a fluorene skeleton can be improved.
- a method for producing a compound having a fluorene skeleton which comprises using at least dimethylformamide as a reaction solvent in the step of obtaining a compound having a fluorene skeleton represented by the following formula (4).
- X 1 and X 2 each independently indicate a halogen atom.
- Z indicates an aromatic group which may independently have a substituent having 6 to 20 carbon atoms.
- Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.
- at least dimethylformamide is used as the reaction solvent.
- Dimethylformamide can achieve both the affinity of the compound used as a base with an aqueous solution and the solubility of the compound represented by the above formula (4).
- the reaction temperature can be increased, the reaction rate can be improved, and the amount of palladium catalyst can be reduced.
- an aromatic hydrocarbon solvent such as toluene in combination with dimethylformamide as the reaction solvent.
- aromatic hydrocarbon solvent used in the production method of the present invention include benzene, toluene, xylene, ethylbenzene, mesitylene, isopropylbenzene and the like, and toluene is preferable.
- the amount of the reaction solvent used in the production method of the present invention is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight, based on 1 part by weight of the compound represented by the formula (1). , More preferably 2 to 10 parts by weight.
- dimethylformamide is preferably used in an amount of 5% by weight or more, more preferably 10% by weight or more, further preferably 20% by weight or more, and particularly preferably 30% by weight or more.
- the ratio of the aromatic hydrocarbon solvent used is preferably 0.1 to 10 parts by weight, more preferably 0 with respect to 1 part by weight of dimethylformamide. .5 to 5 parts by weight, more preferably 1 to 3 parts by weight.
- the total amount of dimethylformamide and the aromatic hydrocarbon solvent in the reaction solvent is more preferably 70% by weight or more, more preferably 80% by weight. It is more preferable to use the above, and it is particularly preferable to use 90% by weight or more.
- X 1 and X 2 each independently represent a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a bromine atom.
- Z is an aromatic group which may independently have a substituent having 6 to 20 carbon atoms.
- Specific examples of the boronic acids represented by the above formula (2) or (3) are 2-anthracemboronic acid, 9-anthracemboronic acid, benzylboronic acid, 2-biphenylboronic acid, 3-biphenylboronic acid, 4-.
- Biphenylboronic acid 2,3-dimethylphenylboronic acid, 2,4-dimethylphenylboronic acid, 2,5-dimethylphenylboronic acid, 2,6-dimethylphenylboronic acid, 3,4-dimethylphenylboronic acid, 3 , 5-Dimethylphenylboronic acid, 2-ethoxyphenylboronic acid, 3-ethoxyphenylboronic acid, 4-ethoxyphenylboronic acid, 6-methoxy-2-naphthalenboronic acid, 2-methylphenylboronic acid, 3-methylphenyl Boronic acid, 4-methylphenylboronic acid, 1-naphthalenboronic acid, 2-naphthalenboronic acid, 9-phenanthrenboronic acid, 10-phenyl-9-anthracemboronic acid, phenylboronic acid, phenylethaneboronic acid, 4-phenyl (Naphthalen-1-yl) Boronic acid, 3-propoxyphenylboronic acid, 3-iso-propoxyphen
- phenylboronic acid, 1-naphthalenboronic acid, 2-naphthalenboronic acid or an anhydride thereof is preferable, and phenylboronic acid or an anhydride thereof is particularly preferable.
- Ar 1 and Ar 2 correspond to Z of the compound represented by the above formula (2) or (3), and the preferred embodiment of Ar 1 and Ar 2 is preferably Z. It is the same as the aspect.
- the ratio of the compound represented by the formula (2) used in the production method of the present invention is preferably 2 to 5 mol, more preferably 2 mol, with respect to 1 mol of the compound represented by the formula (1). It is 0.05 to 3.0 mol, more preferably 2.1 to 2.5 mol.
- the ratio of the compound represented by the formula (3) 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 (1). , More preferably 1-2 mol.
- Examples of the base used in the production method of the present invention 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 ).
- the amount of the base used in the production method of the present invention is preferably 1 to 30 mol, more preferably 2 to 10 mol, still more preferably 2 to 10 mol, based on 1 mol of the compound represented by the formula (1). Is 2-5 mol.
- the base is usually preferably added as an aqueous solution.
- the palladium compound used in Suzuki coupling is preferable, and for example, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, palladium acetate, tris ( Divendilideneacetone) dipalladium, bis (dibenzilidenacetone) palladium, bis [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine palladium dichloride, bis (di-tert-butylprenylphosphine) palladium dichloride , Bis (di-tert-crotylphosphine) palladium dichloride, palladium-based catalyst represented by Pd / SiO 2 and the like.
- tetrakis (triphenylphosphine) palladium is preferable.
- Such a palladium tetrakis (triphenylphosphin
- the amount of the palladium-based catalyst used in the production method of the present invention is preferably 0.1 to 10 mmol in terms of palladium metal atom with respect to 1 mol of the compound represented by the above formula (1), and more preferably. It is 0.5 to 5 mmol.
- the obtained reaction mixture is subjected to separation means such as washing, filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activation charcoal treatment or similar metal removal treatment, and column chromatography.
- separation means such as washing, filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activation charcoal treatment or similar metal removal treatment, and column chromatography.
- it may be separated and purified by a separation means combining these.
- a base since a base is used in the reaction, it is preferable to perform the neutralization treatment thereof. Further, it is preferable to carry out a treatment for removing the salt produced as a by-product in the reaction.
- distilled water is added to the reaction mixture and stirring, liquid separation, and water layer removal are repeated (sometimes abbreviated as liquid separation water washing method), or distilled water is added to the crystals to perform repulp washing. There is a method of repeating filtration and the like, and the liquid separation water washing method is industrially preferable.
- the palladium compound is used in the present invention, it is preferable to perform the removal treatment thereof.
- the palladium removal treatment it is preferable to add activated carbon or metal scavenger to the reaction mixture, stir, and then filter out the activated carbon or metal scavenger.
- the present invention it is preferable to perform recrystallization or crystallization in order to remove impurities such as reaction by-products and unreacted raw materials.
- an aromatic hydrocarbon solvent such as toluene is preferable as the recrystallization solvent, and toluene is particularly preferable.
- crystallization it is preferable to dissolve a compound having a fluorene skeleton in an aromatic hydrocarbon solvent such as toluene, and then use an alcohol solvent such as methanol as a poor solvent.
- crystallization is preferable because a compound having a fluorenone skeleton having a better hue can be obtained.
- the compound produced by the production method of the present invention is a compound having a fluorene skeleton represented by the following formula (4).
- Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.
- Ar 1 and Ar 2 each independently represent an aromatic group which may have a substituent having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. preferable. That is, 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2,7-diphenylfluorene represented by the following formula (5) is more preferable.
- the compound having a fluorene skeleton of the present invention preferably has an APHA of 50 or less, more preferably 40 or less, and even more preferably 30 or less in a 5% by weight solution dissolved in dimethylformamide.
- APHA is 50 or less, the hue of the resin made of the raw material represented by the above formula (4) and the hue of the optical member using the same are good, which is preferable.
- the compound having a fluorene skeleton of the present invention preferably has a sulfur element content of 200 ppm or less, more preferably 100 ppm or less, further preferably 50 ppm or less, and particularly preferably 30 ppm or less.
- the content of the sulfur element is 200 ppm or less, the hue of the resin made of the raw material represented by the above formula (4) and the hue of the optical member using the same are good, which is preferable.
- the compound having a fluorene skeleton of the present invention preferably has a bromine element content of 150 ppm or less, more preferably 50 ppm or less, and even more preferably 20 ppm or less.
- the content of the bromine element is 150 ppm or less, the hue of the resin made of the raw material represented by the above formula (4) and the hue of the optical member using the same are good, which is preferable.
- the compound having a fluorene skeleton of the present invention preferably has a diphenylfluorenone content of 0.2% or less, more preferably 0.1% or less, and further preferably 0.05% or less.
- the content of diphenylfluorene is 0.2% or less, the hue of the resin made of the raw material represented by the above formula (4) and the hue of the optical member using the same are good, which is preferable.
- the compound having a fluorene skeleton of the present invention preferably combines a diphenylfluorene skeleton and a dinaphthylfluorene skeleton with an arene ring, it not only has high refractive index and heat resistance, but also reduces birefringence when made into a polymer. Can be done. Since the compound having a fluorene skeleton of the present invention has a diphenylfluorene skeleton and a dinaphthylfluorene skeleton, the birefringence is small even though the refractive index is high.
- the compound having a fluorene skeleton of the present invention can be used as a raw material (monomer) for various resins.
- resins eg, polyester resin, polycarbonate resin, polyester carbonate resin, polyurethane resin, etc.
- thermosetting resins eg, epoxy resin, phenol resin, thermosetting polyurethane resin, (meth) acrylate ((meth)). It can be used as a polyol component of acrylic acid ester) etc.
- the obtained resin has a high refractive index and a low 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 compatible with birefringence at a high level. Further, since the compound having a fluorene skeleton of the present invention is excellent in hue and therefore the hue of the obtained resin is also excellent, it is suitably used for an optical member such as an optical lens.
- the hue of the resin is preferably 5.0 or less, more preferably 4.5 or less, and even more preferably 4.0 or less in terms of the b * value of the pellets.
- 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.
- DBFN 2,7-dibromofluorenone
- 2-naphthol 28 in a flask equipped with a stirrer, a cooler, a water separator, and a thermometer.
- the progress of the reaction was confirmed by HPLC, and the residual amount of 9,9'-bis (6-hydroxy-2-naphthyl) -2,7-dibromofluorene was confirmed to be 0.0%, and the reaction was terminated. I let you. After completion of the reaction, water and a 25 wt% sodium hydroxide aqueous solution were added to the obtained reaction solution, and the mixture was stirred at 85 ° C. for 1.5 hours, and then the aqueous layer was separated. The obtained reaction solution was concentrated, toluene was added to dissolve it, and then washing with warm water was performed 5 times.
- BNDB 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-dibromofluorene
- Tetrahydrofuran was added to the washed toluene layer and treated with activated carbon, then tetrahydrofuran was distilled off, recrystallization was performed with toluene, and the obtained crystals were heated and dried under reduced pressure overnight to make 9,9-bis [6-( 2-Hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene (hereinafter, may be abbreviated as BNDP) was obtained as white crystals in a yield of 80% and a purity of 98.0%.
- BNDP 9,9-bis [6-( 2-Hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene
- APHA was 50, S was 25 ppm, Br was 1 ppm, Pd was 1 ppm, and diphenylfluorenone (hereinafter, may be abbreviated as DPFN) was 0.0% as measured by HPLC.
- DPFN diphenylfluorenone
- Tetrahydrofuran was added to the washed toluene layer and treated with activated charcoal, then tetrahydrofuran was distilled off, methanol and distilled water were added as a poor solvent to the toluene solution for recrystallization, and the obtained crystals were heated and dried under reduced pressure overnight.
- White crystals of BNDP were obtained with a yield of 78% and a purity of 99.7%.
- APHA was 20
- S was 9 ppm
- Br was 0 ppm
- Pd was 1 ppm
- DPFN was 0.0% as measured by HPLC.
- Example 3 25.91 parts by mass of 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene synthesized in Example 1, 9,9-bis [4- (2- (2-) Hydroxyethoxy) phenyl] Fluolene was placed in a reaction vessel equipped with a stirrer and a distiller in 16.44 parts by mass, diphenyl carbonate 16.23 parts by mass, and sodium hydrogen carbonate 3.15 ⁇ 10 -3 parts by mass, and replaced with nitrogen. After that, the jacket was heated to 200 ° C. to melt the raw materials.
- the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the temperature of the jacket was raised 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.
- the obtained polycarbonate resin was analyzed by 1 H NMR, and the 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene component was 50 mol with respect to all the monomer components. % Confirmed that it has been introduced.
- the obtained polycarbonate resin had a refractive index of 1.682, an Abbe number of 17.1, a Tg of 177 ° C., and a pellet b * value of 4.0.
