JP2020138920A - Compound having binaphthalene skeleton - Google Patents
Compound having binaphthalene skeleton Download PDFInfo
- Publication number
- JP2020138920A JP2020138920A JP2019034292A JP2019034292A JP2020138920A JP 2020138920 A JP2020138920 A JP 2020138920A JP 2019034292 A JP2019034292 A JP 2019034292A JP 2019034292 A JP2019034292 A JP 2019034292A JP 2020138920 A JP2020138920 A JP 2020138920A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- group
- binaphthalene
- formula
- skeleton
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 125000005843 halogen group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000001624 naphthyl group Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- -1 binaphthalene compound Chemical class 0.000 description 9
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OVJPYIRGUFWANT-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)naphthalen-1-yl]naphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3OCCO)=C(OCCO)C=CC2=C1 OVJPYIRGUFWANT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- 125000006704 (C5-C6) cycloalkyl group Chemical group 0.000 description 2
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 2
- SHUPPTRRQACTON-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-6-naphthalen-1-ylnaphthalen-1-yl]-6-naphthalen-1-ylnaphthalen-2-yl]oxyethanol Chemical compound C1(=CC=CC2=CC=CC=C12)C=1C=C2C=CC(=C(C2=CC=1)C1=C(C=CC2=CC(=CC=C12)C1=CC=CC2=CC=CC=C12)OCCO)OCCO SHUPPTRRQACTON-UHFFFAOYSA-N 0.000 description 2
- ZKBUCVUKEWAMGB-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-6-phenylnaphthalen-1-yl]-6-phenylnaphthalen-2-yl]oxyethanol Chemical compound C1(=CC=CC=C1)C=1C=C2C=CC(=C(C2=CC=1)C1=C(C=CC2=CC(=CC=C12)C1=CC=CC=C1)OCCO)OCCO ZKBUCVUKEWAMGB-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 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
- 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 2
- 239000012788 optical film Substances 0.000 description 2
- 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 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JPZZHPUJIFQUFL-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-3-naphthalen-1-ylnaphthalen-1-yl]-3-naphthalen-1-ylnaphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C(=C1)C=CC=C2C3=CC4=CC=CC=C4C(=C3OCCO)C5=C(C(=CC6=CC=CC=C65)C7=CC=CC8=CC=CC=C87)OCCO JPZZHPUJIFQUFL-UHFFFAOYSA-N 0.000 description 1
- LZWDMEOGUYVTEM-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-3-naphthalen-2-ylnaphthalen-1-yl]-3-naphthalen-2-ylnaphthalen-2-yl]oxyethanol Chemical compound OCCOc1c(cc2ccccc2c1-c1c(OCCO)c(cc2ccccc12)-c1ccc2ccccc2c1)-c1ccc2ccccc2c1 LZWDMEOGUYVTEM-UHFFFAOYSA-N 0.000 description 1
- YNLJSWZWJWFIFM-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-3-phenylnaphthalen-1-yl]-3-phenylnaphthalen-2-yl]oxyethanol Chemical compound OCCOc1c(cc2ccccc2c1-c1c(OCCO)c(cc2ccccc12)-c1ccccc1)-c1ccccc1 YNLJSWZWJWFIFM-UHFFFAOYSA-N 0.000 description 1
- QPXZAOFKJPXVNJ-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-4-naphthalen-2-ylnaphthalen-1-yl]-4-naphthalen-2-ylnaphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C=C(C=CC2=C1)C3=CC(=C(C4=CC=CC=C43)C5=C(C=C(C6=CC=CC=C65)C7=CC8=CC=CC=C8C=C7)OCCO)OCCO QPXZAOFKJPXVNJ-UHFFFAOYSA-N 0.000 description 1
- UJBKWXSSNORZOY-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-5-naphthalen-1-ylnaphthalen-1-yl]-5-naphthalen-1-ylnaphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C(=C1)C=CC=C2C3=CC=CC4=C3C=CC(=C4C5=C(C=CC6=C5C=CC=C6C7=CC=CC8=CC=CC=C87)OCCO)OCCO UJBKWXSSNORZOY-UHFFFAOYSA-N 0.000 description 1
- DUAKRCUFQKKRIX-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-5-naphthalen-2-ylnaphthalen-1-yl]-5-naphthalen-2-ylnaphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C=C(C=CC2=C1)C3=CC=CC4=C3C=CC(=C4C5=C(C=CC6=C5C=CC=C6C7=CC8=CC=CC=C8C=C7)OCCO)OCCO DUAKRCUFQKKRIX-UHFFFAOYSA-N 0.000 description 1
- KIOOVKDJQKYQHG-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-5-phenylnaphthalen-1-yl]-5-phenylnaphthalen-2-yl]oxyethanol Chemical compound C1=CC=C(C=C1)C2=CC=CC3=C2C=CC(=C3C4=C(C=CC5=C4C=CC=C5C6=CC=CC=C6)OCCO)OCCO KIOOVKDJQKYQHG-UHFFFAOYSA-N 0.000 description 1
- RFDNUPWFKBZDFC-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-6-naphthalen-2-ylnaphthalen-1-yl]-6-naphthalen-2-ylnaphthalen-2-yl]oxyethanol Chemical compound C1=C(C=CC2=CC=CC=C12)C=1C=C2C=CC(=C(C2=CC=1)C1=C(C=CC2=CC(=CC=C12)C1=CC2=CC=CC=C2C=C1)OCCO)OCCO RFDNUPWFKBZDFC-UHFFFAOYSA-N 0.000 description 1
- NWEFMMCTEGCWBQ-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-7-naphthalen-1-ylnaphthalen-1-yl]-7-naphthalen-1-ylnaphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C(=C1)C=CC=C2C3=CC4=C(C=C3)C=CC(=C4C5=C(C=CC6=C5C=C(C=C6)C7=CC=CC8=CC=CC=C87)OCCO)OCCO NWEFMMCTEGCWBQ-UHFFFAOYSA-N 0.000 description 1
- NPCZIMYOPZKESX-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-7-naphthalen-2-ylnaphthalen-1-yl]-7-naphthalen-2-ylnaphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C=C(C=CC2=C1)C3=CC4=C(C=C3)C=CC(=C4C5=C(C=CC6=C5C=C(C=C6)C7=CC8=CC=CC=C8C=C7)OCCO)OCCO NPCZIMYOPZKESX-UHFFFAOYSA-N 0.000 description 1
