JP6319805B2 - Diol compound having spirobifluorene skeleton and method for producing the same - Google Patents
Diol compound having spirobifluorene skeleton and method for producing the same Download PDFInfo
- Publication number
- JP6319805B2 JP6319805B2 JP2014207534A JP2014207534A JP6319805B2 JP 6319805 B2 JP6319805 B2 JP 6319805B2 JP 2014207534 A JP2014207534 A JP 2014207534A JP 2014207534 A JP2014207534 A JP 2014207534A JP 6319805 B2 JP6319805 B2 JP 6319805B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- spirobifluorene
- represented
- diol compound
- formula
- 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.)
- Expired - Fee Related
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- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical group C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 title claims description 60
- -1 Diol compound Chemical class 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 22
- RBJWZJDOQMJTHO-UHFFFAOYSA-N 1,1'-spirobi[fluorene]-2',3'-diol Chemical compound C12=CC3=CC=CC=C3C2=CC(O)=C(O)C11C2=CC3=CC=CC=C3C2=CC=C1 RBJWZJDOQMJTHO-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 11
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 125000005702 oxyalkylene group Chemical group 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 150000007514 bases Chemical class 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- WLWNRAWQDZRXMB-YLFCFFPRSA-N (2r,3r,4r,5s)-n,3,4,5-tetrahydroxy-1-(4-phenoxyphenyl)sulfonylpiperidine-2-carboxamide Chemical compound ONC(=O)[C@H]1[C@@H](O)[C@H](O)[C@@H](O)CN1S(=O)(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 WLWNRAWQDZRXMB-YLFCFFPRSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000002220 fluorenes Chemical class 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000004580 weight loss Effects 0.000 description 4
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WTBBWTOQIOWOBU-UHFFFAOYSA-N C1C=CC2=C3C=CCC=C3C4(C2=C1)C5=CC=CC=C5C6=CC=CC=C46 Chemical compound C1C=CC2=C3C=CCC=C3C4(C2=C1)C5=CC=CC=C5C6=CC=CC=C46 WTBBWTOQIOWOBU-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000007788 liquid 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
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- OYUVVZBOWIVOHN-UHFFFAOYSA-N 1,1'-spirobi[fluorene]-2'-ol Chemical class C12=CC3=CC=CC=C3C1=CC=CC12C2=CC3=CC=CC=C3C2=CC=C1O OYUVVZBOWIVOHN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 125000004815 1,2-dimethylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([*:2])C([H])([H])[H] 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- SWLXTKJKZRWYCY-UHFFFAOYSA-N 2',3'-dibromo-1,1'-spirobi[fluorene] Chemical class C12=CC3=CC=CC=C3C2=CC(Br)=C(Br)C11C2=CC3=CC=CC=C3C2=CC=C1 SWLXTKJKZRWYCY-UHFFFAOYSA-N 0.000 description 1
- YFTHTJAPODJVSL-UHFFFAOYSA-N 2-(1-benzothiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(SC=C2)C2=C1 YFTHTJAPODJVSL-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical class C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- YTRJCFIZFPKBFV-UHFFFAOYSA-N Oc(cc1)cc(C23c4ccccc4-c4c2cccc4)c1-c(cc1)c3cc1O Chemical compound Oc(cc1)cc(C23c4ccccc4-c4c2cccc4)c1-c(cc1)c3cc1O YTRJCFIZFPKBFV-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 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
- 239000006227 byproduct Substances 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N c(cc12)ccc1-c1ccccc1C21c(cccc2)c2-c2c1cccc2 Chemical compound c(cc12)ccc1-c1ccccc1C21c(cccc2)c2-c2c1cccc2 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 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
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZDQWVKDDJDIVAL-UHFFFAOYSA-N catecholborane Chemical compound C1=CC=C2O[B]OC2=C1 ZDQWVKDDJDIVAL-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 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
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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Images
Description
本発明は、フルオレン構造を有する新規なジオール化合物およびその製造方法に関する。 The present invention relates to a novel diol compound having a fluorene structure and a method for producing the same.
フルオレン構造を有する樹脂材料は高い耐熱性を有し、比較的高い屈折率、かつ複屈折が比較的小さいことが知られていることから、各種ポリマーの原料モノマーとして使用されている。フルオレンの９位に２つのフェニル基を導入した、いわゆる「カルド（蝶つがい）構造」を骨格に有するフルオレン系重合体からなる樹脂は耐熱性が高く、高い屈折率、低い複屈折を示す特徴を有しているために、光学材料の原料として研究開発が行われている。 A resin material having a fluorene structure has high heat resistance, is known to have a relatively high refractive index and relatively low birefringence, and is therefore used as a raw material monomer for various polymers. A resin composed of a fluorene polymer having a so-called “cardo structure” with two phenyl groups introduced at the 9-position of fluorene has a high heat resistance, high refractive index and low birefringence. Therefore, research and development have been conducted as a raw material for optical materials.
例えば、特開平０６−０２５３９８号公報（特許文献１）には、９，９−ビス（４−ヒドロキシフェニル）フルオレン類をジオール成分の一部とするポリカーボネート樹脂が開示されている。特開平０６−０４９１８６号公報（特許文献２）には、９，９−ビス（４−ヒドロキシアルコキシフェニル）フルオレンをジオール成分の一部とする光学材料用ポリエステル重合体が開示されている。また、国際公開２０１１／０１０７４１号パンフレット（特許文献３）には、９，９−ビス［４−（２−ヒドロキシエトキシ）フェニル］フルオレンをジオール成分とする光学レンズ用ポリエステルカーボネート共重合体が開示されている。 For example, Japanese Patent Laid-Open No. 06-025398 (Patent Document 1) discloses a polycarbonate resin having 9,9-bis (4-hydroxyphenyl) fluorenes as a part of a diol component. Japanese Patent Application Laid-Open No. 06-049186 (Patent Document 2) discloses a polyester polymer for an optical material having 9,9-bis (4-hydroxyalkoxyphenyl) fluorene as a part of a diol component. In addition, International Publication 2011/010741 (Patent Document 3) discloses a polyester carbonate copolymer for optical lenses having 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component. ing.
また、上述した９，９’―ジフェニルフルオレン構造よりも、分子内の共役芳香環数が多く、かつ、分子構造の対称性が高いことから、より高屈折率化・低複屈折化できることが期待される構造を有する分子としてスピロビフルオレン類が知られている。このようなスピロ炭素を有する複素環状構造を有する化合物及び該化合物を単位骨格として有する樹脂として、特開２００６−８９５８５号公報（特許文献４）に記載される化合物や特開２０１０−２０９０５４号公報（特許文献５）に記載される化合物が知られている。 In addition, the number of conjugated aromatic rings in the molecule is higher than that of the 9,9'-diphenylfluorene structure described above, and the symmetry of the molecular structure is high, so that higher refractive index and lower birefringence can be expected. Spirobifluorenes are known as molecules having such a structure. As a compound having a heterocyclic structure having such a spiro carbon and a resin having the compound as a unit skeleton, compounds described in JP-A-2006-89585 (Patent Document 4) and JP-A-2010-209054 ( The compounds described in Patent Document 5) are known.
しかしながら、上記特許文献４に記載されるスピロビフルオレン類は、スピロビフルオレン類の融点が高く、例えば２，２’−ジヒドロキシ−９，９’−スピロフルオレンの場合、融点が２８０℃以上であり、そのため、該スピロビフルオレンを単位骨格として有する樹脂はガラス転移温度（Ｔｇ）が３３４〜３４０℃と高くなり、成形加工時にかかるコストや着色が発生しやすいことなど、加熱成形で加工する上での問題点がある。 However, the spirobifluorenes described in Patent Document 4 have a high melting point of spirobifluorenes. For example, in the case of 2,2′-dihydroxy-9,9′-spirofluorene, the melting point is 280 ° C. or higher. Therefore, the resin having the spirobifluorene as a unit skeleton has a glass transition temperature (Tg) as high as 334 to 340 ° C., and the cost and coloration during the molding process are likely to occur. There are problems.
