JP2004091330A - Fluorene compound, method for producing the same and polymer or oligomer - Google Patents
Fluorene compound, method for producing the same and polymer or oligomer Download PDFInfo
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- JP2004091330A JP2004091330A JP2002250948A JP2002250948A JP2004091330A JP 2004091330 A JP2004091330 A JP 2004091330A JP 2002250948 A JP2002250948 A JP 2002250948A JP 2002250948 A JP2002250948 A JP 2002250948A JP 2004091330 A JP2004091330 A JP 2004091330A
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- polymer
- fluorene
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- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- -1 Fluorene compound Chemical class 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 150000002170 ethers Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 28
- 150000002430 hydrocarbons Chemical group 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- CWGRCRZFJOXQFV-UHFFFAOYSA-N 2,7-dibromofluoren-9-one Chemical compound C1=C(Br)C=C2C(=O)C3=CC(Br)=CC=C3C2=C1 CWGRCRZFJOXQFV-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052710 silicon Chemical group 0.000 claims description 3
- 239000010703 silicon Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 16
- 239000010409 thin film Substances 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- 238000006243 chemical reaction Methods 0.000 description 36
- 239000002904 solvent Substances 0.000 description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 14
- BJQRITQEMQPLOU-UHFFFAOYSA-N 2,7-dibromo-9,9-bis(4-methoxy-3-methylphenyl)fluorene Chemical compound C1=C(C)C(OC)=CC=C1C1(C=2C=C(C)C(OC)=CC=2)C2=CC(Br)=CC=C2C2=CC=C(Br)C=C21 BJQRITQEMQPLOU-UHFFFAOYSA-N 0.000 description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 6
- GPCZZKACIMWGBN-UHFFFAOYSA-N 4-[2,7-dibromo-9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC(Br)=CC=C3C3=CC=C(Br)C=C32)C=2C=C(C)C(O)=CC=2)=C1 GPCZZKACIMWGBN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 238000007429 general method Methods 0.000 description 5
- 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 5
- 238000011403 purification operation Methods 0.000 description 5
- 238000001226 reprecipitation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000007800 oxidant agent 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
- 238000000746 purification Methods 0.000 description 4
- 238000006862 quantum yield reaction Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000002211 ultraviolet spectrum Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEHICSHWCHFEMH-UHFFFAOYSA-N CC1COBO1 Chemical compound CC1COBO1 HEHICSHWCHFEMH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical group C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- AFVDZBIIBXWASR-AATRIKPKSA-N (E)-1,3,5-hexatriene Chemical compound C=C\C=C\C=C AFVDZBIIBXWASR-AATRIKPKSA-N 0.000 description 1
- IOAFFMBGDUUARX-UHFFFAOYSA-N 1,2-dibromo-3-(2-phenylphenyl)benzene Chemical group BrC1=CC=CC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1Br IOAFFMBGDUUARX-UHFFFAOYSA-N 0.000 description 1
- IEMXKVCEQAQLOJ-UHFFFAOYSA-N 1,2-dibromo-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(Br)C(Br)=C3NC2=C1 IEMXKVCEQAQLOJ-UHFFFAOYSA-N 0.000 description 1
- MAOWXLISNQNMLK-UHFFFAOYSA-N 1,2-dibromoanthracene Chemical compound C1=CC=CC2=CC3=C(Br)C(Br)=CC=C3C=C21 MAOWXLISNQNMLK-UHFFFAOYSA-N 0.000 description 1
- QGZAUMUFTXCDBD-UHFFFAOYSA-N 1,2-dibromonaphthalene Chemical compound C1=CC=CC2=C(Br)C(Br)=CC=C21 QGZAUMUFTXCDBD-UHFFFAOYSA-N 0.000 description 1
- DTKXKIALXUNASG-UHFFFAOYSA-N 1,2-diiodo-3-(2-phenylphenyl)benzene Chemical group IC=1C(=C(C=CC=1)C=1C(=CC=CC=1)C1=CC=CC=C1)I DTKXKIALXUNASG-UHFFFAOYSA-N 0.000 description 1
- RRYOXYFOAVIETQ-UHFFFAOYSA-N 1,2-diiodo-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(I)C(I)=C3NC2=C1 RRYOXYFOAVIETQ-UHFFFAOYSA-N 0.000 description 1
- UYHYZAYIQAVJCN-UHFFFAOYSA-N 1,2-diiodonaphthalene Chemical compound C1=CC=CC2=C(I)C(I)=CC=C21 UYHYZAYIQAVJCN-UHFFFAOYSA-N 0.000 description 1
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、各種化学品中間体や、有機発光性材料などの機能性ポリマー原料として有用な、２，７−ジブロモ−９，９−ジ（３−置換−４−ヒドロキシフェニル）フルオレンまたはそのエーテル誘導体、その製造方法およびポリマーまたはオリゴマーに関する。
【０００２】
【従来の技術】
従来、薄型でありかつ低消費電力で表示可能なＥＬ素子がディスプレイとして注目されている。ＥＬ素子は薄膜発光層を、少なくとも一方が透明である一対の電極間に挟持された素子であり、電荷の注入によって発光する。ＥＬ素子の発光材料としては無機物と有機物とがあり、有機物としては低分子化合物と高分子化合物とが知られており、特に薄膜形成が容易である高分子発光材料が広く検討されている。
【０００３】
【発明が解決しようとする課題】
上記有機高分子材料は、一般に芳香環が連続した剛直なポリマーであり、かつ重合度が低いポリマーの混合物である。従って一般的に汎用の有機溶剤に対する溶解性が低く、該ポリマーの有機溶剤溶液から電極基板上に薄膜を形成する場合に、混合している低重合度のポリマーが析出したり、結晶化したりして、均質かつｎｍレベルの薄膜形成が困難である。
【０００４】
従って本発明の目的は、分子量分布が狭く、汎用の有機溶剤に溶解性が高く、ポリマーの析出や結晶化が生ぜずに、均質な薄膜が形成可能であるポリマーの原料、その製造方法、およびポリマーまたはオリゴマーを提供することである。
【０００５】
【課題を解決するための手段】