- BZAFEQMQPSPOPY-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-7-phenylnaphthalen-1-yl]-7-phenylnaphthalen-2-yl]oxyethanol Chemical compound OCCOC1=C(C2=CC(=CC=C2C=C1)C1=CC=CC=C1)C1=C(C=CC2=CC=C(C=C12)C1=CC=CC=C1)OCCO BZAFEQMQPSPOPY-UHFFFAOYSA-N 0.000 description 1
- HPJWESNHUFVSIA-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-8-naphthalen-1-ylnaphthalen-1-yl]-8-naphthalen-1-ylnaphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C(=C1)C=CC=C2C3=CC=CC4=C3C(=C(C=C4)OCCO)C5=C(C=CC6=C5C(=CC=C6)C7=CC=CC8=CC=CC=C87)OCCO HPJWESNHUFVSIA-UHFFFAOYSA-N 0.000 description 1
- UYIQSJFYCWJBSJ-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-8-naphthalen-2-ylnaphthalen-1-yl]-8-naphthalen-2-ylnaphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C=C(C=CC2=C1)C3=CC=CC4=C3C(=C(C=C4)OCCO)C5=C(C=CC6=C5C(=CC=C6)C7=CC8=CC=CC=C8C=C7)OCCO UYIQSJFYCWJBSJ-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
- SVMHXXNTXNFJIJ-UHFFFAOYSA-N 2-[6-bromo-1-[6-bromo-2-(2-hydroxyethoxy)naphthalen-1-yl]naphthalen-2-yl]oxyethanol Chemical compound OCCOc1ccc2cc(Br)ccc2c1-c1c(OCCO)ccc2cc(Br)ccc12 SVMHXXNTXNFJIJ-UHFFFAOYSA-N 0.000 description 1
- KNBLDQKPBPTQLD-UHFFFAOYSA-N 2-[[2-(2-hydroxyethoxy)-6-phenyl-1-(6-phenylnaphthalen-1-yl)-3H-naphthalen-2-yl]oxy]ethanol Chemical compound OCCOC1(C(=C2C=CC(=CC2=CC1)C1=CC=CC=C1)C1=CC=CC2=CC(=CC=C12)C1=CC=CC=C1)OCCO KNBLDQKPBPTQLD-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- CSXZTVGZLVMVRY-UHFFFAOYSA-N 3,4-dibromo-1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=C(Br)C(Br)=C3O)=CC=CC2=C1 CSXZTVGZLVMVRY-UHFFFAOYSA-N 0.000 description 1
- OORIFUHRGQKYEV-UHFFFAOYSA-N 6-bromo-1-(6-bromo-2-hydroxynaphthalen-1-yl)naphthalen-2-ol Chemical compound BrC1=CC=C2C(C3=C4C=CC(Br)=CC4=CC=C3O)=C(O)C=CC2=C1 OORIFUHRGQKYEV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、光学レンズや光学フイルムに代表される光学部材を構成する熱可塑性樹脂を形成するモノマーとして好適なビナフタレン骨格を有する化合物に関する。 The present invention relates to a compound having a binaphthalene skeleton suitable as a monomer for forming a thermoplastic resin constituting an optical member represented by an optical lens or an optical film.
近年、２，２’−ビス（２−ヒドロキシエトキシ）−１，１’−ビナフタレン（ＢＮ２ＥＯ）に代表されるビナフタレン骨格を有するアルコールを原料としたポリカーボネート、ポリエステルなどの熱可塑性樹脂材料は、光学特性、耐熱性、成形性などに優れることから、光学レンズや光学シートなどの光学部材として注目されている。例えば、特許文献１には、ＢＮ２ＥＯを有するアルコールを原料としたポリエステル樹脂が開示されているが、該アルコールを使用したポリエステル樹脂の屈折率は１．６７との記載があるものの、近年の急速な技術革新に伴い、前記特性のさらなる向上が要求されている。そこでさらなる高屈折率化を目指し、特許文献２ではＢＮ２ＥＯに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（ＢＮＥＦ）を共重合させたポリカーボネート樹脂が開発されているものの、該特許文献に記載の樹脂も屈折率に未だ改善の余地がある。 In recent years, thermoplastic resin materials such as polycarbonate and polyester made from alcohol having a binaphthalene skeleton represented by 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (BN2EO) have optical properties. Since it is excellent in heat resistance and moldability, it is attracting attention as an optical member such as an optical lens and an optical sheet. For example, Patent Document 1 discloses a polyester resin made from an alcohol having BN2EO, and although there is a description that the refractive index of the polyester resin using the alcohol is 1.67, it has been rapidly in recent years. With the technological innovation, further improvement of the above-mentioned characteristics is required. Therefore, with the aim of further increasing the refractive index, Patent Document 2 has developed a polycarbonate resin obtained by copolymerizing BN2EO with 9,9-bis [6- (2-hydroxyethoxy) 2-naphthyl] fluorene (BNEF). There is still room for improvement in the refractive index of the resin described in the patent document.
ところで、２，２’−ビス（２−ヒドロキシエトキシ）−１，１’−ビナフタレンの製造方法としては、特許文献３に記載された１，１’−ビ−２−ナフトールとエチレンカーボネートを反応させる方法、特許文献４に記載された１，１’−ビ−２−ナフトールとエチレンカーボネートまたはエチレンオキサイドを反応させる方法が開示されており、高純度で着色の少ない製品は得られるものの、該アルコールを原料として用いた熱可塑性樹脂材料の光学特性は未だ満足のいくものではなく改良の余地がある。 By the way, as a method for producing 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene, 1,1'-bi-2-naphthol described in Patent Document 3 is reacted with ethylene carbonate. A method and a method for reacting 1,1'-bi-2-naphthol described in Patent Document 4 with ethylene carbonate or ethylene oxide are disclosed, and although a product having high purity and less coloring can be obtained, the alcohol can be used. The optical properties of the thermoplastic resin material used as the raw material are still unsatisfactory and there is room for improvement.
本発明において分子設計した下記式（１）の化合物は、パラジウム含有量等の特定の金属含有量が少なく、その原料や原料を使った樹脂の色相や種々特性（光学特性、耐熱性、成形性など）に優れた新規なビナフタレン骨格を有する化合物を提供することを目的とする。 The compound of the following formula (1) molecularly designed in the present invention has a small content of a specific metal such as a palladium content, and the hue and various characteristics (optical characteristics, heat resistance, moldability) of the raw material and the resin using the raw material. It is an object of the present invention to provide a compound having a novel binaphthalene skeleton excellent in (etc.).
