JP2017200901A - Crystal of alcohol having fluorene skeleton and method for producing the same - Google Patents
Crystal of alcohol having fluorene skeleton and method for producing the same Download PDFInfo
- Publication number
- JP2017200901A JP2017200901A JP2016132178A JP2016132178A JP2017200901A JP 2017200901 A JP2017200901 A JP 2017200901A JP 2016132178 A JP2016132178 A JP 2016132178A JP 2016132178 A JP2016132178 A JP 2016132178A JP 2017200901 A JP2017200901 A JP 2017200901A
- Authority
- JP
- Japan
- Prior art keywords
- alcohol
- fluorene skeleton
- skeleton represented
- crystal
- above formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 238
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 130
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000011549 crystallization solution Substances 0.000 claims abstract description 51
- 150000002576 ketones Chemical class 0.000 claims abstract description 34
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 31
- 150000003997 cyclic ketones Chemical class 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 31
- -1 phenol compound Chemical class 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 26
- 230000008025 crystallization Effects 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 210000003000 inclusion body Anatomy 0.000 claims description 18
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 6
- 206010037660 Pyrexia Diseases 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 150000002989 phenols Chemical class 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 9
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 235000011181 potassium carbonates Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000007514 bases Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003573 thiols Chemical class 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Chemical class OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KTSVVTQTKRGWGU-UHFFFAOYSA-N 1-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOCCCC KTSVVTQTKRGWGU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229940061334 2-phenylphenol Drugs 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical class CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HBTONAMIPDVQRI-UHFFFAOYSA-N OCCOc1ccc(C2(c3ccccc3-c3c2cccc3)c(cc2)cc(-c3ccccc3)c2OCCO)cc1-c1ccccc1 Chemical compound OCCOc1ccc(C2(c3ccccc3-c3c2cccc3)c(cc2)cc(-c3ccccc3)c2OCCO)cc1-c1ccccc1 HBTONAMIPDVQRI-UHFFFAOYSA-N 0.000 description 1
- FLMZHPQIDVOWEJ-UHFFFAOYSA-N Oc1ccc(C2(c3ccccc3-c3c2cccc3)c(cc2)cc(-c3ccccc3)c2O)cc1-c1ccccc1 Chemical compound Oc1ccc(C2(c3ccccc3-c3c2cccc3)c(cc2)cc(-c3ccccc3)c2O)cc1-c1ccccc1 FLMZHPQIDVOWEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、光学レンズや光学フィルムに代表される光学部材を構成する樹脂（光学樹脂）を形成するモノマーとして好適で、加工性、生産性に優れた新規なフルオレン骨格を有するアルコールの結晶およびその製造方法に関する。 The present invention is suitable as a monomer for forming a resin (optical resin) that constitutes an optical member typified by an optical lens or an optical film, and has a novel fluorene skeleton excellent in processability and productivity, and its crystal It relates to a manufacturing method.
フルオレン骨格を有するアルコールを原料モノマーとするポリカーボネート、ポリエステル、ポリアクリレート、ポリウレタン、エポキシなどの樹脂材料は、光学特性、耐熱性等に優れることから、近年、光学レンズや光学シートなどの新たな光学材料として注目されている。この中でも以下式（１） In recent years, resin materials such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy, which use alcohol having a fluorene skeleton as a raw material monomer, have excellent optical properties and heat resistance. It is attracting attention as. Among these, the following formula (1)
上記式（１）で表されるフルオレン骨格を有するアルコールの製造方法としては、塩基触媒存在下、以下式（２） As a method for producing an alcohol having a fluorene skeleton represented by the above formula (1), the following formula (2) is used in the presence of a base catalyst.
一方、特許文献２記載の方法を改善する方法として、酸触媒及びチオール類存在下、以下式（３）
On the other hand, as a method for improving the method described in
また、特許文献４には特許文献２及び３に記載された製造方法の改善を目的として、酸触媒及び９―フルオレノン類１００重量部に対して３重量部以上のチオール類存在下、上記式（３）で表されるアルコール類と９―フルオレノンを反応させ上記式（１）で表されるフルオレン骨格を有するアルコールを得る方法が提案されている。しかしながら、該方法で得られる上記式（１）で表されるフルオレン骨格を有するアルコールは特許文献３の方法で得られるものよりも着色は少ないものの、その着色改善は十分ではない。また、反応時に多量のチオール類を必要とすることから、上記式（１）で表されるフルオレン骨格を有するアルコールからチオール類を完全に除去することが困難であり、該アルコールを樹脂原料として使用する際、チオール類に由来する硫黄分が樹脂の更なる着色を引き起こすといった問題がある。
Patent Document 4 discloses the above formula (3) in the presence of 3 parts by weight or more of thiols with respect to 100 parts by weight of acid catalyst and 9-fluorenone for the purpose of improving the production methods described in
更に、本願発明者らが上記特許文献２〜４に記載される方法を追試したところ、特許文献３記載の方法では反応が進行しないか、あるいは反応が進行したとしても、上記式（１）で表されるフルオレン骨格を有するアルコールを含むオイル状物が得られるのみで結晶状の上記式（１）で表されるフルオレン骨格を有するアルコールは得られなかった。一方、特許文献２及び４の追試では、結晶状の上記式（１）で表されるフルオレン骨格を有するアルコールが得られるものの、反応や反応後の取り出し操作（晶析操作）で使用した溶媒（芳香族炭化水素類）が上記式（１）で表されるフルオレン骨格を有するアルコールに包接され、包接体となることが判明した。
Furthermore, when the inventors of the present application have additionally tried the methods described in
本発明の目的は、高純度かつ着色が少なく、更には包接体ではない、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶を提供することにある。 An object of the present invention is to provide a crystal of alcohol having a fluorene skeleton represented by the above formula (1), which is highly pure and less colored, and is not an inclusion body.
本発明者らは、前記の課題を解決すべく鋭意研究を重ねた結果、炭素数が４以上の鎖状ケトン類存在下、上記式（２）で表されるフルオレン骨格を有するフェノール化合物とエチレンカーボネートとを反応させ、上記式（１）で表されるフルオレン骨格を有するアルコールを含む反応液を得た後、前記反応液から、炭素数が４以上の鎖状ケトン類を含有し、かつ芳香族炭化水素類及び環状ケトン類の合計含有量が１０重量％未満である晶析溶液を調製し、該晶析溶液から特定温度範囲で結晶を析出させ、析出した結晶を分離することにより、高純度・低着色、かつ包接体でない、上記式（１）で表されるフルオレン骨格を有するアルコールが提供可能であることを見出した。具体的には以下の発明を含む。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a phenol compound having a fluorene skeleton represented by the above formula (2) and ethylene in the presence of a chain ketone having 4 or more carbon atoms. After reacting with carbonate to obtain a reaction liquid containing an alcohol having a fluorene skeleton represented by the above formula (1), the reaction liquid contains a chain ketone having 4 or more carbon atoms and an aromatic By preparing a crystallization solution having a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight, precipitating crystals from the crystallization solution in a specific temperature range, and separating the precipitated crystals. It has been found that an alcohol having a fluorene skeleton represented by the above formula (1), which is pure and low colored and is not an inclusion body, can be provided. Specifically, the following invention is included.