上記目的は以下の本発明によって達成される。すなわち、本発明は、下記一般式（１）で表されることを特徴とする２，７−ジブロモ−９，９−ジ（３−置換−４−ヒドロキシフェニル）フルオレンまたはそのエーテル誘導体、その製造方法、およびこれらの化合物からなる下記一般式（５）で表されるポリマーまたはオリゴマーを提供する。
（上記式中のＲ１は、それぞれ独立に、水素原子、または硫黄、窒素、リン、酸素もしくはケイ素などのヘテロ原子を１以上含んでもよいＣ１ 〜 ２２の炭化水素基を表し、Ｒ２は、それぞれ独立にＣ１ 〜 ６の炭化水素基を表す。）
上記一般式（１）の化合物の中でも、２個のＲ１がともに水素原子であり、２個のＲ２がともにメチル基である前記化合物、および２個のＲ１および２個のＲ２が全てメチル基である前記化合物が特に有用である。
【０００７】
【０００８】
なお、本発明において２個のＲ１で表される「炭化水素基」とは、水素および炭素を含む有機基を意味し、例えば、脂肪族基、芳香族基、環式脂肪族基、および複素環式化合物を意味し、これらの基は、硫黄、窒素、リン、酸素もしくはケイ素などのヘテロ原子を含んでもよい。また、本発明において２個のＲ２で表される「炭化水素基」としては直鎖状、もしくは分岐鎖状のアルキル基が代表的である。好ましいＲ１は炭素数１〜８のアルキル基である。
【０００９】
【発明の実施の形態】
次に好ましい実施の形態を挙げて本発明をさらに詳細に説明する。
本発明の前記一般式（１）で表される化合物の製造方法を、Ｒ１が水素原子であり、Ｒ２がメチル基である場合を代表例としてさらに詳しく説明する。この製造方法には２種の方法があり、第１の方法は、酸性条件下で、２，７−ジブロモ−９−フルオレノンと２当量のｏ−クレゾールを縮合反応させる方法である。さらに詳しくは、２，７−ジブロモ−９−フルオレノン（１モル）とｏ−クレゾール（２モル）を酸（１ミリモル〜１０モル）および触媒（１ミリモル〜５モル）の存在下で反応する。反応により得られる粗生成物は必要に応じて抽出、蒸留および再結晶などで精製を行う。反応溶媒としてはｏ−クレゾール自身を溶媒とすることも可能である（使用量：２モル〜１００モル）し、ベンゼン、トルエン、キシレン、その他の一般的な化合物を溶媒に用いることも可能である。
【００１０】
上記で使用する酸としては、硫酸、塩酸、メタンスルホン酸、ポリリン酸、その他の酸を使用することが可能であり、触媒としてはβ−メルカプトプロピオン酸などの化合物が使用できる。反応温度は、原料仕込み量、溶媒量、溶媒の種類などにより異なるが、反応混合物が固化して反応が進まなくなる温度以上である必要があり、溶媒、原料などが揮散により大量に消失する温度以下である必要がある。一般的には２０℃〜１４０℃、好ましくは４０℃〜１００℃の範囲である。反応時間は約１〜４８時間である。
【００１１】
第２の方法は、９，９−ジ（３−メチル−４−ヒドロキシフェニル）フルオレンの２，７位置のジブロム化による方法である。さらに詳しくは、９，９−ジ（３−メチル−４−ヒドロキシフェニル）フルオレン（１モル）の有機溶液もしくは水などへの分散液に、臭素（Ｂｒ２）（１モル〜１００モル）または臭素（Ｂｒ２）−触媒類を加えて反応させる。反応により得られる粗生成物は必要に応じて抽出、蒸留、再結晶などで精製を行う。反応溶媒としてはハロゲン化炭化水素、ベンゼン、トルエン、キシレン、その他の一般的な化合物を溶媒に用いることが可能である。臭素化反応に際しては、反応を促進するために、触媒や添加剤などを用いることも好ましい。
【００１２】
触媒や添加剤の例としては、硫酸、塩酸、臭化水素酸などの鉱酸類、塩化鉄、塩化亜鉛などのルイス酸類、ヨウ素（Ｉ２）などの臭素（Ｂｒ２）以外のハロゲン類、鉄、ニッケルなどの重金属類、過酸化水素水、過ヨウ素酸などの酸化剤類などが挙げられる。臭素化反応においては、臭化水素酸が副生するが、臭素（Ｂｒ２）の使用量を低減するために、この副生臭化水素酸を、系内で過酸化水素水などの酸化剤を用いて、酸化により臭素（Ｂｒ２）へと戻しながら反応を行うことも好ましい方法である。反応温度は、原料仕込み量、溶媒量、溶媒の種類などにより異なるが、反応混合物が固化して反応が進まなくなる温度以上である必要があり、溶媒、原料などが揮散により大量に消失する温度以下である必要がある。一般的には−２０℃〜１００℃、好ましくは０℃〜８０℃の範囲である。反応時間は約１〜２４時間である。
【００１３】
前記一般式（１）において、２個のＲ１および２個のＲ２がともに炭化水素基である場合の製造方法を、２個のＲ１がともにメチル基であり、２個のＲ２がともにメチル基である場合を代表例として説明する。この方法には次の２種の方法が挙げられる。第１の方法は、アルカリ条件下での、２，７−ジブロモ−９，９−ジ（３−メチル−４−ヒドロキシフェニル）フルオレンとハロゲン化メチルの反応によるメチルエーテル合成による方法である。さらに詳しくは、２，７−ジブロモ−９，９−ジ（３−メチル−４−ヒドロキシフェニル）フルオレン（１モル）とアルカリ化剤（２モル〜１００モル）の反応溶液にハロゲン化メチル（２モル〜１００モル）を添加しメチルエーテル化合物を合成する方法である。
【００１４】
上記反応により得られる粗生成物は必要に応じて抽出、蒸留、再結晶などで精製を行う。反応溶媒としてはアセトン、トルエン、キシレン、その他の一般的な化合物を使用することが可能である。以上はハロゲン化剤としてハロゲン化メチルを使用する場合を代表例として説明したが、ハロゲン化化合物としては、前記以外のハロゲン化アルキル、不飽和炭化水素のハロゲン化物、芳香族ハロゲン化化合物などが挙げられる。ここでアルキル基は、炭素数１〜２２のアルキル基であり、例としては、前記メチル基以外に、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、ドコシル基、イソブチル基、２−エチルヘキシル基などを挙げることができる。また、窒素、酸素、硫黄などのヘテロ原子を一つ以上含むアルキル基や不飽和結合を含むものも使用することが可能である。反応温度は、原料仕込み量、溶媒量、溶媒の種類などにより異なるが、反応混合物が固化して反応が進まなくなる温度以上である必要があり、溶媒、原料などが揮散により大量に消失する温度以下である必要がある。一般的には０℃〜１２０℃、好ましくは５０℃〜１００℃の範囲である。反応時間は約１〜４８時間である。
【００１５】
第２の方法は、９，９−ジ（３−メチル−４−メトキシフェニル）フルオレンの２，７位のジブロモ化による合成法である。さらに詳しくは、９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン（１モル）の有機溶液もしくは水などの懸濁液に臭素（Ｂｒ２）（１モル〜１００モル）または臭素（Ｂｒ２）−触媒類を加えて反応させる。反応により得られる粗生成物は必要に応じて抽出、蒸留、再結晶などで精製を行う。反応溶媒としてはハロゲン化炭化水素、ベンゼン、トルエン、キシレンその他の一般的な化合物を溶媒に用いることが可能である。臭素化反応に際しては、反応を促進するために、触媒や添加剤などを用いることも好ましい。
【００１６】
触媒や添加剤の例としては、硫酸、塩酸、臭化水素酸などの鉱酸類、塩化鉄、塩化亜鉛などのルイス酸類、ヨウ素（Ｉ２）などの臭素（Ｂｒ２）以外のハロゲン類、鉄、ニッケルなどの重金属類、過酸化水素水、過ヨウ素酸などの酸化剤類などが挙げられる。臭素化反応においては、臭化水素酸が副生するが、臭素（Ｂｒ２）の使用量を低減するために、この副生臭化水素酸を、系内で過酸化水素水などの酸化剤を用いて、酸化により臭素（Ｂｒ２）へと戻しながら反応を行うことも好ましい方法である。
【００１７】
以上の説明は、メチルエステルを代表例としたが、その他のエーテル誘導体としては、アルキルエーテル、不飽和炭化水素エーテル、芳香族炭化水素エーテルなどが挙げられる。ここでアルキル基は、炭素数１〜２２のアルキル基であり、例としては、前記メチル基以外に、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、ドコシル基、イソブチル基、２−エチルヘキシル基などを挙げることができる。また、窒素、酸素、硫黄などのヘテロ原子を一つ以上含むアルキル基や不飽和結合を含むものも使用することが可能である。反応温度は、原料仕込み量、溶媒量、溶媒の種類などにより異なるが、反応混合物が固化して反応が進まなくなる温度以上である必要があり、溶媒、原料などが揮散により大量に消失する温度以下である必要がある。一般的には−２０℃〜１００℃、好ましくは０℃〜８０℃の範囲である。反応時間は約１〜２４時間である。
【００１８】
本発明の一般式（１）の化合物を用いて前記一般式（５）で表されるポリマー（オリゴマー）を製造する方法を、２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレンを用いる方法を代表例として説明する。
第１の方法は、２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレンをグリニヤール化し、金属触媒を用いる方法である。さらに詳しくは、不活性ガス雰囲気下で、２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン（１モル）を金属マグネシウム（１モル）と反応させてグリニヤール化し、ニッケル、パラジウム、鉄、クロムなどのハロゲン化物（１ミリモル〜１モル）、０価錯体、２価錯体（無ハロゲン）などを触媒として重合する方法である。
【００１９】
溶媒は、テトラヒドロフラン、ジアルキルエーテルなどのエーテルなどが使用可能である。反応温度は、原料仕込み量、溶媒量、溶媒の種類などにより異なるが、反応混合物が固化して反応が進まなくなる温度以上である必要があり、溶媒、原料などが揮散により大量に消失する温度以下である必要がある。一般的には０℃以上である。反応時間は約１〜７２時間である。重合のクエンチ、後処理、ポリマー精製は一般的な方法で行うことが可能である。また、他のジハロゲン化モノマー（一般式（５）における「Ｘ」のジハライドまたは炭化水素）との組み合わせによりランダムコポリマー（オリゴマー）の合成も可能である。
【００２０】
第２の方法は、ニッケル０価錯体を使用する２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレンの単独重合法である。さらに詳しくは、不活性ガス雰囲気下で、２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン（１モル）とニッケル０価錯体（１〜２０モル）を溶媒中で反応させる方法である。
【００２１】
