JP4434679B2 - フルオレン誘導体の製造方法 - Google Patents
フルオレン誘導体の製造方法 Download PDFInfo
- Publication number
- JP4434679B2 JP4434679B2 JP2003339830A JP2003339830A JP4434679B2 JP 4434679 B2 JP4434679 B2 JP 4434679B2 JP 2003339830 A JP2003339830 A JP 2003339830A JP 2003339830 A JP2003339830 A JP 2003339830A JP 4434679 B2 JP4434679 B2 JP 4434679B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorenone
- fluorene
- group
- alkyl
- sulfuric acid
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 76
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 58
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 35
- 150000002220 fluorenes Chemical class 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 150000003573 thiols Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 22
- 239000011541 reaction mixture Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- -1 phenoxy alcohols Chemical class 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- 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 8
- 239000008346 aqueous phase Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 5
- JYINMLPNDRBKKZ-UHFFFAOYSA-N hydroperoxybenzene Chemical compound OOC1=CC=CC=C1 JYINMLPNDRBKKZ-UHFFFAOYSA-N 0.000 description 5
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 4
- 229960005323 phenoxyethanol Drugs 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241001550224 Apha Species 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 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 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- 125000006564 (C4-C8) cycloalkyl group Chemical group 0.000 description 1
- 125000006704 (C5-C6) cycloalkyl group Chemical group 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- GRCCRGZIGHCSEO-UHFFFAOYSA-N 1-(2,5-dimethylphenoxy)ethanol Chemical compound CC(O)OC1=CC(C)=CC=C1C GRCCRGZIGHCSEO-UHFFFAOYSA-N 0.000 description 1
- MMLWQANUZJTBLY-UHFFFAOYSA-N 1-(2,6-dimethylphenoxy)ethanol Chemical compound CC(O)OC1=C(C)C=CC=C1C MMLWQANUZJTBLY-UHFFFAOYSA-N 0.000 description 1
- GSOBKKBOWPKAMP-UHFFFAOYSA-N 1-(2-phenylphenoxy)ethanol Chemical compound CC(O)OC1=CC=CC=C1C1=CC=CC=C1 GSOBKKBOWPKAMP-UHFFFAOYSA-N 0.000 description 1
- GUFGXAIZAAYYKA-UHFFFAOYSA-N 1-(3-ethylphenoxy)ethanol Chemical compound CCC1=CC=CC(OC(C)O)=C1 GUFGXAIZAAYYKA-UHFFFAOYSA-N 0.000 description 1
- LKJDBVNNYVCLRZ-UHFFFAOYSA-N 1-(3-methylphenoxy)ethanol Chemical compound CC(O)OC1=CC=CC(C)=C1 LKJDBVNNYVCLRZ-UHFFFAOYSA-N 0.000 description 1