［１］
示差走査熱量分析による融解吸熱最大温度が１７３〜１７６℃である、以下式（１）
The melting endothermic maximum temperature by differential scanning calorimetry is 173 to 176 ° C., the following formula (1)
［２］
Ｃｕ−Ｋα線による粉末Ｘ線回折パターンにおいて、回折角２θ＝７．７±０．２°、１７．２±０．２°、１８．３±０．２°、１９．６±０．２°、２０．８±０．２°および２１．４±０．２°にピークを有する、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶。
[2]
In a powder X-ray diffraction pattern by Cu-Kα rays, diffraction angles 2θ = 7.7 ± 0.2 °, 17.2 ± 0.2 °, 18.3 ± 0.2 °, 19.6 ± 0.2 ° Crystals of alcohol having a fluorene skeleton represented by the above formula (1) having peaks at 20.8 ± 0.2 ° and 21.4 ± 0.2 °.
［３］
示差走査熱量分析による融解吸熱最大温度が１９０〜１９６℃である、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶。
[3]
The crystal | crystallization of the alcohol which has the fluorene frame | skeleton represented by the said Formula (1) whose melting | fever endothermic maximum temperature by differential scanning calorimetry is 190-196 degreeC.
［４］
Ｃｕ−Ｋα線による粉末Ｘ線回折パターンにおいて、回折角２θ＝１４．９±０．２°、１７．８±０．２°、１８．９±０．２°、１９．７±０．２°、２０．０±０．２°および２１．０±０．２°にピークを有する、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶。
[4]
In a powder X-ray diffraction pattern by Cu-Kα rays, diffraction angles 2θ = 14.9 ± 0.2 °, 17.8 ± 0.2 °, 18.9 ± 0.2 °, 19.7 ± 0.2 ° Crystals of alcohol having a fluorene skeleton represented by the above formula (1) having peaks at 20.0 ± 0.2 ° and 21.0 ± 0.2 °.
［５］
示差走査熱量分析による融解吸熱最大温度が１６７〜１７０℃である、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶。
[5]
A crystal of alcohol having a fluorene skeleton represented by the above formula (1), wherein the maximum endothermic temperature of melting by differential scanning calorimetry is 167 to 170 ° C.
［６］
Ｃｕ−Ｋα線による粉末Ｘ線回折パターンにおいて、回折角２θ＝９．８±０．２°、１４．９±０．２°、１７．６±０．２°、１８．８±０．２°、１９．４±０．２°、２０．０±０．２および２０．６±０．２°にピークを有する、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶。
[6]
In the powder X-ray diffraction pattern by Cu-Kα rays, diffraction angles 2θ = 9.8 ± 0.2 °, 14.9 ± 0.2 °, 17.6 ± 0.2 °, 18.8 ± 0.2 A crystal of alcohol having a fluorene skeleton represented by the above formula (1) having peaks at °, 19.4 ± 0.2 °, 20.0 ± 0.2, and 20.6 ± 0.2 °.
［７］
示差走査熱量分析により得られる吸熱ピークを１６７〜１７６℃の範囲に少なくとも一つ有する、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶。
[7]
A crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which has at least one endothermic peak obtained by differential scanning calorimetry in the range of 167 to 176 ° C.
［８］
包接体ではない、［１］〜［７］いずれかに記載の上記式（１）で表されるフルオレン骨格を有するアルコールの結晶。
[8]
A crystal of an alcohol having a fluorene skeleton represented by the above formula (1) according to any one of [1] to [7], which is not an inclusion body.
［９］
上記式（１）で表されるフルオレン骨格を有するアルコール１２ｇを、純度９９重量％以上のＮ，Ｎ−ジメチルホルムアミド３０ｍＬに溶解させた溶液の黄色度（ＹＩ値）が１０以下となる、［１］〜［８］いずれかに記載の、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶。
[9]
The yellowness (YI value) of a solution obtained by dissolving 12 g of alcohol having a fluorene skeleton represented by the above formula (1) in 30 mL of N, N-dimethylformamide having a purity of 99% by weight or more is 10 or less, [1 ]-[8] The crystal | crystallization of alcohol which has a fluorene skeleton represented by the said Formula (1) in any one.
［１０］
芳香族炭化水素類の含量が１重量％以下である、［１］〜［９］いずれかに記載の、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶。
[10]
The crystal | crystallization of the alcohol which has a fluorene skeleton represented by the said Formula (1) in any one of [1]-[9] whose content of aromatic hydrocarbons is 1 weight% or less.
［１１］
以下（ａ）〜（ｃ）の工程をこの順で含む、［１］又は［２］の上記式（１）で表されるフルオレン骨格を有するアルコールの製造方法。
（ａ）
炭素数が４以上の鎖状ケトン類存在下、下記式（２）
（ｂ）
前記反応液から、炭素数が４以上の鎖状ケトン類を含有し、かつ芳香族炭化水素類及び環状ケトン類の合計含有量が１０重量％未満である晶析溶液を調製する工程。
（ｃ）
前記晶析溶液から７５〜８５℃で結晶を析出させ、析出した結晶を分離する工程。
[11]
The manufacturing method of the alcohol which has the fluorene skeleton represented by the said Formula (1) of [1] or [2] including the process of (a)-(c) in this order below.
(A)
In the presence of a chain ketone having 4 or more carbon atoms, the following formula (2)
(B)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(C)
A step of depositing crystals at 75 to 85 ° C. from the crystallization solution and separating the precipitated crystals.
［１２］
以下（ｄ）〜（ｆ）の工程をこの順で含む、［３］又は［４］記載の上記式（１）で表されるフルオレン骨格を有するアルコールの製造方法。
（ｄ）
炭素数が４以上の鎖状ケトン類存在下、上記式（２）で表されるフルオレン骨格を有するフェノール化合物とエチレンカーボネートとを反応させ、上記式（１）で表されるフルオレン骨格を有するアルコールを含む反応液を得る工程。
（ｅ）
前記反応液から、炭素数が４以上の鎖状ケトン類を含有し、かつ芳香族炭化水素類及び環状ケトン類の合計含有量が１０重量％未満である晶析溶液を調製する工程。
（ｆ）
前記晶析溶液から９０〜１００℃で結晶を析出させ、析出した結晶を分離する工程。
[12]
A method for producing an alcohol having a fluorene skeleton represented by the above formula (1) according to [3] or [4], comprising the following steps (d) to (f) in this order.