本発明は、上記従来技術の問題点を解決するために検討した結果達成されたものであって、一定の品質を有し、ポリマー原料として優れたビナフタレン骨格を有する化合物を提供することである。具体的には、本発明は、以下に示すビナフタレン骨格を有する化合物に関する。 The present invention has been achieved as a result of studies for solving the above-mentioned problems of the prior art, and is to provide a compound having a certain quality and having an excellent binaphthalene skeleton as a polymer raw material. Specifically, the present invention relates to a compound having a binaphthalene skeleton shown below.
［１］下記式（１）で示されるビナフタレン骨格を有する化合物であって、
ビナフタレン骨格を有する化合物中のパラジウム元素の含有量が下記式（２）を満たすビナフタレン骨格を有する化合物。
０ ≦ Ｐｄ ≦ ５０ｐｐｍ （２）
[1] A compound having a vinaphthalene skeleton represented by the following formula (1).
A compound having a vinaphthalene skeleton in which the content of the palladium element in the compound having a vinaphthalene skeleton satisfies the following formula (2).
0 ≤ Pd ≤ 50 ppm (2)
［２］前記式（１）が下記式（１ａ）〜（１ｆ）で示されるうちの少なくとも１つである前項１に記載のビナフタレン骨格を有する化合物。
［３］前記式（１）が前記式（１ｄ）である前項２に記載のビナフタレン骨格を有する化合物。
［４］前記式（１）中のＡｒ１またはＡｒ２がフェニル基またはナフチル基である前項１〜３のいずれかに記載のビナフタレン骨格を有する化合物。
［５］熱可塑性樹脂の原料としての、前項１に記載のビナフタレン骨格を有する化合物の使用方法。
[3] The compound having a vinaphthalene skeleton according to item 2 above, wherein the formula (1) is the formula (1d).
[4] The compound having a binaphthalene skeleton according to any one of the above items 1 to 3, wherein Ar 1 or Ar 2 in the formula (1) is a phenyl group or a naphthyl group.
[5] A method for using a compound having a binaphthalene skeleton according to the above item 1 as a raw material for a thermoplastic resin.
本発明により製造された該ビナフタレン化合物は、屈折率が高く、合成時に使用するパラジウム系触媒の使用量を適正化することによりパラジウム含有量等の特定の金属含有量が少なくなるため、活性炭処理あるいはそれと酷似した金属の除去処理で容易に除去することができるため、非常に効率よく金属含有量の少ないビナフタレン骨格を有する化合物を製造することができる。さらに、該ビナフタレン化合物は反応性の高いヒドロキシ基を２つ有しているため、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）のモノマー成分としても好適に利用できる。 The vinaphthalene compound produced according to the present invention has a high refractive index, and by optimizing the amount of the palladium-based catalyst used at the time of synthesis, the specific metal content such as the palladium content is reduced. Since it can be easily removed by a metal removal treatment very similar to that, a compound having a binaphthalene skeleton having a low metal content can be produced very efficiently. Further, since the binaphthalene compound has two highly reactive hydroxy groups, it can be suitably used as a monomer component of a thermoplastic resin (for example, polyester resin, polycarbonate resin, polyester carbonate resin, polyurethane resin, etc.).
本発明を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の代表例であり、これらの内容に限定されるものではない。 Although the present invention will be described in detail, the description of the constituent elements described below is a typical example of the embodiment of the present invention, and is not limited to these contents.
［ビナフタレン骨格を有する化合物］
本発明の化合物は、下記式（１）で表されるビナフタレン骨格を有する化合物、すなわち、ナフタレンの１，１’位が直接結合したビナフタレン部位のナフタレン環の２〜８位および２’〜８’位のいずれかに少なくとも１つのヒドロキシ基を有する炭化水素が１つ置換または付加し、さらには炭素数６〜１０の置換基を有してもよい芳香族基が１つ置換または付加した化合物である。
[Compound having a binaphthalene skeleton]
The compound of the present invention is a compound having a binaphthalene skeleton represented by the following formula (1), that is, the 2 to 8 positions and 2'to 8'of the naphthalene ring of the binaphthalene moiety to which the 1,1'position of naphthalene is directly bonded. A compound in which one hydrocarbon having at least one hydroxy group is substituted or added to any of the positions, and further, one aromatic group optionally having a substituent having 6 to 10 carbon atoms is substituted or added. is there.
上記式（１）において、Ｒ１およびＲ２はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜１２の芳香族基を含んでいてもよい炭化水素基を示し、水素原子、メチル基またはフェニル基が好ましい。 In the above formula (1), R 1 and R 2 independently represent a hydrocarbon group which may contain a hydrogen atom, a halogen atom, and an aromatic group having 1 to 12 carbon atoms, and are a hydrogen atom and a methyl group. Alternatively, a phenyl group is preferable.
上記式（１）において、Ｒ１およびＲ２で表される炭化水素基としては、アルキル基、シクロアルキル基、アリール基、ナフチル基、アラルキル基などが例示できる。アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ−ブチル基などのＣ１−６アルキル基、Ｃ１−４アルキル基、Ｃ１−３アルキル基が好ましく、Ｃ１−３アルキル基がさらに好ましく、その中でメチル基またはエチル基がよりさらに好ましい。 Examples of the hydrocarbon group represented by R 1 and R 2 in the above formula (1) include an alkyl group, a cycloalkyl group, an aryl group, a naphthyl group, and an aralkyl group. Specific examples of the alkyl group include C 1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group, C 1-4 alkyl group and C 1-3 alkyl group. Preferably, a C 1-3 alkyl group is even more preferred, of which a methyl or ethyl group is even more preferred.
また、シクロアルキル基の具体例としては、シクロペンチル基、シクロヘキシル基などのＣ５−８シクロアルキル基、Ｃ５−６シクロアルキル基などが好ましく、Ｃ５−６シクロアルキル基がより好ましい。 Further, as specific examples of the cycloalkyl group, a C 5-8 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a C 5-6 cycloalkyl group and the like are preferable, and a C 5-6 cycloalkyl group is more preferable.