- the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the temperature of the jacket was raised 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.
- the obtained polycarbonate resin was analyzed by 1 H NMR, and the 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene component was 50 mol with respect to all the monomer components. % Confirmed that it has been introduced.
- the obtained polycarbonate resin had a refractive index of 1.682, an Abbe number of 17.1, a Tg of 177 ° C., and a pellet b * value of 5.9.
- novel fluorene derivative obtained by the production method of the present invention is suitable as a monomer for forming a resin constituting an optical member represented by an optical lens or an optical film.
Abstract
Provided are: a method for producing a compound having a fluorene skeleton, the method being characterized by including a step for obtaining a compound having a fluorene skeleton and represented by formula (4) by reacting a compound represented by formula (1) with boronic acids represented by formula (2) or (3) in a reaction solvent in the presence of a base and a palladium-based catalyst, wherein at least dimethylformamide is used as the reaction solvent; a compound which has a fluorene skeleton and is represented by formula (4), and in which the Hazen unit color number (APHA) of a 5 wt% solution dissolved in dimethylformamide is at most 50; a compound having an improved hue and a novel fluorene skeleton; and a method for producing the same. (In the formula, X1 and X2 each independently represent a halogen atom.) (In the formula, Z's each independently represent a C6-C20 aromatic group which may have a substituent.) (In the formula, Ar1 and Ar2 each independently represent a C6-C20 aromatic group which may have a substituent.)
Description
本発明は、フルオレン骨格を有する化合物の製造方法およびフルオレン骨格を有する化合物に関する。
The present invention relates to a method for producing a compound having a fluorene skeleton and a compound having a fluorene skeleton.
近年、９，９－ビス（４－（２－ヒドロキシエトキシ）フェニル）フルオレンなどのフルオレン骨格を有する化合物は、耐熱性、透明性に優れ、高屈折率を備えたポリマー（例えばエポキシ樹脂、ポリエステル、ポリエーテル、ポリカーボネート等）を製造するための原料として有望であり、光学レンズ、フィルム、プラスチック光ファイバー、光ディスク基盤、耐熱性樹脂やエンジニヤリングプラスチックなどの素材原料として期待されている（特許文献１）。また、９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］フルオレン（特許文献２）、９，９－ビス［４－（２－ヒドロキシエトキシ）フェニル］－２，７－ジフェニルフルオレン（特許文献３）等、各種フルオレン骨格を有する化合物が開発されている。これら化合物の開発により素材の高機能化が進む一方、フルオレン骨格を有する化合物の構造が複雑化しているため、その製造方法も複雑化しており、製造方法の複雑化による得られる化合物の色相劣化の改善や、製造方法自体の効率化などが求められている。
In recent years, compounds having a fluorene skeleton such as 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene have excellent heat resistance, transparency, and high refractive index polymers (for example, epoxy resin, polyester, etc.). It is promising as a raw material for producing (polyester, polycarbonate, etc.), and is expected as a raw material for optical lenses, films, plastic optical fibers, optical disk substrates, heat-resistant resins, engineering plastics, and the like (Patent Document 1). Further, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene (Patent Document 2), 9,9-bis [4- (2-hydroxyethoxy) phenyl] -2,7-diphenyl Compounds having various fluorene skeletons such as fluorene (Patent Document 3) have been developed. While the development of these compounds has promoted the sophistication of materials, the structure of compounds having a fluorene skeleton has become complicated, so that the manufacturing method has also become complicated. Improvements and efficiency improvement of the manufacturing method itself are required.
本発明の目的は、色相の改善されたフルオレン骨格を有する化合物の製造方法および色相の改善されたフルオレン骨格を有する化合物を提供することにある。また、本発明の目的は、収率および生産性を向上させるフルオレン骨格を有する化合物の製造方法を提供することにある。
An object of the present invention is to provide a method for producing a compound having a fluorene skeleton with an improved hue and a compound having a fluorene skeleton with an improved hue. Another object of the present invention is to provide a method for producing a compound having a fluorene skeleton that improves yield and productivity.
本発明者らは、以下の態様を有する本発明により、上記課題を解決できることを見出した。
《態様１》
下記式（１）で表される化合物と下記式（２）または（３）で表されるボロン酸類とを反応溶媒中、塩基およびパラジウム系触媒の存在下で反応し、下記式（４）で表されるフルオレン骨格を有する化合物を得る工程において、反応溶媒として少なくともジメチルホルムアミドを使用することを特徴とするフルオレン骨格を有する化合物の製造方法。 The present inventors have found that the above-mentioned problems can be solved by the present invention having the following aspects.
<< Aspect 1 >>
The compound represented by the following formula (1) and the boronic acid represented by the following formula (2) or (3) are reacted in a reaction solvent in the presence of a base and a palladium-based catalyst, and the following formula (4) is used. A method for producing a compound having a fluorene skeleton, which comprises using at least dimethylformamide as a reaction solvent in the step of obtaining the compound having the fluorene skeleton represented.
《態様１》
下記式（１）で表される化合物と下記式（２）または（３）で表されるボロン酸類とを反応溶媒中、塩基およびパラジウム系触媒の存在下で反応し、下記式（４）で表されるフルオレン骨格を有する化合物を得る工程において、反応溶媒として少なくともジメチルホルムアミドを使用することを特徴とするフルオレン骨格を有する化合物の製造方法。 The present inventors have found that the above-mentioned problems can be solved by the present invention having the following aspects.
<< Aspect 1 >>
The compound represented by the following formula (1) and the boronic acid represented by the following formula (2) or (3) are reacted in a reaction solvent in the presence of a base and a palladium-based catalyst, and the following formula (4) is used. A method for producing a compound having a fluorene skeleton, which comprises using at least dimethylformamide as a reaction solvent in the step of obtaining the compound having the fluorene skeleton represented.
（式中、Ｘ1、Ｘ2はそれぞれ独立にハロゲン原子を示す。）
(In the formula, X 1 and X 2 each independently indicate a halogen atom.)
（式中、Ｚはそれぞれ独立に炭素数が６～２０の置換基を有してもよい芳香族基を示す。）
(In the formula, Z indicates an aromatic group which may independently have a substituent having 6 to 20 carbon atoms.)
（式中、Ａｒ1、Ａｒ2はそれぞれ独立に炭素数が６～２０の置換基を有してもよい芳香族基を示す。）
《態様２》
反応溶媒として少なくともジメチルホルムアミドおよび芳香族炭化水素系溶媒を使用することを特徴とする態様１に記載のフルオレン骨格を有する化合物の製造方法。
《態様３》
ジメチルホルムアミドに溶解させた５重量％溶液のハーゼン単位色数（ＡＰＨＡ）が５０以下である下記式（４）で示されるフルオレン骨格を有する化合物。 (In the formula, Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.)
<< Aspect 2 >>
The method for producing a compound having a fluorene skeleton according to the first aspect, wherein at least dimethylformamide and an aromatic hydrocarbon solvent are used as the reaction solvent.
<< Aspect 3 >>
A compound having a fluorene skeleton represented by the following formula (4) in which the Hazen unit color number (APHA) of a 5% by weight solution dissolved in dimethylformamide is 50 or less.
《態様２》
反応溶媒として少なくともジメチルホルムアミドおよび芳香族炭化水素系溶媒を使用することを特徴とする態様１に記載のフルオレン骨格を有する化合物の製造方法。
《態様３》
ジメチルホルムアミドに溶解させた５重量％溶液のハーゼン単位色数（ＡＰＨＡ）が５０以下である下記式（４）で示されるフルオレン骨格を有する化合物。 (In the formula, Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.)
<< Aspect 2 >>
The method for producing a compound having a fluorene skeleton according to the first aspect, wherein at least dimethylformamide and an aromatic hydrocarbon solvent are used as the reaction solvent.
<< Aspect 3 >>
A compound having a fluorene skeleton represented by the following formula (4) in which the Hazen unit color number (APHA) of a 5% by weight solution dissolved in dimethylformamide is 50 or less.
（式中、Ａｒ1、Ａｒ2はそれぞれ独立に炭素数が６～２０の置換基を有してもよい芳香族基を示す。）
《態様４》
熱可塑性樹脂の原料としての、態様３に記載のフルオレン骨格を有する化合物の使用方法。
《態様５》
態様３に記載のフルオレン骨格を有する化合物を重合することにより得られる熱可塑性樹脂。 (In the formula, Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.)
<< Aspect 4 >>
The method for using a compound having a fluorene skeleton according to Aspect 3 as a raw material for a thermoplastic resin.
<< Aspect 5 >>
A thermoplastic resin obtained by polymerizing the compound having the fluorene skeleton according to the third aspect.
《態様４》
熱可塑性樹脂の原料としての、態様３に記載のフルオレン骨格を有する化合物の使用方法。
《態様５》
態様３に記載のフルオレン骨格を有する化合物を重合することにより得られる熱可塑性樹脂。 (In the formula, Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.)
<< Aspect 4 >>
The method for using a compound having a fluorene skeleton according to Aspect 3 as a raw material for a thermoplastic resin.
<< Aspect 5 >>
A thermoplastic resin obtained by polymerizing the compound having the fluorene skeleton according to the third aspect.
本発明によれば、色相に優れたフルオレン骨格を有する化合物を得ることができる。
また、フルオレン骨格を有する化合物を製造する際の収率および生産性を向上させることができる。 According to the present invention, a compound having a fluorene skeleton having an excellent hue can be obtained.
In addition, the yield and productivity of producing a compound having a fluorene skeleton can be improved.
また、フルオレン骨格を有する化合物を製造する際の収率および生産性を向上させることができる。 According to the present invention, a compound having a fluorene skeleton having an excellent hue can be obtained.
In addition, the yield and productivity of producing a compound having a fluorene skeleton can be improved.
《フルオレン骨格を有する化合物の製造方法》
本発明の製造方法は、下記式（１）で表される化合物と下記式（２）または（３）で表されるボロン酸類とを反応溶媒中、塩基およびパラジウム系触媒の存在下で反応し、下記式（４）で表されるフルオレン骨格を有する化合物を得る工程において、反応溶媒として少なくともジメチルホルムアミドを使用することを特徴とするフルオレン骨格を有する化合物の製造方法である。 << Method for producing a compound having a fluorene skeleton >>
In the production method of the present invention, a compound represented by the following formula (1) and a boronic acid represented by the following formula (2) or (3) are reacted in a reaction solvent in the presence of a base and a palladium-based catalyst. , A method for producing a compound having a fluorene skeleton, which comprises using at least dimethylformamide as a reaction solvent in the step of obtaining a compound having a fluorene skeleton represented by the following formula (4).
本発明の製造方法は、下記式（１）で表される化合物と下記式（２）または（３）で表されるボロン酸類とを反応溶媒中、塩基およびパラジウム系触媒の存在下で反応し、下記式（４）で表されるフルオレン骨格を有する化合物を得る工程において、反応溶媒として少なくともジメチルホルムアミドを使用することを特徴とするフルオレン骨格を有する化合物の製造方法である。 << Method for producing a compound having a fluorene skeleton >>
In the production method of the present invention, a compound represented by the following formula (1) and a boronic acid represented by the following formula (2) or (3) are reacted in a reaction solvent in the presence of a base and a palladium-based catalyst. , A method for producing a compound having a fluorene skeleton, which comprises using at least dimethylformamide as a reaction solvent in the step of obtaining a compound having a fluorene skeleton represented by the following formula (4).
（式中、Ｘ1、Ｘ2はそれぞれ独立にハロゲン原子を示す。）
(In the formula, X 1 and X 2 each independently indicate a halogen atom.)
（式中、Ｚはそれぞれ独立に炭素数が６～２０の置換基を有してもよい芳香族基を示す。）
(In the formula, Z indicates an aromatic group which may independently have a substituent having 6 to 20 carbon atoms.)