(D)
An alcohol having a fluorene skeleton represented by the above formula (1) by reacting a phenol compound having a fluorene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a chain ketone having 4 or more carbon atoms. The process of obtaining the reaction liquid containing this.
(E)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(F)
A step of depositing crystals from the crystallization solution at 90 to 100 ° C. and separating the precipitated crystals.
［１３］
以下（ｇ）〜（ｉ）の工程をこの順で含む、［５］又は［６］記載の上記式（１）で表されるフルオレン骨格を有するアルコールの製造方法。
（ｇ）
炭素数が４以上の鎖状ケトン類存在下、上記式（２）で表されるフルオレン骨格を有するフェノール化合物とエチレンカーボネートとを反応させ、上記式（１）で表されるフルオレン骨格を有するアルコールを含む反応液を得る工程。
（ｈ）
前記反応液から、炭素数が４以上の鎖状ケトン類を含有し、かつ芳香族炭化水素類及び環状ケトン類の合計含有量が１０重量％未満である晶析溶液を調製する工程。
（ｉ）
前記晶析溶液から７０℃以下で結晶を析出させ、析出した結晶を分離する工程。
[13]
A method for producing an alcohol having a fluorene skeleton represented by the above formula (1) according to [5] or [6], comprising the following steps (g) to (i) in this order.
(G)
An alcohol having a fluorene skeleton represented by the above formula (1) by reacting a phenol compound having a fluorene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a chain ketone having 4 or more carbon atoms. The process of obtaining the reaction liquid containing this.
(H)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(I)
A step of depositing crystals from the crystallization solution at 70 ° C. or lower and separating the precipitated crystals.
本発明によれば、高純度かつ着色が少なく、更には、包接体ではない、上記式（１）で表されるフルオレン骨格を有するアルコールの結晶が提供可能となる。 According to the present invention, it is possible to provide a crystal of alcohol having a fluorene skeleton represented by the above formula (1), which is highly pure and less colored and is not an inclusion body.
特に上記式（１）で表されるフルオレン骨格を有するアルコールの結晶が包接体である場合、該包接体にアクリル酸等を反応させ他の化合物とする際、包接体が包接している化合物（以下、ゲスト分子と称することもある）が反応を阻害し、反応によっては使用できないといった問題があり、また、そのまま溶融等し樹脂原料として使用する際も、溶融中に発生するゲスト分子に由来する蒸気を系外へと除去する必要があったり、ゲスト分子の影響で、得られる樹脂の品質が一定とならないといった問題を引き起こすことがある。更には、引火点の低いゲスト分子（前記引例の場合、芳香族炭化水素類）を包接し得ることから、上記式（１）で表されるフルオレン骨格を有するアルコールを保管したり輸送したりする際、火災が起こりやすくなるといった防災上の懸念も存在する。 In particular, when the alcohol crystal having the fluorene skeleton represented by the above formula (1) is an inclusion body, when the inclusion body is reacted with acrylic acid or the like to form another compound, the inclusion body is included. Compound (hereinafter sometimes referred to as guest molecule) inhibits the reaction and cannot be used depending on the reaction, and also when used as a resin raw material by melting as it is, guest molecules generated during melting It may be necessary to remove the vapor originating from the system, and the quality of the resulting resin may not be constant due to the influence of guest molecules. Furthermore, since the guest molecule having a low flash point (in the case of the above-mentioned reference, aromatic hydrocarbons) can be included, the alcohol having the fluorene skeleton represented by the above formula (1) is stored or transported. There is also a concern for disaster prevention that fires are likely to occur.
しかしながら、前述の通り、公知の方法に基づき上記式（１）で表されるフルオレン骨格を有するアルコールを結晶として得ようとした場合、ゲスト分子を包接した包接体として得られ、包接体でない上記式（１）で表されるフルオレン骨格を有するアルコールの結晶を得る方法は知られていなかった。一方で、包接体に含まれるゲスト分子は、ゲスト分子の沸点以上の温度で結晶を乾燥させるといった、一般的に実施される方法により除去することは困難であり、一旦結晶を融点以上に加熱し溶融させた後にゲスト分子を除去する等、工業的実施が困難、あるいは非常にコストのかかる方法に依らなければならないので、包接体でない上記式（１）で表されるフルオレン骨格を有するアルコールの結晶及びその製造方法を見出した本発明は、特に工業的規模で上記式（１）で表されるフルオレン骨格を有するアルコールの結晶を製造、使用するに当たり、非常に意義があるものであると言える。 However, as described above, when an alcohol having a fluorene skeleton represented by the above formula (1) is obtained as a crystal based on a known method, the clathrate is obtained as an clathrate including a guest molecule. A method for obtaining an alcohol crystal having a fluorene skeleton represented by the above formula (1) has not been known. On the other hand, it is difficult to remove the guest molecules contained in the clathrate by a generally practiced method such as drying the crystals at a temperature higher than the boiling point of the guest molecules. The alcohol having a fluorene skeleton represented by the above formula (1), which is not an inclusion body, is difficult to implement industrially, such as removing guest molecules after being melted, or has to depend on a very expensive method. The present invention, which has found a crystal of the above and its production method, is extremely significant in producing and using a crystal of an alcohol having a fluorene skeleton represented by the above formula (1) on an industrial scale. I can say that.
＜上記式（１）で表されるフルオレン骨格を有するアルコールの結晶＞
本発明の上記式（１）で表されるフルオレン骨格を有するアルコールの結晶（以下本発明の結晶と称することもある）は、示差走査熱量分析（ＤＳＣ）による融解吸熱最大温度、および粉末Ｘ線回折パターンにおける回折角２θの少なくとも１つの特徴を有する。
<Crystal of alcohol having a fluorene skeleton represented by the above formula (1)>
The crystal of alcohol having a fluorene skeleton represented by the above formula (1) of the present invention (hereinafter also referred to as the crystal of the present invention) is a melting endothermic maximum temperature by differential scanning calorimetry (DSC), and a powder X-ray. It has at least one characteristic of a diffraction angle 2θ in the diffraction pattern.