一方、上記特許文献５に記載されるスピロビフルオレン類はその融点が１８０℃と低く、その結果、該スピロビフルオレンを単位骨格として有する樹脂はガラス転移温度が低くなるものの、該スピロビフルオレン類を融点より高い温度とすると、原因は不明であるがその重量が大幅に減少することが判明した。そのため、該スピロビフルオレンを使用し工業的にポリマー化する際、特にモノマーを溶融させ、かつ減圧下に重合する溶融重合法を用いて該スピロビフルオレン類を樹脂化する場合、重合中に原料である該スピロビフルオレンが反応系外へと消失し、当量以上の該スピロビフルオレンが必要であるといった問題が生じることが判明した。また、２，２’位にオキシアルキレン基を有するスピロビフルオレン類は官能基がほぼ直角方向に位置するため一般的にポリマー化する際、立体障害が大きく高分子化が困難になり、得られたポリマーは加工性、耐熱性、耐衝撃性等が劣る。 On the other hand, the spirobifluorenes described in Patent Document 5 have a melting point as low as 180 ° C., and as a result, the resin having the spirobifluorene as a unit skeleton has a low glass transition temperature, but the spirobifluorenes When the temperature is higher than the melting point, it has been found that the weight is greatly reduced although the cause is unknown. Therefore, when the spirobifluorene is polymerized industrially, particularly when the spirobifluorene is resinized by using a melt polymerization method in which the monomer is melted and polymerized under reduced pressure, the raw material is used during the polymerization. This spirobifluorene disappears to the outside of the reaction system, and it has been found that there is a problem that an equivalent amount or more of the spirobifluorene is necessary. In addition, since spirobifluorenes having an oxyalkylene group at the 2,2′-position have functional groups located in a substantially perpendicular direction, they generally have a large steric hindrance when polymerized, making it difficult to obtain a polymer. Polymers are inferior in processability, heat resistance, impact resistance and the like.
本発明は上記課題に鑑み、より高屈折率化・低複屈折化できることが期待される構造であるスピロビフルオレン骨格を有し、かつ、その融点が低く、また、融点以上の温度としてもその重量が大幅に減少することがない、新規なスピロビフルオレン骨格を有するジオール化合物およびその製造方法を提供することにある。 In view of the above problems, the present invention has a spirobifluorene skeleton, which is a structure that is expected to have a higher refractive index and lower birefringence, and has a low melting point and a temperature equal to or higher than the melting point. An object of the present invention is to provide a novel diol compound having a spirobifluorene skeleton and a method for producing the same, which do not significantly reduce the weight.
本発明は以下のものを含む。 The present invention includes the following.
〔１〕
下記式（１）
[1]
Following formula (1)
（式中、Ｒ１、Ｒ２は水素、アルキル基、シクロアルキル基又はアリール基を示し、同一であっても異なっても良い。Ｒ３は分岐を有しても良い炭素数２〜６のアルキレン基を示し、ｎは１〜５の整数を示す。）
で表されるスピロビフルオレン骨格を有するジオール化合物。
(In the formula, R 1 and R 2 represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different. R 3 may have a branch and has 2 to 6 carbon atoms. Represents an alkylene group, and n represents an integer of 1 to 5.)
A diol compound having a spirobifluorene skeleton represented by:
〔２〕
前記式（１）で表わされる化合物のＲ１、Ｒ２が水素である〔１〕記載のスピロビフルオレン骨格を有するジオール化合物。
[2]
The diol compound having a spirobifluorene skeleton according to [1], wherein R 1 and R 2 of the compound represented by the formula (1) are hydrogen.
〔３〕
前記式（１）で表わされる化合物のオキシアルキレン基（（ＯＲ３）ｎＯＨ）（式中、Ｒ３及びｎは上述の通りである。）の結合位置が同一フルオレン骨格上の２位及び７位である〔１〕または〔２〕記載のスピロビフルオレン骨格を有するジオール化合物。
[3]
The bonding position of the oxyalkylene group ((OR 3 ) n OH) (wherein R 3 and n are as described above) of the compound represented by the formula (1) are the 2nd and 7th positions on the same fluorene skeleton. A diol compound having a spirobifluorene skeleton according to [1] or [2].
〔４〕
下記式（２）
[4]
Following formula (2)
（式中、Ｒ１〜Ｒ２は上述の通りである。）
で表されるジヒドロキシスピロビフルオレン類のヒドロキシル基をオキシアルキレン基（（ＯＲ３）ｎＯＨ）（式中、Ｒ３及びｎは上述の通りである。）に変換する工程を含む、〔１〕〜〔３〕記載のスピロビフルオレン骨格を有するジオール化合物の製造方法。
(In the formula, R 1 to R 2 are as described above.)
A step of converting a hydroxyl group of dihydroxyspirobifluorene represented by the formula (1) into an oxyalkylene group ((OR 3 ) n OH) (wherein R 3 and n are as described above), [1] A process for producing a diol compound having a spirobifluorene skeleton according to [3].
〔５〕
下記式（３）
[5]
Following formula (3)
で表されるスピロビフルオレン骨格を有するジボロン酸エステル化合物のジボロン酸エステル部位を水酸基に変換し、上記式（２）で表されるジヒドロキシスピロビフルオレン類を製造する工程を含む〔４〕記載のスピロビフルオレン骨格を有するジオール化合物の製造方法。
The process according to [4], which comprises the step of converting the diboronic acid ester moiety of the diboronic acid ester compound having a spirobifluorene skeleton represented by formula (2) to a hydroxyl group to produce dihydroxyspirobifluorenes represented by the above formula (2). A method for producing a diol compound having a spirobifluorene skeleton.
本発明によれば、高耐熱性、高屈折率などの特徴を有し、かつ融点以上の温度としてもその重量が大幅に減少することがない新規なスピロビフルオレン骨格を有するジオール化合物およびその製造方法が提供可能となる。また、本発明のスピロビフルオレン骨格を有するジオール化合物は融点以上の温度としてもその重量が大幅に減少することがないので、特に溶融重合法を用いて樹脂化をするための原料として好適に用いることが可能である。 According to the present invention, a diol compound having a novel spirobifluorene skeleton having characteristics such as high heat resistance and a high refractive index, and the weight of which is not significantly reduced even at a temperature higher than the melting point, and the production thereof A method can be provided. Further, since the weight of the diol compound having a spirobifluorene skeleton of the present invention is not significantly reduced even at a temperature equal to or higher than the melting point, it is particularly suitable as a raw material for resinification using a melt polymerization method. It is possible.
また、本発明の新規なスピロビフルオレン骨格を有するジオール化合物は、その構造に起因するためか、該ジオール化合物を重合成分に含む樹脂が高耐熱性、高屈折率、低複屈折、低誘電性といった特性を有する為、光学レンズ、光学フィルム、光ファイバー、光学ディスク等の光学部材を構成する光学樹脂や、低誘電材料などの電子・光学材料、光半導体封止などの封止材料、自動車用内装部品類として使用されることも期待される。更には、同一フルオレン上にオキシアルキレン基を有していることから主鎖の分子運動が阻害されず、また側鎖のフルオレン構造の立体障害効果により加工性、耐熱性、耐衝撃性等の特性に優れたポリマーを得られることが期待される。 Also, because the diol compound having a novel spirobifluorene skeleton of the present invention is due to its structure, the resin containing the diol compound as a polymerization component has high heat resistance, high refractive index, low birefringence, and low dielectric property. Therefore, optical resins that make up optical members such as optical lenses, optical films, optical fibers, and optical disks, electronic and optical materials such as low dielectric materials, sealing materials such as optical semiconductor encapsulation, and automotive interiors It is also expected to be used as parts. In addition, since it has an oxyalkylene group on the same fluorene, the molecular motion of the main chain is not hindered, and the steric hindrance effect of the side chain fluorene structure has characteristics such as processability, heat resistance, and impact resistance. It is expected that an excellent polymer can be obtained.
＜本発明のスピロビフルオレン骨格を有するジオール化合物について＞
本発明のスピロビフルオレン骨格を有するジオール化合物は以下式（１）に示す構造を有する。
<Diol compound having a spirobifluorene skeleton of the present invention>
The diol compound having a spirobifluorene skeleton of the present invention has a structure represented by the following formula (1).