- YDYBDUBVAZNWQB-UHFFFAOYSA-N 1-(3-tert-butylphenoxy)ethanol Chemical compound C(C)(C)(C)C=1C=C(OC(C)O)C=CC1 YDYBDUBVAZNWQB-UHFFFAOYSA-N 0.000 description 1
- LZVCNBQHXSUTTL-UHFFFAOYSA-N 1-[1-[4-[9-[4-[2-(2-hydroxypropoxy)propoxy]phenyl]fluoren-9-yl]phenoxy]propan-2-yloxy]propan-2-ol Chemical compound C1=CC(OCC(C)OCC(O)C)=CC=C1C1(C=2C=CC(OCC(C)OCC(C)O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 LZVCNBQHXSUTTL-UHFFFAOYSA-N 0.000 description 1
- BWWOFKDFAGVASS-UHFFFAOYSA-N 1-[4-[9-[4-(2-hydroxypropoxy)-3-methylphenyl]fluoren-9-yl]-2-methylphenoxy]propan-2-ol Chemical compound C1=C(C)C(OCC(O)C)=CC=C1C1(C=2C=C(C)C(OCC(C)O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 BWWOFKDFAGVASS-UHFFFAOYSA-N 0.000 description 1
- PCALKHSQMLZQEQ-UHFFFAOYSA-N 1-phenoxybutan-1-ol Chemical compound CCCC(O)OC1=CC=CC=C1 PCALKHSQMLZQEQ-UHFFFAOYSA-N 0.000 description 1
- OAAZUWWNSYWWHG-UHFFFAOYSA-N 1-phenoxypropan-1-ol Chemical compound CCC(O)OC1=CC=CC=C1 OAAZUWWNSYWWHG-UHFFFAOYSA-N 0.000 description 1
- GPGBVWNYNZYQAK-UHFFFAOYSA-N 2-[2,6-ditert-butyl-4-[9-[3,5-ditert-butyl-4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound OCCOC1=C(C=C(C=C1C(C)(C)C)C1(C2=CC=CC=C2C=2C=CC=CC12)C1=CC(=C(C(=C1)C(C)(C)C)OCCO)C(C)(C)C)C(C)(C)C GPGBVWNYNZYQAK-UHFFFAOYSA-N 0.000 description 1
- CEVZRJOSWSQXCC-UHFFFAOYSA-N 2-[2-[4-[9-[4-[2-(2-hydroxyethoxy)ethoxy]phenyl]fluoren-9-yl]phenoxy]ethoxy]ethanol Chemical compound C1=CC(OCCOCCO)=CC=C1C1(C=2C=CC(OCCOCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 CEVZRJOSWSQXCC-UHFFFAOYSA-N 0.000 description 1
- SEAMZPPCCXCLAU-UHFFFAOYSA-N 2-[2-[9-[2-(2-hydroxyethoxy)-4-methylphenyl]fluoren-9-yl]-5-methylphenoxy]ethanol Chemical compound OCCOC1=C(C=CC(=C1)C)C1(C2=CC=CC=C2C=2C=CC=CC1=2)C1=C(C=C(C=C1)C)OCCO SEAMZPPCCXCLAU-UHFFFAOYSA-N 0.000 description 1
- YBHWVDKCKDWQBX-UHFFFAOYSA-N 2-[2-cyclohexyl-4-[9-[3-cyclohexyl-4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound OCCOC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C2CCCCC2)C=C1C1CCCCC1 YBHWVDKCKDWQBX-UHFFFAOYSA-N 0.000 description 1
- VYPZHMOPRNFKBI-UHFFFAOYSA-N 2-[2-ethyl-4-[9-[3-ethyl-4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=C(OCCO)C(CC)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(CC)C(OCCO)=CC=2)=C1 VYPZHMOPRNFKBI-UHFFFAOYSA-N 0.000 description 1
- CUPZWXCTZHAVPP-UHFFFAOYSA-N 2-[2-tert-butyl-4-[9-[3-tert-butyl-4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=C(OCCO)C(C(C)(C)C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C(C)(C)C)=C1 CUPZWXCTZHAVPP-UHFFFAOYSA-N 0.000 description 1