本発明の結晶は、示差走査熱量分析による融解吸熱最大温度によって３種類の結晶に区別され得る。具体的には、該融解吸熱最大温度が１７３〜１７６℃であるもの（以下、結晶Ｂと称することがある。）、１９０〜１９６℃であるもの（以下、結晶Ｃと称することがある。）及び、１６７〜１７０℃であるもの（以下、結晶Ｄと称することがある。）である。なお、公知の、上記式（１）で表されるフルオレン骨格を有するアルコールの包接体（ゲスト分子として芳香族炭化水素類を包接した包接体。以下、結晶Ａと称することもある）の示差走査熱量分析による融解吸熱最大温度は１２５〜１４７℃である。 The crystals of the present invention can be distinguished into three types of crystals according to the melting endothermic maximum temperature by differential scanning calorimetry. Specifically, the melting endothermic maximum temperature is 173 to 176 ° C. (hereinafter sometimes referred to as crystal B), and 190 to 196 ° C. (hereinafter sometimes referred to as crystal C). And it is what is 167-170 degreeC (henceforth the crystal | crystallization D). In addition, a known clathrate of alcohol having a fluorene skeleton represented by the above formula (1) (a clathrate in which an aromatic hydrocarbon is clathrated as a guest molecule. Hereinafter also referred to as crystal A) The maximum endothermic temperature of melting by differential scanning calorimetry is 125 to 147 ° C.
また、結晶Ｂ及びＤの混合結晶が得られる場合があり、該混合結晶は示差走査熱量分析により得られる吸熱ピークを１６７〜１７６℃の範囲に少なくとも一つ有する。なお、結晶Ｂ及びＤの混合結晶であっても高純度かつ着色が少なく、更には包接体でないといった、下記する本発明の結晶の特徴と同じ特徴を有する結晶となる。 Moreover, a mixed crystal of crystals B and D may be obtained, and the mixed crystal has at least one endothermic peak obtained by differential scanning calorimetry in a range of 167 to 176 ° C. Note that even a mixed crystal of crystals B and D is a crystal having the same characteristics as those of the crystal of the present invention described below, such as high purity and low coloration, and further not being an inclusion body.
本発明における示差走査熱量分析による融解吸熱最大温度とは、後述する条件にて示差走査熱量分析を実施した際、最大吸熱ピークが観測される温度のことをいう。なお、本発明の結晶が示す融解吸熱最大温度は、いくつかの要因により、上下に変動することがある。このような偏差に関与する要因としては、分析を実施する際の試料の加熱速度、試料量、使用される校正標準、機器の校正方法、分析環境の相対湿度および試料の化学的純度がある。与えられた試料について観察される融解吸熱最大温度は、装置毎に異なることがあるが、一般に、装置が適正に校正されていれば、本願に定義される範囲内となる。 The maximum melting endothermic temperature by differential scanning calorimetry in the present invention refers to the temperature at which the maximum endothermic peak is observed when differential scanning calorimetry is performed under the conditions described later. Note that the melting endothermic maximum temperature exhibited by the crystal of the present invention may fluctuate up and down due to several factors. Factors involved in such deviation include the heating rate of the sample when performing the analysis, the sample amount, the calibration standard used, the calibration method of the instrument, the relative humidity of the analysis environment, and the chemical purity of the sample. The maximum melting endothermic temperature observed for a given sample may vary from device to device, but generally will be within the range defined in this application if the device is properly calibrated.
本発明の結晶の内、結晶Ｂは、Ｃｕ−Ｋα線による粉末Ｘ線回折パターンにおいて、回折角２θ＝７．７±０．２°、１７．２±０．２°、１８．３±０．２°、１９．６±０．２°、２０．８±０．２°および２１．４±０．２°に特徴的なピークを有する。結晶Ｃは、回折角２θ＝１４．９±０．２°、１７．８±０．２°、１８．９±０．２°、１９．７±０．２°、２０．０±０．２°および２１．０±０．２°に特徴的なピークを有する。結晶Ｄは、回折角２θ＝９．８±０．２°、１４．９±０．２°、１７．６±０．２°、１８．８±０．２°、１９．４±０．２°、２０．０±０．２および２０．６±０．２°に特徴的なピークを有する。一方、公知の結晶Ａは、回折角２θ＝７．６±０．２°、１５．６±０．２°、１６．４±０．２°、１８．７±０．２°、１９．０±０．２°、２０．５±０．２°および２３．６±０．２°に特徴的なピークを有する。 Among the crystals of the present invention, the crystal B has a diffraction angle 2θ = 7.7 ± 0.2 °, 17.2 ± 0.2 °, 18.3 ± 0 in the powder X-ray diffraction pattern by Cu—Kα ray. With characteristic peaks at .2 °, 19.6 ± 0.2 °, 20.8 ± 0.2 ° and 21.4 ± 0.2 °. Crystal C has diffraction angles 2θ = 14.9 ± 0.2 °, 17.8 ± 0.2 °, 18.9 ± 0.2 °, 19.7 ± 0.2 °, 20.0 ± 0. It has characteristic peaks at 2 ° and 21.0 ± 0.2 °. Crystal D has diffraction angles 2θ = 9.8 ± 0.2 °, 14.9 ± 0.2 °, 17.6 ± 0.2 °, 18.8 ± 0.2 °, 19.4 ± 0.2. It has characteristic peaks at 2 °, 20.0 ± 0.2 and 20.6 ± 0.2 °. On the other hand, the known crystal A has diffraction angles 2θ = 7.6 ± 0.2 °, 15.6 ± 0.2 °, 16.4 ± 0.2 °, 18.7 ± 0.2 °, 19. It has characteristic peaks at 0 ± 0.2 °, 20.5 ± 0.2 ° and 23.6 ± 0.2 °.
本発明の結晶の純度は、後述する方法により決定されるＨＰＬＣ純度が通常９０％以上、好ましくは９５％以上、より好ましくは９８％以上である。また、結晶Ｂの嵩密度は０．２〜０．５ｇ／ｃｍ３、結晶Ｃの嵩密度は０．６〜０．８ｇ／ｃｍ３、結晶Ｄの嵩密度は０．４〜０．６ｇ／ｃｍ３である。一方、公知の結晶Ａの嵩密度は０．２〜０．４ｇ／ｃｍ３である。このように、本発明の結晶の中でも結晶Ｃは、公知の結晶Ａに対し１．５〜４倍もの嵩密度の改善がみられることから、本発明の結晶の中でも結晶Ｃは、該結晶の製造時は勿論、輸送・保管・使用時においても大幅な容積効率の改善が可能となる。嵩密度は例えば、パウダーテスターと呼ばれる粉体特性評価装置を用いて測定したり、メスシリンダー中に本発明の結晶の結晶を入れ、所定体積を入れた際の重量から算出することで測定することができる。 As for the purity of the crystal of the present invention, the HPLC purity determined by the method described later is usually 90% or more, preferably 95% or more, more preferably 98% or more. The bulk density of the crystal B is 0.2-0.5 g / cm 3, the bulk density of the crystal C is 0.6~0.8g / cm 3, the bulk density of the crystal D is 0.4 to 0.6 g / cm 3 . On the other hand, the bulk density of the known crystal A is 0.2 to 0.4 g / cm 3 . Thus, among the crystals of the present invention, the crystal C has an improvement in bulk density of 1.5 to 4 times that of the known crystal A. Therefore, among the crystals of the present invention, the crystal C is Volumetric efficiency can be greatly improved not only during production but also during transportation, storage, and use. The bulk density is measured, for example, by using a powder characteristic evaluation device called a powder tester, or by measuring the weight of the crystal of the present invention in a graduated cylinder and putting a predetermined volume into it. Can do.