また、アリール基の具体例としては、フェニル基、アルキルフェニル基（モノまたはジメチルフェニル基、トリル基、２−メチルフェニル基、キシリル基など）などが好ましく、フェニル基がより好ましい。 Further, as specific examples of the aryl group, a phenyl group, an alkylphenyl group (mono or dimethylphenyl group, tolyl group, 2-methylphenyl group, xsilyl group, etc.) and the like are preferable, and a phenyl group is more preferable.
また、アラルキル基の具体例としては、ベンジル基、フェネチル基などのＣ６−１０アリール−Ｃ１−４アルキル基などが好ましく例示できる。
また、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子などが好ましい。
Further, as a specific example of the aralkyl group, a C 6-10 aryl-C 1-4 alkyl group such as a benzyl group and a phenethyl group can be preferably exemplified.
Further, as the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and the like are preferable.
上記式（１）において、Ｒ１およびＲ２の置換基数ｎ１およびｎ２は、ｎ１が０〜４（例えば１〜３）であればよく、好ましくは０〜２、さらに好ましくは０〜１である。また、ｎ２が０〜３（例えば１〜３）であればよく、好ましくは０〜２、さらに好ましくは０〜１である。なお、ｎ１およびｎ２はそれぞれのナフタレン環において、同一または異なる数であってもよく、また、異なるナフタレン環において同一または異なる数であってもよい。また、置換基Ｒ１およびＲ２は、前記と同じであり、同一のナフタレン環および異なるナフタレン環においてそれぞれ、同一または異なる置換基であってもよい。 In the above formula (1), the number of the substituents n1 and n2 of R 1 and R 2 may be any n1 is 0-4 (e.g. 1-3), it is preferably 0 to 2, more preferably 0 to 1 .. Further, n2 may be 0 to 3 (for example, 1 to 3), preferably 0 to 2, and more preferably 0 to 1. In addition, n1 and n2 may be the same or different numbers in each naphthalene ring, and may be the same or different numbers in different naphthalene rings. Further, the substituents R 1 and R 2 are the same as described above, and may be the same or different substituents in the same naphthalene ring and different naphthalene rings, respectively.
上記式（１）において、Ｌ１およびＬ２はそれぞれ独立に２価の連結基を示し、炭素数１〜１２のアルキレン基であり、炭素数１〜５のアルキレン基であることがより好ましく、エチレン基であるとさらに好ましい。通常、Ｌ１およびＬ２はビナフタレン環において、同一のアルキレン基であってもよい。また、Ｌ１およびＬ２は、異なるナフタレン環において、互いに同一又は異なっていてもよく、通常、同一であってもよい。 In the above formula (1), L 1 and L 2 each independently represent a divalent linking group, which is an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. It is more preferably an ethylene group. Generally, L 1 and L 2 may be the same alkylene group in the vinaphthalene ring. Further, L 1 and L 2 may be the same or different from each other in different naphthalene rings, and may be usually the same.
オキシアルキレン基（ＯＬ１）および（ＯＬ２）の数（付加モル数）ｊおよびｋは、それぞれ０〜５の範囲から選択でき、下限は好ましくは０以上であり、上限は好ましくは４以下、より好ましくは３以下、さらに好ましくは２以下である。特に好ましくは０または１であり、もっとも好ましくは１である。なお、ｊおよびｋは、整数でも平均値であってもよく、異なるナフタレン環において、同一であっても、異なっていてもよい。 The number of oxyalkylene groups (OL 1 ) and (OL 2 ) (number of added moles) j and k can be selected from the range of 0 to 5, respectively, the lower limit is preferably 0 or more, and the upper limit is preferably 4 or less. It is more preferably 3 or less, still more preferably 2 or less. It is particularly preferably 0 or 1, and most preferably 1. Note that j and k may be integers or average values, and may be the same or different in different naphthalene rings.
上記式（１）において、Ａｒ１およびＡｒ２は、それぞれ独立に炭素原子数６〜１０の芳香族基を示し、フェニル基またはナフチル基が好ましい。基Ａｒ１およびＡｒ２はたがいに異なっていてもよく同一であってもよいが、通常、同一である。また、Ａｒ１およびＡｒ２のそれぞれの結合位置はビナフタレン環の３位と３’位、４位と４’位、５位と５’位、６位と６’位、７位と７’位または８位と８’位であると好ましく、４位と４’位、６位と６’位または７位と７’位であるとより好ましく、６位と６’位であるとさらに好ましい。 In the above formula (1), Ar 1 and Ar 2 each independently represent an aromatic group having 6 to 10 carbon atoms, and a phenyl group or a naphthyl group is preferable. The groups Ar 1 and Ar 2 may be different or the same, but are usually the same. The bonding positions of Ar 1 and Ar 2 are the 3rd and 3'positions of the vinaphthalene ring, the 4th and 4'positions, the 5th and 5'positions, the 6th and 6'positions, and the 7th and 7'positions, respectively. Alternatively, the 8th and 8'positions are preferable, the 4th and 4'positions, the 6th and 6'positions, or the 7th and 7'positions are more preferable, and the 6th and 6'positions are even more preferable.
上記式（１）において、Ａｒ１およびＡｒ２の置換数ｍ１およびｍ２はｍ１＋ｍ２≧１であればよく、例えば、ｍ１は０〜４であればよく、好ましくは０〜２、さらに好ましくは０〜１である。また、ｍ２は０〜３であればよく、好ましくは０〜２、さらに好ましくは０〜１である。なお、ｍ１およびｍ２は、それぞれのナフタレン環において同一または異なる数であってもよく、また異なるナフタレン環において同一または異なる数であってもよい。 In the above formula (1), the substitution numbers m1 and m2 of Ar 1 and Ar 2 may be m1 + m2 ≧ 1, for example, m1 may be 0 to 4, preferably 0 to 2, and more preferably 0 to 0. It is 1. Further, m2 may be 0 to 3, preferably 0 to 2, and more preferably 0 to 1. In addition, m1 and m2 may be the same or different numbers in each naphthalene ring, and may be the same or different numbers in different naphthalene rings.
以下に前記式（１）で表されるジオール成分の代表例を示すが、本発明の前記式（１）に用いられる原料としては、それらによって限定されるものではない。 Representative examples of the diol component represented by the formula (1) are shown below, but the raw materials used in the formula (1) of the present invention are not limited thereto.