（式中、Ｒ１、Ｒ２は水素、アルキル基、シクロアルキル基又はアリール基を示し、同一であっても異なっても良い。Ｒ３は炭素数２〜６のアルキレン基を示し、ｎは１〜５の整数を示す。）
(Wherein R 1 and R 2 represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different. R 3 represents an alkylene group having 2 to 6 carbon atoms, and n represents Represents an integer of 1 to 5.)
上記式（１）における２つのオキシアルキレン基（（ＯＲ３）ｎＯＨ）は、上記式（１）示す通り２つのフルオレン骨格の内、同一のフルオレン骨格上に結合している（同一平面上に存在している）必要がある。好ましくは同一フルオレン骨格上の２位及び７位に結合する。なお、引用文献５に記載されるスピロビフルオレン骨格を有するジオール化合物のように、２つのフルオレン骨格の内、別々のフルオレン骨格上に存在する場合、理由は定かではないが、該ジオール化合物を融点以上の温度とした場合にその重量が大幅に減少する。 The two oxyalkylene groups ((OR 3 ) n OH) in the above formula (1) are bonded to the same fluorene skeleton among the two fluorene skeletons as shown in the above formula (1) (on the same plane). Must exist). Preferably, it is bonded to the 2nd and 7th positions on the same fluorene skeleton. In addition, when it exists on a separate fluorene skeleton among two fluorene skeletons, like the diol compound having a spirobifluorene skeleton described in Cited Document 5, the reason is not clear, but the diol compound has a melting point. In the case of the above temperature, the weight is greatly reduced.
上記式（１）における２つのオキシアルキレン基（（ＯＲ３）ｎＯＨ）中のＲ３及びｎの内、Ｒ３は炭素数２〜６の分岐を有してもよいアルキレン基であり、好ましくは炭素数が２〜４であり、特に好ましくは２である。具体的に例えばエチレン基、プロピレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等が例示される。 Of R 3 and n in the two oxyalkylene groups ((OR 3 ) n OH) in the above formula (1), R 3 is an alkylene group which may have a branch having 2 to 6 carbon atoms. Has 2 to 4 carbon atoms, particularly preferably 2. Specific examples include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
オキシアルキレン基中の（ＯＲ３）ユニット数を表すｎは１〜５の整数であり、好ましくは１〜３であり、より好ましくは１又は２であって、特に好ましくは１である。ｎが２以上のとき、（ＯＲ３）ユニットは同一の（ＯＲ３）ユニットで構成されていてもよく、２種以上の異なる（ＯＲ３）ユニットで構成されていてもよい。また、一般式（１）で表わされるフルオレン系ジオール化合物が有する２つのオキシアルキレン基（（ＯＲ３）ｎＯＨ）は、互いに異なる繰り返し数ｎを有し得る。 N representing the number of (OR 3 ) units in the oxyalkylene group is an integer of 1 to 5, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. When n is 2 or more, the (OR 3 ) unit may be composed of the same (OR 3 ) unit, or may be composed of two or more different (OR 3 ) units. Moreover, the two oxyalkylene groups ((OR 3 ) n OH) possessed by the fluorene-based diol compound represented by the general formula (1) may have different repeating numbers n.
上記式（１）における置換基であるＲ１、Ｒ２は水素、アルキル基、シクロアルキル基又はアリール基を示し、同一であっても異なっても良い。Ｒ１、Ｒ２におけるアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基等の炭素数１〜２０の直鎖状又は分岐状アルキル基を挙げることができる。アルキル基は、好ましくは炭素数１〜８の直鎖状又は分岐状アルキル基であり、より好ましくは炭素数１〜６の直鎖状又は分岐状アルキル基であり、さらに好ましくは炭素数１〜３の直鎖状又は分岐状アルキル基である。 R 1 and R 2 which are substituents in the above formula (1) represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different. Examples of the alkyl group in R 1 and R 2 include carbon numbers such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, and hexyl group. Mention may be made of 1-20 linear or branched alkyl groups. The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, still more preferably 1 to 1 carbon atom. 3 linear or branched alkyl groups.
シクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、アルキル（例えば、炭素数１〜４のアルキル）置換シクロペンチル基、アルキル（例えば、炭素数１〜４のアルキル）置換シクロヘキシル基等の炭素数４〜１６（好ましくは炭素数５〜８）のシクロアルキル基又はアルキル置換シクロアルキル基を挙げることができる。シクロアルキル基は、好ましくはシクロペンチル基又はシクロヘキシル基である。 Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, an alkyl (for example, alkyl having 1 to 4 carbon atoms) substituted cyclopentyl group, an alkyl (for example, an alkyl having 1 to 4 carbon atoms) substituted cyclohexyl group, and the like. Examples thereof include a cycloalkyl group having ˜16 (preferably having 5 to 8 carbon atoms) or an alkyl-substituted cycloalkyl group. The cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group.
アリール基としては、例えば、フェニル基、アルキル（例えば、炭素数１〜４のアルキル）置換フェニル基、ナフチル基を挙げることができる。アリール基は、好ましくはフェニル基又はアルキル置換フェニル基（例えば、メチルフェニル基、ジメチルフェニル基、エチルフェニル基等）であり、より好ましくはフェニル基である。 As an aryl group, a phenyl group, an alkyl (for example, C1-C4 alkyl) substituted phenyl group, and a naphthyl group can be mentioned, for example. The aryl group is preferably a phenyl group or an alkyl-substituted phenyl group (for example, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, etc.), and more preferably a phenyl group.
上記アルキル基、シクロアルキル基、アリール基は、アルキル基以外の置換基（例えば、アルコキシル基、アシル基、ハロゲン原子等）を有していてもよい。 The alkyl group, cycloalkyl group, and aryl group may have a substituent other than the alkyl group (for example, an alkoxyl group, an acyl group, a halogen atom, etc.).
これら列挙した上記式（１）における置換基であるＲ１、Ｒ２の内、水素、炭素数１〜４のアルキル基、他に置換基を有さないフェニル基、炭素数１〜４のアルキル基に置換されたアルキル基置換フェニル基が好ましく、特に水素が好ましい。 Among R 1 and R 2 which are substituents in the above-mentioned formula (1), hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group having no other substituent, an alkyl having 1 to 4 carbon atoms An alkyl group-substituted phenyl group substituted with a group is preferred, and hydrogen is particularly preferred.
＜本発明のスピロビフルオレン骨格を有するジオール化合物の製造方法について＞
続いて、本発明のスピロビフルオレン骨格を有するジオール化合物の製造法について一例を用いて詳述する。
<About the manufacturing method of the diol compound which has the spirobifluorene skeleton of this invention>
Subsequently, the method for producing a diol compound having a spirobifluorene skeleton of the present invention will be described in detail using an example.
本発明のスピロビフルオレン骨格を有するジオール化合物は例えば以下式（２） The diol compound having a spirobifluorene skeleton of the present invention is represented by, for example, the following formula (2)
で表されるジヒドロキシスピロビフルオレン類と以下式（４）
Dihydroxyspirobifluorenes represented by the following formula (4)
で表されるカーボネート類またはエチレンオキサイド、プロピレンオキサイド等のエポキシ類を反応させることにより製造することができるが、毒性、安全性、取扱いの容易さの点から上記式（４）で表されるカーボネート類と反応させることが好ましい。
Or carbonates represented by the above formula (4) from the standpoint of toxicity, safety, and ease of handling. It is preferable to make it react with a kind.
上記式（１）におけるオキシアルキレン基（（ＯＲ３）ｎＯＨ）のｎ数は、上記式（２）で表されるジヒドロキシスピロビフルオレン類と上記式（４）で表されるカーボネート類またはエポキシ類を一旦反応させた後、必要に応じ複数回更にカーボネート類またはエポキシ類を反応させることにより適宜調整することができる。 The number of n of the oxyalkylene group ((OR 3 ) n OH) in the above formula (1) is the dihydroxyspirobifluorene represented by the above formula (2) and the carbonate or epoxy represented by the above formula (4). After once reacting, the compound can be appropriately adjusted by further reacting with carbonates or epoxies a plurality of times as necessary.