また、本発明の結晶は後述する方法で測定するＹＩ値が通常１０以下、好ましくは７以下となる。一方、公知の結晶Ａは通常３０以上となる。そのため、本発明の結晶は、特に光学用途等、着色が問題となり得る分野で好適に用いることができる。 Further, the crystal of the present invention has a YI value measured by the method described later of usually 10 or less, preferably 7 or less. On the other hand, the known crystal A is usually 30 or more. Therefore, the crystal of the present invention can be suitably used in fields where coloring can be a problem, particularly for optical applications.
更に本発明の結晶は包接体でない（ゲスト分子を包接していない）という特徴を有することができる。従って、公知の、結晶Ａ中の芳香族炭化水素類の含量は３〜６重量％であるのに対し、本発明の結晶に含まれる芳香族炭化水素類の含量は通常１重量％以下、好ましくは０．５重量％以下、更に好ましくは０．１重量％以下とすることができる。また、他の有機化合物を包接していないので、１０１．３ｋＰａにおける沸点が１５０℃以下の有機溶媒の含有量を通常１重量％以下、好ましくは０．５重量％以下、更に好ましくは０．１重量％以下とすることも可能である。そのため、上記式（１）で表されるフルオレン骨格を有するアルコールを保管したり輸送したりする際、火災が起こりやすくなるといった防災上の懸念を低減させることが可能であることから、ポリカーボネート、ポリエステル、ポリアクリレート、ポリウレタン、エポキシなどの樹脂材料として好適に用いられることは勿論のこと、包接されているゲスト分子が問題となる分野、例えば医農薬用の原料（中間体）としても好適に用いることができる。 Furthermore, the crystal of the present invention can be characterized by not being an inclusion body (not including a guest molecule). Therefore, the known aromatic hydrocarbon content in the crystal A is 3 to 6% by weight, whereas the aromatic hydrocarbon content in the crystal of the present invention is usually 1% by weight or less, preferably Is 0.5% by weight or less, more preferably 0.1% by weight or less. In addition, since no other organic compound is included, the content of the organic solvent having a boiling point at 101.3 kPa of 150 ° C. or less is usually 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1%. It is also possible to make it into the weight% or less. Therefore, when storing or transporting the alcohol having the fluorene skeleton represented by the above formula (1), it is possible to reduce a disaster risk such that a fire easily occurs. Of course, it is suitably used as a resin material such as polyacrylate, polyurethane, epoxy, etc., but also as a raw material (intermediate) for medical and agricultural chemicals, for example, in which the guest molecules included are problematic. be able to.
包接体であるか否かは、例えば、ＴＧ−ＤＴＡ（示差熱熱重量同時測定）分析、Ｘ線解析、ＮＭＲ分析といった方法の他、得られた結晶を、ゲスト分子の沸点以上となる条件で重量変化がない程度に十分に乾燥させた後、得られた結晶を溶媒に溶解させ、ガスクロマトグラフィーや高速液体クロマトグラフィーを用いて分析し、ゲスト分子に相当するピークがあるか否かで判断することができる。また、前記ＴＧ−ＤＴＡ分析を用いる方法では、測定サンプルを一定の速度で昇温した際の重量変化と、それに伴う吸熱・発熱挙動を測定でき、重量変化と吸熱（又は発熱）とが同時に観測された時点で、ゲスト分子が放出されたことを判断することもできる。 Whether or not it is an inclusion body is determined by, for example, TG-DTA (simultaneous differential thermothermal gravimetric measurement) analysis, X-ray analysis, NMR analysis, etc. After the sample is sufficiently dried so that there is no change in weight, the obtained crystals are dissolved in a solvent and analyzed using gas chromatography or high-performance liquid chromatography to determine whether there is a peak corresponding to the guest molecule. Judgment can be made. In the method using TG-DTA analysis, the change in weight when the sample is heated at a constant rate and the associated endothermic / exothermic behavior can be measured, and the change in weight and endothermic (or exothermic) are observed simultaneously. At this point, it can also be determined that the guest molecule has been released.
＜上記式（１）で表されるフルオレン骨格を有するアルコールの製造方法＞
本発明の結晶は、炭素数が４以上の鎖状ケトン類存在下、上記式（２）で表されるフルオレン骨格を有するフェノール化合物とエチレンカーボネートとを反応させ、上記式（１）で表されるフルオレン骨格を有するアルコールを含む反応液を得る工程（以下、反応工程と称することもある）、前記反応液から、炭素数が４以上の鎖状ケトン類を含有し、かつ芳香族炭化水素類及び環状ケトン類の合計含有量が１０重量％未満である晶析溶液を調製する工程（以下、晶析溶液調製工程と称することもある）及び前記晶析溶液から特定温度範囲で結晶を析出させ、析出した結晶を分離する工程（以下、晶析工程と称することもある）を経ることによって得られる。以下、各工程について詳述する。
<Method for producing alcohol having fluorene skeleton represented by formula (1)>
The crystal of the present invention is represented by the above formula (1) by reacting a phenol compound having a fluorene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a chain ketone having 4 or more carbon atoms. A step of obtaining a reaction solution containing an alcohol having a fluorene skeleton (hereinafter also referred to as a reaction step), a chain ketone having 4 or more carbon atoms from the reaction solution, and an aromatic hydrocarbon And a step of preparing a crystallization solution having a total content of cyclic ketones of less than 10% by weight (hereinafter sometimes referred to as a crystallization solution preparation step), and crystals are precipitated from the crystallization solution in a specific temperature range. It is obtained through a step of separating the precipitated crystals (hereinafter sometimes referred to as a crystallization step). Hereinafter, each process is explained in full detail.