ジフェニルビナフタレンタイプとしては、２，２’−ビス（２−ヒドロキシエトキシ）−３，３’−ジフェニル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−４，４’−ジフェニル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−５，５’−ジフェニル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジフェニル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−７，７’−ジフェニル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−８，８’−ジフェニル−１，１’−ビナフタレン等が好ましく挙げられる。なかでも、下記式（１−ａ）に示す２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジフェニル−１，１’−ビナフタレンが好ましい。 The diphenyl binaphthalene types include 2,2'-bis (2-hydroxyethoxy) -3,3'-diphenyl-1,1'-binaphthalene and 2,2'-bis (2-hydroxyethoxy) -4,4. '-Diphenyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -5,5'-diphenyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -7,7'-diphenyl-1,1'-binaphthalene, 2,2'-bis (2) -Hydroxyethoxy) -8,8'-diphenyl-1,1'-binaphthalene and the like are preferably mentioned. Of these, 2,2'-bis (2-hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthalene represented by the following formula (1-a) is preferable.
ジナフチルビナフタレンタイプとしては、２，２’−ビス（２−ヒドロキシエトキシ）−３，３’−ジ−１−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−４，４’−ジ−１−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−５，５’−ジ−１−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジ−１−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−７，７’−ジ−１−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−８，８’−ジ−１−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−３，３’−ジ−２−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−４，４’−ジ−２−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−５，５’−ジ−２−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジ−２−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−７，７’−ジ−２−ナフチル−１，１’−ビナフタレン、２，２’−ビス（２−ヒドロキシエトキシ）−８，８’−ジ−２−ナフチル−１，１’−ビナフタレン等が好ましく挙げられる。なかでも、下記式（１−ｂ）および（１−ｃ）に示す下記式（１−ｂ）２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジ−２−ナフチル−１，１’−ビナフタレンおよび下記式（１−ｃ）２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジ−１−ナフチル−１，１’−ビナフタレンが好ましい。 The dinaphthyl binaphthalene type includes 2,2'-bis (2-hydroxyethoxy) -3,3'-di-1-naphthyl-1,1'-binaphthalene and 2,2'-bis (2-hydroxyethoxy). ) -4,4'-di-1-naphthyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -5,5'-di-1-naphthyl-1,1'-binaphthalene , 2,2'-bis (2-hydroxyethoxy) -6,6'-di-1-naphthyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -7,7'- Di-1-naphthyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -8,8'-di-1-naphthyl-1,1'-binaphthalene, 2,2'-bis (2-Hydroxyethoxy) -3,3'-di-2-naphthyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -4,4'-di-2-naphthyl-1 , 1'-Binaphthalene, 2,2'-bis (2-hydroxyethoxy) -5,5'-di-2-naphthyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy)- 6,6'-di-2-naphthyl-1,1'-binaphthalene, 2,2'-bis (2-hydroxyethoxy) -7,7'-di-2-naphthyl-1,1'-binaphthalene, 2 , 2'-Bis (2-hydroxyethoxy) -8,8'-di-2-naphthyl-1,1'-binaphthalene and the like are preferable. Among them, the following formulas (1-b) 2,2'-bis (2-hydroxyethoxy) -6,6'-di-2-naphthyl-1 represented by the following formulas (1-b) and (1-c) , 1'-Binaphthalene and the following formula (1-c) 2,2'-bis (2-hydroxyethoxy) -6,6'-di-1-naphthyl-1,1'-binaphthalene are preferable.
本発明のビナフタレン骨格を有する化合物は、パラジウム元素の含有量が下記式（２）を満足する。
０ ≦ Ｐｄ ≦ ５０ｐｐｍ （２）
好ましくは、下記式（２−１）を満足する。
０ ≦ Ｐｄ ≦ ４０ｐｐｍ （２−１）
より好ましくは、下記式（２−２）を満足する。
０ ≦ Ｐｄ ≦ ２５ｐｐｍ （２−２）
さらに好ましくは、下記式（２−３）を満足する。
０ ≦ Ｐｄ ≦ １０ｐｐｍ （２−３）
よりさらに好ましくは、下記式（２−４）を満足する。
０ ≦ Ｐｄ ≦ ５ｐｐｍ （２−４）
特に好ましくは、下記式（２−５）を満足する。
０ ≦ Ｐｄ ≦ ３ｐｐｍ （２−５）
もっとも好ましくは、下記式（２−６）を満足する。
０ ≦ Ｐｄ ≦ １ｐｐｍ （２−６）
上記範囲の上限を超えると、前記式（１）で表される原料アルコールを使った樹脂の色相やそれを使った光学部材に悪影響を及ぼすため、好ましくない。パラジウム元素の含有量の下限は、０．０１ｐｐｍ以上、０．０５ｐｐｍ以上、または０．１０ｐｐｍ以上であってもよい。
The compound having a binaphthalene skeleton of the present invention has a palladium element content satisfying the following formula (2).
0 ≤ Pd ≤ 50 ppm (2)
Preferably, the following formula (2-1) is satisfied.
0 ≤ Pd ≤ 40 ppm (2-1)
More preferably, the following formula (2-2) is satisfied.
0 ≤ Pd ≤ 25 ppm (2-2)
More preferably, the following formula (2-3) is satisfied.
0 ≤ Pd ≤ 10 ppm (2-3)
Even more preferably, the following equation (2-4) is satisfied.
0 ≤ Pd ≤ 5 ppm (2-4)
Particularly preferably, the following formula (2-5) is satisfied.
0 ≤ Pd ≤ 3 ppm (2-5)
Most preferably, the following formula (2-6) is satisfied.
0 ≤ Pd ≤ 1 ppm (2-6)
If the upper limit of the above range is exceeded, the hue of the resin using the raw material alcohol represented by the formula (1) and the optical member using the same are adversely affected, which is not preferable. The lower limit of the content of the palladium element may be 0.01 ppm or more, 0.05 ppm or more, or 0.10 ppm or more.
また、本発明のビナフタレン骨格を有する化合物のＨＰＬＣで測定した純度は、好ましくは９５％以上、より好ましくは９８％以上、さらに好ましくは９９％以上である。 The purity of the compound having a binaphthalene skeleton of the present invention measured by HPLC is preferably 95% or more, more preferably 98% or more, still more preferably 99% or more.