溶媒としては、トルエン、ジメチルホルムアミド、テトラヒドロフランなどが使用可能である。反応温度は、原料仕込み量、溶媒量、溶媒の種類などにより異なるが、反応混合物が固化して反応が進まなくなる温度以上である必要があり、溶媒、原料などが揮散により大量に消失する温度以下である必要がある。一般的には２０℃〜１１０℃、好ましくは４０℃〜９０℃の範囲である。反応時間は約１〜７２時間である。重合のクエンチ、後処理、ポリマーの精製は一般的な方法で行うことが可能である。また、他のジハロゲン化モノマーまたは炭化水素との組み合わせによりランダムコポリマー（オリゴマー）の合成も可能である。
【００２２】
第３の方法は、２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレンとボロン酸エステルまたはスズ化合物との金属触媒を用いる共重合または単独重合による方法である。さらに詳しくは、不活性ガス雰囲気下で、２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン（１モル）と芳香族、ヘテロ環化合物などのジボロン酸エステルまたはジスズ化合物（１モル）をパラジウム０価錯体などの金属触媒（０．１ミリモル〜１モル）と炭酸ナトリウム、炭酸カリウム、水酸化ナトリウムなどのアルカリ試薬（１モル〜１００モル）を反応試剤として溶媒中で反応させ得られる。
【００２３】
溶媒は、トルエン、テトラヒドロフラン、アセトンなどの化合物が使用可能であり、アルカリ水溶液との２相反応、１相反応、相間移動触媒を添加した系での重合が可能である。反応温度は、原料仕込み量、溶媒量、溶媒の種類などにより異なるが、反応混合物が固化して反応が進まなくなる温度以上である必要があり、溶媒、原料などが揮散により大量に消失する温度以下である必要がある。一般的には３０℃〜１３０℃、好ましくは５０℃〜１１０℃の範囲である。反応時間は約１〜７２時間である。重合のクエンチ、後処理、ポリマーの精製は一般的な方法で行うことが可能である。また、２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン自身をボロン酸エステルまたはスズ化合物に変換し、ジハロゲン化化合物または炭化水素とのカップリングを行うことも可能である。
【００２４】
第４の方法は、２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレンのニッケル２価錯体による重合法である。さらに詳しくは、不活性ガス雰囲気下で、２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン（１モル）、亜鉛（０．１〜２０モル）、ニッケル錯体（０．１ミリモル〜１モル）を溶媒中で反応させる方法である。反応溶媒としては、アセトン、ジメチルホルムアミド、テトラヒドロフラン、アセトニトリルを含む種々の溶媒が使用可能である。反応温度は、原料仕込み量、溶媒量、溶媒の種類などにより異なるが、反応混合物が固化して反応が進まなくなる温度以上である必要があり、溶媒、原料などが揮散により大量に消失する温度以下である必要がある。一般的には２０℃〜１００℃で、１〜４８時間程度反応を行う。重合のクエンチ、後処理、ポリマーの精製は一般的な方法で行うことが可能である。また、他のジハロゲン化モノマーまたは炭化水素との組み合わせによりランダムコポリマー（オリゴマー）の合成も可能である。
以上のフルオレン系化合物およびポリマーの製造は、Ｒ１が水素原子またはメチル基であり、Ｒ２がメチル基である場合について説明したが、Ｒ１およびＲ２が他の炭化水素基である場合も同様である。重合法についても以上の方法に限定されるものではなく、Ｈｅｃｋ反応、Ｓｏｎｏｇａｓｈｉｒａ反応、Ｈｏｎｅｒ−Ｗｉｔｔｉｇ−Ｅｍｍｏｎｓ反応などのような一般的な手法を使用することが可能である。
【００２５】
コモノマーの具体例としては下記の如き化合物が挙げられる。芳香族化合物としては、例えば、２，７−ジブロモ−９，９−ジアリールフルオレン、２，７−ジヨード−９，９−ジアリールフルオレン、２，７−ジブロモ−９，９−ジアルキルフルオレン、２，７−ジヨード−９，９−ジアルキルフルオレン、２，５−ジブロモチオフェン、２，５−ジヨードチオフェン、２，５−ジブロモ−３−ヘキシルチオフェン、２，５−ジヨード−３−メチルチオフェン、ジブロモビチオフェン、ジヨードビチオフェン、ジブロモターチオフェン、ジヨードターチオフェン、ジブロモビピリジン、ジヨードビピリジン、ジブロモターピリジン、ジヨードターピリジン、ジブロモピリジン、ジヨードピリジン、１，４−ジブロモベンゼン、１，４−ジヨードベンゼン、ジブロモベンゾチアジアゾール、ジヨードベンゾチアジアゾール、ジブロモカルバゾール、ジヨードカルバゾール、ジブロモナフタレン、ジヨードナフタレン、ジブロモアントラセン、ジヨードアントラセン、ジブロモキノリン、ジヨードキノリン、ジブロモビフェニル、ジヨードビフェニル、ジブロモターフェニル、ジヨードターフェニル、ジブロモフェナントロリン、ジヨードフェナントロリン、１，４−ジビニルベンゼン（Ｈｅｃｋ反応にて重合可能）が挙げられ、その他の炭化水素としては、例えば、脂肪族化合物としては、エチレン、ブタジエン、ヘキサトリエン、アセチレン誘導体（Ｓｏｎｏｇａｓｈｉｒａ反応にて重合可能）などの共役系の脂肪族化合物が挙げられる。これらのコモノマーのうちでは芳香族コモノマーが好ましい。以上の化合物は例示であり、本発明は上記例示化合物に限定されるものではない。
ポリマー中のコモノマーユニット（Ｘ）の割合は、交互共重合などの特殊な場合を除いては０〜９９．９重量％までの範囲が可能である。
【００２６】
本発明のポリマーの数平均分子量（Ｍｎ）および重量平均分子量（Ｍｗ）は、使用する原料種や反応条件によって異なるが、重量平均分子量（Ｍｗ）は約１，０００〜１，０００，０００、好ましくは２，０００〜５００，０００、より好ましくは５，０００〜５００，０００で、かつＭｗ／Ｍｎ（多分散度）は１〜１０．０、好ましくは１〜４．０、より好ましくは１〜２．０である（ＧＰＣ、ポリスチレン換算）。
【００２７】
以上の４例の方法では、２，７−ジブロモ−９，９−ジ（３−メチル−４−ヒドロキシフェニル）フルオレンもしくはそのエーテル誘導体を直接ポリマー原料として用い、新たに炭素−炭素結合を形成している。このようなポリマーはＥＬ素子の発光性材料、電荷注入材料、電荷輸送材料などとして有用である。また、例えば、２，７位置の臭素原子をカルボン酸に変換し、ポリアミドなどのポリマーのモノマーとしても使用可能である。さらにポリマー原料だけでなく、２，７位置の臭素原子を修飾や変換するなどの低分子材料合成の原料にも使用可能である。
【００２８】
【実施例】
次に実施例を挙げて本発明をさらに具体的に説明する。
実施例１ ２，７−ジブロモ−９，９−ジ（３−メチル−４−ヒドロキシフェニル）フルオレン
２００ミリリットルのフラスコに２，７−ジブロモフルオレノン４．００ｇ（１１．８ミリモル）、ｏ−クレゾール１５．７ｇ（０．１４５モル）、β−メルカプトプロピオン酸０．２０ｇ（１．９ミリモル）およびメタンスルホン酸０．６７ｇ（７．０ミリモル）を入れ、得られた混合物を６０℃で２４時間攪拌および反応した。反応後、反応混合物を水で洗浄し、得られた粗生成物をろ別回収し、トルエン１００ミリリットルに溶かし炭酸水素ナトリウム水溶液および水で洗浄した。得られた有機溶液を硫酸ナトリウムで乾燥、ろ過後、溶媒の濃縮を行い０℃にて静置し白色の固体を析出させた。これを濾過した後、冷トルエンで洗浄後、乾燥させ、３．９５ｇの白色の固体を得た。これをガスクロマトグラフで分析したところ、１１．４重量％のトルエンを含み、目的物に対して０．７５当量のトルエンを結晶溶媒として包含した結晶であった（６．５２ミリモル、５５％収率）。
【００２９】
この生成物を液体クロマトグラフで分析したところ、トルエン分を除去した純度は、９９．９％であった。母液を濃縮し、同様な操作を行い、２次結晶を回収した（１．４０ｇ、２．３１ミリモル、純度９９．８％）。この精製物の分析結果は以下の通りであり、下記構造を有することが確認された。
１Ｈ ＮＭＲ（ＤＭＳＯ−ｄ６，ｐｐｍ）／１．９９（６Ｈ，Ａｒ−ＣＨ３）；２．２８（２．３Ｈ，トルエン：Ａｒ−ＣＨ３）；６．６５−６．７８（６Ｈ，ＡｒＨ）；７．１０−７．２５（３．８Ｈ，トルエン：ＡｒＨ）７．４８（２Ｈ，ＡｒＨ）；７．５５（２Ｈ，ＡｒＨ）；７．８６（２Ｈ，ＡｒＨ）；９．２８（２Ｈ，ＯＨ）（０．７５当量のトルエンが包含されている）
１３Ｃ ＮＭＲ（ＤＭＳＯ−ｄ６，ｐｐｍ）／１６．１、２１．０、６４．０、１１４．５、１２１．０、１２２．６、１２３．７、１２５．２、１２５．９、１２８．１、１２８．５、１２８．８、１２９．５、１３０．５、１３４．４、１３７．３、１３７．５、１５４．０、１５４．４（前記トルエンのピークを含む）
元素分析／ｃａｌｃｄ．：Ｃ＝６３．９９、Ｈ＝４．３３、Ｏ＝５．２９、Ｂｒ＝２６．４０（０．７５当量のトルエンを含有しているとした値）
ｆｏｕｎｄ：Ｃ＝６４．００、Ｈ＝４．４８、Ｏ＝５．４１、Ｂｒ＝２３．７３
融点／２１４〜２１５℃
実施例２ ２，７−ジブロモ−９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン
５００ミリリットルのフラスコに２，７−ジブロモ−９，９−ジ（３−メチル−４−ヒドロキシフェニル）フルオレン２５．２ｇ（４７．０ミリモル）、炭酸カリウム３３ｇ（０．２４モル）、およびアセトン２５０ミリリットルを入れ、得られた混合物にヨウ化メチル３５ｇ（０．２５モル）を滴下し、溶媒還流温度で１４時間攪拌および反応した。反応後、反応混合物をろ過し得られた有機溶液の溶媒を除去後、粗生成物をトルエンに溶解し、１０％水酸化ナトリウム水溶液および水で洗浄した。得られた有機溶液を硫酸ナトリウムで乾燥、ろ過後、溶媒の濃縮を行い６〜７℃にて静置し白色の固体を析出させた。これを濾過した後、冷トルエンで洗浄後、乾燥させ、１７．３ｇ（３０．７ミリモル、６５％収率）の白色の固体を得た。この生成物を液体クロマトグラフで分析したところ、純度９９．５％であった。この精製物の分析結果は以下の通りであり、下記構造を有することが確認された。
【００３１】
１Ｈ ＮＭＲ（ＣＤＣｌ３，ｐｐｍ）／２．１７（６Ｈ，Ａｒ−ＣＨ３）；３．７７（６Ｈ，Ｏ−ＣＨ３）；６．７８（２Ｈ，ＡｒＨ）；７．０５（４Ｈ，ＡｒＨ）；７．４６（４Ｈ，ＡｒＨ）；７．５７（２Ｈ，ＡｒＨ）
１３Ｃ ＮＭＲ（ＣＤＣｌ３，ｐｐｍ）／３０．９、５５．２、６４．４、１１３．９、１２１．５、１２１．８、１２９．０、１２９．３、１３０．８、１３６．５、１３７．９、１５３．７、１５８．７
元素分析／ｃａｌｃｄ．：Ｃ＝６１．７２、Ｈ＝４．２９、Ｏ＝５．６７、Ｂｒ＝２８．３２
ｆｏｕｎｄ：Ｃ＝６１．４９、Ｈ＝４．４１、Ｏ＝５．７８、Ｂｒ＝２８．００
融点／１８９〜１９０℃
実施例３ ポリ（９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン−２，７’−ジイル）