（式中、Ａｒ1、Ａｒ2はそれぞれ独立に炭素数が６～２０の置換基を有してもよい芳香族基を示す。）
本発明の製造方法では、反応溶媒として少なくともジメチルホルムアミドを使用する。ジメチルホルムアミドは、塩基として使用する化合物の水溶液との親和性と上記式（４）で表される化合物の溶解性を両立することができる。また、反応温度を高くすることができ、反応速度の向上やパラジウム触媒量を低減することができる。 (In the formula, Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.)
In the production method of the present invention, at least dimethylformamide is used as the reaction solvent. Dimethylformamide can achieve both the affinity of the compound used as a base with an aqueous solution and the solubility of the compound represented by the above formula (4). In addition, the reaction temperature can be increased, the reaction rate can be improved, and the amount of palladium catalyst can be reduced.
本発明の製造方法では、反応溶媒として少なくともジメチルホルムアミドを使用する。ジメチルホルムアミドは、塩基として使用する化合物の水溶液との親和性と上記式（４）で表される化合物の溶解性を両立することができる。また、反応温度を高くすることができ、反応速度の向上やパラジウム触媒量を低減することができる。 (In the formula, Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.)
In the production method of the present invention, at least dimethylformamide is used as the reaction solvent. Dimethylformamide can achieve both the affinity of the compound used as a base with an aqueous solution and the solubility of the compound represented by the above formula (4). In addition, the reaction temperature can be increased, the reaction rate can be improved, and the amount of palladium catalyst can be reduced.
本発明の製造方法では、反応溶媒として、ジメチルホルムアミドに加え、トルエン等の芳香族炭化水素系溶媒を併用することが好ましい。芳香族炭化水素系溶媒を併用することで、反応後に有機層と水層に分離することができ、反応後の精製が容易になる。
In the production method of the present invention, it is preferable to use an aromatic hydrocarbon solvent such as toluene in combination with dimethylformamide as the reaction solvent. By using an aromatic hydrocarbon solvent in combination, the organic layer and the aqueous layer can be separated after the reaction, and purification after the reaction becomes easy.
本発明の製造方法で使用する芳香族炭化水素系溶媒の具体例として、ベンゼン、トルエン、キシレン、エチルベンゼン、メシチレン、イソプロピルベンゼン等が挙げられ、トルエンが好ましい。
Specific examples of the aromatic hydrocarbon solvent used in the production method of the present invention include benzene, toluene, xylene, ethylbenzene, mesitylene, isopropylbenzene and the like, and toluene is preferable.
本発明の製造方法で使用する反応溶媒の使用量は、前記式（１）で示される化合物１重量部に対して好ましくは０．１～１００重量部、より好ましくは１～５０重量部であり、さらに好ましくは２～１０重量部である。
The amount of the reaction solvent used in the production method of the present invention is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight, based on 1 part by weight of the compound represented by the formula (1). , More preferably 2 to 10 parts by weight.
反応溶媒中、ジメチルホルムアミドは５重量％以上使用することが好ましく、１０重量％以上使用することがより好ましく、２０重量％以上使用することがさらに好ましく、３０重量％以上使用することが特に好ましい。
In the reaction solvent, dimethylformamide is preferably used in an amount of 5% by weight or more, more preferably 10% by weight or more, further preferably 20% by weight or more, and particularly preferably 30% by weight or more.
本発明の製造方法において芳香族炭化水素系溶媒を併用する場合、芳香族炭化水素系溶媒の使用割合は、ジメチルホルムアミド１重量部に対して好ましくは０．１～１０重量部、より好ましくは０．５～５重量部であり、さらに好ましくは１～３重量部である。
When an aromatic hydrocarbon solvent is used in combination in the production method of the present invention, the ratio of the aromatic hydrocarbon solvent used is preferably 0.1 to 10 parts by weight, more preferably 0 with respect to 1 part by weight of dimethylformamide. .5 to 5 parts by weight, more preferably 1 to 3 parts by weight.
反応溶媒としてジメチルホルムアミドと芳香族炭化水素系溶媒を併用する場合、反応溶媒中、ジメチルホルムアミドと芳香族炭化水素系溶媒との合計量は、７０重量％以上使用することがより好ましく、８０重量％以上使用することがさらに好ましく、９０重量％以上使用することが特に好ましい。
When dimethylformamide and an aromatic hydrocarbon solvent are used in combination as the reaction solvent, the total amount of dimethylformamide and the aromatic hydrocarbon solvent in the reaction solvent is more preferably 70% by weight or more, more preferably 80% by weight. It is more preferable to use the above, and it is particularly preferable to use 90% by weight or more.
本発明の上記式（１）において、Ｘ1、Ｘ2はそれぞれ独立にハロゲン原子を示し、塩素原子または臭素原子であると好ましく、臭素原子であるとより好ましい。
In the above formula (1) of the present invention, X 1 and X 2 each independently represent a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a bromine atom.
本発明の上記式（２）および（３）において、Ｚはそれぞれ独立に炭素数が６～２０の置換基を有してもよい芳香族基である。上記式（２）または（３）で表されるボロン酸類の具体例として、２－アントラセンボロン酸、９－アントラセンボロン酸、ベンジルボロン酸、２－ビフェニルボロン酸、３－ビフェニルボロン酸、４－ビフェニルボロン酸、２，３－ジメチルフェニルボロン酸、２，４－ジメチルフェニルボロン酸、２，５－ジメチルフェニルボロン酸、２，６－ジメチルフェニルボロン酸、３，４－ジメチルフェニルボロン酸、３，５－ジメチルフェニルボロン酸、２－エトキシフェニルボロン酸、３－エトキシフェニルボロン酸、４－エトキシフェニルボロン酸、６－メトキシ－２－ナフタレンボロン酸、２－メチルフェニルボロン酸、３－メチルフェニルボロン酸、４－メチルフェニルボロン酸、１－ナフタレンボロン酸、２－ナフタレンボロン酸、９－フェナントレンボロン酸、１０－フェニル－９－アントラセンボロン酸、フェニルボロン酸、フェニルエタンボロン酸、４－フェニル（ナフタレン－１－イル）ボロン酸、３－プロポキシフェニルボロン酸、３－イソ－プロポキシフェニルボロン酸、４－イソ－プロポキシフェニルボロン酸、４－プロピルフェニルボロン酸、４－イソ－プロピルフェニルボロン酸、１０－（ナフタレン－１－イル）－９－アントラセンボロン酸、１０－（ナフタレン－２－イル）－９－アントラセンボロン酸、ベンゾフラン－２－ボロン酸、ジベンゾフラン－４－ボロン酸、５－フォルミル－２－フランボロン酸、５－フォルミルチオフェン－２－ボロン酸、フラン－２－ボロン酸、フラン－３－ボロン酸、ピリジン－３－ボロン酸、ピリジン－４－ボロン酸、キノリン－２－ボロン酸、キノリン－３－ボロン酸、キノリン－４－ボロン酸、キノリン－５－ボロン酸、キノリン－６－ボロン酸、キノリン－８－ボロン酸、イソ－キノリン－４－ボロン酸、２－チオフェンボロン酸、３－チオフェンボロン酸、５－ピリミジンボロン酸、ベンゾチオフェン－２－ボロン酸、ジベンゾチオフェン－２－ボロン酸、ベンゾチオフェン－４－ボロン酸やこれらの無水物が含まれる。これらは単独で使用してもよく、または２種以上を混合してもよく、目的により任意に選ぶことができる。本発明では好ましくはフェニルボロン酸、１－ナフタレンボロン酸、２－ナフタレンボロン酸またはその無水物であり、特に好ましくはフェニルボロン酸またはその無水物である。
In the above formulas (2) and (3) of the present invention, Z is an aromatic group which may independently have a substituent having 6 to 20 carbon atoms. Specific examples of the boronic acids represented by the above formula (2) or (3) are 2-anthracemboronic acid, 9-anthracemboronic acid, benzylboronic acid, 2-biphenylboronic acid, 3-biphenylboronic acid, 4-. Biphenylboronic acid, 2,3-dimethylphenylboronic acid, 2,4-dimethylphenylboronic acid, 2,5-dimethylphenylboronic acid, 2,6-dimethylphenylboronic acid, 3,4-dimethylphenylboronic acid, 3 , 5-Dimethylphenylboronic acid, 2-ethoxyphenylboronic acid, 3-ethoxyphenylboronic acid, 4-ethoxyphenylboronic acid, 6-methoxy-2-naphthalenboronic acid, 2-methylphenylboronic acid, 3-methylphenyl Boronic acid, 4-methylphenylboronic acid, 1-naphthalenboronic acid, 2-naphthalenboronic acid, 9-phenanthrenboronic acid, 10-phenyl-9-anthracemboronic acid, phenylboronic acid, phenylethaneboronic acid, 4-phenyl (Naphthalen-1-yl) Boronic acid, 3-propoxyphenylboronic acid, 3-iso-propoxyphenylboronic acid, 4-iso-propoxyphenylboronic acid, 4-propylphenylboronic acid, 4-iso-propylphenylboronic acid 10- (Naphthalen-1-yl) -9-anthracemboronic acid, 10- (naphthalen-2-yl) -9-anthracemboronic acid, benzofuran-2-boronic acid, dibenzofuran-4-boronic acid, 5-formyl -2-Franboronic acid, 5-formylthiophene-2-boronic acid, furan-2-boronic acid, furan-3-boronic acid, pyridine-3-boronic acid, pyridine-4-boronic acid, quinoline-2-boronic acid Acid, quinoline-3-boronic acid, quinoline-4-boronic acid, quinoline-5-boronic acid, quinoline-6-boronic acid, quinoline-8-boronic acid, iso-quinolin-4-boronic acid, 2-thiophenboron Includes acids, 3-thiopheneboronic acid, 5-pyrimidineboronic acid, benzothiophene-2-boronic acid, dibenzothiophene-2-boronic acid, benzothiophene-4-boronic acid and anhydrides thereof. These may be used alone or in combination of two or more, and may be arbitrarily selected depending on the purpose. In the present invention, phenylboronic acid, 1-naphthalenboronic acid, 2-naphthalenboronic acid or an anhydride thereof is preferable, and phenylboronic acid or an anhydride thereof is particularly preferable.
本発明の上記式（４）において、Ａｒ1、Ａｒ2は前記式（２）または（３）で表される化合物のＺと対応しており、Ａｒ1、Ａｒ2の好ましい態様はＺの好ましい態様と同様である。
In the above formula (4) of the present invention, Ar 1 and Ar 2 correspond to Z of the compound represented by the above formula (2) or (3), and the preferred embodiment of Ar 1 and Ar 2 is preferably Z. It is the same as the aspect.
本発明の製造方法で使用する前記式（２）で表される化合物の使用比率は、前記式（１）で表される化合物１モルに対して好ましくは２～５モル、より好ましくは、２．０５～３．０モル、さらに好ましくは２．１～２．５モルである。また、前記式（３）で表される化合物の使用比率は、前記式（１）で表される化合物１モルに対して好ましくは０．７～５モル、より好ましくは０．８～３モル、さらに好ましくは１～２モルである。
The ratio of the compound represented by the formula (2) used in the production method of the present invention is preferably 2 to 5 mol, more preferably 2 mol, with respect to 1 mol of the compound represented by the formula (1). It is 0.05 to 3.0 mol, more preferably 2.1 to 2.5 mol. The ratio of the compound represented by the formula (3) 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 (1). , More preferably 1-2 mol.