- XNXRACMTZLYRAK-UHFFFAOYSA-N 2-[3-[9-[5-(2-hydroxyethoxy)-2-methylphenyl]fluoren-9-yl]-4-methylphenoxy]ethanol Chemical compound OCCOC=1C=C(C(=CC=1)C)C1(C2=CC=CC=C2C=2C=CC=CC1=2)C1=CC(=CC=C1C)OCCO XNXRACMTZLYRAK-UHFFFAOYSA-N 0.000 description 1
- APGPNPCFMNCAOG-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-2-methylphenyl]fluoren-9-yl]-3-methylphenoxy]ethanol Chemical compound CC1=CC(OCCO)=CC=C1C1(C=2C(=CC(OCCO)=CC=2)C)C2=CC=CC=C2C2=CC=CC=C21 APGPNPCFMNCAOG-UHFFFAOYSA-N 0.000 description 1
- IRTFFZWZLVOXMG-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluoren-9-yl]-2,6-dimethylphenoxy]ethanol Chemical compound CC1=C(OCCO)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(OCCO)=C(C)C=2)=C1 IRTFFZWZLVOXMG-UHFFFAOYSA-N 0.000 description 1
- HFKGBZQCCOAKRX-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3-methoxyphenyl]fluoren-9-yl]-2-methoxyphenoxy]ethanol Chemical compound OCCOC1=C(C=C(C=C1)C1(C2=CC=CC=C2C=2C=CC=CC12)C1=CC(=C(C=C1)OCCO)OC)OC HFKGBZQCCOAKRX-UHFFFAOYSA-N 0.000 description 1
- LUXQHIIWBDDUDE-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3-methylphenyl]fluoren-9-yl]-2-methylphenoxy]ethanol Chemical compound C1=C(OCCO)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(OCCO)=CC=2)=C1 LUXQHIIWBDDUDE-UHFFFAOYSA-N 0.000 description 1
- HBTONAMIPDVQRI-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3-phenylphenyl]fluoren-9-yl]-2-phenylphenoxy]ethanol Chemical compound OCCOC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 HBTONAMIPDVQRI-UHFFFAOYSA-N 0.000 description 1
- QXHPJWAXVTUDBA-UHFFFAOYSA-N 2-oxo-2-sulfanylacetic acid Chemical compound OC(=O)C(S)=O QXHPJWAXVTUDBA-UHFFFAOYSA-N 0.000 description 1
- ZZURXLMHTYYCST-UHFFFAOYSA-N 2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS ZZURXLMHTYYCST-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- LXWSTHQLWACMOU-UHFFFAOYSA-N OCCOC1=CC(=C(C(=C1)C)C1=C(C=2CC3=CC=CC=C3C2C=C1)C1=C(C=C(C=C1C)OCCO)C)C Chemical compound OCCOC1=CC(=C(C(=C1)C)C1=C(C=2CC3=CC=CC=C3C2C=C1)C1=C(C=C(C=C1C)OCCO)C)C LXWSTHQLWACMOU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007529 inorganic bases 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000013308 plastic optical fiber Substances 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
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic s-acid Chemical compound CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
で表される化合物とを反応させて、式(II)