上記式（２）で表されるジヒドロキシスピロビフルオレン類はどのような方法で製造されたものでも良いが、以下式（３） The dihydroxyspirobifluorenes represented by the above formula (2) may be produced by any method, but the following formula (3)
（式中、Ｒ１、Ｒ２は上述の通りである。Ｒ４、Ｒ５は互いに同一、若しくは異なってアルキル基を表すか、又はＲ４、Ｒ５とが末端で結合して、アルキル基で置換されてもよいアルキレン基、若しくはｏ−フェニレン基を形成する。）
で表されるスピロビフルオレン骨格を有するジボロン酸エステル化合物のボロン酸エステル部位を水酸基に変換することにより、上記式（２）で表されるジヒドロキシスピロビフルオレン類を製造することにより、ハロゲン原子を含む有機溶媒や、自然発火性の反応剤を使用するまでもなく上記式（２）で表されるジヒドロキシスピロビフルオレン類が合成可能となる為、環境的観点や防災的観点から好ましい。以下、上記式（３）で表されるスピロビフルオレン骨格を有するジボロン酸エステル化合物のボロン酸エステル部位を水酸基に変換する方法について詳述する。
(In the formula, R 1 and R 2 are as described above. R 4 and R 5 are the same as or different from each other, and represent an alkyl group, or R 4 and R 5 are bonded to each other at the end to form an alkyl group. An alkylene group which may be substituted with or o-phenylene group.
By converting the boronic acid ester moiety of the diboronic acid ester compound having a spirobifluorene skeleton represented by formula (2) to a hydroxyl group, the dihydroxyspirobifluorenes represented by the above formula (2) are produced, thereby producing halogen atoms. Since the dihydroxyspirobifluorene represented by the above formula (2) can be synthesized without using an organic solvent or a pyrophoric reactant, it is preferable from an environmental viewpoint and a disaster prevention viewpoint. Hereinafter, a method for converting the boronic acid ester moiety of the diboronic acid ester compound having a spirobifluorene skeleton represented by the above formula (3) into a hydroxyl group will be described in detail.
上記式（３）で表されるスピロビフルオレン骨格を有するジボロン酸エステル化合物のＲ４、Ｒ５で表されるアルキル基としては、直鎖状、分枝鎖状及び環状のいずれであってもよく、炭素数１〜６の直鎖状又は炭素数３〜６の分枝鎖状のアルキル基及び炭素数４〜６の環状のアルキル基が挙げられる。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基等を、環状のアルキル基としては、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。前記アルキル基のうち、好ましいものはメチル基、エチル基、プロピル基であり、より好ましいものはメチル基である。 The alkyl group represented by R 4 and R 5 of the diboronic acid ester compound having a spirobifluorene skeleton represented by the above formula (3) may be linear, branched or cyclic. Well, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms and a cyclic alkyl group having 4 to 6 carbon atoms may be mentioned. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, etc., and a cyclic alkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group. Groups and the like. Of the alkyl groups, preferred are a methyl group, an ethyl group, and a propyl group, and more preferred is a methyl group.
Ｒ４とＲ５が末端で結合してアルキル基で置換されていてもよいアルキレン基としては、炭素数２〜１０のアルキル基で置換されていても良いアルキレン基が挙げられ、具体的には例えば、エチレン基、トリメチレン基、テトラメチレン基、１，２−ジメチルエチレン基、２，２―ジメチルトリメチレン基、１，１，２，２−テトラメチルエチレン基等が挙げられる。 Examples of the alkylene group which may be substituted with an alkyl group by bonding R 4 and R 5 at the terminal include an alkylene group which may be substituted with an alkyl group having 2 to 10 carbon atoms, specifically For example, ethylene group, trimethylene group, tetramethylene group, 1,2-dimethylethylene group, 2,2-dimethyltrimethylene group, 1,1,2,2-tetramethylethylene group and the like can be mentioned.
Ｒ４とＲ５が末端で結合して形成されるｏ−フェニレン基としては、フェニル基、ナフタレン基等が挙げられる。 Examples of the o-phenylene group formed by bonding R 4 and R 5 at the terminal include a phenyl group and a naphthalene group.
以上詳述したＲ４とＲ５が末端で結合して形成される、アルキル基で置換されていてもよいアルキル基若しくはｏ−フェニレン基の具体例としては
以下式（５）
Specific examples of the alkyl group or o-phenylene group which may be substituted with an alkyl group formed by bonding R 4 and R 5 described in detail above at the terminal are represented by the following formula (5):
で表されるピナコラートボラン、
以下式（６）
Pinacolatoborane, represented by
Equation (6) below
以下式（７）
Equation (7) below
これら列挙した上記式（３）における置換基であるＲ４、Ｒ５としては、メチル基、エチル基、上記式（７）で表される２，２―ジメチルトリメチレン基、上記式（５）で表される１，１，２，２−テトラメチルエチレン基が好ましく、１，１，２，２−テトラメチルエチレン基が特に好ましい。 Examples of the substituents R 4 and R 5 in the above-described formula (3) include a methyl group, an ethyl group, a 2,2-dimethyltrimethylene group represented by the formula (7), and the formula (5). 1,1,2,2-tetramethylethylene group represented by the formula is preferred, and 1,1,2,2-tetramethylethylene group is particularly preferred.
上記式（３）で表されるスピロビフルオレン骨格を有するジボロン酸エステル化合物は、例えば特開２００８−２４７８９５号公報の実施例４に記載される通り、ジブロモスピロビフルオレン類とビス（ピナコラート）ジボロン等、所望の構造を有する有機ボロン酸とを反応させることにより製造可能である。 The diboronic acid ester compound having a spirobifluorene skeleton represented by the above formula (3) includes dibromospirobifluorenes and bis (pinacolato) diboron as described in Example 4 of Japanese Patent Application Laid-Open No. 2008-247895, for example. It can be produced by reacting with an organic boronic acid having a desired structure.
上記式（３）で表されるスピロビフルオレン骨格を有するジボロン酸エステル化合物のボロン酸エステル部位を水酸基に変換する反応は、ボロン酸エステル部位を酸化剤により酸化することによって行うことができる。使用可能な酸化剤としては過酸化水素、メタクロロ安息香酸、オキソン、ｔ−ブチルヒドロペルオキシド等の一般的な酸化剤が使用可能であり、これらの中でも過酸化水素、メタクロロ安息香酸が好ましい。酸化剤の使用量としては上記式（３）で表されるスピロビフルオレン骨格を有するジボロン酸エステル化合物１モルに対し通常２〜４倍モル、好ましくは２〜３倍モルである。 The reaction for converting the boronic acid ester moiety of the diboronic acid ester compound having a spirobifluorene skeleton represented by the above formula (3) into a hydroxyl group can be performed by oxidizing the boronic acid ester moiety with an oxidizing agent. Usable oxidizing agents include general oxidizing agents such as hydrogen peroxide, metachlorobenzoic acid, oxone, and t-butyl hydroperoxide. Among these, hydrogen peroxide and metachlorobenzoic acid are preferable. The amount of the oxidizing agent used is usually 2 to 4 times mol, preferably 2 to 3 times mol for 1 mol of the diboronic acid ester compound having a spirobifluorene skeleton represented by the above formula (3).
ボロン酸エステル部位を酸化する反応は、通常、溶媒存在下に行う。使用可能な溶媒として例えば、メタノール、エタノール、プロパノール等のアルコール類、トルエン、キシレン等の芳香族炭化水素類、シクロペンチルメチルエーテル等のエーテル類や水が例示され、これらは単独であっても必要に応じ混合して使用しても良い。これら溶媒の中でもアルコールと水との混合物が好ましく、メタノール及び／又はエタノールと水との混合物がより好ましい。溶媒の使用量としては、上記式（３）で表されるスピロビフルオレン骨格を有するジボロン酸エステル化合物１重量倍に対し通常１〜１０重量倍、好ましくは２〜５重量倍である。 The reaction for oxidizing the boronic ester site is usually carried out in the presence of a solvent. Examples of usable solvents include alcohols such as methanol, ethanol and propanol, aromatic hydrocarbons such as toluene and xylene, ethers such as cyclopentyl methyl ether, and water, which may be used alone. You may mix and use according to it. Among these solvents, a mixture of alcohol and water is preferable, and a mixture of methanol and / or ethanol and water is more preferable. As the usage-amount of a solvent, it is 1-10 weight times normally with respect to 1 weight times of diboronic acid ester compounds which have the spirobifluorene skeleton represented by the said Formula (3), Preferably it is 2-5 weight times.