本発明の製造方法で使用する塩基としては、例えば、水酸化ナトリウム、水酸化カリウムなどの水酸化物、炭酸ナトリウム（Ｎａ2ＣＯ3）、炭酸カリウム（Ｋ2ＣＯ3）、炭酸セシウム（Ｃｓ2ＣＯ3）などの炭酸塩、酢酸ナトリウム、酢酸カリウムなどの酢酸塩、リン酸ナトリウム（Ｎａ3ＰＯ4）、リン酸カリウム（Ｋ3ＰＯ4）などのリン酸塩などの無機塩、トリエチルアミン類、ピリジン、モルホリン、キノリン、ピペリジン、アニリン類、テトラｎブチルアンモニウムアセテートなどのアンモニウム塩などの有機塩などが挙げられる。なかでも、炭酸塩が好ましく用いられ、炭酸カリウム、炭酸ナトリウムが好ましく、炭酸カリウムがより好ましい。これら塩基は、単独で用いてもよく、また、２種類以上併用して用いることもできる。
Examples of the base used in the production method of the present invention 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 ). Carbonates such as CO 3 ), acetates such as sodium acetate and potassium acetate, inorganic salts such as phosphates such as sodium phosphate (Na 3 PO 4 ) and potassium phosphate (K 3 PO 4 ), triethylamines, Examples thereof include organic salts such as pyridine, morpholine, quinoline, piperidine, aniline, and ammonium salts such as tetranbutylammonium acetate. Among them, carbonate is preferably used, potassium carbonate and sodium carbonate are preferable, and potassium carbonate is more preferable. These bases may be used alone or in combination of two or more.
本発明の製造方法で使用する塩基の使用量は、前記式（１）で表される化合物１モルに対して好ましくは１～３０モルであり、より好ましくは２～１０モルであり、さらに好ましくは２～５モルである。塩基は通常、水溶液として添加することが好ましい。
The amount of the base used in the production method of the present invention is preferably 1 to 30 mol, more preferably 2 to 10 mol, still more preferably 2 to 10 mol, based on 1 mol of the compound represented by the formula (1). Is 2-5 mol. The base is usually preferably added as an aqueous solution.
本発明の製造方法で使用するパラジウム系触媒としては、鈴木カップリングで使用されるパラジウム化合物が好ましく、例えば、テトラキス（トリフェニルホスフィン）パラジウム、ビス（トリフェニルホスフィン）パラジウムジクロリド、酢酸パラジウム、トリス（ジベンジリデンアセトン）ジパラジウム、ビス(ジベンジリデンアセトン)パラジウム、ビス[４－（Ｎ, Ｎ－ジメチルアミノ）フェニル]ジ－ｔｅｒｔ－ブチルホスフィンパラジウムジクロリド、ビス（ジ－ｔｅｒｔ－ブチルプレニルホスフィン）パラジウムジクロリド、ビス（ジ－ｔｅｒｔ－クロチルホスフィン）パラジウムジクロリド、Ｐｄ／ＳｉＯ2で表されるパラジウム系触媒などが挙げられる。なかでも、テトラキス（トリフェニルホスフィン）パラジウムが好ましい。このようなパラジウム系触媒は、単独で用いてもよく、また、２種以上併用して用いることもできる。
As the palladium-based catalyst used in the production method of the present invention, the palladium compound used in Suzuki coupling is preferable, and for example, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, palladium acetate, tris ( Divendilideneacetone) dipalladium, bis (dibenzilidenacetone) palladium, bis [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine palladium dichloride, bis (di-tert-butylprenylphosphine) palladium dichloride , Bis (di-tert-crotylphosphine) palladium dichloride, palladium-based catalyst represented by Pd / SiO 2 and the like. Of these, tetrakis (triphenylphosphine) palladium is preferable. Such a palladium-based catalyst may be used alone or in combination of two or more.
本発明の製造方法で使用するパラジウム系触媒の使用量は、前記式（１）で示される化合物１モルに対して、パラジウム金属原子換算で好ましくは０．１～１０ミリモルであり、より好ましくは０．５～５ミリモルである。
The amount of the palladium-based catalyst used in the production method of the present invention is preferably 0.1 to 10 mmol in terms of palladium metal atom with respect to 1 mol of the compound represented by the above formula (1), and more preferably. It is 0.5 to 5 mmol.
本発明では、反応終了後、得られた反応混合物は、洗浄、ろ過、濃縮、抽出、晶析、再結晶、再沈殿、活性炭処理あるいはそれと酷似した金属の除去処理、カラムクロマトグラフィーなどの分離手段や、これらを組み合わせた分離手段により分離精製しても良い。
In the present invention, after the reaction is completed, the obtained reaction mixture is subjected to separation means such as washing, filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activation charcoal treatment or similar metal removal treatment, and column chromatography. Alternatively, it may be separated and purified by a separation means combining these.
本発明では、反応で塩基を使用するため、その中和処理を行うことが好ましい。また、反応で副生する塩の除去処理を行うことが好ましい。中和処理や塩の除去処理は、反応混合物に蒸留水を加え撹拌、分液、水層除去を繰り返す方法（分液水洗法と省略することがある）や結晶に蒸留水を加えリパルプ洗浄、ろ過を繰り返す方法等があり、分液水洗法が工業的に好ましい。
In the present invention, since a base is used in the reaction, it is preferable to perform the neutralization treatment thereof. Further, it is preferable to carry out a treatment for removing the salt produced as a by-product in the reaction. For the neutralization treatment and salt removal treatment, distilled water is added to the reaction mixture and stirring, liquid separation, and water layer removal are repeated (sometimes abbreviated as liquid separation water washing method), or distilled water is added to the crystals to perform repulp washing. There is a method of repeating filtration and the like, and the liquid separation water washing method is industrially preferable.
本発明では、パラジウム化合物を使用するため、その除去処理を行うことが好ましい。パラジウムの除去処理は反応混合物に活性炭や金属スカベンジャーを加え撹拌後、活性炭や金属スカベンジャーを濾別することが好ましい。
Since the palladium compound is used in the present invention, it is preferable to perform the removal treatment thereof. For the palladium removal treatment, it is preferable to add activated carbon or metal scavenger to the reaction mixture, stir, and then filter out the activated carbon or metal scavenger.
本発明では、反応副生物や未反応原料等の不純物を除去するため、再結晶や晶析を行うことが好ましい。再結晶を行う場合、再結晶溶媒として、トルエン等の芳香族炭化水素系溶媒が好ましく、特にトルエンが好ましい。また、晶析を行う場合、フルオレン骨格を有する化合物をトルエン等の芳香族炭化水素系溶媒に溶解後、貧溶媒としてメタノール等のアルコール系溶媒を使用することが好ましい。本発明では、晶析を行うと色相がより良いフルオレノン骨格を有する化合物を得ることができ好ましい。
《フルオレン骨格を有する化合物》
本発明の製造方法で製造される化合物は、下記式（４）で表されるフルオレン骨格を有する化合物である。 In the present invention, it is preferable to perform recrystallization or crystallization in order to remove impurities such as reaction by-products and unreacted raw materials. When recrystallization is performed, an aromatic hydrocarbon solvent such as toluene is preferable as the recrystallization solvent, and toluene is particularly preferable. When crystallization is performed, it is preferable to dissolve a compound having a fluorene skeleton in an aromatic hydrocarbon solvent such as toluene, and then use an alcohol solvent such as methanol as a poor solvent. In the present invention, crystallization is preferable because a compound having a fluorenone skeleton having a better hue can be obtained.
<< Compound with fluorene skeleton >>
The compound produced by the production method of the present invention is a compound having a fluorene skeleton represented by the following formula (4).
《フルオレン骨格を有する化合物》
本発明の製造方法で製造される化合物は、下記式（４）で表されるフルオレン骨格を有する化合物である。 In the present invention, it is preferable to perform recrystallization or crystallization in order to remove impurities such as reaction by-products and unreacted raw materials. When recrystallization is performed, an aromatic hydrocarbon solvent such as toluene is preferable as the recrystallization solvent, and toluene is particularly preferable. When crystallization is performed, it is preferable to dissolve a compound having a fluorene skeleton in an aromatic hydrocarbon solvent such as toluene, and then use an alcohol solvent such as methanol as a poor solvent. In the present invention, crystallization is preferable because a compound having a fluorenone skeleton having a better hue can be obtained.
<< Compound with fluorene skeleton >>
The compound produced by the production method of the present invention is a compound having a fluorene skeleton represented by the following formula (4).
（式中、Ａｒ1、Ａｒ2はそれぞれ独立に炭素数が６～２０の置換基を有してもよい芳香族基を示す。）
上記式（４）において、Ａｒ1およびＡｒ2は、それぞれ独立に炭素数が６～２０の置換基を有してもよい芳香族基を示し、フェニル基およびナフチル基が好ましく、フェニル基がより好ましい。すなはち、下記式（５）で表される９，９－ビス（４－（２－ヒドロキシエトキシ）フェニル）－２，７－ジフェニルフルオレンがより好ましい。 (In the formula, Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.)
In the above formula (4), Ar 1 and Ar 2 each independently represent an aromatic group which may have a substituent having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. preferable. That is, 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2,7-diphenylfluorene represented by the following formula (5) is more preferable.
上記式（４）において、Ａｒ1およびＡｒ2は、それぞれ独立に炭素数が６～２０の置換基を有してもよい芳香族基を示し、フェニル基およびナフチル基が好ましく、フェニル基がより好ましい。すなはち、下記式（５）で表される９，９－ビス（４－（２－ヒドロキシエトキシ）フェニル）－２，７－ジフェニルフルオレンがより好ましい。 (In the formula, Ar 1 and Ar 2 each independently indicate an aromatic group which may have a substituent having 6 to 20 carbon atoms.)
In the above formula (4), Ar 1 and Ar 2 each independently represent an aromatic group which may have a substituent having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. preferable. That is, 9,9-bis (4- (2-hydroxyethoxy) phenyl) -2,7-diphenylfluorene represented by the following formula (5) is more preferable.
本発明のフルオレン骨格を有する化合物は、ジメチルホルムアミドに溶解させた５重量％溶液のＡＰＨＡが５０以下であると好ましく、４０以下であるとより好ましく、３０以下であるとさらに好ましい。ＡＰＨＡが５０以下であると前記式（４）で表される原料からなる樹脂の色相やそれを使った光学部材の色相が良好になり好ましい。
The compound having a fluorene skeleton of the present invention preferably has an APHA of 50 or less, more preferably 40 or less, and even more preferably 30 or less in a 5% by weight solution dissolved in dimethylformamide. When APHA is 50 or less, the hue of the resin made of the raw material represented by the above formula (4) and the hue of the optical member using the same are good, which is preferable.
本発明のフルオレン骨格を有する化合物は、硫黄元素の含有量が２００ｐｐｍ以下であると好ましく、１００ｐｐｍ以下であるとより好ましく、５０ｐｐｍ以下であるとさらに好ましく、３０ｐｐｍ以下であると特に好ましい。硫黄元素の含有量が２００ｐｐｍ以下であると前記式（４）で表される原料からなる樹脂の色相やそれを使った光学部材の色相が良好になり好ましい。
The compound having a fluorene skeleton of the present invention preferably has a sulfur element content of 200 ppm or less, more preferably 100 ppm or less, further preferably 50 ppm or less, and particularly preferably 30 ppm or less. When the content of the sulfur element is 200 ppm or less, the hue of the resin made of the raw material represented by the above formula (4) and the hue of the optical member using the same are good, which is preferable.
本発明のフルオレン骨格を有する化合物は、臭素元素の含有量が１５０ｐｐｍ以下であると好ましく、５０ｐｐｍ以下であるとより好ましく、２０ｐｐｍ以下であるとさらに好ましい。臭素元素の含有量が１５０ｐｐｍ以下であると前記式（４）で表される原料からなる樹脂の色相やそれを使った光学部材の色相が良好になり好ましい。
The compound having a fluorene skeleton of the present invention preferably has a bromine element content of 150 ppm or less, more preferably 50 ppm or less, and even more preferably 20 ppm or less. When the content of the bromine element is 150 ppm or less, the hue of the resin made of the raw material represented by the above formula (4) and the hue of the optical member using the same are good, which is preferable.
また、本発明のフルオレン骨格を有する化合物は、ジフェニルフルオレノンの含有量が０．２％以下であると好ましく、０．１％以下であるとより好ましく、０．０５％以下であるとさらに好ましい。ジフェニルフルオレンの含有量が０．２％以下であると前記式（４）で表される原料からなる樹脂の色相やそれを使った光学部材の色相が良好になり好ましい。
Further, the compound having a fluorene skeleton of the present invention preferably has a diphenylfluorenone content of 0.2% or less, more preferably 0.1% or less, and further preferably 0.05% or less. When the content of diphenylfluorene is 0.2% or less, the hue of the resin made of the raw material represented by the above formula (4) and the hue of the optical member using the same are good, which is preferable.