で表されるフルオレン誘導体を製造する方法であって、フルオレノンと前記化合物(I)との反応により生成する酸性反応混合液を、アルカリ水溶液を添加した後、C 1−10 アルキルアルコールで構成された晶析溶媒を添加し、前記フルオレン誘導体と硫酸塩とを共沈させる。
攪拌機、冷却管及びビュレットを備えたガラス製反応器に純度99.5重量%のフルオレノン350g(1.94モル)とフェノキシエタノール1070g(7.78モル)を仕込み、β−メルカプトプロピオン酸2.3gを加えて撹拌した混合液に、反応温度を50℃に保持しつつ、98重量%の硫酸570gを60分かけて滴下した。滴下終了後、反応温度を50℃に保ち、さらに5時間撹拌することにより反応を完結させた。
実施例1と同じ方法で反応を完結させたのち、水酸化ナトリウムを添加することなく、反応混合物にメタノール2.5kgを投入し、10℃に冷却することによって、9,9−ビス(4−(2−ヒドロキシエトキシ)フェニル)フルオレンの結晶を析出させた。
Claims (9)
- 式(I)において、AがC2−6アルキレン基、RがC1−4アルキル基、nが1〜5の整数、mが0又は1である請求項1記載の方法。
- チオール類がメルカプトカルボン酸である請求請1記載の方法。
- アルカリがアルカリ金属の水酸化物である請求項1記載の方法。
- フルオレノンと硫酸との割合(重量比)が、フルオレノン/硫酸=1/0.3〜1/5である請求項1記載の方法。
- フルオレノンとチオール類との割合(重量比)が、フルオレノン/チオール類=1/0.001〜1/0.1である請求項1記載の方法。
- 共沈物を、水と、この水に対して分液可能な有機溶媒とで構成された抽剤を用いて、フルオレン誘導体を有機相に分配させる請求項1記載の方法。
- β−メルカプトプロピオン酸及び硫酸の共存下、フルオレノンと、フェノキシC2−4アルキルアルコール及びC1−4アルキルフェノキシC2−4アルキルアルコールから選択された少なくとも一種とを縮合反応させ、得られた酸性反応液に、加温下でアルカリ金属水酸化物水溶液を添加した後、C 1−6 アルキルアルコールで構成された晶析溶媒を添加し、目的化合物と硫酸塩との混合結晶を析出させ、混合結晶から精製した9,9−ビス(4−(ヒドロキシC2−4アルコキシ)フェニル)フルオレン及び9,9−ビス(4−(ヒドロキシC2−4アルコキシ)−3−C1−4アルキルフェニル)フルオレンから選択された少なくとも一種を抽出する方法。
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JP4671231B2 (ja) * | 2005-06-16 | 2011-04-13 | 田岡化学工業株式会社 | フルオレン誘導体の製造方法 |
JP5192641B2 (ja) * | 2005-10-07 | 2013-05-08 | 大阪瓦斯株式会社 | フルオレン骨格を有する化合物およびその製造方法 |
JP4671235B2 (ja) * | 2006-01-26 | 2011-04-13 | 田岡化学工業株式会社 | フルオレン誘導体の製造方法 |
US8093434B2 (en) | 2007-02-15 | 2012-01-10 | Taoka Chemical Company, Limited | Crystal polymorph of fluorene derivative and production method thereof |
JP5325627B2 (ja) * | 2008-03-27 | 2013-10-23 | 大阪瓦斯株式会社 | フルオレン骨格を有するアルコールの製造方法 |
JP5230015B2 (ja) * | 2009-07-27 | 2013-07-10 | 田岡化学工業株式会社 | フルオレン誘導体の製造法 |
EP2420485B1 (en) | 2009-04-13 | 2014-04-09 | Taoka Chemical Co., Ltd. | Method for producing fluorene derivative |
JP5230019B2 (ja) * | 2009-10-02 | 2013-07-10 | 田岡化学工業株式会社 | 9,9−ビス(4−(2−ヒドロキシエトキシ)フェニル)フルオレンの製造法 |
KR101726889B1 (ko) * | 2009-06-11 | 2017-04-13 | 타오카 케미컬 컴퍼니 리미티드 | 플루오렌 유도체의 비결정질 형태 및 그의 제조방법 |
JP5513825B2 (ja) * | 2009-09-28 | 2014-06-04 | 大阪ガスケミカル株式会社 | フルオレン骨格を有するアルコールの製造方法 |
JP5193353B2 (ja) * | 2011-11-30 | 2013-05-08 | 大阪瓦斯株式会社 | フルオレン骨格を有する化合物およびその製造方法 |
CN104144904A (zh) * | 2012-03-09 | 2014-11-12 | 本州化学工业株式会社 | 9,9-双(4-(2-羟基乙氧基)苯基)芴的制造方法、其结晶体及其结晶体的制造方法 |
JP5564091B2 (ja) * | 2012-11-06 | 2014-07-30 | 大阪瓦斯株式会社 | フルオレン骨格を有する化合物およびその製造方法 |
JP5883461B2 (ja) * | 2014-01-09 | 2016-03-15 | 大阪ガスケミカル株式会社 | フルオレン骨格を有するアルコール及び樹脂 |
JP6415519B2 (ja) * | 2016-11-17 | 2018-10-31 | 帝人株式会社 | フルオレン誘導体からなる熱可塑性樹脂 |
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