［ビナフタレン骨格を有する化合物の製造方法］
本発明において、ビナフタレン骨格を有する化合物の製造方法としては、例えばジブロモ−ビナフトールとエチレンカーボネートとを反応させ、得られた合成物とフェニルボロン酸またはナフチルボロン酸とを、反応溶媒中、塩基およびパラジウム系触媒の存在下反応させる方法により行うことができる。
[Method for producing a compound having a binaphthalene skeleton]
In the present invention, as a method for producing a compound having a binaphthalene skeleton, for example, dibromo-binaphthol is reacted with ethylene carbonate, and the obtained compound and phenylboronic acid or naphthylboronic acid are mixed with a base and palladium in a reaction solvent. It can be carried out by a method of reacting in the presence of a system catalyst.
得られた反応物は、活性炭処理あるいはそれと酷似した金属の除去処理をして、パラジウム系触媒を除去することができる。 The obtained reaction product can be treated with activated carbon or a metal removal treatment very similar thereto to remove the palladium-based catalyst.
［ビナフタレン骨格を有する化合物の特徴および用途］
本発明のビナフタレン骨格を有する化合物は、好ましくはビナフタレン骨格とアリール基と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。これまで屈折率を向上させるために、ビナフタレン骨格を有する化合物として２，２’−ビス−（２−ヒドロキシエトキシ）−１，１’−ビナフタレンが用いられているが、これでは複屈折は低いものの屈折率は改良の余地がある。これに対し、本発明のビナフタレン骨格を有する化合物は、ビナフタレン骨格にジアリール基を導入しているためか、複屈折は変わらず低く屈折率が効率よく高くなる。さらに、ビナフタレン環には、１つ以上のヒドロキシル基を有し、ビナフタ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、本発明のビナフタ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。本発明のビナフタ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、ビナフタレン骨格の６，６’位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。
[Characteristics and applications of compounds having a binaphthalene skeleton]
Since the compound having a binaphthalene skeleton of the present invention preferably combines a binaphthalene skeleton and an aryl group, it not only has high refractive index and heat resistance, but also can reduce birefringence when made into a polymer. So far, 2,2'-bis- (2-hydroxyethoxy) -1,1'-binaphthalene has been used as a compound having a binaphthalene skeleton in order to improve the refractive index, but this has low birefringence. There is room for improvement in the refractive index. On the other hand, the compound having a binaphthalene skeleton of the present invention has a low birefringence and an efficient high refractive index, probably because a diaryl group is introduced into the binaphthalene skeleton. Further, since the binaphthalene ring has one or more hydroxyl groups and the entire binaphthalene compound has a plurality of hydroxyl groups, the reactivity is high. Therefore, the compound having a binaphthalene skeleton of the present invention can be used as a raw material (monomer) for various resins. For example, thermoplastic resins (eg, polyester resins, polycarbonate resins, polyester carbonate resins, polyurethane resins, etc.) and thermosetting resins (eg, epoxy resins, phenolic resins, thermosetting polyurethane resins, (meth) acrylates ((meth)). It can be used as a polyol component of) such as acrylic acid ester). When the compound having a binaphthalene skeleton of the present invention is used as a polyol component, the obtained resin has a high level of high refractive index and low birefringence, probably because it has a diaryl group at the 6,6'position of the binaphthalene skeleton. It has the advantage that it can be compatible with.
また、本発明のビナフタレン骨格を有する化合物は、汎用な溶媒中で効率よく誘導体を調製できる。 In addition, the compound having a binaphthalene skeleton of the present invention can efficiently prepare a derivative in a general-purpose solvent.
本発明のビナフタレン骨格を有する化合物の融点は、５０〜２００℃の広い範囲から選択でき、好ましくは７０〜１８０℃、より好ましくは８０〜１６０℃、さらに好ましくは９０〜１５０℃である。 The melting point of the compound having a binaphthalene skeleton of the present invention can be selected from a wide range of 50 to 200 ° C., preferably 70 to 180 ° C., more preferably 80 to 160 ° C., still more preferably 90 to 150 ° C.
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
実施例で得られた化合物を下記の装置、条件にて測定し、純度を求めた。
使用機器：Ｗａｔｅｒｓ社製
カラム：ＡＣＱＵＩＴＹ ＵＰＬＣ＠ＢＥＨ Ｃ１８ ２．１×１５０ｍｍ
溶出液（体積）：ジメチルホルムアミド：超純水（０．１重量％トリフルオロ酢酸）＝７０／３０。
（２）ＮＭＲ測定
実施例１で得られた化合物を下記の装置、溶媒にて測定した。
装置：日本電子社製 ＪＮＭ−ＡＬ４００（４００ＭＨｚ）
溶媒：ＣＤＣｌ３
（３）ＩＣＰ測定
実施例で得られた化合物を下記の装置にてパラジウム元素量を測定した。
使用機器：Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ
装置：Ａｇｉｌｅｎｔ５１００ ＩＣＰ−ＯＥＳ
（４）屈折率（ｎＤ）
装置：ＡＴＡＧＯ社製 ＤＲ−Ｍ２アッベ屈折計
手法：実施例で得られた化合物をジメチルスルホキシドに溶解させ、２５℃における屈折率（波長：５８９ｎｍ）を測定した。その溶液屈折率を用いてホモポリマーとしての屈折率を概算した。
In the examples, various measurements were performed as follows.
(1) HPLC measurement The compound obtained in the example was measured with the following equipment and conditions to determine the purity.
Equipment used: Waters column: ACQUITY UPLC @ BEH C18 2.1 x 150 mm
Eluate (volume): Dimethylformamide: Ultrapure water (0.1 wt% trifluoroacetic acid) = 70/30.
(2) NMR measurement The compound obtained in Example 1 was measured with the following apparatus and solvent.
Equipment: JNM-AL400 (400MHz) manufactured by JEOL Ltd.
Solvent: CDCl 3
(3) ICP measurement The amount of palladium element of the compound obtained in the example was measured by the following apparatus.
Equipment used: Agilent Technologies
Equipment: Agent5100 ICP-OES
(4) Refractive index (nD)
Instrument: DR-M2 Abbe refractometer manufactured by ATAGO Method: The compound obtained in the example was dissolved in dimethyl sulfoxide, and the refractive index (wavelength: 589 nm) at 25 ° C. was measured. The refractive index as a homopolymer was estimated using the solution refractive index.