本発明のフルオレン骨格を有する化合物は、好ましくはジフェニルフルオレン骨格およびジナフチルフルオレン骨格とアレーン環を組み合わせているため、屈折率、耐熱性が高いだけでなくポリマーにした際に複屈折を軽減させることができる。本発明のフルオレン骨格を有する化合物は、ジフェニルフルオレン骨格およびジナフチルフルオレン骨格を有しているため、屈折率が高いにも関わらず、複屈折も小さくなる。さらに、アレーン環には、１つ以上のヒドロキシル基を有し、フルオレン化合物全体で複数のヒドロキシル基を有しているため、反応性が高い。そのため、本発明のフルオレン骨格を有する化合物は、種々の樹脂の原料（モノマー）として利用できる。例えば、熱可塑性樹脂（例えば、ポリエステル樹脂、ポリカーボネート樹脂、ポリエステルカーボネート樹脂、ポリウレタン樹脂など）や熱硬化性樹脂（例えば、エポキシ樹脂、フェノール樹脂、熱硬化性ポリウレタン樹脂、（メタ）アクリレート（（メタ）アクリル酸エステル）など）のポリオール成分として用いることができる。本発明のフルオレン骨格を有する化合物をポリオール成分として用いると、フルオレン骨格の９位にナフタレン環が置換され、かつフルオレン骨格にジアリール基を有しているためか、得られる樹脂は高い屈折率と低複屈折性とを高レベルで両立できるという利点を備える。また、本発明のフルオレン骨格を有する化合物は色相に優れるため、得られる樹脂の色相も優れるため、光学レンズ等の光学部材に好適に用いられる。樹脂の色相としては、ペレットのｂ*値で５．０以下が好ましく、４．５以下がより好ましく、４．０以下がさらに好ましい。
Since the compound having a fluorene skeleton of the present invention preferably combines a diphenylfluorene skeleton and a dinaphthylfluorene skeleton with an arene ring, it not only has high refractive index and heat resistance, but also reduces birefringence when made into a polymer. Can be done. Since the compound having a fluorene skeleton of the present invention has a diphenylfluorene skeleton and a dinaphthylfluorene skeleton, the birefringence is small even though the refractive index is high. Further, since the arene ring has one or more hydroxyl groups and the entire fluorene compound has a plurality of hydroxyl groups, the reactivity is high. Therefore, the compound having a fluorene skeleton of the present invention can be used as a raw material (monomer) for various resins. For example, thermoplastic resins (eg, polyester resin, polycarbonate resin, polyester carbonate resin, polyurethane resin, etc.) and thermosetting resins (eg, epoxy resin, phenol resin, thermosetting polyurethane resin, (meth) acrylate ((meth)). It can be used as a polyol component of acrylic acid ester) etc.). When 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 a low 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 compatible with birefringence at a high level. Further, since the compound having a fluorene skeleton of the present invention is excellent in hue and therefore the hue of the obtained resin is also excellent, it is suitably used for an optical member such as an optical lens. The hue of the resin is preferably 5.0 or less, more preferably 4.5 or less, and even more preferably 4.0 or less in terms of the b * value of the pellets.
以下、本発明を実施例により詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
なお、実施例において、各種測定は以下のように行った。
（１）ＨＰＬＣ測定
日立製高速液体クロマトグラフＬ－２３５０を用い、表１の測定条件で測定した。実施例中、特に断らない限り％はＨＰＬＣにおける溶媒を除いて補正した面積百分率値である。 In the examples, various measurements were performed as follows.
(1) HPLC measurement Using a high performance liquid chromatograph L-2350 manufactured by Hitachi, measurement was performed under the measurement conditions shown in Table 1. In the examples,% is the area percentage value corrected by excluding the solvent in HPLC unless otherwise specified.
（１）ＨＰＬＣ測定
日立製高速液体クロマトグラフＬ－２３５０を用い、表１の測定条件で測定した。実施例中、特に断らない限り％はＨＰＬＣにおける溶媒を除いて補正した面積百分率値である。 In the examples, various measurements were performed as follows.
(1) HPLC measurement Using a high performance liquid chromatograph L-2350 manufactured by Hitachi, measurement was performed under the measurement conditions shown in Table 1. In the examples,% is the area percentage value corrected by excluding the solvent in HPLC unless otherwise specified.
（２）ＩＣＰ測定
実施例で得られた化合物を下記の装置にて測定した。
使用機器：Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ
装置：Ａｇｉｌｅｎｔ５１００ ＩＣＰ－ＯＥＳ
（３）燃焼イオンクロマトグラフィー測定
三菱ケミカル製自動試料燃焼装置ＡＱＦ－２１００およびサーモフィッシャー製イオンクロマトグラフィーシステムＤＩＯＮＥＸ ＡＱＵＩＯＮを用い、下記測定条件で、硫黄元素の含有量（Ｓ量）および臭素元素の含有量（Ｂｒ量）の測定を行った。尚、検量線作成は、ＷＡＫＯ製臭化物イオン標準液（Ｂｒ－１０００）および硫酸イオン標準液（ＳＯ４（２－）：１０００）を用い行った。 (2) ICP measurement The compound obtained in the example was measured with the following device.
Equipment used: Agilent Technologies
Equipment: Agent5100 ICP-OES
(3) Combustion ion chromatography measurement Using Mitsubishi Chemical's automatic sample combustion device AQF-2100 and Thermo Fisher's ion chromatography system DIONEX AQUION, the sulfur element content (S amount) and bromine element content are contained under the following measurement conditions. The amount (Br amount) was measured. The calibration curve was prepared using WAKO's bromide ion standard solution (Br-1000) and sulfate ion standard solution (SO4 (2-): 1000).
実施例で得られた化合物を下記の装置にて測定した。
使用機器：Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ
装置：Ａｇｉｌｅｎｔ５１００ ＩＣＰ－ＯＥＳ
（３）燃焼イオンクロマトグラフィー測定
三菱ケミカル製自動試料燃焼装置ＡＱＦ－２１００およびサーモフィッシャー製イオンクロマトグラフィーシステムＤＩＯＮＥＸ ＡＱＵＩＯＮを用い、下記測定条件で、硫黄元素の含有量（Ｓ量）および臭素元素の含有量（Ｂｒ量）の測定を行った。尚、検量線作成は、ＷＡＫＯ製臭化物イオン標準液（Ｂｒ－１０００）および硫酸イオン標準液（ＳＯ４（２－）：１０００）を用い行った。 (2) ICP measurement The compound obtained in the example was measured with the following device.
Equipment used: Agilent Technologies
Equipment: Agent5100 ICP-OES
(3) Combustion ion chromatography measurement Using Mitsubishi Chemical's automatic sample combustion device AQF-2100 and Thermo Fisher's ion chromatography system DIONEX AQUION, the sulfur element content (S amount) and bromine element content are contained under the following measurement conditions. The amount (Br amount) was measured. The calibration curve was prepared using WAKO's bromide ion standard solution (Br-1000) and sulfate ion standard solution (SO4 (2-): 1000).
測定温度：９００℃→１０００℃
吸収液：過酸化水素入り超純水
カラム：ＡＳ－１７／ＡＧ－１７
流速：１ｍｌ／ｍｉｎ
セル温度：４０℃、カラム温度：３５℃
（４）ＡＰＨＡ測定
測定試料０．５ｇをジメチルホルムアミド１０ｍｌに溶解させた溶液をφ２５ｍｍの試験管に入れ、日本電色製工業（株）製ＴＺ６０００を用いて測定した。
（５）ガラス転移温度（Ｔｇ）測定、示差走査熱量測定（ＤＳＣ）
実施例で得られた樹脂を下記の装置、条件にて測定した。
装置：ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ製Ｄｉｓｃｏｖｅｒｙ ＤＳＣ２５
条件：昇温速度２０℃／ｍｉｎ
（６）ペレットｂ*値測定
実施例で得られた樹脂を下記の装置にて測定した。
装置： Ｘ－Ｒｉｔｅ社製 積分球分光光度計ＣＥ－７０００A
（７）屈折率（ｎＤ）、アッベ数測定
実施例で得られた樹脂を下記の装置、手法にて測定した。
装置：ＡＴＡＧＯ社製 ＤＲ－Ｍ２アッベ屈折計
手法：重合終了後に得られた樹脂ペレットを塩化メチレンに溶解させ、ガラスシャーレ上にキャスト、乾燥し、作成したフイルムの２５℃における屈折率（波長：５８９ｎｍ）およびアッベ数（波長：４８６ｎｍ、５８９ｎｍ、６５６ｎｍにおける屈折率から下記式を用いて算出）を測定した。 Measurement temperature: 900 ° C → 1000 ° C
Absorbent: Ultrapure water containing hydrogen peroxide Column: AS-17 / AG-17
Flow rate: 1 ml / min
Cell temperature: 40 ° C, column temperature: 35 ° C
(4) 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.
(5) Glass transition temperature (Tg) measurement, differential scanning calorimetry (DSC)
The resin obtained in the examples was measured with the following equipment and conditions.
Equipment: Discovery DSC25 manufactured by TA Instruments
Conditions: Temperature rise rate 20 ° C / min
(6) Pellet b * value measurement The resin obtained in the example was measured with the following device.
Equipment: X-Rite Integrating Sphere Spectrophotometer CE-7000A
(7) Measurement of refractive index (nD) and Abbe number The resin obtained in the examples was measured by the following devices and methods.
Equipment: ATAGO DR-M2 Abbe refractometer Method: The resin pellet obtained after completion of polymerization is dissolved in methylene chloride, cast on a glass chalet, dried, and the refractive index of the prepared film at 25 ° C. (wavelength: 589 nm). ) And the Abbe number (calculated from the refractive indexes at wavelengths: 486 nm, 589 nm, and 656 nm using the following formula).
吸収液：過酸化水素入り超純水
カラム：ＡＳ－１７／ＡＧ－１７
流速：１ｍｌ／ｍｉｎ
セル温度：４０℃、カラム温度：３５℃
（４）ＡＰＨＡ測定
測定試料０．５ｇをジメチルホルムアミド１０ｍｌに溶解させた溶液をφ２５ｍｍの試験管に入れ、日本電色製工業（株）製ＴＺ６０００を用いて測定した。
（５）ガラス転移温度（Ｔｇ）測定、示差走査熱量測定（ＤＳＣ）
実施例で得られた樹脂を下記の装置、条件にて測定した。
装置：ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ製Ｄｉｓｃｏｖｅｒｙ ＤＳＣ２５
条件：昇温速度２０℃／ｍｉｎ
（６）ペレットｂ*値測定
実施例で得られた樹脂を下記の装置にて測定した。
装置： Ｘ－Ｒｉｔｅ社製 積分球分光光度計ＣＥ－７０００A
（７）屈折率（ｎＤ）、アッベ数測定
実施例で得られた樹脂を下記の装置、手法にて測定した。
装置：ＡＴＡＧＯ社製 ＤＲ－Ｍ２アッベ屈折計
手法：重合終了後に得られた樹脂ペレットを塩化メチレンに溶解させ、ガラスシャーレ上にキャスト、乾燥し、作成したフイルムの２５℃における屈折率（波長：５８９ｎｍ）およびアッベ数（波長：４８６ｎｍ、５８９ｎｍ、６５６ｎｍにおける屈折率から下記式を用いて算出）を測定した。 Measurement temperature: 900 ° C → 1000 ° C
Absorbent: Ultrapure water containing hydrogen peroxide Column: AS-17 / AG-17
Flow rate: 1 ml / min
Cell temperature: 40 ° C, column temperature: 35 ° C
(4) 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.
(5) Glass transition temperature (Tg) measurement, differential scanning calorimetry (DSC)
The resin obtained in the examples was measured with the following equipment and conditions.