ボロン酸エステル部位を酸化する反応は反応器にスピロビフルオレン骨格を有するジボロン酸エステル化合物、酸化剤及び必要に応じ溶媒を添加した後、通常、５０〜０℃、更に好ましくは３０〜１０℃で撹拌することにより実施される。 The reaction for oxidizing the boronic acid ester moiety is usually performed at 50 to 0 ° C., more preferably 30 to 10 ° C., after adding a diboronic acid ester compound having a spirobifluorene skeleton, an oxidizing agent and a solvent as necessary to the reactor. It is carried out by stirring.
反応終了後、得られた上記式（２）で表されるジヒドロキシスピロビフルオレン類と上記式（４）で表されるカーボネート類とをそのまま反応させても良いし、必要に応じ有機溶媒を用いて上記式（２）で表されるジヒドロキシスピロビフルオレン類を抽出し、反応で使用した酸化剤を定法により除去した後、得られた上記式（２）で表されるジヒドロキシスピロビフルオレン類を晶析等の方法により単離を行っても良い。 After completion of the reaction, the obtained dihydroxyspirobifluorenes represented by the above formula (2) and the carbonates represented by the above formula (4) may be reacted as they are, and if necessary, an organic solvent may be used. Then, the dihydroxyspirobifluorenes represented by the above formula (2) are extracted and the oxidizing agent used in the reaction is removed by a conventional method, and then the obtained dihydroxyspirobifluorenes represented by the above formula (2) are obtained. Isolation may be performed by a method such as crystallization.
続いて、上記式（２）で表されるジヒドロキシスピロビフルオレン類と上記式（４）で表されるカーボネート類との反応について詳述する。 Subsequently, the reaction between the dihydroxyspirobifluorenes represented by the above formula (2) and the carbonates represented by the above formula (4) will be described in detail.
本発明において使用する上記式（４）で表されるカーボネート類は、通常上記式（２）で表されるジヒドロキシスピロビフルオレン類１モルに対して１．９〜２．４倍モル、好ましくは２．０〜２．３倍モル使用する。カーボネート類の使用量が１．９倍モルより少ないと、反応が進行しないか反応が著しく遅延したり、反応が進行した場合においても原料のジヒドロキシスピロビフルオレン類や１モル付加体などの未反応物が多く残存し、収率や純度が低下する場合がある。エチレンカーボネートの使用量が２．４倍モルより多いと３モル付加体、４モル以上付加体や重合体などの副反応物の増加により、収率や純度が低下する場合がある。 The carbonates represented by the above formula (4) used in the present invention are usually 1.9 to 2.4 moles, preferably 1 to 2.4 moles per mole of the dihydroxyspirobifluorenes represented by the above formula (2). Use from 2.0 to 2.3 moles. If the amount of carbonate used is less than 1.9 moles, the reaction does not proceed or the reaction is significantly delayed, or even when the reaction proceeds, the raw materials such as dihydroxyspirobifluorenes and 1 mole adducts are not reacted. Many products remain, and the yield and purity may decrease. When the amount of ethylene carbonate used is more than 2.4 times mol, the yield and purity may be lowered due to the increase of side reaction products such as 3 mol adduct, 4 mol or more adduct and polymer.
上記式（２）で表されるジヒドロキシスピロビフルオレン類と上記式（４）で表されるカーボネート類とを反応させる際、通常塩基性化合物の存在下に反応を行う。使用可能な塩基性化合物としては例えば、炭酸カリウム、炭酸ナトリウム、炭酸リチウム、炭酸セシウム等の炭酸塩類、炭酸水素カリウム、炭酸水素ナトリウム、炭酸水素リチウム、炭酸水素セシウム等の炭酸水素塩類、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等の水酸化塩類、トリエチルアミン、トリフェニルホスフィン等の有機塩基類が例示され、好ましくは炭酸カリウム、炭酸ナトリウム、トリフェニルホスフィンである。これら塩基性化合物は１種類、あるいは必要に応じ２種類以上を混合して使用しても良い。また、塩基性化合物の使用量は通常、上記式（２）で表されるジヒドロキシスピロビフルオレン類１モルに対して０．０１〜０．２モル、好ましくは０．０５〜０．２モルである。塩基性化合物の使用量が０．０１モルより少ないと反応が進行しないか、反応が遅延する場合がある。塩基性化合物の使用量が０．２モルより多いと、多量体などの副反応物の増加による収率や純度の低下、着色等の品質低下を引き起こす場合がある。 When the dihydroxyspirobifluorene represented by the above formula (2) is reacted with the carbonate represented by the above formula (4), the reaction is usually carried out in the presence of a basic compound. Usable basic compounds include, for example, carbonates such as potassium carbonate, sodium carbonate, lithium carbonate and cesium carbonate, bicarbonates such as potassium bicarbonate, sodium bicarbonate, lithium bicarbonate and cesium bicarbonate, sodium hydroxide Examples thereof include hydroxide salts such as potassium hydroxide and lithium hydroxide, and organic bases such as triethylamine and triphenylphosphine, and potassium carbonate, sodium carbonate and triphenylphosphine are preferable. These basic compounds may be used alone or as a mixture of two or more if necessary. Moreover, the usage-amount of a basic compound is 0.01-0.2 mol normally with respect to 1 mol of dihydroxy spirobifluorenes represented by the said Formula (2), Preferably it is 0.05-0.2 mol. is there. If the amount of the basic compound used is less than 0.01 mol, the reaction may not proceed or the reaction may be delayed. When the amount of the basic compound used is more than 0.2 mol, the yield and purity may decrease due to an increase in by-products such as multimers, and quality such as coloring may be deteriorated.
上記式（２）で表されるジヒドロキシスピロビフルオレン類と上記式（４）で表されるカーボネート類の反応は溶媒存在下であっても溶媒非存在下であっても良いが、好ましくは溶媒非存在下で行う。使用可能な溶媒としては、エチレンカーボネートと反応しない溶媒であればよく、例えば、アセトン、メチルエチルケトン、ブチルメチルケトンなどのケトン類、トルエン、キシレン、メシチレンなどの芳香族炭化水素類、クロロベンゼン、ジクロロベンゼンなどのハロゲン化芳香族炭化水素、ペンタン、ヘキサン、ヘプタンなどの脂肪族炭化水素、ジクロロメタン、１，２−ジクロロエタンなどのハロゲン化脂肪族炭化水素溶媒、ジエチルエーテル、ジ−イソ−プロピルエーテル、メチル−ターシャリー−ブチルエーテル、シクロペンチルメチルエーテル、ジフェニルエーテルなどのエーテル類、酢酸エチル、酢酸ブチルなどのエステル類、アセトニトリルなどの脂肪族ニトリル類、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド類、ジメチルスルホキシドなどのスルホキシド類などが挙げられる。好ましくは芳香族炭化水素類、ケトン類又はエーテル類である。これら有機溶媒は１種類、あるいは必要に応じ２種類以上混合して使用しても良い。溶媒を使用する場合の使用量は、通常、上記式（２）で表されるジヒドロキシスピロビフルオレン類１重量倍に対し、通常０．１〜５重量倍、好ましくは０．５〜３重量倍である。 The reaction between the dihydroxyspirobifluorenes represented by the above formula (2) and the carbonates represented by the above formula (4) may be in the presence of a solvent or in the absence of a solvent. Perform in the absence. As a usable solvent, any solvent that does not react with ethylene carbonate may be used. For example, ketones such as acetone, methyl ethyl ketone, and butyl methyl ketone, aromatic hydrocarbons such as toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and the like. Halogenated aromatic hydrocarbons, aliphatic hydrocarbons such as pentane, hexane, heptane, halogenated aliphatic hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, diethyl ether, di-iso-propyl ether, methyl-tarsha Ethers such as Li-butyl ether, cyclopentyl methyl ether and diphenyl ether; esters such as ethyl acetate and butyl acetate; aliphatic nitriles such as acetonitrile; dimethylformamide and dimethylacetamide Earth, etc. sulfoxides such as dimethyl sulfoxide. Aromatic hydrocarbons, ketones or ethers are preferred. These organic solvents may be used alone or as a mixture of two or more if necessary. The amount used in the case of using a solvent is usually 0.1 to 5 times by weight, preferably 0.5 to 3 times by weight, based on 1 times by weight of dihydroxyspirobifluorenes represented by the above formula (2). It is.