［実施例１］
＜工程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６，６’−ジブロモ−１，１’−ビ−２−ナフトール（以下、ＢＮ−６Ｂｒと略記することがある）５ｇ（１１．３ミリモル）、エチレンカーボネート２．３ｇ（２５．９ミリモル）、炭酸カリウム０．１６ｇ（１．９ミリモル）、トルエン１５ｇを仕込み、１１０℃で５時間反応した。反応の進行具合は適宜ＨＰＬＣにて確認し、ＢＮ−６Ｂｒの残存量が０．１重量％以下であることを確認し反応を終了させた。得られた反応混合物にトルエン６５ｇを加え希釈した後、１０重量％水酸化ナトリウム水溶液８ｇを加え８５℃で１時間撹拌後、水層を分液除去した。有機層を濃縮したのち、酢酸エチルに溶解させ水洗後に水層を分液除去した。さらにヘキサンを加えてそのまま再結晶した結果、目的の２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジブロモ−１，１’−ビナフタレン（以下、ＢＮ２ＥＯ−６Ｂｒと略記することがある）の白色固体を３．７ｇ（収率６１％、純度９８．８％）得た。得られたサンプルはそのまま工程２の反応に使用した。
[Example 1]
<Step 1>
6,6'-dibromo-1,1'-bi-2-naphthol (hereinafter sometimes abbreviated as BN-6Br) 5 g (11.3) in a flask equipped with a stirrer, a cooler, and a thermometer. Millimole), 2.3 g (25.9 mmol) of ethylene carbonate, 0.16 g (1.9 mmol) of potassium carbonate, and 15 g of toluene were charged and reacted at 110 ° C. for 5 hours. The progress of the reaction was appropriately confirmed by HPLC, and it was confirmed that the residual amount of BN-6Br was 0.1% by weight or less, and the reaction was terminated. 65 g of toluene was added to the obtained reaction mixture for dilution, 8 g of a 10 wt% sodium hydroxide aqueous solution was added, and the mixture was stirred at 85 ° C. for 1 hour, and the aqueous layer was separated and removed. After concentrating the organic layer, it was dissolved in ethyl acetate, washed with water, and then the aqueous layer was separated and removed. As a result of further adding hexane and recrystallizing as it is, the desired 2,2'-bis (2-hydroxyethoxy) -6,6'-dibromo-1,1'-binaphthalene (hereinafter, abbreviated as BN2EO-6Br) can be abbreviated. 3.7 g (yield 61%, purity 98.8%) was obtained. The obtained sample was used as it was for the reaction in step 2.
＜工程２＞
窒素雰囲気下、撹拌機、冷却器、さらには温度計を備え付けたフラスコに工程２で得られたＢＮ２ＥＯ−６Ｂｒ３．５ｇ（６．６ミリモル）、フェニルボロン酸２．１０ｇ（１６．５ミリモル）、テトラキス（トリフェニルホスフィン）パラジウム０．１１２ｇ（０．１ミリモル）、２Ｍ炭酸カリウム水溶液９ｍＬ、トルエン３３ｍＬ、エタノール１２ｍＬを仕込み、８０℃で２時間反応した。反応の進行具合は適宜ＨＰＬＣにて確認し、ＢＮ２ＥＯ−６Ｂｒの残存が０．１重量％以下であることを確認し反応を終了させた。得られた反応混合物を濃縮後、１Ｍ水酸化ナトリウム水溶液を加えクロロホルムで抽出した。得られた有機層に活性炭を加え１時間撹拌したのち、活性炭を濾別後に有機層を濃縮した。濃縮後、シリカゲルカラムクロマトグラフィーにより精製を行った結果、目的の２，２−ビス（２−ヒドロキシエトキシ）−６，６’−ジフェニル−１，１’−ビナフタレン（以下、ＢＮ２ＥＯ−６Ｐｈと略記することがある）の白色結晶を２．６ｇ（収率７５％、純度９９．２％）得た。ＩＣＰにより残存金属量を測定したところ、Ｐｄは７ｐｐｍであった。また、得られたＢＮ２ＥＯ−６Ｐｈを１Ｈ ＮＭＲにより分析し、ビナフタレン環の６，６’位がフェニル基に置換された目的物であることを確認した（図１）。さらに、得られたＢＮ２ＥＯ−６Ｐｈを用いて屈折率を測定した結果、ホモポリマー換算値で１．７０となった。
<Process 2>
BN2EO-6Br 3.5 g (6.6 mmol), phenylboronic acid 2.10 g (16.5 mmol), obtained in step 2 in a flask equipped with a stirrer, a cooler, and a thermometer under a nitrogen atmosphere. 0.112 g (0.1 mmol) of tetrakis (triphenylphosphine) palladium, 9 mL of a 2M potassium carbonate aqueous solution, 33 mL of toluene, and 12 mL of ethanol were charged and reacted at 80 ° C. for 2 hours. The progress of the reaction was appropriately confirmed by HPLC, and it was confirmed that the residual amount of BN2EO-6Br was 0.1% by weight or less, and the reaction was terminated. The obtained reaction mixture was concentrated, a 1 M aqueous sodium hydroxide solution was added, and the mixture was extracted with chloroform. Activated carbon was added to the obtained organic layer, and the mixture was stirred for 1 hour. After filtering the activated carbon, the organic layer was concentrated. As a result of purification by silica gel column chromatography after concentration, the desired 2,2-bis (2-hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthalene (hereinafter abbreviated as BN2EO-6Ph). (Sometimes), 2.6 g (yield 75%, purity 99.2%) was obtained. When the amount of residual metal was measured by ICP, Pd was 7 ppm. In addition, the obtained BN2EO-6Ph was analyzed by 1H NMR, and it was confirmed that the 6 and 6'positions of the vinaphthalene ring were the target products substituted with phenyl groups (FIG. 1). Further, as a result of measuring the refractive index using the obtained BN2EO-6Ph, it was 1.70 in terms of homopolymer.