不活性ガスで置換した５０ミリリットルのシュレンクに、ビスシクロオクタジエニルニッケル（０価）０．７０６ｇ（２．５７ミリモル）、脱水ジメチルホルムアミド２０ミリリットル、シクロオクタジエン０．４０ｇ（３．７ミリモル）、２，２’−ビピリジル０．４０３ｇ（２．５８ミリモル）を入れ、室温で１時間撹拌後、２，７−ジブロモ−９，９−ビス（３−メチル−４−メトキシフェニル）フルオレン０．４８４ｇ（０．８５８ミリモル）を入れ、得られた混合物を６０℃で２日間攪拌および反応した。反応後、反応溶液をメタノール−濃塩酸混合物（９：１）に入れ重合を停止した。ろ過により生成物を回収し、酸洗浄、アルカリ洗浄、再沈殿などの通常のポリマー精製操作を行った後、乾燥させ、０．２５６ｇ（７４％収率）の薄い黄色の粉末を得た。この粉末の分析結果は以下の通りであり、下記構造を有することが確認された。
【００３３】
１Ｈ ＮＭＲ（ＣＤＣｌ３，ｐｐｍ）／２．０９（６Ｈ，Ａｒ−ＣＨ３）；３．７６（６Ｈ，Ｏ−ＣＨ３）；６．６５（２Ｈ，ＡｒＨ）；７．０１（４Ｈ，ＡｒＨ）；７．５４（４Ｈ，ＡｒＨ）；７．７５（２Ｈ，ＡｒＨ）
ＧＰＣ（ＣＤＣｌ３）／Ｍｎ＝７，５００、Ｍｗ＝２３，７００
Ｍｗ／Ｍｎ（多分散度）＝３．２
元素分析／ｃａｌｃｄ．：Ｃ＝８６．１１、Ｈ＝５．９８、Ｏ＝７．９１
ｆｏｕｎｄ：Ｃ＝８３．６６、Ｈ＝６．２５、Ｏ＝８．７１
蛍光スペクトル（ＣＨＣｌ３）／４１９、４４３ｎｍ（励起波長：３９０ｎｍ）
ＵＶスペクトル（ＣＨＣｌ３）／λｍａｘ＝３８７ｎｍ
蛍光量子収率（ＣＨＣｌ３溶液）＝８０％
実施例４ ポリ（９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン−２，７’−ジイル）
不活性ガスで置換した５０ミリリットルのシュレンクに、ビスシクロオクタジエニルニッケル（０価）０．７２６ｇ（２．６４ミリモル）、脱水トルエン２０ミリリットル、シクロオクタジエン０．３３ｇ（３．１ミリモル）、２，２’−ビピリジル０．４１２ｇ（２．６４ミリモル）を入れ、室温で１時間撹拌後、２，７−ジブロモ−９，９−ビス（３−メチル−４−メトキシフェニル）フルオレン０．５００ｇ（０．８８６ミリモル）を入れ、得られた混合物を６０℃で２日間攪拌および反応した。反応後、反応溶液をメタノール−濃塩酸混合物（９：１）に入れ重合を停止した。ろ過により生成物を回収し、酸洗浄、アルカリ洗浄、再沈殿などの通常のポリマー精製操作を行った後、乾燥させ、０．３３２ｇ（９３％収率）の薄い黄色の粉末を得た。この粉末の分析結果は以下の通りであり、下記構造を有することが確認された。
【００３５】
ＧＰＣ（ＣＤＣｌ３）／Ｍｎ＝１３，０００、Ｍｗ＝１１３，０００
Ｍｗ／Ｍｎ（多分散度）＝８．７
元素分析／ｃａｌｃｄ．：Ｃ＝８６．１１、Ｈ＝５．９８、Ｏ＝７．９１
ｆｏｕｎｄ：Ｃ＝８５．０４、Ｈ＝６．４０、Ｏ＝７．９７
蛍光スペクトル（ＣＨＣｌ３）／４１９、４４４ｎｍ（励起波長：３９０ｎｍ）
ＵＶスペクトル（ＣＨＣｌ３）／λｍａｘ＝３９３ｎｍ
蛍光量子収率（ＣＨＣｌ３溶液）＝７２％
実施例５ ポリ（９，９−ジ（３−メチル−４−ヒドロキシフェニル）フルオレン−２，７’−ジイル−ｃｏ−９，９−ジオクチルフルオレン−２，７’−ジイル）
不活性ガスで置換した５０ミリリットルのシュレンクに、テトラキス（トリフェニルホスフィン）パラジウム（０価）２０．２ｍｇ（０．０１７５ミリモル）、９，９−ジオクチルフルオレン−２，７−ジ（プロピレンボロネート）０．３２６ｇ（０．５８４ミリモル）、２，７−ジブロモ−９，９−ビス（３−メチル−４−ヒドロキシフェニル）フルオレン０．３１３ｇ（０．５８４ミリモル）、脱気トルエン５．２ミリリットル、脱気炭酸カリウム水溶液（２モル／リットル）５．２ミリリットル（１０．４ミリモル）を入れ、９０℃で３日間攪拌および反応した。反応後、反応溶液をメタノール−水混合物（９：１）に入れ重合を停止した。ろ過により生成物を回収し、酸洗浄、アルカリ洗浄、再沈殿などの通常のポリマー精製操作を行った後、乾燥させ、０．２７１ｇ（６１％収率）の薄い茶色の粉末を得た。
【００３７】
１Ｈ ＮＭＲ（ＣＤＣｌ３，ｐｐｍ）／０．５７−０．９０（１０Ｈ，−ＣＨ２−ＣＨ３）；０．９５−１．２５（２０Ｈ，−ＣＨ２−）；２．０３（４Ｈ，−ＣＨ２−）；２．１７（６Ｈ，Ａｒ−ＣＨ３）；４．６４（２Ｈ，ＯＨ）；６．６９（２Ｈ，ＡｒＨ）；７．０５−７．１５（４Ｈ，ＡｒＨ）；７．４５−７．９５（１２Ｈ，ＡｒＨ）
元素分析／ｃａｌｃｄ．：Ｃ＝８７．９１、Ｈ＝７．９１、Ｏ＝４．１８
ｆｏｕｎｄ：Ｃ＝８５．９４、Ｈ＝７．６４、Ｏ＝４．６８
実施例６ ポリ（９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン−２，７’−ジイル−ｃｏ−９，９−ジオクチルフルオレン−２，７’−ジイル）
不活性ガスで置換した５０ミリリットルのシュレンクに、テトラキス（トリフェニルホスフィン）パラジウム（０価）２０．１ｍｇ（０．０１７４ミリモル）、９，９−ジオクチルフルオレン−２，７−ジ（プロピレンボロネート）０．３２４ｇ（０．５８０ミリモル）、２，７−ジブロモ−９，９−ビス（３−メチル−４−メトキシフェニル）フルオレン０．３３３ｇ（０．５９０ミリモル）、脱気トルエン５．２ミリリットル、脱気炭酸カリウム水溶液（２モル／リットル）２．９ミリリットル（５．８ミリモル）、相間移動触媒０．０４ｇ（０．０９９ミリモル）を入れ、９０℃で３日間攪拌および反応した。反応後、反応溶液をメタノール−濃塩酸混合物（９：１）に入れ重合を停止した。ろ過により生成物を回収し、酸洗浄、アルカリ洗浄、再沈殿などの通常のポリマー精製操作を行った後、乾燥させ、０．４６０ｇ（９６％収率）の薄い黄色の粉末を得た。この粉末の分析結果は以下の通りであり、下記構造を有することが確認された。
【００３９】
１Ｈ ＮＭＲ（ＣＤＣｌ３，ｐｐｍ）／０．６０−０．９５（１０Ｈ，−ＣＨ２−ＣＨ３）；０．９５−１．３５（２０Ｈ，−ＣＨ２−）；１．９０−２．１０（４Ｈ，−ＣＨ２−）；２．１５（６Ｈ，Ａｒ−ＣＨ３）；３．７９（６Ｈ，Ｏ−ＣＨ３）；６．６５−７．２５（６Ｈ，ＡｒＨ）；７．４０−７．９５（１２Ｈ，ＡｒＨ）
ＧＰＣ（ＣＤＣｌ３）／Ｍｎ＝９，８００、Ｍｗ＝３０，６００
Ｍｗ／Ｍｎ（多分散度）＝３．１
元素分析／ｃａｌｃｄ．：Ｃ＝８７．８３、Ｈ＝８．１３、Ｏ＝４．０３
ｆｏｕｎｄ：Ｃ＝８６．８１、Ｈ＝８．２４、Ｏ＝４．６６
蛍光スペクトル（ＣＨＣｌ３）／４１９、４４４ｎｍ（励起波長：３８６ｎｍ）
ＵＶスペクトル（ＣＨＣｌ３）／λｍａｘ＝３８９ｎｍ
蛍光量子収率（ＣＨＣｌ３溶液）＝７４％
実施例７ ポリ（９，９−ジ（３−メチル−４−メトキシフェニル）フルオレン−２，７’−ジイル−ｃｏ−９，９−ジオクチルフルオレン−２，７’−ジイル）
不活性ガスで置換した５０ミリリットルのシュレンクに、テトラキストリフェニルホスフィンパラジウム（０価）２１．３ｍｇ（０．０１８４ミリモル）、９，９−ジオクチルフルオレン−２，７−ジ（プロピレンボロネート）０．３４８ｇ（０．６２３ミリモル）、２，７−ジブロモ−９，９−ビス（３−メチル−４−メトキシフェニル）フルオレン０．３５２ｇ（０．６２４ミリモル）、脱気トルエン５．５ミリリットル、脱気炭酸カリウム水溶液（２モル／リットル）３．１ミリリットル（６．２ミリモル）を入れ、９０℃で３日間攪拌および反応した。反応後、反応溶液をメタノール−水混合物（９：１）に入れ重合を停止した。ろ過により生成物を回収し、酸洗浄、アルカリ洗浄、再沈殿などの通常のポリマー精製操作を行った後、乾燥させ、０．４９４ｇ（８５％収率）の淡い黄色の粉末を得た。この粉末の分析結果は以下の通りであり、下記構造を有することが確認された。
【００４１】
ＧＰＣ（ＣＤＣｌ３）／Ｍｎ＝１，７００、Ｍｗ＝２，７００
Ｍｗ／Ｍｎ（多分散度）＝１．６
蛍光スペクトル（ＣＨＣｌ３）／４１７、４３９ｎｍ（励起波長：３７１ｎｍ）
ＵＶスペクトル（ＣＨＣｌ３）／λｍａｘ＝３７１ｎｍ
蛍光量子収率（ＣＨＣｌ３溶液）＝６９％
使用例
実施例３で得られたポリマーをクロロホルムに濃度３０ｍｇ／ミリリットルになるように溶解し、スピンコーティング法により、インジウム／錫オキサイドで被覆されたガラス基板（陽極）に塗布および乾燥し、均一な層を形成した。この際ポリマーの析出はなく、均一な薄膜が形成された。この層の表面にＭｇ／Ａｇ（８０／２０）を蒸気蒸着させて陰極とし、ＥＬ素子とした。上記の電極の間に電圧を印加すると青色の蛍光発光が認められた。実施例４〜７のポリマーについても同様であった。
【００４３】
【発明の効果】
本発明によれば、新規化合物である２，７−ジブロモ−９，９−ビス（３−置換−４−ヒドロキシフェニル）フルオレンとそのエーテル誘導体の合成が可能であり、また、これらのフルオレン系化合物はポリマー原料、有機合成の原料として使用することができる。また、本発明のポリマーを、特にＥＬ素子の発光層に用いた場合に、製膜性に優れるとともに、ＥＬ素子の電荷注入層材料や電荷輸送層材料としても有用である。
【図面の簡単な説明】
【図１】実施例４で得られたポリマーの蛍光スペクトル。
【図２】実施例４で得られたポリマーの吸光度。
【図３】実施例６で得られたポリマーの蛍光スペクトル。
【図４】実施例６で得られたポリマーの吸光度。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to 2,7-dibromo-9,9-di (3-substituted-4-hydroxyphenyl) fluorene or an ether thereof useful as a raw material for functional polymers such as various chemical intermediates and organic luminescent materials. The present invention relates to a derivative, a production method thereof, and a polymer or oligomer.
[0002]
[Prior art]
2. Description of the Related Art Heretofore, an EL element which is thin and can be displayed with low power consumption has attracted attention as a display. An EL element is an element in which a thin film light emitting layer is sandwiched between a pair of electrodes at least one of which is transparent, and emits light by injection of electric charge. Light-emitting materials for EL elements include inorganic substances and organic substances, and low-molecular compounds and high-molecular compounds are known as organic substances. In particular, polymer light-emitting materials that can easily form a thin film have been widely studied.