上記式（２）で表されるジヒドロキシスピロビフルオレン類と上記式（４）で表されるカーボネート類の反応は通常、反応容器に上記式（２）で表されるジヒドロキシスピロビフルオレン類、上記式（４）で表されるカーボネート類及び必要に応じ塩基性化合物と溶媒を反応容器に添加後、通常１５０℃以下、好ましくは１４０〜４０℃、更に好ましくは１２０〜９０℃で実施する。 The reaction of the dihydroxyspirobifluorenes represented by the above formula (2) and the carbonates represented by the above formula (4) is usually conducted in a reaction vessel with the dihydroxyspirobifluorenes represented by the above formula (2), After adding the carbonate represented by the formula (4) and, if necessary, a basic compound and a solvent to the reaction vessel, the reaction is usually performed at 150 ° C. or lower, preferably 140 to 40 ° C., more preferably 120 to 90 ° C.
上述した反応終了後、反応生成物中には目的とするスピロビフルオレン骨格を有するジオール化合物の他、反応で用いた触媒及びその残渣、未反応ジヒドロキシスピロビフルオレン類、ジヒドロキシスピロビフルオレン類のモノヒドロキシアルキルエーテル［以下「１モル付加体」と表記する場合がある］、ジヒドロキシスピロビフルオレン類にアルキレンカーボネートが３モル以上反応した化合物［以下「３モル以上付加体」と表記する場合がある］が生成している為、必要に応じ反応生成物に溶媒と水を添加し撹拌混合後水層を除去する水洗操作や、活性炭等による吸着処理、晶析やカラムクロマトグラフィー等の精製操作を経て反応生成物から目的とするスピロビフルオレン骨格を有するジオール化合物を取り出すことができる。得られたスピロビフルオレン骨格を有するジオール化合物はそのまま使用しても良いが、必要に応じ再度溶媒を加えて再晶析操作を行う事も出来る。また、吸着、水蒸気蒸留などの通常の精製操作を繰り返し実施することもできる。 After completion of the above-mentioned reaction, the reaction product contains a target diol compound having a spirobifluorene skeleton, the catalyst used in the reaction and its residue, unreacted dihydroxyspirobifluorenes, and monohydroxyspirobifluorenes. Hydroxyalkyl ether [hereinafter sometimes referred to as “1 mol adduct”], compound obtained by reacting 3 mol or more of alkylene carbonate with dihydroxyspirobifluorene [hereinafter sometimes referred to as “3 mol or more adduct”] Therefore, if necessary, after adding water and solvent to the reaction product and mixing with stirring, the water layer is removed, followed by adsorption treatment with activated carbon, purification operations such as crystallization and column chromatography. A diol compound having a target spirobifluorene skeleton can be extracted from the reaction product. The obtained diol compound having a spirobifluorene skeleton may be used as it is, but if necessary, a re-crystallization operation may be performed by adding a solvent again. Ordinary purification operations such as adsorption and steam distillation can be repeated.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
＜分析条件＞
〔１〕ＨＰＬＣ純度
次の測定条件でＨＰＬＣ測定を行ったときの面積百分率値をＨＰＬＣ純度とした。
装置：（株）島津製作所製「ＬＣ−２０１０ＡＨＴ」、
カラム：ＹＭＣ−Ｐａｃｋ ＯＤＳ−Ａ（５μｍ、４．６φ×１５０ｍｍ）
移動相：Ａ液：超純水 Ｂ液：アセトニトリル
流量：１．０ｍｌ／ｍｉｎ
カラム温度：４０℃
検出波長：２５４ｎｍ
移動相グラジエント（体積％濃度）：Ｂ液濃度：５０％（０分）→（３０分）→８０％（２０分保持）
<Analysis conditions>
[1] HPLC purity The area percentage value when HPLC measurement was performed under the following measurement conditions was defined as HPLC purity.
Apparatus: “LC-2010AHT” manufactured by Shimadzu Corporation
Column: YMC-Pack ODS-A (5 μm, 4.6 φ × 150 mm)
Mobile phase: Liquid A: Ultrapure water Liquid B: Acetonitrile Flow rate: 1.0 ml / min
Column temperature: 40 ° C
Detection wavelength: 254 nm
Mobile phase gradient (volume% concentration): Liquid B concentration: 50% (0 minutes) → (30 minutes) → 80% (20 minutes hold)
〔２〕融点
示差走査熱量計（エスアイアイナノテクノロジー（株）製「ＥＸＳＴＡＲ ＤＳＣ ７０２０」）を用いて、昇温速度１０℃／分で測定した際の吸熱最大ピーク温度を融点とした。
[2] Melting point The maximum endothermic peak temperature when measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (“EXSTAR DSC 7020” manufactured by SII Nano Technology Co., Ltd.) was defined as the melting point.
〔３〕ＮＭＲ測定
１Ｈ−ＮＭＲは、内標準としてテトラメチルシランを用い、溶媒として重クロロホルムを用いて、ＪＥＯＬ−ＥＳＣ４００分光計によって記録した。
[3] NMR measurement
1 H-NMR was recorded with a JEOL-ESC400 spectrometer using tetramethylsilane as internal standard and deuterated chloroform as solvent.
〔４〕屈折率及びアッベ数
実施例及び比較例で記載した屈折率及びアッベ数は以下の方法で算出した。
＜装置及び測定条件＞
アッベ屈折計（（株）アタゴ製「多波長アッベ屈折計 ＤＲ−２Ｍ」）を用い、下記方法にて調製したサンプルについて、２０℃における屈折率（波長：５８９ｎｍ）及び２０℃におけるアッベ数（波長：４８６、５８９、６５６ｎｍ）を測定した。
＜サンプル調製条件及び屈折率、アッベ数の算出方法＞
得られたスピロビフルオレン骨格を有するジオール化合物をＮ−メチルピロリドンに溶解し、１０重量％、２０重量％及び３０重量％溶液を調製した。調製した各溶液について上述の条件にて屈折率及びアッベ数を測定した。
次に、得られた３点の測定値から近似曲線を導き、これを１００重量％に外挿したときの値をスピロビフルオレン系ジオール化合物の屈折率及びアッベ数とした。
[4] Refractive index and Abbe number The refractive index and Abbe number described in Examples and Comparative Examples were calculated by the following methods.
<Apparatus and measurement conditions>
For samples prepared by the following method using an Abbe refractometer ("Multi-wavelength Abbe refractometer DR-2M" manufactured by Atago Co., Ltd.), the refractive index at 20 ° C (wavelength: 589 nm) and the Abbe number at 20 ° C (wavelength) : 486, 589, 656 nm).
<Sample preparation conditions, refractive index, and Abbe number calculation method>
The obtained diol compound having a spirobifluorene skeleton was dissolved in N-methylpyrrolidone to prepare 10 wt%, 20 wt% and 30 wt% solutions. The refractive index and Abbe number of each prepared solution were measured under the above conditions.
Next, an approximate curve was derived from the obtained three measured values, and values obtained by extrapolating the approximate curve to 100% by weight were used as the refractive index and Abbe number of the spirobifluorene diol compound.
〔５〕赤外吸収分析（ＩＲ）測定
ＩＲ測定は、ＩＲＰｒｅｓｔｉｇｅ−２１（島津製作所）を用い、ＫＢｒ錠剤法にて測定した。装置の設定条件は下記の通り。
分解能 ：２ｃｍ−１
スキャン回数：５０回
波数 ：４０００〜４００ｃｍ−１
また、サンプル調製方法は以下の通り。
本発明のスピロビフルオレン骨格を有する新規ジオール化合物１ｍｇと、ＫＢｒ０．１５ｇを試料に添加し、混合物が十分に混合されるまで持続的に摩砕した。次に混合物を金型に移し、油圧プレスを用いてディスクに成形した。
[5] Infrared absorption analysis (IR) measurement The IR measurement was carried out using the IPrestige-21 (Shimadzu Corporation) by the KBr tablet method. The setting conditions of the device are as follows.
Resolution: 2cm -1
Number of scans: 50 times Wave number: 4000 to 400 cm −1
The sample preparation method is as follows.