［実施例２］
工程２におけるフェニルボロン酸を２−ナフタレンボロン酸に変更した以外は実施例１と同様にして２，２−ビス（２−ヒドロキシエトキシ）−６，６’−ジ−２−ナフチル−１，１’−ビナフタレン（以下、ＢＮ２ＥＯ−６（２Ｎｐ）と略記することがある）の白色固体を３．１ｇ（収率７５％、純度９９．２％）得た。ＩＣＰにより残存金属量を測定したところ、Ｐｄは７ｐｐｍであった。得られたＢＮ２ＥＯ−６（２Ｎｐ）を用いて屈折率を測定した結果、ホモポリマー換算値で１．７６となった。
[Example 2]
2,2-bis (2-hydroxyethoxy) -6,6'-di-2-naphthyl-1,1 in the same manner as in Example 1 except that the phenylboronic acid in step 2 was changed to 2-naphthalene boronic acid. 3.1 g (yield 75%, purity 99.2%) of a white solid of ′ -vinaphthalene (hereinafter, sometimes abbreviated as BN2EO-6 (2Np)) was obtained. When the amount of residual metal was measured by ICP, Pd was 7 ppm. As a result of measuring the refractive index using the obtained BN2EO-6 (2Np), it was 1.76 in terms of homopolymer.
［実施例３］
工程２におけるフェニルボロン酸を１−ナフタレンボロン酸に変更した以外は実施例１と同様にして２，２−ビス（２−ヒドロキシエトキシ）−６，６’−ジ−１−ナフチル−１，１’−ビナフタレン（以下、ＢＮ２ＥＯ−６（１Ｎｐ）と略記することがある）の白色固体を２．９ｇ（収率７０％、純度９９．１％）得た。ＩＣＰにより残存金属量を測定したところ、Ｐｄは８ｐｐｍであった。得られたＢＮ２ＥＯ−６（１Ｎｐ）を用いて屈折率を測定した結果、ホモポリマー換算値で１．７０となった。
[Example 3]
2,2-bis (2-hydroxyethoxy) -6,6'-di-1-naphthyl-1,1 in the same manner as in Example 1 except that the phenylboronic acid in step 2 was changed to 1-naphthaleneboronic acid. 2.9 g (yield 70%, purity 99.1%) of a white solid of ′ -vinaphthalene (hereinafter, sometimes abbreviated as BN2EO-6 (1Np)) was obtained. When the amount of residual metal was measured by ICP, Pd was 8 ppm. As a result of measuring the refractive index using the obtained BN2EO-6 (1Np), it was 1.70 in terms of homopolymer.
［比較例１］
工程２における脱Ｐｄ処理として活性炭処理をしない以外は実施例１と同様にしてＢＮ２ＥＯ−６Ｐｈの薄黄色固体を２．６ｇ（収率７５％、純度９９．２％）得た。ＩＣＰにより残存金属量を測定したところ、Ｐｄは８０ｐｐｍであった。
[Comparative Example 1]
2.6 g (yield 75%, purity 99.2%) of a pale yellow solid of BN2EO-6Ph was obtained in the same manner as in Example 1 except that the activated carbon treatment was not performed as the de-Pd treatment in the step 2. When the amount of residual metal was measured by ICP, Pd was 80 ppm.
［比較例２］
工程２における脱Ｐｄ処理として活性炭処理をしない以外は実施例２と同様にしてＢＮ２ＥＯ−６（２Ｎｐ）の薄黄色固体を３．１ｇ（収率７５％、純度９９．２％）得た。ＩＣＰにより残存金属量を測定したところ、Ｐｄは８０ｐｐｍであった。
[Comparative Example 2]
3.1 g (yield 75%, purity 99.2%) of a pale yellow solid of BN2EO-6 (2Np) was obtained in the same manner as in Example 2 except that the activated carbon treatment was not performed as the de-Pd treatment in the step 2. When the amount of residual metal was measured by ICP, Pd was 80 ppm.
［比較例３］
工程２における脱Ｐｄ処理として活性炭処理をしない以外は実施例３と同様にしてＢＮ２ＥＯ−６（１Ｎｐ）を２．９ｇ（収率７０％、純度９９．１％）得た。ＩＣＰにより残存金属量を測定したところ、Ｐｄは８０ｐｐｍであった。
[Comparative Example 3]
2.9 g (yield 70%, purity 99.1%) of BN2EO-6 (1Np) was obtained in the same manner as in Example 3 except that activated carbon treatment was not performed as the de-Pd treatment in step 2. When the amount of residual metal was measured by ICP, Pd was 80 ppm.
本発明のビナフタレン骨格を有する化合物を原料（モノマー）とする樹脂は、例えば、フイルム、レンズ、プリズム、光ディスク、透明導電性基板、光カード、シート、光ファイバー、光学膜、光学フィルター、ハードコート膜等の光学部材に用いることができ、特にレンズに極めて有用である。 The resin using the compound having a binaphthalene skeleton of the present invention as a raw material (monomer) is, for example, a film, a lens, a prism, an optical disk, a transparent conductive substrate, an optical card, a sheet, an optical fiber, an optical film, an optical filter, a hard coat film, etc. It can be used for optical members of the above, and is extremely useful especially for lenses.
Claims (5)
ビナフタレン骨格を有する化合物中のパラジウム元素の含有量が下記式（２）を満たすビナフタレン骨格を有する化合物。
０ ≦ Ｐｄ ≦ ５０ｐｐｍ （２） A compound having a vinaphthalene skeleton represented by the following formula (1).
A compound having a vinaphthalene skeleton in which the content of the palladium element in the compound having a vinaphthalene skeleton satisfies the following formula (2).
0 ≤ Pd ≤ 50 ppm (2)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019034292A JP2020138920A (en) | 2019-02-27 | 2019-02-27 | Compound having binaphthalene skeleton |
| CN202080016683.3A CN113474321B (en) | 2019-02-27 | 2020-02-21 | Compound having binaphthyl skeleton and method for producing compound having binaphthyl skeleton |
| EP20763864.4A EP3932898A4 (en) | 2019-02-27 | 2020-02-21 | Compound having binaphthalene skeleton and method for producing compound having binaphthalene skeleton |
| PCT/JP2020/007001 WO2020175353A1 (en) | 2019-02-27 | 2020-02-21 | Compound having binaphthalene skeleton and method for producing compound having binaphthalene skeleton |
| TW109105967A TW202043185A (en) | 2019-02-27 | 2020-02-25 | Compound having binaphthalene skeleton and method for producing compound having binaphthalene skeleton |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021042154A (en) * | 2019-09-10 | 2021-03-18 | 帝人株式会社 | Method for producing compound having binaphthalene skeleton |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021042154A (en) * | 2019-09-10 | 2021-03-18 | 帝人株式会社 | Method for producing compound having binaphthalene skeleton |
| JP7303076B2 (en) | 2019-09-10 | 2023-07-04 | 帝人株式会社 | Method for producing compound having binaphthalene skeleton |
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