[0003]
[Problems to be solved by the invention]
The organic polymer material is generally a rigid polymer having a continuous aromatic ring and a mixture of polymers having a low degree of polymerization. Therefore, in general, the solubility in general-purpose organic solvents is low, and when a thin film is formed on an electrode substrate from a solution of the polymer in an organic solvent, the mixed polymer having a low degree of polymerization may precipitate or crystallize. Therefore, it is difficult to form a uniform and nm-level thin film.
[0004]
Therefore, the object of the present invention is a narrow molecular weight distribution, high solubility in general-purpose organic solvents, without causing polymer precipitation and crystallization, a polymer raw material capable of forming a homogeneous thin film, a method for producing the same, and To provide a polymer or oligomer.
[0005]
[Means for Solving the Problems]
The above object is achieved by the present invention described below. That is, the present invention provides 2,7-dibromo-9,9-di (3-substituted-4-hydroxyphenyl) fluorene or an ether derivative thereof, characterized by the following general formula (1): A method and a polymer or oligomer represented by the following general formula (5) comprising these compounds are provided.
(R in the above formula1Is independently a hydrogen atom or a C atom which may contain one or more heteroatoms such as sulfur, nitrogen, phosphorus, oxygen or silicon.1 ~ 22Represents a hydrocarbon group of2Is independently C1 ~ 6Represents a hydrocarbon group. )
Among the compounds of the above general formula (1), two R1Are both hydrogen atoms, and two R2Is a methyl group, and two R1And two R2Are particularly useful.
[0007]
[0008]
In the present invention, two R1The `` hydrocarbon group '' represented by means an organic group containing hydrogen and carbon, such as an aliphatic group, an aromatic group, a cycloaliphatic group, and a heterocyclic compound. The groups may contain heteroatoms such as sulfur, nitrogen, phosphorus, oxygen or silicon. In the present invention, two R2The “hydrocarbon group” represented by is typically a straight-chain or branched-chain alkyl group. Preferred R1Is an alkyl group having 1 to 8 carbon atoms.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, the present invention will be described in more detail with reference to preferred embodiments.
The method for producing the compound represented by the general formula (1) of the present invention is described by R1Is a hydrogen atom, and R2Is a methyl group as a representative example. There are two methods for this production method. The first method is a method in which 2,7-dibromo-9-fluorenone and 2 equivalents of o-cresol are subjected to a condensation reaction under acidic conditions. More specifically, 2,7-dibromo-9-fluorenone (1 mol) is reacted with o-cresol (2 mol) in the presence of an acid (1 mmol to 10 mol) and a catalyst (1 mmol to 5 mol). The crude product obtained by the reaction is purified by extraction, distillation, recrystallization, or the like, if necessary. As a reaction solvent, o-cresol itself can be used as the solvent (use amount: 2 mol to 100 mol), and benzene, toluene, xylene, and other general compounds can be used as the solvent. .
[0010]
As the acid used above, sulfuric acid, hydrochloric acid, methanesulfonic acid, polyphosphoric acid and other acids can be used, and as the catalyst, a compound such as β-mercaptopropionic acid can be used. The reaction temperature varies depending on the amount of the raw materials charged, the amount of the solvent, the type of the solvent, and the like. Need to be Generally, it is in the range of 20C to 140C, preferably 40C to 100C. The reaction time is about 1 to 48 hours.
[0011]
The second method is a method by dibromination of 2,9-position of 9,9-di (3-methyl-4-hydroxyphenyl) fluorene. More specifically, bromine (Br) is added to a dispersion of 9,9-di (3-methyl-4-hydroxyphenyl) fluorene (1 mol) in an organic solution or water.2) (1 mol to 100 mol) or bromine (Br)2) —React by adding catalysts. The crude product obtained by the reaction is purified by extraction, distillation, recrystallization, etc., if necessary. As the reaction solvent, halogenated hydrocarbons, benzene, toluene, xylene, and other general compounds can be used as the solvent. In the bromination reaction, it is also preferable to use a catalyst, an additive or the like in order to promote the reaction.