Equipment: Discovery DSC25 manufactured by TA Instruments
Conditions: Temperature rise rate 20 ° C / min
(6) Pellet b * value measurement The resin obtained in the example was measured with the following device.
Equipment: X-Rite Integrating Sphere Spectrophotometer CE-7000A
(7) Measurement of refractive index (nD) and Abbe number The resin obtained in the examples was measured by the following devices and methods.
Equipment: ATAGO DR-M2 Abbe refractometer Method: The resin pellet obtained after completion of polymerization is dissolved in methylene chloride, cast on a glass chalet, dried, and the refractive index of the prepared film at 25 ° C. (wavelength: 589 nm). ) And the Abbe number (calculated from the refractive indexes at wavelengths: 486 nm, 589 nm, and 656 nm using the following formula).
ν＝（ｎＤ－１）／（ｎＦ－ｎＣ）
なお、本発明においては、
ｎＤ：波長５８９ｎｍでの屈折率、
ｎＣ：波長６５６ｎｍでの屈折率、
ｎＦ：波長４８６ｎｍでの屈折率を意味する。
［参考例１］
撹拌機、冷却器、水分離器、さらには温度計を備え付けたフラスコに２，７－ジブロモフルオレノン（以下、ＤＢＦＮと略記することがある）２８．１ｇ（０．０８モル）、２－ナフトール２８．８ｇ（０．２０モル）、ｎ－ドデカンチオール１．８ｇ（０．０１モル）、１２タングスト（ＶＩ）リン酸ｎ水和物（Ｈ3［ＰＷ12Ｏ40］・ｎＨ2Ｏ）０．４ｇ（０．１２ミリモル）、トルエン３０ｍｌ、エチレンカーボネート７．７ｇを加えたのち、５０ｋＰａに減圧後、１００℃まで昇温し、同温度で５時間撹拌した。反応の進行具合はＨＰＬＣにて確認し、ＤＢＦＮの残存量が０．０％であることを確認し反応を終了させた。 ν = (nD-1) / (nF-nC)
In the present invention, it should be noted that
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.
[Reference Example 1]
28.1 g (0.08 mol) of 2,7-dibromofluorenone (hereinafter abbreviated as DBFN), 2-naphthol 28 in a flask equipped with a stirrer, a cooler, a water separator, and a thermometer. 0.8 g (0.20 mol), 1.8 g (0.01 mol) of n-dodecanethiol, 12 tonguest (VI) phosphate n hydrate (H 3 [PW 12 O 40 ] · nH 2 O) 0. After adding 4 g (0.12 mmol), 30 ml of toluene and 7.7 g of ethylene carbonate, the pressure was reduced to 50 kPa, the temperature was raised to 100 ° C., and the mixture was stirred at the same temperature for 5 hours. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of DBFN was 0.0%, and the reaction was terminated.
なお、本発明においては、
ｎＤ：波長５８９ｎｍでの屈折率、
ｎＣ：波長６５６ｎｍでの屈折率、
ｎＦ：波長４８６ｎｍでの屈折率を意味する。
［参考例１］
撹拌機、冷却器、水分離器、さらには温度計を備え付けたフラスコに２，７－ジブロモフルオレノン（以下、ＤＢＦＮと略記することがある）２８．１ｇ（０．０８モル）、２－ナフトール２８．８ｇ（０．２０モル）、ｎ－ドデカンチオール１．８ｇ（０．０１モル）、１２タングスト（ＶＩ）リン酸ｎ水和物（Ｈ3［ＰＷ12Ｏ40］・ｎＨ2Ｏ）０．４ｇ（０．１２ミリモル）、トルエン３０ｍｌ、エチレンカーボネート７．７ｇを加えたのち、５０ｋＰａに減圧後、１００℃まで昇温し、同温度で５時間撹拌した。反応の進行具合はＨＰＬＣにて確認し、ＤＢＦＮの残存量が０．０％であることを確認し反応を終了させた。 ν = (nD-1) / (nF-nC)
In the present invention, it should be noted that
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.
[Reference Example 1]
28.1 g (0.08 mol) of 2,7-dibromofluorenone (hereinafter abbreviated as DBFN), 2-naphthol 28 in a flask equipped with a stirrer, a cooler, a water separator, and a thermometer. 0.8 g (0.20 mol), 1.8 g (0.01 mol) of n-dodecanethiol, 12 tonguest (VI) phosphate n hydrate (H 3 [PW 12 O 40 ] · nH 2 O) 0. After adding 4 g (0.12 mmol), 30 ml of toluene and 7.7 g of ethylene carbonate, the pressure was reduced to 50 kPa, the temperature was raised to 100 ° C., and the mixture was stirred at the same temperature for 5 hours. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of DBFN was 0.0%, and the reaction was terminated.
反応後、２５重量％水酸化ナトリウム水溶液を加えて１２タングスト（ＶＩ）リン酸ｎ水和物（Ｈ3［ＰＷ12Ｏ40］・ｎＨ2Ｏ）を中和したのち、１２０℃で系内の水を留去した。その後、炭酸カリウム０．６ｇ（４．１６ミリモル）、エチレンカーボネート２８．９ｇ（０．３３モル）、ジメチルホルムアミド１００ｍＬを加えて、１１０℃で５時間撹拌し反応をおこなった。反応の進行具合をＨＰＬＣで確認し、９，９’－ビス（６－ヒドロキシ－２－ナフチル）－２，７－ジブロモフルオレンの残存量が０．０％であることを確認して反応を終了させた。反応終了後、得られた反応液に水および２５重量％水酸化ナトリウム水溶液を加え８５℃で１．５時間撹拌した後、水層を分離した。得られた反応液を濃縮し、トルエンを加え溶解させた後、温水洗浄を５回行った。その後、メタノールで再結晶を２回行い、一晩減圧加熱乾燥し、９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジブロモフルオレン（以下、ＢＮＤＢと略記することがある）の白色結晶を収率７７％、純度９７．４％で得た。
［実施例１］
撹拌機、冷却器、さらには温度計を備え付けたフラスコに、参考例１で製造したＢＮＤＢ４４．７ｇ（０．０６モル）、フェニルボロン酸１７．２ｇ（０．１４モル）、テトラキス（トリフェニルホスフィン）パラジウム０．０９ｇ（０．０８ミリモル）、２Ｍ炭酸カリウム水溶液７１ｍｌ、トルエン１５４ｍｌ、ジメチルホルムアミド７７ｍｌを加えた後、１００℃で３時間撹拌した。反応の進行具合はＨＰＬＣにて確認し、ＢＮＤＢの残存量が０．０％であることを確認し反応を終了させた。反応終了後、トルエンを加え反応液を希釈した後、撹拌を停止しトルエン層と水層を分離し、回収したトルエン層を温水で５回洗浄した。洗浄後のトルエン層にテトラヒドロフランを加え活性炭処理を行った後、テトラヒドロフランを留去し、トルエンで再結晶を行い、得られた結晶を一晩減圧加熱乾燥し、９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレン（以下、ＢＮＤＰと略記することがある）の白色結晶を収率８０％、純度９８．０％で得た。また、ＡＰＨＡは５０、Ｓは２５ｐｐｍ、Ｂｒは１ｐｐｍ、Ｐｄは１ｐｐｍ、ジフェニルフルオレノン（以下、ＤＰＦＮと省略することがある）はＨＰＬＣにて測定し０．０％だった。
［実施例２］
撹拌機、冷却器、さらには温度計を備え付けたフラスコに、参考例１で製造したＢＮＤＢ４４．７ｇ（０．０６モル）、フェニルボロン酸１７．２ｇ（０．１４モル）、テトラキス（トリフェニルホスフィン）パラジウム０．０９ｇ（０．０８ミリモル）、２Ｍ炭酸カリウム水溶液７１ｍｌ、トルエン１５４ｍｌ、ジメチルホルムアミド７７ｍｌを加えた後、１００℃で３時間撹拌した。反応の進行具合はＨＰＬＣにて確認し、ＢＮＤＢの残存量が０．０％であることを確認し反応を終了させた。反応終了後、トルエンを加え反応液を希釈した後、撹拌を停止しトルエン層と水層を分離し、回収したトルエン層を温水で５回洗浄した。洗浄後のトルエン層にテトラヒドロフランを加え活性炭処理を行った後、テトラヒドロフランを留去し、トルエン溶液に貧溶媒としてメタノールおよび蒸留水を加え再結晶し、得られた結晶を一晩減圧加熱乾燥し、ＢＮＤＰの白色結晶を収率７８％、純度９９．７％で得た。また、ＡＰＨＡは２０、Ｓは９ｐｐｍ、Ｂｒは０ｐｐｍ、Ｐｄは１ｐｐｍ、ＤＰＦＮはＨＰＬＣにて測定し０．０％だった。
［実施例３］
実施例１で合成した９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレンを２５．９１質量部、９，９－ビス［４－（２－ヒドロキシエトキシ）フェニル］フルオレンを１６．４４質量部、ジフェニルカーボネート１６．２３質量部、及び炭酸水素ナトリウム３．１５×１０-3質量部を撹拌機および留出装置付きの反応釜に入れ、窒素置換を３度行った後、ジャケットを２００℃に加熱し、原料を溶融させた。完全溶解後、５分かけて２０ｋＰａまで減圧すると同時に、６０℃／ｈｒの速度でジャケットを２６０℃まで昇温し、エステル交換反応を行った。その後、ジャケットを２６０℃に保持したまま、５０分かけて０．１３ｋＰａまで減圧し、２６０℃、０．１３ｋＰａ以下の条件下で所定のトルクに到達するまで重合反応を行った。反応終了後、生成した樹脂をペレタイズしながら抜き出し、ポリカーボネート樹脂のペレットを得た。得られたポリカーボネート樹脂を、1Ｈ ＮＭＲにより分析し、９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレン成分が全モノマー成分に対して、５０ｍｏｌ％導入されていることを確認した。得られたポリカーボネート樹脂の屈折率は１．６８２、アッベ数は１７．１、Ｔｇは１７７℃、ペレットｂ*値は４．０であった。
［比較例１］
撹拌機、冷却器、さらには温度計を備え付けたフラスコに、参考例１で製造したＢＮＤＢ４４．７ｇ（０．０６モル）、フェニルボロン酸１７．２ｇ（０．１４モル）、テトラキス（トリフェニルホスフィン）パラジウム０．７ｇ（０．６４ミリモル）、２Ｍ炭酸カリウム水溶液７８ｍｌ、トルエン２９２ｍｌ、エタノール９６ｍｌを加えた後、８０℃で３時間撹拌した。反応の進行具合はＨＰＬＣにて確認し、ＢＮＤＢの残存量が０．０％であることを確認し反応を終了させた。反応後、ＢＮＤＰは析出していた。反応液を冷却後、貧溶媒として蒸留水およびメタノールを加え、ＢＮＤＰを完全に析出させ、ろ過回収した。回収したＢＮＤＰ結晶を蒸留水でリパルプ洗浄し、ＢＮＤＰ結晶をろ過回収する操作を２回繰り返した後、ＢＮＤＰ結晶をテトラヒドロフランに溶解させ活性炭処理を行った。その後、トルエンで再結晶を行い、得られた結晶を一晩減圧加熱乾燥し、ＢＮＤＰの白色結晶を収率７４％、純度９９．２％で得た。また、ＡＰＨＡは６０、Ｓは２０ｐｐｍ、Ｂｒは８ｐｐｍ、Ｐｄは５ｐｐｍ、ＤＰＦＮはＨＰＬＣにて測定し０．０％だった。 After the reaction, 12 tonguest (VI) phosphoric acid n hydrate (H 3 [PW 12 O 40 ], nH 2 O) was neutralized by adding a 25 wt% sodium hydroxide aqueous solution, and then the temperature in the system was 120 ° C. Distilled water. Then, 0.6 g (4.16 mmol) of potassium carbonate, 28.9 g (0.33 mol) of ethylene carbonate and 100 mL of dimethylformamide were added, and the mixture was stirred at 110 ° C. for 5 hours to carry out the reaction. The progress of the reaction was confirmed by HPLC, and the residual amount of 9,9'-bis (6-hydroxy-2-naphthyl) -2,7-dibromofluorene was confirmed to be 0.0%, and the reaction was terminated. I let you. After completion of the reaction, water and a 25 wt% sodium hydroxide aqueous solution were added to the obtained reaction solution, and the mixture was stirred at 85 ° C. for 1.5 hours, and then the aqueous layer was separated. The obtained reaction solution was concentrated, toluene was added to dissolve it, and then washing with warm water was performed 5 times. Then, recrystallization was performed twice with methanol, and the mixture was dried under reduced pressure overnight to dry with 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-dibromofluorene (hereinafter abbreviated as BNDB). White crystals were obtained with a yield of 77% and a purity of 97.4%.