＜反応工程＞
反応工程で用いられる、上記式（２）で表されるフルオレン骨格を有するフェノール化合物は市販品を用いても良く、また、酸触媒存在下、フルオレノンと２―フェニルフェノールとを反応させて製造することもできる。
<Reaction process>
The phenol compound having a fluorene skeleton represented by the above formula (2) used in the reaction step may be a commercially available product, or is produced by reacting fluorenone with 2-phenylphenol in the presence of an acid catalyst. You can also
反応工程で用いられる炭素数が４以上の鎖状ケトン類として例えば、メチルエチルケトン、メチルイソブチルケトン、メチルイソアミルケトン、２−ヘプタノン、２−オクタノン、ジイソブチルケトン等が挙げられる。炭素数が４以上の鎖状ケトン類を用いることによって、十分な反応速度が得られ、上記式（１）で表されるフルオレン骨格を有するアルコールが工業的有利に得られる。なお、炭素数４未満のケトン類を使用した場合、反応が進行しないか、進行したとしても反応速度が非常に遅くなり、また、環状ケトン類を使用した場合、反応は進行するものの、環状ケトン類が包接され包接体となる為、包接体でない上記式（１）で表されるフルオレン骨格を有するアルコールを得ることが困難となる。 Examples of chain ketones having 4 or more carbon atoms used in the reaction step include methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, and diisobutyl ketone. By using a chain ketone having 4 or more carbon atoms, a sufficient reaction rate can be obtained, and an alcohol having a fluorene skeleton represented by the above formula (1) can be obtained industrially advantageously. When ketones having less than 4 carbon atoms are used, the reaction does not proceed, or even if they proceed, the reaction rate is very slow. When cyclic ketones are used, the reaction proceeds, but cyclic ketones. Since the clathrate is clathrated and becomes a clathrate, it is difficult to obtain an alcohol having a fluorene skeleton represented by the above formula (1) that is not a clathrate.
炭素数が４以上の鎖状ケトン類の使用量は、上記式（２）で表されるフルオレン骨格を有するフェノール化合物１重量倍に対し、通常０．１〜５重量倍、好ましくは０．５〜３重量倍である。これら炭素数が４以上の鎖状ケトン類は１種、あるいは必要に応じ２種以上混合して使用しても良い。 The amount of chain ketones having 4 or more carbon atoms is usually 0.1 to 5 times by weight, preferably 0.5 to 1 time by weight of the phenol compound having a fluorene skeleton represented by the above formula (2). ~ 3 times by weight. These chain ketones having 4 or more carbon atoms may be used alone or as a mixture of two or more if necessary.
反応工程を実施する際、炭素数が４以上の鎖状ケトン類以外に芳香族炭化水素類、環状ケトン類以外の他の有機溶媒を併用しても良い。芳香族炭化水素類および環状ケトン類を併用した場合、晶析工程実施前に芳香族炭化水素類および環状ケトン類を除去する必要があるが、上記式（１）で表されるフルオレン骨格を有するアルコールに芳香族炭化水素類又は環状ケトン類が包接されやすいため、その除去が困難であり、その結果、得られる結晶は芳香族炭化水素類又は環状ケトン類を包接した結晶となりやすく、本発明の結晶を得ることが困難となる。 When carrying out the reaction step, in addition to chain ketones having 4 or more carbon atoms, other organic solvents other than aromatic hydrocarbons and cyclic ketones may be used in combination. When aromatic hydrocarbons and cyclic ketones are used in combination, it is necessary to remove aromatic hydrocarbons and cyclic ketones before carrying out the crystallization step, but they have a fluorene skeleton represented by the above formula (1). Since aromatic hydrocarbons or cyclic ketones are likely to be included in alcohol, it is difficult to remove them. As a result, the resulting crystals tend to be crystals including aromatic hydrocarbons or cyclic ketones. It becomes difficult to obtain the crystals of the invention.
本発明で併用可能な芳香族炭化水類及び環状ケトン類以外の溶媒としては、上記式（２）で表されるフルオレン骨格を有するフェノール化合物及びエチレンカーボネートに対して不活性なものであれば良く、このような有機溶媒としては脂肪族炭化水素類、ハロゲン化脂肪族炭化水素類、エーテル類、グリコールジエーテル類、エステル類、脂肪族ニトリル類、アミド類、スルホキシド類等が例示される。より具体的には、脂肪族炭化水素としてペンタン、ヘキサン、ヘプタン等が、ハロゲン化脂肪族炭化水素類としてジクロロメタン、１，２−ジクロロエタン等が、エーテル類としてジ−イソ−プロピルエーテル、メチル−ターシャリー−ブチルエーテル、シクロペンチルメチルエーテル、ジフェニルエーテル等が、グリコールジエーテル類としてジグライム、トリグライム、トリエチレングリコールジブチルエーテル等が、エステル類として酢酸エチル、酢酸ブチル等が、脂肪族ニトリル類としてはアセトニトリル等が、アミド類としてジメチルホルムアミド、ジメチルアセトアミド等が、スルホキシド類としてジメチルスルホキシド等が例示される。これら併用可能な有機溶媒の中でも入手性や取扱性、及び反応性の良さから、１０１．３ｋＰａにおける沸点が８０℃以上のエーテル類又はグリコールジエーテル類が好適に用いられる。これら有機溶媒は１種類、あるいは必要に応じ２種類以上混合して使用しても良い。これら有機溶媒の使用量は、上記式（２）で表されるフルオレン骨格を有するフェノール化合物１重量倍に対し、通常０．１〜５重量倍、好ましくは０．５〜３重量倍である。 Solvents other than aromatic hydrocarbons and cyclic ketones that can be used in combination with the present invention may be those that are inactive with respect to the phenol compound having a fluorene skeleton represented by the above formula (2) and ethylene carbonate. Examples of such organic solvents include aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, glycol diethers, esters, aliphatic nitriles, amides, sulfoxides, and the like. More specifically, pentane, hexane, heptane, etc. are used as aliphatic hydrocarbons, dichloromethane, 1,2-dichloroethane, etc. are used as halogenated aliphatic hydrocarbons, and di-iso-propyl ether, methyl-tertha are used as ethers. Lee-butyl ether, cyclopentyl methyl ether, diphenyl ether, etc., glycol diethers as diglyme, triglyme, triethylene glycol dibutyl ether, etc., esters as ethyl acetate, butyl acetate, etc., aliphatic nitriles as acetonitrile, etc., Examples of amides include dimethylformamide and dimethylacetamide, and examples of sulfoxides include dimethyl sulfoxide. Among these organic solvents that can be used in combination, ethers or glycol diethers having a boiling point of 80 ° C. or higher at 101.3 kPa are preferably used because of their availability, handleability, and good reactivity. These organic solvents may be used alone or as a mixture of two or more if necessary. The amount of these organic solvents used is usually 0.1 to 5 times by weight, preferably 0.5 to 3 times by weight, with respect to 1 time by weight of the phenol compound having a fluorene skeleton represented by the above formula (2).
本発明で使用するエチレンカーボネートは、上記式（２）で表されるフルオレン骨格を有するフェノール化合物１モルに対し通常、２〜１０モル、好ましくは２〜４モル使用する。２モル以上使用することにより十分な反応速度を得ることができ、使用量を１０モル以下とすることにより、より経済的に上記式（２）で表されるフルオレン骨格を有するアルコールを製造することができる。 The ethylene carbonate used in the present invention is usually used in an amount of 2 to 10 mol, preferably 2 to 4 mol, per 1 mol of the phenol compound having a fluorene skeleton represented by the above formula (2). A sufficient reaction rate can be obtained by using 2 mol or more, and an alcohol having a fluorene skeleton represented by the above formula (2) can be produced more economically by setting the amount used to 10 mol or less. Can do.