1 mg of a novel diol compound having a spirobifluorene skeleton of the present invention and 0.15 g of KBr were added to the sample, and continuously milled until the mixture was well mixed. The mixture was then transferred to a mold and formed into a disk using a hydraulic press.
〔６〕５％重量減少温度測定
示差熱天秤（リガク（株）製Ｔｈｅｒｍｏ ｐｌｕｓ ＥＶＯ２／ＴＧ−ＤＴＡシリーズ）を用いて、昇温速度１０℃／分で測定した際の重量が５％減少した際の温度を５％重量減少温度（℃）とした。
[6] 5% weight reduction temperature measurement When a differential thermal balance (Thermo plus EVO2 / TG-DTA series manufactured by Rigaku Corporation) was used, when the weight when measured at a heating rate of 10 ° C./min was reduced by 5% The temperature of was 5% weight loss temperature (° C.).
＜製造例１＞ ２，７−ジ（４，５，５，５−テトラメチル−１，３，２−ジオキサボロラン）−９，９’−スピロビフルオレンの製造
攪拌器、冷却器、および温度計を備えたガラス製反応器に、２，７−ブロモ−９，９’−スピロビフルオレン１８０．０ｇ（０．３７９ｍｏｌ）、１，１’−ビス（ジフェニルホスフィノ）フェロセン）ジクロロパラジウム（ＰｄＣｌ２ｄｐｐｆ）８．５０ｇ（０．０１２１ｍｏｌ）、ビス（ピナコーラート）ジボロン２４２．５ｇ（０．９５ｍｏｌ）、酢酸カリウム２３０．１０ｇ（２．３４ｍｏｌ）およびジメチルグリコール９００ｇを仕込み、窒素気流下、還流がかかるまで昇温し、還流下にて５時間撹拌した。
撹拌終了後、反応生成物を濃縮しジメチルグリコールを除去した後、反応器にトルエン３６５０ｇ、活性炭４５ｇ、イオン交換水１８０ｇを加え、８０℃まで昇温したのち、同温度で１時間撹拌した。撹拌後、熱濾過により活性炭を取り除き、得られた溶液を７５℃で静置し水層を除去した後、更に７５℃でイオン交換水５５０ｇを添加、７５℃で撹拌後再度静置し水層を除去した。
その後、有機層に活性炭１８０ｇを加え、８０℃まで昇温したのち、同温度で１時間撹拌した。撹拌後、熱濾過で活性炭を取り除いた後、得られた有機層を濃縮し溶媒を除去した。
得られた濃縮物にアセトニトリル１６３４．１ｇを添加、室温で撹拌後、結晶をろ別、乾燥することにより目的とする２，７−ジ（４，５，５，５−テトラメチル−１，３，２−ジオキサボロラン）−９，９’−スピロビフルオレンの白色結晶２１９．４ｇ（収率８９．４％、ＨＰＬＣ純度８８％）を得た。
<Production Example 1> Production of 2,7-di (4,5,5,5-tetramethyl-1,3,2-dioxaborolane) -9,9'-spirobifluorene Stirrer, cooler, and thermometer In a glass reactor equipped with 180.0 g (0.379 mol) of 2,7-bromo-9,9′-spirobifluorene, 1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (PdCl 2 ). dppf) 8.50 g (0.0121 mol), bis (pinacolato) diboron 242.5 g (0.95 mol), potassium acetate 230.10 g (2.34 mol) and dimethyl glycol 900 g were charged until reflux was applied under a nitrogen stream. The temperature was raised, and the mixture was stirred for 5 hours under reflux.
After completion of the stirring, the reaction product was concentrated to remove dimethyl glycol, and then 3650 g of toluene, 45 g of activated carbon and 180 g of ion-exchanged water were added to the reactor, and the temperature was raised to 80 ° C., followed by stirring at the same temperature for 1 hour. After stirring, the activated carbon was removed by hot filtration, and the resulting solution was allowed to stand at 75 ° C. to remove the aqueous layer. Further, 550 g of ion-exchanged water was added at 75 ° C., stirred at 75 ° C., and then allowed to stand again to leave the aqueous layer. Was removed.
Thereafter, 180 g of activated carbon was added to the organic layer, the temperature was raised to 80 ° C., and the mixture was stirred at the same temperature for 1 hour. After stirring, the activated carbon was removed by hot filtration, and then the obtained organic layer was concentrated to remove the solvent.
After adding 1634.1 g of acetonitrile to the obtained concentrate and stirring at room temperature, the crystals were filtered off and dried to obtain the desired 2,7-di (4,5,5,5-tetramethyl-1,3. , 2-dioxaborolane) -9,9′-spirobifluorene, 219.4 g (yield 89.4%, HPLC purity 88%).
＜実施例１＞ ２，７−ジヒドロ−９，９’−スピロビフルオレンの製造
攪拌器、および温度計を備えたガラス製反応器に、製造例１で得られた２，７−ジ（４，５，５，５−テトラメチル−１，３，２−ジオキサボロラン）−９，９’−スピロビフルオレン３０ｇ（０．０８８ｍｏｌ）、エタノール６０ｇ、イオン交換水３０ｇを仕込み、メタクロロ過安息香酸２６．６ｇ（０．１５６ｍｏｌ）を加え２５℃で３時間撹拌した。
撹拌終了後、反応生成物にトルエン１００ｇを加え室温で撹拌、静置し水層を除去した。さらに５％重層水１００ｇを添加し、室温で撹拌後再度静置し水層を除去した。その後、５％亜硫酸ナトリウム水溶液１００ｇを加え、室温で撹拌後再度静置し水層を除去し過酸化物を除去した。
更にトルエン３００ｇ加え、８０℃まで昇温し結晶を溶解後、室温まで冷却し結晶を析出させ、析出した結晶をろ別、乾燥することにより、２，７−ジヒドロ−９，９’−スピロビフルオレン１２．０ｇを得た（収率７３％ ＨＰＬＣ純度７９．２％）。
<Example 1> Production of 2,7-dihydro-9,9'-spirobifluorene 2,7-di (4) obtained in Production Example 1 was added to a glass reactor equipped with a stirrer and a thermometer. , 5,5,5-tetramethyl-1,3,2-dioxaborolane) -9,9'-spirobifluorene (30 g, 0.088 mol), ethanol 60 g, and ion-exchanged water 30 g were added. 6 g (0.156 mol) was added and stirred at 25 ° C. for 3 hours.
After completion of stirring, 100 g of toluene was added to the reaction product, and the mixture was stirred and allowed to stand at room temperature to remove the aqueous layer. Further, 100 g of 5% multistory water was added, stirred at room temperature, and allowed to stand again to remove the aqueous layer. Thereafter, 100 g of a 5% aqueous sodium sulfite solution was added, and the mixture was stirred at room temperature and allowed to stand again to remove the aqueous layer and remove the peroxide.
Further, 300 g of toluene was added, and the temperature was raised to 80 ° C. to dissolve the crystals. Then, the crystals were cooled to room temperature to precipitate crystals, and the precipitated crystals were separated by filtration and dried to give 2,7-dihydro-9,9′-spirobi. 12.0 g of fluorene was obtained (yield 73% HPLC purity 79.2%).