[Example 1]
In a flask equipped with a stirrer, a cooler, and a thermometer, 44.7 g (0.06 mol) of BNDB, 17.2 g (0.14 mol) of phenylboronic acid, and tetrakis (triphenylphosphine) produced in Reference Example 1 were placed. ) 0.09 g (0.08 mmol) of palladium, 71 ml of a 2M aqueous potassium carbonate solution, 154 ml of toluene and 77 ml of dimethylformamide were added, and the mixture was stirred at 100 ° C. for 3 hours. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of BNDB was 0.0%, and the reaction was terminated. After completion of the reaction, toluene was added to dilute the reaction solution, stirring was stopped, the toluene layer and the aqueous layer were separated, and the recovered toluene layer was washed 5 times with warm water. Tetrahydrofuran was added to the washed toluene layer and treated with activated carbon, then tetrahydrofuran was distilled off, recrystallization was performed with toluene, and the obtained crystals were heated and dried under reduced pressure overnight to make 9,9-bis [6-( 2-Hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene (hereinafter, may be abbreviated as BNDP) was obtained as white crystals in a yield of 80% and a purity of 98.0%. APHA was 50, S was 25 ppm, Br was 1 ppm, Pd was 1 ppm, and diphenylfluorenone (hereinafter, may be abbreviated as DPFN) was 0.0% as measured by HPLC.
[Example 2]
In a flask equipped with a stirrer, a cooler, and a thermometer, 44.7 g (0.06 mol) of BNDB, 17.2 g (0.14 mol) of phenylboronic acid, and tetrakis (triphenylphosphine) produced in Reference Example 1 were placed. ) 0.09 g (0.08 mmol) of palladium, 71 ml of a 2M aqueous potassium carbonate solution, 154 ml of toluene and 77 ml of dimethylformamide were added, and the mixture was stirred at 100 ° C. for 3 hours. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of BNDB was 0.0%, and the reaction was terminated. After completion of the reaction, toluene was added to dilute the reaction solution, stirring was stopped, the toluene layer and the aqueous layer were separated, and the recovered toluene layer was washed 5 times with warm water. Tetrahydrofuran was added to the washed toluene layer and treated with activated charcoal, then tetrahydrofuran was distilled off, methanol and distilled water were added as a poor solvent to the toluene solution for recrystallization, and the obtained crystals were heated and dried under reduced pressure overnight. White crystals of BNDP were obtained with a yield of 78% and a purity of 99.7%. APHA was 20, S was 9 ppm, Br was 0 ppm, Pd was 1 ppm, and DPFN was 0.0% as measured by HPLC.
[Example 3]
25.91 parts by mass of 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene synthesized in Example 1, 9,9-bis [4- (2- (2-) Hydroxyethoxy) phenyl] Fluolene was placed in a reaction vessel equipped with a stirrer and a distiller in 16.44 parts by mass, diphenyl carbonate 16.23 parts by mass, and sodium hydrogen carbonate 3.15 × 10 -3 parts by mass, and replaced with nitrogen. After that, the jacket was heated to 200 ° C. to melt the raw materials. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the temperature of the jacket was raised 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. The obtained polycarbonate resin was analyzed by 1 H NMR, and the 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene component was 50 mol with respect to all the monomer components. % Confirmed that it has been introduced. The obtained polycarbonate resin had a refractive index of 1.682, an Abbe number of 17.1, a Tg of 177 ° C., and a pellet b * value of 4.0.
[Comparative Example 1]
In a flask equipped with a stirrer, a cooler, and a thermometer, 44.7 g (0.06 mol) of BNDB, 17.2 g (0.14 mol) of phenylboronic acid, and tetrakis (triphenylphosphine) produced in Reference Example 1 were placed. ) 0.7 g (0.64 mmol) of palladium, 78 ml of a 2M aqueous potassium carbonate solution, 292 ml of toluene and 96 ml of ethanol were added, and the mixture was stirred at 80 ° C. for 3 hours. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of BNDB was 0.0%, and the reaction was terminated. After the reaction, BNDP was precipitated. After cooling the reaction solution, distilled water and methanol were added as poor solvents to completely precipitate BNDP, which was then collected by filtration. The recovered BNDP crystals were re-pulp washed with distilled water, and the operation of filtering and recovering the BNDP crystals was repeated twice, and then the BNDP crystals were dissolved in tetrahydrofuran and treated with activated carbon. Then, recrystallization was performed with toluene, and the obtained crystals were dried by heating under reduced pressure overnight to obtain white crystals of BNDP with a yield of 74% and a purity of 99.2%. APHA was 60, S was 20 ppm, Br was 8 ppm, Pd was 5 ppm, and DPFN was 0.0% as measured by HPLC.
［実施例１］
撹拌機、冷却器、さらには温度計を備え付けたフラスコに、参考例１で製造したＢＮＤＢ４４．７ｇ（０．０６モル）、フェニルボロン酸１７．２ｇ（０．１４モル）、テトラキス（トリフェニルホスフィン）パラジウム０．０９ｇ（０．０８ミリモル）、２Ｍ炭酸カリウム水溶液７１ｍｌ、トルエン１５４ｍｌ、ジメチルホルムアミド７７ｍｌを加えた後、１００℃で３時間撹拌した。反応の進行具合はＨＰＬＣにて確認し、ＢＮＤＢの残存量が０．０％であることを確認し反応を終了させた。反応終了後、トルエンを加え反応液を希釈した後、撹拌を停止しトルエン層と水層を分離し、回収したトルエン層を温水で５回洗浄した。洗浄後のトルエン層にテトラヒドロフランを加え活性炭処理を行った後、テトラヒドロフランを留去し、トルエンで再結晶を行い、得られた結晶を一晩減圧加熱乾燥し、９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレン（以下、ＢＮＤＰと略記することがある）の白色結晶を収率８０％、純度９８．０％で得た。また、ＡＰＨＡは５０、Ｓは２５ｐｐｍ、Ｂｒは１ｐｐｍ、Ｐｄは１ｐｐｍ、ジフェニルフルオレノン（以下、ＤＰＦＮと省略することがある）はＨＰＬＣにて測定し０．０％だった。
［実施例２］
撹拌機、冷却器、さらには温度計を備え付けたフラスコに、参考例１で製造したＢＮＤＢ４４．７ｇ（０．０６モル）、フェニルボロン酸１７．２ｇ（０．１４モル）、テトラキス（トリフェニルホスフィン）パラジウム０．０９ｇ（０．０８ミリモル）、２Ｍ炭酸カリウム水溶液７１ｍｌ、トルエン１５４ｍｌ、ジメチルホルムアミド７７ｍｌを加えた後、１００℃で３時間撹拌した。反応の進行具合はＨＰＬＣにて確認し、ＢＮＤＢの残存量が０．０％であることを確認し反応を終了させた。反応終了後、トルエンを加え反応液を希釈した後、撹拌を停止しトルエン層と水層を分離し、回収したトルエン層を温水で５回洗浄した。洗浄後のトルエン層にテトラヒドロフランを加え活性炭処理を行った後、テトラヒドロフランを留去し、トルエン溶液に貧溶媒としてメタノールおよび蒸留水を加え再結晶し、得られた結晶を一晩減圧加熱乾燥し、ＢＮＤＰの白色結晶を収率７８％、純度９９．７％で得た。また、ＡＰＨＡは２０、Ｓは９ｐｐｍ、Ｂｒは０ｐｐｍ、Ｐｄは１ｐｐｍ、ＤＰＦＮはＨＰＬＣにて測定し０．０％だった。
［実施例３］
実施例１で合成した９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレンを２５．９１質量部、９，９－ビス［４－（２－ヒドロキシエトキシ）フェニル］フルオレンを１６．４４質量部、ジフェニルカーボネート１６．２３質量部、及び炭酸水素ナトリウム３．１５×１０-3質量部を撹拌機および留出装置付きの反応釜に入れ、窒素置換を３度行った後、ジャケットを２００℃に加熱し、原料を溶融させた。完全溶解後、５分かけて２０ｋＰａまで減圧すると同時に、６０℃／ｈｒの速度でジャケットを２６０℃まで昇温し、エステル交換反応を行った。その後、ジャケットを２６０℃に保持したまま、５０分かけて０．１３ｋＰａまで減圧し、２６０℃、０．１３ｋＰａ以下の条件下で所定のトルクに到達するまで重合反応を行った。反応終了後、生成した樹脂をペレタイズしながら抜き出し、ポリカーボネート樹脂のペレットを得た。得られたポリカーボネート樹脂を、1Ｈ ＮＭＲにより分析し、９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレン成分が全モノマー成分に対して、５０ｍｏｌ％導入されていることを確認した。得られたポリカーボネート樹脂の屈折率は１．６８２、アッベ数は１７．１、Ｔｇは１７７℃、ペレットｂ*値は４．０であった。
［比較例１］
撹拌機、冷却器、さらには温度計を備え付けたフラスコに、参考例１で製造したＢＮＤＢ４４．７ｇ（０．０６モル）、フェニルボロン酸１７．２ｇ（０．１４モル）、テトラキス（トリフェニルホスフィン）パラジウム０．７ｇ（０．６４ミリモル）、２Ｍ炭酸カリウム水溶液７８ｍｌ、トルエン２９２ｍｌ、エタノール９６ｍｌを加えた後、８０℃で３時間撹拌した。反応の進行具合はＨＰＬＣにて確認し、ＢＮＤＢの残存量が０．０％であることを確認し反応を終了させた。反応後、ＢＮＤＰは析出していた。反応液を冷却後、貧溶媒として蒸留水およびメタノールを加え、ＢＮＤＰを完全に析出させ、ろ過回収した。回収したＢＮＤＰ結晶を蒸留水でリパルプ洗浄し、ＢＮＤＰ結晶をろ過回収する操作を２回繰り返した後、ＢＮＤＰ結晶をテトラヒドロフランに溶解させ活性炭処理を行った。その後、トルエンで再結晶を行い、得られた結晶を一晩減圧加熱乾燥し、ＢＮＤＰの白色結晶を収率７４％、純度９９．２％で得た。また、ＡＰＨＡは６０、Ｓは２０ｐｐｍ、Ｂｒは８ｐｐｍ、Ｐｄは５ｐｐｍ、ＤＰＦＮはＨＰＬＣにて測定し０．０％だった。 After the reaction, 12 tonguest (VI) phosphoric acid n hydrate (H 3 [PW 12 O 40 ], nH 2 O) was neutralized by adding a 25 wt% sodium hydroxide aqueous solution, and then the temperature in the system was 120 ° C. Distilled water. Then, 0.6 g (4.16 mmol) of potassium carbonate, 28.9 g (0.33 mol) of ethylene carbonate and 100 mL of dimethylformamide were added, and the mixture was stirred at 110 ° C. for 5 hours to carry out the reaction. The progress of the reaction was confirmed by HPLC, and the residual amount of 9,9'-bis (6-hydroxy-2-naphthyl) -2,7-dibromofluorene was confirmed to be 0.0%, and the reaction was terminated. I let you. After completion of the reaction, water and a 25 wt% sodium hydroxide aqueous solution were added to the obtained reaction solution, and the mixture was stirred at 85 ° C. for 1.5 hours, and then the aqueous layer was separated. The obtained reaction solution was concentrated, toluene was added to dissolve it, and then washing with warm water was performed 5 times. Then, recrystallization was performed twice with methanol, and the mixture was dried under reduced pressure overnight to dry with 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-dibromofluorene (hereinafter abbreviated as BNDB). White crystals were obtained with a yield of 77% and a purity of 97.4%.