[0012]
Examples of catalysts and additives include mineral acids such as sulfuric acid, hydrochloric acid and hydrobromic acid, Lewis acids such as iron chloride and zinc chloride, iodine (I2) And other bromine (Br2), Heavy metals such as iron and nickel, and oxidizing agents such as aqueous hydrogen peroxide and periodic acid. In the bromination reaction, hydrobromic acid is by-produced, but bromine (Br)2), The by-product hydrobromic acid is oxidized by using an oxidizing agent such as aqueous hydrogen peroxide in the system to obtain bromine (Br).2It is also a preferable method to carry out the reaction while returning to (1). The reaction temperature varies depending on the amount of the raw materials charged, the amount of the solvent, the type of the solvent, and the like. Need to be Generally, it is in the range of -20C to 100C, preferably 0C to 80C. The reaction time is about 1 to 24 hours.
[0013]
In the general formula (1), two R1And two R2Are both hydrocarbon groups, two R1Are both methyl groups, and two R2Are both methyl groups. This method includes the following two methods. The first method is a method in which methyl ether is synthesized by reacting 2,7-dibromo-9,9-di (3-methyl-4-hydroxyphenyl) fluorene with methyl halide under alkaline conditions. More specifically, methyl halide (2 mol) is added to a reaction solution of 2,7-dibromo-9,9-di (3-methyl-4-hydroxyphenyl) fluorene (1 mol) and an alkalizing agent (2 mol to 100 mol). Mol to 100 mol) to synthesize a methyl ether compound.
[0014]
The crude product obtained by the above reaction is purified by extraction, distillation, recrystallization or the like as necessary. As the reaction solvent, acetone, toluene, xylene, and other general compounds can be used. Above, the case where methyl halide is used as the halogenating agent has been described as a typical example. Examples of the halogenated compound include alkyl halides other than those described above, halides of unsaturated hydrocarbons, and aromatic halogenated compounds. Can be Here, the alkyl group is an alkyl group having 1 to 22 carbon atoms, and examples thereof include, in addition to the methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, isobutyl group, 2-ethylhexyl group and the like. In addition, an alkyl group containing one or more hetero atoms such as nitrogen, oxygen, and sulfur and a compound containing an unsaturated bond can also be used. The reaction temperature varies depending on the amount of the raw materials charged, the amount of the solvent, the type of the solvent, and the like. Need to be Generally, it is in the range of 0 ° C to 120 ° C, preferably 50 ° C to 100 ° C. The reaction time is about 1 to 48 hours.
[0015]
The second method is a synthesis method of 2,9-di (3-methyl-4-methoxyphenyl) fluorene by dibromination at the 2,7-position. More specifically, bromine (Br) is added to a suspension of 9,9-di (3-methyl-4-methoxyphenyl) fluorene (1 mol) in an organic solution or water.2) (1 mol to 100 mol) or bromine (Br)2) —React by adding catalysts. The crude product obtained by the reaction is purified by extraction, distillation, recrystallization, etc., if necessary. As the reaction solvent, halogenated hydrocarbons, benzene, toluene, xylene and other general compounds can be used as the solvent. In the bromination reaction, it is also preferable to use a catalyst, an additive or the like in order to promote the reaction.
[0016]
Examples of catalysts and additives include mineral acids such as sulfuric acid, hydrochloric acid and hydrobromic acid, Lewis acids such as iron chloride and zinc chloride, iodine (I2) And other bromine (Br2), Heavy metals such as iron and nickel, and oxidizing agents such as aqueous hydrogen peroxide and periodic acid. In the bromination reaction, hydrobromic acid is by-produced, but bromine (Br)2), The by-product hydrobromic acid is oxidized by using an oxidizing agent such as aqueous hydrogen peroxide in the system to obtain bromine (Br).2It is also a preferable method to carry out the reaction while returning to (1).
[0017]
In the above description, a methyl ester was used as a representative example, but other ether derivatives include an alkyl ether, an unsaturated hydrocarbon ether, and an aromatic hydrocarbon ether. Here, the alkyl group is an alkyl group having 1 to 22 carbon atoms, and examples thereof include, in addition to the methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, isobutyl group, 2-ethylhexyl group and the like. In addition, an alkyl group containing one or more hetero atoms such as nitrogen, oxygen, and sulfur and a compound containing an unsaturated bond can also be used. The reaction temperature varies depending on the amount of the raw materials charged, the amount of the solvent, the type of the solvent, and the like. Need to be Generally, it is in the range of -20C to 100C, preferably 0C to 80C. The reaction time is about 1 to 24 hours.
[0018]
The method for producing a polymer (oligomer) represented by the general formula (5) using the compound of the general formula (1) of the present invention is described by 2,7-dibromo-9,9-di (3-methyl-4). A method using (-methoxyphenyl) fluorene will be described as a typical example.
The first method is a method in which 2,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene is Grignarded and a metal catalyst is used. More specifically, under an inert gas atmosphere, 2,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene (1 mol) is reacted with metallic magnesium (1 mol) to form a Grignard. , Nickel, palladium, iron, chromium, and other halides (1 mmol to 1 mol), a zero-valent complex, a divalent complex (halogen-free), or the like as a catalyst.
[0019]
As the solvent, ethers such as tetrahydrofuran and dialkyl ether can be used. The reaction temperature varies depending on the amount of the raw materials charged, the amount of the solvent, the type of the solvent, and the like. Need to be Generally, it is 0 ° C. or higher. The reaction time is about 1 to 72 hours. Quenching, post-treatment, and polymer purification of the polymerization can be performed by a general method. In addition, a random copolymer (oligomer) can be synthesized by a combination with another dihalogenated monomer (dihalide or hydrocarbon represented by “X” in the general formula (5)).
[0020]
The second method is a homopolymerization method of 2,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene using a nickel zero-valent complex. More specifically, under an inert gas atmosphere, 2,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene (1 mol) and a nickel zero-valent complex (1 to 20 mol) are dissolved in a solvent. It is a method to make it react in.
[0021]
As the solvent, toluene, dimethylformamide, tetrahydrofuran and the like can be used. The reaction temperature varies depending on the amount of the raw materials charged, the amount of the solvent, the type of the solvent, and the like. Need to be Generally, it is in the range of 20C to 110C, preferably 40C to 90C. The reaction time is about 1 to 72 hours. Quenching of the polymerization, post-treatment, and purification of the polymer can be performed by a general method. It is also possible to synthesize a random copolymer (oligomer) by combination with another dihalogenated monomer or hydrocarbon.
[0022]
The third method is a method of copolymerization or homopolymerization of 2,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene and a boronic acid ester or a tin compound using a metal catalyst. . More specifically, under an inert gas atmosphere, 2,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene (1 mol) and a diboronic ester such as an aromatic or heterocyclic compound or A ditin compound (1 mol) is reacted with a metal catalyst (0.1 mmol to 1 mol) such as palladium zero-valent complex and an alkali reagent (1 mol to 100 mol) such as sodium carbonate, potassium carbonate and sodium hydroxide as a reaction reagent. In the reaction.
[0023]
As the solvent, compounds such as toluene, tetrahydrofuran, and acetone can be used, and two-phase reaction with an aqueous alkali solution, one-phase reaction, and polymerization in a system to which a phase transfer catalyst is added can be performed. The reaction temperature varies depending on the amount of the raw materials charged, the amount of the solvent, the type of the solvent, and the like. Need to be Generally, it is in the range of 30C to 130C, preferably 50C to 110C. The reaction time is about 1 to 72 hours. Quenching of the polymerization, post-treatment, and purification of the polymer can be performed by a general method. It is also possible to convert 2,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene itself into a boronic acid ester or a tin compound and perform coupling with a dihalogenated compound or a hydrocarbon. It is possible.
[0024]
A fourth method is a polymerization method using a nickel divalent complex of 2,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene. More specifically, under an inert gas atmosphere, 2,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene (1 mol), zinc (0.1 to 20 mol), nickel complex (0.1 mmol to 1 mol) in a solvent. Various solvents including acetone, dimethylformamide, tetrahydrofuran, and acetonitrile can be used as the reaction solvent. The reaction temperature varies depending on the amount of the raw materials charged, the amount of the solvent, the type of the solvent, and the like. Need to be In general, the reaction is carried out at 20 ° C to 100 ° C for about 1 to 48 hours. Quenching of the polymerization, post-treatment, and purification of the polymer can be performed by a general method. It is also possible to synthesize a random copolymer (oligomer) by combination with another dihalogenated monomer or hydrocarbon.
The production of the above-mentioned fluorene-based compound and polymer is carried out by R1Is a hydrogen atom or a methyl group;2Is a methyl group.1And R2Is the same when other hydrocarbon groups. The polymerization method is not limited to the above method, and a general method such as a Heck reaction, a Sonogashira reaction, a Honer-Wittig-Emmons reaction, or the like can be used.