＜実施例２＞ ２，７−（２−ヒドロキシエトキシ）−９，９’−スピロビフルオレンの製造
攪拌器、冷却器、および温度計を備えたガラス製反応器に、実施例１で得られた２，７−ジヒドロ−９，９’−スピロビフルオレン１２．０ｇ（０．０３４ｍｏｌ）、エチレンカーボネート６．９４ｇ（０．０７８ｍｏｌ）、炭酸カリウム０．３５ｇ（０．００３ｍｏｌ）およびシクロペンチルメチルエーテル３０ｇを仕込み、１１０℃まで昇温した後、同温度で１６時間反応した。反応終了後、２，７−ジヒドロ−９，９’−スピロビフルオレンの残存量をＨＰＬＣで確認した所、残存量は０．１％（ＨＰＬＣ面積百分率値）以下であった。
得られた反応生成物にシクロペンチルメチルエーテル３０ｇ、１２％水酸化ナトリウム水溶液５０ｇを添加し８０℃で１時間撹拌後、水層を除去し、更に水層が中性となるまでイオン交換水の添加・撹拌・静置・水層の除去操作を繰り返した。
その後、有機層を濃縮し、濃縮物をシリカゲルカラムクロマトグラフィーにて単離・精製することにより、目的とする２，７−（２−ヒドロキシエトキシ）−９，９’−スピロビフルオレン（以下式１ａで表される化合物）を４．０２ｇ得た（収率２８．７％、ＨＰＬＣ純度９８％）。
<Example 2> Production of 2,7- (2-hydroxyethoxy) -9,9'-spirobifluorene A glass reactor equipped with a stirrer, a cooler, and a thermometer was obtained in Example 1. 2,7-dihydro-9,9'-spirobifluorene 12.0 g (0.034 mol), ethylene carbonate 6.94 g (0.078 mol), potassium carbonate 0.35 g (0.003 mol) and cyclopentyl methyl ether 30 g The mixture was heated to 110 ° C. and reacted at the same temperature for 16 hours. After completion of the reaction, the residual amount of 2,7-dihydro-9,9′-spirobifluorene was confirmed by HPLC, and the residual amount was 0.1% (HPLC area percentage value) or less.
To the obtained reaction product, 30 g of cyclopentyl methyl ether and 50 g of 12% aqueous sodium hydroxide solution were added and stirred at 80 ° C. for 1 hour. The aqueous layer was removed, and ion-exchanged water was added until the aqueous layer became neutral. -Stirring, standing, and removal of the aqueous layer were repeated.
Thereafter, the organic layer is concentrated, and the concentrate is isolated and purified by silica gel column chromatography to obtain the desired 2,7- (2-hydroxyethoxy) -9,9′-spirobifluorene (hereinafter represented by the following formula). 4.02 g of a compound represented by 1a) was obtained (yield 28.7%, HPLC purity 98%).
得られた２，７−（２−ヒドロキシエトキシ）−９，９’−スピロビフルオレン（１ａ）の
１Ｈ−ＮＭＲチャートを図１に、ＤＳＣチャートを図２に、ＩＲチャートを図３に示す。
また図１に示す１Ｈ−ＮＭＲチャートのピーク形状及び積分値は以下の通り。（単位：ｐｐｍ）
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：１．９８（ｓ、２Ｈ）、３．７７（ｑ、４Ｈ）、３．８６（ｑ、４Ｈ）、６．２３（ｄ、２Ｈ）、６．７４（ｄ、２Ｈ）、６．８７（ｄｄ、２Ｈ）、７．０９（ｔｄ、２Ｈ）、７．３４（ｔｄ、２Ｈ）、７．６３（ｄ、２Ｈ）、７．８１（ｄ、２Ｈ）
Of the obtained 2,7- (2-hydroxyethoxy) -9,9′-spirobifluorene (1a)
FIG. 1 shows a 1 H-NMR chart, FIG. 2 shows a DSC chart, and FIG. 3 shows an IR chart.
Moreover, the peak shape and integral value of the 1H-NMR chart shown in FIG. 1 are as follows. (Unit: ppm)
1 H-NMR (CDCl 3 ): 1.98 (s, 2H), 3.77 (q, 4H), 3.86 (q, 4H), 6.23 (d, 2H), 6.74 (d 2H), 6.87 (dd, 2H), 7.09 (td, 2H), 7.34 (td, 2H), 7.63 (d, 2H), 7.81 (d, 2H)
下記に得られた２，７−（２−ヒドロキシエトキシ）−９，９’−スピロビフルオレンの融点、屈折率、アッベ数、５％重量減少温度（℃）を表１に示す。 Table 1 shows the melting point, refractive index, Abbe number, and 5% weight loss temperature (° C) of 2,7- (2-hydroxyethoxy) -9,9'-spirobifluorene obtained below.
なお、表１には参考データとして９，９−ビス［４−（２−ヒドロキシエトキシ）フェニル］フルオレン（以下式（８）、田岡化学工業（株）製）及びスピロビフルオレン骨格を有するジオール化合物（以下式（９）、特開２０１０−２０９０５４号公報記載の方法で製造）を記載した。
In Table 1, as reference data, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (hereinafter represented by formula (8), manufactured by Taoka Chemical Co., Ltd.) and a diol compound having a spirobifluorene skeleton (Hereinafter, formula (9), manufactured by the method described in JP 2010-209054 A) was described.
上記表１で示した通り、本発明のスピロビフルオレン骨格を有するジオール化合物１ａは融点が化合物５及び６と同程度であるので、該ジオール化合物１ａを単位骨格として有する樹脂を前述した溶融重合法により製造が可能となり、また、得られる樹脂はガラス転移温度（Ｔｇ）が低くなることが期待される。更には、屈折率が公知のスピロビフルオレン構造を有さないフルオレン類（８）よりも高く、アッベ数が低い為、（９）で表されるスピロビフルオレン構造を有する化合物と同様、特に光学材料としての使用が期待される。 As shown in Table 1 above, since the diol compound 1a having a spirobifluorene skeleton of the present invention has a melting point similar to that of the compounds 5 and 6, the above-described melt polymerization method using a resin having the diol compound 1a as a unit skeleton. Can be produced, and the obtained resin is expected to have a low glass transition temperature (Tg). Furthermore, since the refractive index is higher than that of the fluorenes (8) having no known spirobifluorene structure and the Abbe number is low, in particular, as with the compound having the spirobifluorene structure represented by (9), optical Use as a material is expected.
更には、５％重量減少温度が（９）で表されるスピロビフルオレン構造を有する化合物の場合、融点と殆ど差がない為、前述の通り溶融重合法により該スピロビフルオレン類を樹脂化する場合、重合中に原料である該スピロビフルオレンが反応系外へと消失し、重合条件のコントロールが困難となり、必要以上の該スピロビフルオレンが必要であるといった問題が生じる一方で、本発明のスピロビフルオレン骨格を有するジオール化合物１ａの５％重量減少温度は３１７℃と融点より圧倒的に高く、公知のスピロビフルオレン構造を有さないフルオレン類（８）と同程度であるので、安定的に溶融重合法により樹脂化することが可能となる。 Further, in the case of a compound having a spirobifluorene structure whose 5% weight loss temperature is represented by (9), since there is almost no difference from the melting point, the spirobifluorenes are resinized by the melt polymerization method as described above. In this case, the spirobifluorene as a raw material disappears outside the reaction system during the polymerization, making it difficult to control the polymerization conditions, and the problem that the spirobifluorene is necessary more than necessary arises. The 5% weight loss temperature of the diol compound 1a having a spirobifluorene skeleton is 317 ° C., which is much higher than the melting point, and is similar to the fluorenes (8) having no known spirobifluorene structure. In addition, it can be made into a resin by a melt polymerization method.
Claims (3)
で表されるスピロビフルオレン骨格を有するジオール化合物。 Following formula (1)
A diol compound having a spirobifluorene skeleton represented by:
で表されるスピロビフルオレン骨格を有するジボロン酸エステル化合物のジボロン酸エステル部位を水酸基に変換し、上記式（２）で表されるジヒドロキシスピロビフルオレン類を製造する工程を含む請求項２記載のスピロビフルオレン骨格を有するジオール化合物の製造方法。 Following formula (3)
Of in diboronic acid ester compound having a spirobifluorene skeleton represented diboron ester site is converted to a hydroxyl group, according to claim 2 further comprising the step of producing the dihydroxy spirobifluorene compound represented by the formula (2) A method for producing a diol compound having a spirobifluorene skeleton.
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| CN115141473A (en) * | 2022-07-20 | 2022-10-04 | 亚洲泰格集团有限公司 | Low-dielectric-constant liquid crystal polymer film and preparation method thereof |
| CN115093686A (en) * | 2022-07-20 | 2022-09-23 | 亚洲泰格集团有限公司 | Liquid crystal polymer film and preparation method thereof |
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| TW200940491A (en) * | 2007-12-19 | 2009-10-01 | Glaxo Group Ltd | Compounds which potentiate the AMPA receptor and uses thereof in medicine |
| JP5451120B2 (en) * | 2009-03-12 | 2014-03-26 | キヤノン株式会社 | Dihydric alcohols, polycarbonate resins, polyester resins, molded articles comprising them, and optical elements |
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