[Example 1]
In a flask equipped with a stirrer, a cooler, and a thermometer, 44.7 g (0.06 mol) of BNDB, 17.2 g (0.14 mol) of phenylboronic acid, and tetrakis (triphenylphosphine) produced in Reference Example 1 were placed. ) 0.09 g (0.08 mmol) of palladium, 71 ml of a 2M aqueous potassium carbonate solution, 154 ml of toluene and 77 ml of dimethylformamide were added, and the mixture was stirred at 100 ° C. for 3 hours. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of BNDB was 0.0%, and the reaction was terminated. After completion of the reaction, toluene was added to dilute the reaction solution, stirring was stopped, the toluene layer and the aqueous layer were separated, and the recovered toluene layer was washed 5 times with warm water. Tetrahydrofuran was added to the washed toluene layer and treated with activated carbon, then tetrahydrofuran was distilled off, recrystallization was performed with toluene, and the obtained crystals were heated and dried under reduced pressure overnight to make 9,9-bis [6-( 2-Hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene (hereinafter, may be abbreviated as BNDP) was obtained as white crystals in a yield of 80% and a purity of 98.0%. APHA was 50, S was 25 ppm, Br was 1 ppm, Pd was 1 ppm, and diphenylfluorenone (hereinafter, may be abbreviated as DPFN) was 0.0% as measured by HPLC.
[Example 2]
In a flask equipped with a stirrer, a cooler, and a thermometer, 44.7 g (0.06 mol) of BNDB, 17.2 g (0.14 mol) of phenylboronic acid, and tetrakis (triphenylphosphine) produced in Reference Example 1 were placed. ) 0.09 g (0.08 mmol) of palladium, 71 ml of a 2M aqueous potassium carbonate solution, 154 ml of toluene and 77 ml of dimethylformamide were added, and the mixture was stirred at 100 ° C. for 3 hours. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of BNDB was 0.0%, and the reaction was terminated. After completion of the reaction, toluene was added to dilute the reaction solution, stirring was stopped, the toluene layer and the aqueous layer were separated, and the recovered toluene layer was washed 5 times with warm water. Tetrahydrofuran was added to the washed toluene layer and treated with activated charcoal, then tetrahydrofuran was distilled off, methanol and distilled water were added as a poor solvent to the toluene solution for recrystallization, and the obtained crystals were heated and dried under reduced pressure overnight. White crystals of BNDP were obtained with a yield of 78% and a purity of 99.7%. APHA was 20, S was 9 ppm, Br was 0 ppm, Pd was 1 ppm, and DPFN was 0.0% as measured by HPLC.
[Example 3]
25.91 parts by mass of 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene synthesized in Example 1, 9,9-bis [4- (2- (2-) Hydroxyethoxy) phenyl] Fluolene was placed in a reaction vessel equipped with a stirrer and a distiller in 16.44 parts by mass, diphenyl carbonate 16.23 parts by mass, and sodium hydrogen carbonate 3.15 × 10 -3 parts by mass, and replaced with nitrogen. After that, the jacket was heated to 200 ° C. to melt the raw materials. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the temperature of the jacket was raised 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. The obtained polycarbonate resin was analyzed by 1 H NMR, and the 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene component was 50 mol with respect to all the monomer components. % Confirmed that it has been introduced. The obtained polycarbonate resin had a refractive index of 1.682, an Abbe number of 17.1, a Tg of 177 ° C., and a pellet b * value of 4.0.
[Comparative Example 1]
In a flask equipped with a stirrer, a cooler, and a thermometer, 44.7 g (0.06 mol) of BNDB, 17.2 g (0.14 mol) of phenylboronic acid, and tetrakis (triphenylphosphine) produced in Reference Example 1 were placed. ) 0.7 g (0.64 mmol) of palladium, 78 ml of a 2M aqueous potassium carbonate solution, 292 ml of toluene and 96 ml of ethanol were added, and the mixture was stirred at 80 ° C. for 3 hours. The progress of the reaction was confirmed by HPLC, and it was confirmed that the residual amount of BNDB was 0.0%, and the reaction was terminated. After the reaction, BNDP was precipitated. After cooling the reaction solution, distilled water and methanol were added as poor solvents to completely precipitate BNDP, which was then collected by filtration. The recovered BNDP crystals were re-pulp washed with distilled water, and the operation of filtering and recovering the BNDP crystals was repeated twice, and then the BNDP crystals were dissolved in tetrahydrofuran and treated with activated carbon. Then, recrystallization was performed with toluene, and the obtained crystals were dried by heating under reduced pressure overnight to obtain white crystals of BNDP with a yield of 74% and a purity of 99.2%. APHA was 60, S was 20 ppm, Br was 8 ppm, Pd was 5 ppm, and DPFN was 0.0% as measured by HPLC.
実施例１および実施例２の製造方法は、目的物が溶媒に溶解しているため、精製処理時のろ過回数が減り、目的物の収率および生産性を向上させることができる。また、得られた結晶の色相がより良好であり、光学部材を構成する樹脂を形成するモノマーとして好適である。
［比較例２］
比較例１で合成した９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレンを２５．９１質量部、９，９－ビス［４－（２－ヒドロキシエトキシ）フェニル］フルオレンを１６．４４質量部、ジフェニルカーボネート１６．２３質量部、及び炭酸水素ナトリウム３．１５×１０-3質量部を撹拌機および留出装置付きの反応釜に入れ、窒素置換を３度行った後、ジャケットを２００℃に加熱し、原料を溶融させた。完全溶解後、５分かけて２０ｋＰａまで減圧すると同時に、６０℃／ｈｒの速度でジャケットを２６０℃まで昇温し、エステル交換反応を行った。その後、ジャケットを２６０℃に保持したまま、５０分かけて０．１３ｋＰａまで減圧し、２６０℃、０．１３ｋＰａ以下の条件下で所定のトルクに到達するまで重合反応を行った。反応終了後、生成した樹脂をペレタイズしながら抜き出し、ポリカーボネート樹脂のペレットを得た。得られたポリカーボネート樹脂を、1Ｈ ＮＭＲにより分析し、９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレン成分が全モノマー成分に対して、５０ｍｏｌ％導入されていることを確認した。得られたポリカーボネート樹脂の屈折率は１．６８２、アッベ数は１７．１、Ｔｇは１７７℃、ペレットｂ*値は５．９であった。 In the production methods of Examples 1 and 2, since the target product is dissolved in a solvent, the number of filtrations during the purification treatment can be reduced, and the yield and productivity of the target product can be improved. Further, the hue of the obtained crystal is better, and it is suitable as a monomer for forming a resin constituting an optical member.
[Comparative Example 2]
25.91 parts by mass of 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene synthesized in Comparative Example 1, 9,9-bis [4- (2- (2-) Hydroxyethoxy) phenyl] Fluolene was placed in a reaction vessel equipped with a stirrer and a distiller in 16.44 parts by mass, diphenyl carbonate 16.23 parts by mass, and sodium hydrogen carbonate 3.15 × 10 -3 parts by mass, and replaced with nitrogen. After that, the jacket was heated to 200 ° C. to melt the raw materials. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the temperature of the jacket was raised 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. The obtained polycarbonate resin was analyzed by 1 H NMR, and the 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene component was 50 mol with respect to all the monomer components. % Confirmed that it has been introduced. The obtained polycarbonate resin had a refractive index of 1.682, an Abbe number of 17.1, a Tg of 177 ° C., and a pellet b * value of 5.9.
［比較例２］
比較例１で合成した９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレンを２５．９１質量部、９，９－ビス［４－（２－ヒドロキシエトキシ）フェニル］フルオレンを１６．４４質量部、ジフェニルカーボネート１６．２３質量部、及び炭酸水素ナトリウム３．１５×１０-3質量部を撹拌機および留出装置付きの反応釜に入れ、窒素置換を３度行った後、ジャケットを２００℃に加熱し、原料を溶融させた。完全溶解後、５分かけて２０ｋＰａまで減圧すると同時に、６０℃／ｈｒの速度でジャケットを２６０℃まで昇温し、エステル交換反応を行った。その後、ジャケットを２６０℃に保持したまま、５０分かけて０．１３ｋＰａまで減圧し、２６０℃、０．１３ｋＰａ以下の条件下で所定のトルクに到達するまで重合反応を行った。反応終了後、生成した樹脂をペレタイズしながら抜き出し、ポリカーボネート樹脂のペレットを得た。得られたポリカーボネート樹脂を、1Ｈ ＮＭＲにより分析し、９，９－ビス［６－（２－ヒドロキシエトキシ）－２－ナフチル］－２，７－ジフェニルフルオレン成分が全モノマー成分に対して、５０ｍｏｌ％導入されていることを確認した。得られたポリカーボネート樹脂の屈折率は１．６８２、アッベ数は１７．１、Ｔｇは１７７℃、ペレットｂ*値は５．９であった。 In the production methods of Examples 1 and 2, since the target product is dissolved in a solvent, the number of filtrations during the purification treatment can be reduced, and the yield and productivity of the target product can be improved. Further, the hue of the obtained crystal is better, and it is suitable as a monomer for forming a resin constituting an optical member.
[Comparative Example 2]
25.91 parts by mass of 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene synthesized in Comparative Example 1, 9,9-bis [4- (2- (2-) Hydroxyethoxy) phenyl] Fluolene was placed in a reaction vessel equipped with a stirrer and a distiller in 16.44 parts by mass, diphenyl carbonate 16.23 parts by mass, and sodium hydrogen carbonate 3.15 × 10 -3 parts by mass, and replaced with nitrogen. After that, the jacket was heated to 200 ° C. to melt the raw materials. After complete dissolution, the pressure was reduced to 20 kPa over 5 minutes, and at the same time, the temperature of the jacket was raised 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. The obtained polycarbonate resin was analyzed by 1 H NMR, and the 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] -2,7-diphenylfluorene component was 50 mol with respect to all the monomer components. % Confirmed that it has been introduced. The obtained polycarbonate resin had a refractive index of 1.682, an Abbe number of 17.1, a Tg of 177 ° C., and a pellet b * value of 5.9.
本発明の製造方法で得られる新規なフルオレン誘導体は、光学レンズや光学フィルムに代表される光学部材を構成する樹脂を形成するモノマーとして好適である。
The novel fluorene derivative obtained by the production method of the present invention is suitable as a monomer for forming a resin constituting an optical member represented by an optical lens or an optical film.
Claims (5)
- 下記式（１）で表される化合物と下記式（２）または（３）で表されるボロン酸類とを反応溶媒中、塩基およびパラジウム系触媒の存在下で反応し、下記式（４）で表されるフルオレン骨格を有する化合物を得る工程において、反応溶媒として少なくともジメチルホルムアミドを使用することを特徴とするフルオレン骨格を有する化合物の製造方法。
- 反応溶媒として少なくともジメチルホルムアミドおよび芳香族炭化水素系溶媒を使用することを特徴とする請求項１に記載のフルオレン骨格を有する化合物の製造方法。 The method for producing a compound having a fluorene skeleton according to claim 1, wherein at least dimethylformamide and an aromatic hydrocarbon solvent are used as the reaction solvent.
- ジメチルホルムアミドに溶解させた５重量％溶液のハーゼン単位色数（ＡＰＨＡ）が５０以下である下記式（４）で示されるフルオレン骨格を有する化合物。
- 熱可塑性樹脂の原料としての、請求項３に記載のフルオレン骨格を有する化合物の使用方法。 The method for using a compound having a fluorene skeleton according to claim 3, as a raw material for a thermoplastic resin.
- 請求項３に記載のフルオレン骨格を有する化合物を重合することにより得られる熱可塑性樹脂。 A thermoplastic resin obtained by polymerizing the compound having a fluorene skeleton according to claim 3.
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