[0025]
Specific examples of the comonomer include the following compounds. As the aromatic compound, for example, 2,7-dibromo-9,9-diarylfluorene, 2,7-diiodo-9,9-diarylfluorene, 2,7-dibromo-9,9-dialkylfluorene, 2,7 -Diiodo-9,9-dialkylfluorene, 2,5-dibromothiophene, 2,5-diiodothiophene, 2,5-dibromo-3-hexylthiophene, 2,5-diiodo-3-methylthiophene, dibromobithiophene , Diiodobithiophene, dibromoterthiophene, diiodoterthiophene, dibromobipyridine, diiodobipyridine, dibromoterpyridine, diiodoterpyridine, dibromopyridine, diiodopyridine, 1,4-dibromobenzene, 1,4-di Iodobenzene, dibromobenzothiadiazole, diiodoben Thiadiazole, dibromocarbazole, diiodocarbazole, dibromonaphthalene, diiodonaphthalene, dibromoanthracene, diiodoanthracene, dibromoquinoline, diiodoquinoline, dibromobiphenyl, diiodobiphenyl, dibromoterphenyl, diiodoterphenyl, dibromophenanthroline, dibromo Examples of iodophenanthroline and 1,4-divinylbenzene (which can be polymerized by the Heck reaction) include other hydrocarbons such as, for example, aliphatic compounds such as ethylene, butadiene, hexatriene, and acetylene derivatives (by the Sonogashira reaction). And a conjugated aliphatic compound such as a polymerizable compound. Of these comonomers, aromatic comonomers are preferred. The above compounds are examples, and the present invention is not limited to the above compounds.
The proportion of the comonomer unit (X) in the polymer can be in the range of 0 to 99.9% by weight, except for special cases such as alternating copolymerization.
[0026]
Although the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer of the present invention vary depending on the kind of the starting material used and the reaction conditions, the weight average molecular weight (Mw) is preferably about 1,000 to 1,000,000, preferably Is 2,000 to 500,000, more preferably 5,000 to 500,000, and Mw / Mn (polydispersity) is 1 to 10.0, preferably 1 to 4.0, more preferably 1 to 4.0. 2.0 (GPC, converted to polystyrene).
[0027]
In the above four methods, 2,7-dibromo-9,9-di (3-methyl-4-hydroxyphenyl) fluorene or its ether derivative is directly used as a polymer raw material to newly form a carbon-carbon bond. ing. Such a polymer is useful as a luminescent material, a charge injection material, a charge transport material and the like of an EL device. Further, for example, a bromine atom at the 2,7 position can be converted into a carboxylic acid, and the bromine atom can be used as a monomer of a polymer such as polyamide. Further, it can be used not only as a raw material for a polymer but also as a raw material for synthesizing a low-molecular material such as modifying or converting a bromine atom at the 2,7-position.
[0028]
【Example】
Next, the present invention will be described more specifically with reference to examples.
Example 12,7-dibromo-9,9-di (3-methyl-4-hydroxyphenyl) fluorene
In a 200 ml flask, 4.00 g (11.8 mmol) of 2,7-dibromofluorenone, 15.7 g (0.145 mol) of o-cresol, 0.20 g (1.9 mmol) of β-mercaptopropionic acid and methane 0.67 g (7.0 mmol) of sulfonic acid was added, and the resulting mixture was stirred and reacted at 60 ° C. for 24 hours. After the reaction, the reaction mixture was washed with water, and the obtained crude product was collected by filtration, dissolved in 100 ml of toluene, and washed with an aqueous sodium hydrogen carbonate solution and water. The obtained organic solution was dried over sodium sulfate, filtered, concentrated, and allowed to stand at 0 ° C. to precipitate a white solid. This was filtered, washed with cold toluene, and dried to obtain 3.95 g of a white solid. When this was analyzed by gas chromatography, it was a crystal containing 11.4% by weight of toluene and containing 0.75 equivalents of toluene as a crystallization solvent with respect to the target substance (6.52 mmol, 55% yield). ).
[0029]
When the product was analyzed by liquid chromatography, the purity from which toluene was removed was 99.9%. The mother liquor was concentrated and the same operation was carried out to collect a secondary crystal (1.40 g, 2.31 mmol, purity 99.8%). The results of analysis of this purified product are as follows, and it was confirmed that the product had the following structure.
1H NMR (DMSO-d6, Ppm) /1.99 (6H, Ar-CH3); 2.28 (2.3H, toluene: Ar-CH)3); 6.65-6.78 (6H, ArH); 7.10-7.25 (3.8H, toluene: ArH) 7.48 (2H, ArH); 7.55 (2H, ArH); .86 (2H, ArH); 9.28 (2H, OH) (contains 0.75 equivalents of toluene)
ThirteenC NMR (DMSO-d6, 16.1), 21.0, 64.0, 114.5, 121.0, 122.6, 123.7, 125.2, 125.9, 128.1, 128.5, 128. 8, 129.5, 130.5, 134.4, 137.3, 137.5, 154.0, 154.4 (including the toluene peak)
Elemental analysis / calcd. : C = 63.99, H = 4.33, O = 5.29, Br = 26.40 (value containing 0.75 equivalent of toluene)
found: C = 64.00, H = 4.48, O = 5.41, Br = 23.73
Melting point / 214-215 ° C
Example 22,7-dibromo-9,9-di (3-methyl-4-methoxyphenyl) fluorene
In a 500 ml flask, 25.2 g (47.0 mmol) of 2,7-dibromo-9,9-di (3-methyl-4-hydroxyphenyl) fluorene, 33 g (0.24 mol) of potassium carbonate, and 250 ml of acetone Milliliter was added, 35 g (0.25 mol) of methyl iodide was added dropwise to the resulting mixture, and the mixture was stirred and reacted at the reflux temperature of the solvent for 14 hours. After the reaction, the reaction mixture was filtered to remove the solvent of the obtained organic solution, and then the crude product was dissolved in toluene and washed with a 10% aqueous sodium hydroxide solution and water. The obtained organic solution was dried over sodium sulfate, filtered, concentrated, and allowed to stand at 6 to 7 ° C. to precipitate a white solid. This was filtered, washed with cold toluene and dried to obtain 17.3 g (30.7 mmol, 65% yield) of a white solid. The product was analyzed by liquid chromatography and found to have a purity of 99.5%. The results of analysis of this purified product are as follows, and it was confirmed that the product had the following structure.
[0031]
1H NMR (CDCl3, Ppm) /2.17 (6H, Ar-CH3); 3.77 (6H, O-CH)3); 6.78 (2H, ArH); 7.05 (4H, ArH); 7.46 (4H, ArH); 7.57 (2H, ArH).
ThirteenC NMR (CDCl3, Ppm) /30.9, 55.2, 64.4, 113.9, 121.5, 121.8, 129.0, 129.3, 130.8, 136.5, 137.9, 153. 7, 158.7
Elemental analysis / calcd. : C = 61.72, H = 4.29, O = 5.67, Br = 28.32.
found: C = 61.49, H = 4.41, O = 5.78, Br = 28.00
Melting point / 189-190 ° C
Example 3Poly (9,9-di (3-methyl-4-methoxyphenyl) fluorene-2,7'-diyl)
In a 50 ml Schlenk purged with an inert gas, add 0.706 g (2.57 mmol) of biscyclooctadienyl nickel (0 value), 20 ml of dehydrated dimethylformamide, 0.40 g (3.7 mmol) of cyclooctadiene. And 0.42 g (2.58 mmol) of 2,2'-bipyridyl were added thereto, and the mixture was stirred at room temperature for 1 hour. 484 g (0.858 mmol) were charged, and the resulting mixture was stirred and reacted at 60 ° C. for 2 days. After the reaction, the reaction solution was placed in a mixture of methanol and concentrated hydrochloric acid (9: 1) to terminate the polymerization. The product was recovered by filtration, subjected to ordinary polymer purification operations such as acid washing, alkali washing, and reprecipitation, and then dried to obtain 0.256 g (74% yield) of a pale yellow powder. The results of analysis of this powder are as follows, and it was confirmed that the powder had the following structure.
[0033]
1H NMR (CDCl3, Ppm) /2.09 (6H, Ar-CH3); 3.76 (6H, O-CH)3); 6.65 (2H, ArH); 7.01 (4H, ArH); 7.54 (4H, ArH); 7.75 (2H, ArH).
GPC (CDCl3) / Mn = 7,500, Mw = 23,700
Mw / Mn (polydispersity) = 3.2
Elemental analysis / calcd. : C = 86.11, H = 5.98, O = 7.91
found: C = 83.66, H = 6.25, O = 8.71
Fluorescence spectrum (CHCl3) / 419, 443 nm (excitation wavelength: 390 nm)
UV spectrum (CHCl3) / Λmax = 387 nm
Fluorescence quantum yield (CHCl3Solution) = 80%
Example 4Poly (9,9-di (3-methyl-4-methoxyphenyl) fluorene-2,7'-diyl)
To 50 ml of Schlenk replaced with an inert gas, 0.726 g (2.64 mmol) of biscyclooctadienyl nickel (0 value), 20 ml of dehydrated toluene, 0.33 g (3.1 mmol) of cyclooctadiene, 0.42 g (2.64 mmol) of 2,2'-bipyridyl was added, and the mixture was stirred at room temperature for 1 hour, and then 0.500 g of 2,7-dibromo-9,9-bis (3-methyl-4-methoxyphenyl) fluorene. (0.886 mmol) was added and the resulting mixture was stirred and reacted at 60 ° C. for 2 days. After the reaction, the reaction solution was placed in a mixture of methanol and concentrated hydrochloric acid (9: 1) to terminate the polymerization. The product was collected by filtration, subjected to ordinary polymer purification operations such as acid washing, alkali washing, and reprecipitation, and then dried to obtain 0.332 g (93% yield) of a pale yellow powder. The results of analysis of this powder are as follows, and it was confirmed that the powder had the following structure.