上記式（２）で表されるフルオレン骨格を有するフェノール化合物とエチレンカーボネートとを反応させる際、必要に応じ塩基性化合物存在下にて反応を行う。反応工程で用いられる塩基性化合物として例えば、炭酸塩類、炭酸水素塩類、水酸化物類、有機塩基類等が例示される。より具体的には炭酸塩類として炭酸カリウム、炭酸ナトリウム、炭酸リチウム、炭酸セシウム等が、炭酸水素塩類として炭酸水素カリウム、炭酸水素ナトリウム、炭酸水素リチウム、炭酸水素セシウム等が、水酸化物類として水酸化ナトリウム、水酸化カリウム、水酸化リチウム等が、有機塩基類としてトリエチルアミン、ジメチルアミノピリジン、トリフェニルホスフィン、テトラメチルアンモニウムブロミド、テトラメチルアンモニウムクロリド等が例示される。これら塩基性化合物の中でも取扱性の良さの点から炭酸カリウム、炭酸ナトリウム、トリフェニルホスフィンが好適に使用される。これら塩基性化合物を使用する際の使用量は、上記式（２）で表されるフルオレン骨格を有するフェノール化合物１モルに対し、通常０．０１〜１．０モル、好ましくは０．０３〜０．２モルである。 When the phenol compound having a fluorene skeleton represented by the above formula (2) is reacted with ethylene carbonate, the reaction is performed in the presence of a basic compound as necessary. Examples of basic compounds used in the reaction step include carbonates, bicarbonates, hydroxides, organic bases and the like. More specifically, the carbonates include potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, etc., the hydrogen carbonates include potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, cesium bicarbonate, etc., and the hydroxides include water. Examples of the organic bases include sodium oxide, potassium hydroxide, lithium hydroxide and the like, and examples of the organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride and the like. Among these basic compounds, potassium carbonate, sodium carbonate, and triphenylphosphine are preferably used from the viewpoint of good handleability. The usage-amount at the time of using these basic compounds is 0.01-1.0 mol normally with respect to 1 mol of phenolic compounds which have the fluorene skeleton represented by the said Formula (2), Preferably it is 0.03-0. .2 moles.
上記式（２）で表されるフルオレン骨格を有するフェノール化合物とエチレンカーボネートとの反応は、上記式（２）で表されるフルオレン骨格を有するフェノール化合物、エチレンカーボネート、炭素数が４以上の鎖状ケトン類及び必要に応じ塩基性化合物、併用可能な有機溶媒を反応容器に添加し、通常３０〜１５０℃、好ましくは１００〜１３０℃で実施される。 The reaction between the phenol compound having a fluorene skeleton represented by the above formula (2) and ethylene carbonate is a phenol compound having a fluorene skeleton represented by the above formula (2), ethylene carbonate, a chain having 4 or more carbon atoms. Ketones and, if necessary, a basic compound and an organic solvent that can be used in combination are added to the reaction vessel, and the reaction is usually carried out at 30 to 150 ° C., preferably 100 to 130 ° C.
こうして得られた上記式（１）で表されるフルオレン骨格を有するアルコールを含む反応液はそのまま濃縮・乾固した後、晶析溶液調製工程に用いても良く、水洗・吸着処理等の後処理や、晶析・カラム精製等の定法にて精製した後、晶析溶液調製工程に用いても良いが、下記する水洗工程を実施した後、晶析溶液調製工程にて用いることにより、上記式（１）で表されるフルオレン骨格を有するアルコールの純度をより向上させることが可能であることから好ましい。以下、水洗工程について詳述する。 The reaction solution containing the alcohol having the fluorene skeleton represented by the above formula (1) thus obtained may be concentrated and dried as it is, and then used in the crystallization solution preparation step, and post-treatment such as washing and adsorption treatment. Alternatively, after purification by a conventional method such as crystallization and column purification, it may be used for the crystallization solution preparation step, but after carrying out the water washing step described below, it is used in the crystallization solution preparation step. It is preferable because the purity of the alcohol having the fluorene skeleton represented by (1) can be further improved. Hereinafter, the water washing process will be described in detail.
水洗工程は、得られた反応液に、反応で使用した上記式（２）で表されるフルオレン骨格を有するフェノール化合物１重量倍に対し０．１〜１０重量倍、好ましくは０．５〜５重量倍の水を添加し、６０〜９５℃、好ましくは７０〜９０℃で撹拌し、その後静置、水層を分離することによって実施される。水を０．１重量倍以上使用することにより水洗工程の効果がより発現し、使用量を１０重量倍以下とすることにより、容積効率を改善することが可能となる。また、水洗温度は６０℃以上とすることにより、静置時の分液速度がより速くなり、９５℃以下とすることにより、水洗時の上記式（１）で表されるフルオレン骨格を有するアルコールの分解を抑制することが可能となる。 In the water washing step, the obtained reaction solution is used in an amount of 0.1 to 10 times, preferably 0.5 to 5 times the weight of the phenol compound having a fluorene skeleton represented by the above formula (2) used in the reaction. It is carried out by adding water by weight and stirring at 60 to 95 ° C., preferably 70 to 90 ° C., followed by standing and separating the aqueous layer. By using water 0.1 times or more, the effect of the water washing step is more manifested, and by making the amount used 10 times or less, the volumetric efficiency can be improved. Further, by setting the washing temperature to 60 ° C. or higher, the liquid separation speed at the time of standing is faster, and by setting it to 95 ° C. or lower, the alcohol having the fluorene skeleton represented by the above formula (1) at the time of washing. Can be prevented.
水洗工程は必要に応じて複数回実施しても良い。また、水洗工程実施時、水と併せて塩基や酸を添加し、副生物等を分解・水層へと除去しても良い。 You may implement a water-washing process in multiple times as needed. Further, at the time of carrying out the water washing step, a base and an acid may be added together with water, and by-products and the like may be decomposed and removed into the aqueous layer.