[0035]
GPC (CDCl3) / Mn = 13,000, Mw = 113,000
Mw / Mn (polydispersity) = 8.7
Elemental analysis / calcd. : C = 86.11, H = 5.98, O = 7.91
found: C = 85.04, H = 6.40, O = 7.97
Fluorescence spectrum (CHCl3) / 419, 444 nm (excitation wavelength: 390 nm)
UV spectrum (CHCl3) / Λmax = 393 nm
Fluorescence quantum yield (CHCl3Solution) = 72%
Example 5Poly (9,9-di (3-methyl-4-hydroxyphenyl) fluorene-2,7'-diyl-co-9,9-dioctylfluorene-2,7'-diyl)
In 50 ml of Schlenk substituted with an inert gas, 20.2 mg (0.0175 mmol) of tetrakis (triphenylphosphine) palladium (0 valence), 9,9-dioctylfluorene-2,7-di (propylene boronate) were added. 0.326 g (0.584 mmol), 0.313 g (0.584 mmol) of 2,7-dibromo-9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 5.2 ml of degassed toluene, 5.2 mL (10.4 mmol) of a degassed aqueous potassium carbonate solution (2 mol / L) was added, and the mixture was stirred and reacted at 90 ° C. for 3 days. After the reaction, the reaction solution was put into a methanol-water mixture (9: 1) to terminate the polymerization. The product was collected by filtration, subjected to ordinary polymer purification operations such as acid washing, alkali washing, and reprecipitation, and then dried to obtain 0.271 g (61% yield) of a light brown powder.
[0037]
1H NMR (CDCl3, Ppm) /0.57-0.90 (10H, -CH2-CH3); 0.95-1.25 (20H, -CH2−); 2.03 (4H, —CH2-); 2.17 (6H, Ar-CH3); 4.64 (2H, OH); 6.69 (2H, ArH); 7.05-7.15 (4H, ArH); 7.45-7.95 (12H, ArH).
Elemental analysis / calcd. : C = 87.91, H = 7.91, O = 4.18
found: C = 85.94, H = 7.64, O = 4.68
Example 6Poly (9,9-di (3-methyl-4-methoxyphenyl) fluorene-2,7'-diyl-co-9,9-dioctylfluorene-2,7'-diyl)
In 50 ml of Schlenk substituted with an inert gas, 20.1 mg (0.0174 mmol) of tetrakis (triphenylphosphine) palladium (0 valence), 9,9-dioctylfluorene-2,7-di (propylene boronate) were added. 0.324 g (0.580 mmol), 0.333 g (0.590 mmol) of 2,7-dibromo-9,9-bis (3-methyl-4-methoxyphenyl) fluorene, 5.2 ml of degassed toluene, 2.9 mL (5.8 mmol) of a degassed aqueous potassium carbonate solution (2 mol / L) and 0.04 g (0.099 mmol) of a phase transfer catalyst were added, and the mixture was stirred and reacted at 90 ° C. for 3 days. After the reaction, the reaction solution was placed in a mixture of methanol and concentrated hydrochloric acid (9: 1) to terminate the polymerization. The product was recovered by filtration, subjected to ordinary polymer purification operations such as acid washing, alkali washing, and reprecipitation, and then dried to obtain 0.460 g (96% yield) of a pale yellow powder. The results of analysis of this powder are as follows, and it was confirmed that the powder had the following structure.
[0039]
1H NMR (CDCl3, Ppm) /0.60-0.95 (10H, -CH2-CH3); 0.95-1.35 (20H, -CH2-); 1.90-2.10 (4H, -CH2-); 2.15 (6H, Ar-CH3); 3.79 (6H, O-CH)3); 6.65-7.25 (6H, ArH); 7.40-7.95 (12H, ArH)
GPC (CDCl3) / Mn = 9,800, Mw = 30,600
Mw / Mn (polydispersity) = 3.1
Elemental analysis / calcd. : C = 87.83, H = 8.13, O = 4.03
found: C = 86.81, H = 8.24, O = 4.66
Fluorescence spectrum (CHCl3) / 419,444 nm (excitation wavelength: 386 nm)
UV spectrum (CHCl3) / Λmax = 389 nm
Fluorescence quantum yield (CHCl3Solution) = 74%
Example 7Poly (9,9-di (3-methyl-4-methoxyphenyl) fluorene-2,7'-diyl-co-9,9-dioctylfluorene-2,7'-diyl)
In 50 ml of Schlenk purged with an inert gas, 21.3 mg (0.0184 mmol) of tetrakistriphenylphosphine palladium (0 valence) and 0.99-dioctylfluorene-2,7-di (propylene boronate) were added. 348 g (0.623 mmol), 0.37 g (0.624 mmol) of 2,7-dibromo-9,9-bis (3-methyl-4-methoxyphenyl) fluorene, 5.5 ml of degassed toluene, degassing 3.1 ml (6.2 mmol) of an aqueous potassium carbonate solution (2 mol / l) was added, and the mixture was stirred and reacted at 90 ° C. for 3 days. After the reaction, the reaction solution was put into a methanol-water mixture (9: 1) to terminate the polymerization. The product was collected by filtration, subjected to ordinary polymer purification operations such as acid washing, alkali washing, and reprecipitation, and then dried to obtain 0.494 g (85% yield) of a pale yellow powder. The results of analysis of this powder are as follows, and it was confirmed that the powder had the following structure.
[0041]
GPC (CDCl3) / Mn = 1,700, Mw = 2,700
Mw / Mn (polydispersity) = 1.6
Fluorescence spectrum (CHCl3) / 417, 439 nm (excitation wavelength: 371 nm)
UV spectrum (CHCl3) / Λmax = 371 nm
Fluorescence quantum yield (CHCl3Solution) = 69%
Example of use
The polymer obtained in Example 3 was dissolved in chloroform to a concentration of 30 mg / milliliter, applied to a glass substrate (anode) coated with indium / tin oxide by a spin coating method, and dried to form a uniform layer. Formed. At this time, no polymer was deposited and a uniform thin film was formed. Mg / Ag (80/20) was vapor-deposited on the surface of this layer to form a cathode, thereby obtaining an EL device. When a voltage was applied between the above electrodes, blue fluorescent light emission was observed. The same applies to the polymers of Examples 4 to 7.
[0043]
【The invention's effect】
According to the present invention, it is possible to synthesize a novel compound, 2,7-dibromo-9,9-bis (3-substituted-4-hydroxyphenyl) fluorene and an ether derivative thereof, and these fluorene compounds Can be used as a raw material for a polymer or a raw material for organic synthesis. In addition, when the polymer of the present invention is used particularly for a light emitting layer of an EL device, it is excellent in film-forming properties and is also useful as a charge injection layer material and a charge transport layer material of an EL device.
[Brief description of the drawings]
FIG. 1 is a fluorescence spectrum of the polymer obtained in Example 4.
FIG. 2 shows the absorbance of the polymer obtained in Example 4.
FIG. 3 is a fluorescence spectrum of the polymer obtained in Example 6.
FIG. 4 shows the absorbance of the polymer obtained in Example 6.
Claims (7)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119709A (en) * | 2005-02-16 | 2007-05-17 | Sumitomo Chemical Co Ltd | Method for producing aromatic polymer |
| JP2007321023A (en) * | 2006-05-31 | 2007-12-13 | Sumitomo Chemical Co Ltd | Polymer light-emitting element, organic transistor and composition useful for them |
| JP2011504654A (en) * | 2007-11-21 | 2011-02-10 | ケンブリッジ ディスプレイ テクノロジー リミテッド | Light emitting device and material therefor |
| JP2012524054A (en) * | 2009-04-16 | 2012-10-11 | ケンブリッジ ディスプレイ テクノロジー リミテッド | Monomer, polymer, and method for producing the same |
| US9109081B2 (en) | 2005-02-16 | 2015-08-18 | Sumitomo Chemical Company, Limited | Method for producing aromatic polymer |
| US10906855B2 (en) | 2017-01-19 | 2021-02-02 | Jfe Chemical Corporation | Method for producing fluorenylidene diallylphenols, and fluorenylidene diallylphenols |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5048463B2 (en) * | 2007-11-22 | 2012-10-17 | Ｊｆｅケミカル株式会社 | Method for producing polymer compound and method for producing light emitting material |
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2002
- 2002-08-29 JP JP2002250948A patent/JP4223766B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007119709A (en) * | 2005-02-16 | 2007-05-17 | Sumitomo Chemical Co Ltd | Method for producing aromatic polymer |
| US9109081B2 (en) | 2005-02-16 | 2015-08-18 | Sumitomo Chemical Company, Limited | Method for producing aromatic polymer |
| JP2007321023A (en) * | 2006-05-31 | 2007-12-13 | Sumitomo Chemical Co Ltd | Polymer light-emitting element, organic transistor and composition useful for them |
| JP2011504654A (en) * | 2007-11-21 | 2011-02-10 | ケンブリッジ ディスプレイ テクノロジー リミテッド | Light emitting device and material therefor |
| JP2012524054A (en) * | 2009-04-16 | 2012-10-11 | ケンブリッジ ディスプレイ テクノロジー リミテッド | Monomer, polymer, and method for producing the same |
| US10906855B2 (en) | 2017-01-19 | 2021-02-02 | Jfe Chemical Corporation | Method for producing fluorenylidene diallylphenols, and fluorenylidene diallylphenols |
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