＜晶析溶液調製工程＞
前述の方法で製造された反応液に芳香族炭化水素類及び／又は環状ケトン類が含まれている場合、蒸留・濃縮等の操作によって芳香族炭化水素類及び／又は環状ケトン類を除去し、晶析溶液中に含まれる芳香族炭化水素類及び環状ケトン類の合計含有量を１０重量％未満、好ましくは５重量％以下とする必要がある。晶析溶液中に芳香族炭化水素類及び／又は環状ケトン類が１０重量％以上含まれている場合、上記式（１）で表されるフルオレン骨格を有するアルコールが芳香族炭化水素類及び／又は環状ケトン類を包接してしまい、本発明の結晶が得られない。また、５重量％以下であっても、得られる結晶の一部が包接体となる場合がある為、結晶Ａを確実に含まないようにするためには、晶析溶液中の芳香族炭化水素類及び環状ケトン類の合計含有量を１重量％未満とすることが好ましい。
<Crystallizing solution preparation process>
When aromatic hydrocarbons and / or cyclic ketones are contained in the reaction solution produced by the above method, the aromatic hydrocarbons and / or cyclic ketones are removed by operations such as distillation and concentration, The total content of aromatic hydrocarbons and cyclic ketones contained in the crystallization solution needs to be less than 10% by weight, preferably 5% by weight or less. When the crystallization solution contains 10% by weight or more of aromatic hydrocarbons and / or cyclic ketones, the alcohol having a fluorene skeleton represented by the above formula (1) is aromatic hydrocarbons and / or Since the cyclic ketones are included, the crystal of the present invention cannot be obtained. In addition, even if it is 5% by weight or less, some of the obtained crystals may become an inclusion body. Therefore, in order to ensure that crystals A are not included, aromatic carbonization in the crystallization solution The total content of hydrogen and cyclic ketones is preferably less than 1% by weight.
晶析溶液に含まれる炭素数が４以上の鎖状ケトン類は、上述した反応工程で使用され得る鎖状ケトン類と同じものが使用可能である。これら鎖状ケトン類は１種、あるいは必要に応じ２種以上混合して使用しても良い。晶析溶液に含まれる炭素数が４以上の鎖状ケトン類は、上記式（１）で表されるフルオレン骨格を有するアルコール１重量倍に対し、結晶Ｂを得る場合は０．５〜１０重量倍、好ましくは１〜５重量倍に、結晶Ｃを得る場合は０．１〜５重量倍、好ましくは０．５〜４重量倍に、結晶Ｄを得る場合は１〜１５重量倍、好ましくは２〜１０重量倍とする。前述した使用量範囲とすることにより、晶析工程においてそれぞれ、所望の温度範囲で結晶を析出させやすくなることから好ましい。 As the chain ketones having 4 or more carbon atoms contained in the crystallization solution, the same chain ketones that can be used in the above-described reaction step can be used. These chain ketones may be used alone or as a mixture of two or more if necessary. The chain ketones having 4 or more carbon atoms contained in the crystallization solution are 0.5 to 10 weights when the crystal B is obtained with respect to 1 weight times the alcohol having a fluorene skeleton represented by the above formula (1). Times, preferably 1 to 5 times by weight, 0.1 to 5 times by weight, preferably 0.5 to 4 times by weight when obtaining crystal C, 1 to 15 times by weight to obtain crystal D, preferably 2-10 weight times. By setting it as the usage-amount range mentioned above, since it becomes easy to precipitate a crystal | crystallization in each desired temperature range in a crystallization process, it is preferable.
晶析溶液中には炭素数が４以上の鎖状ケトン類の他、得られる結晶Ｂ、Ｃ又はＤの得量を向上する観点から、脂肪族炭化水素類（例えばヘキサン、ヘプタン、オクタン等）を併用することが好ましい。脂肪族炭化水素類を併用する場合の使用量は通常、上記式（１）で表されるフルオレン骨格を有するアルコール１重量倍に対し０．３〜５重量倍、好ましくは０．５〜３重量倍とする。また、上記式（１）で表されるフルオレン骨格を有するアルコールに不活性な脂肪族炭化水素類以外の溶媒（但し芳香族炭化水素類及び環状ケトン類を除く）を併用することも可能であるが、より確実に本発明の結晶を得る為には、脂肪族炭化水素類以外の他の溶媒は併用しないことが好ましい。 In addition to the chain ketones having 4 or more carbon atoms in the crystallization solution, aliphatic hydrocarbons (for example, hexane, heptane, octane, etc.) are used from the viewpoint of improving the yield of the obtained crystals B, C, or D. It is preferable to use together. In the case of using aliphatic hydrocarbons in combination, the amount used is usually 0.3 to 5 times, preferably 0.5 to 3 times the weight of the alcohol having the fluorene skeleton represented by the above formula (1). Double. It is also possible to use a solvent other than the aliphatic hydrocarbons inert to the alcohol having the fluorene skeleton represented by the above formula (1) (except for aromatic hydrocarbons and cyclic ketones). However, in order to obtain the crystal of the present invention more reliably, it is preferable not to use any other solvent other than the aliphatic hydrocarbons in combination.
＜晶析工程＞
前述の通り得られた晶析溶液は、晶析溶液に結晶が含まれている場合、該結晶を完溶させた後冷却し、結晶Ｂを得る場合は７５〜８５℃で結晶を析出させ、結晶Ｃを得る場合は９０〜１００℃で結晶を析出させ、結晶Ｄを得る場合は７０℃以下で結晶を析出させる。以下、該温度範囲で結晶を析出させる方法について詳述する。
<Crystal crystallization process>
The crystallization solution obtained as described above is cooled after completely dissolving the crystal when the crystallization solution contains a crystal, and when crystal B is obtained, the crystal is precipitated at 75 to 85 ° C. When crystal C is obtained, the crystal is precipitated at 90 to 100 ° C., and when crystal D is obtained, the crystal is precipitated at 70 ° C. or lower. Hereinafter, a method for precipitating crystals in the temperature range will be described in detail.
７５〜８５℃で結晶を析出させる場合、晶析溶液を７５℃以上、晶析溶液の沸点以下、好ましくは１００〜１１０℃まで加熱した後、０．３℃〜１．０℃／分、好ましくは０．５〜０．９℃／分で冷却し、その後７５〜８５℃で結晶を析出させる。
７５〜８５℃で結晶を析出させる方法としては、結晶が析出するまで同温度で撹拌を継続する方法、上記温度範囲で種晶を接種する方法等が例示される。種晶を添加する場合、結晶Ｂ、結晶Ｃ、結晶Ｄまたは公知の結晶Ａでも良いが、より確実に結晶Ｂを得る為には結晶Ｂを種晶として用いることが好ましい。また、結晶析出後、一定時間同温度で保持し結晶を成長させる方が、より確実に本発明の結晶が得られるため好ましい。
When the crystal is precipitated at 75 to 85 ° C., the crystallization solution is heated to 75 ° C. or more and below the boiling point of the crystallization solution, preferably 100 to 110 ° C., and then 0.3 to 1.0 ° C./min, preferably Is cooled at 0.5 to 0.9 ° C./min, and then crystals are precipitated at 75 to 85 ° C.
Examples of the method for precipitating crystals at 75 to 85 ° C. include a method in which stirring is continued at the same temperature until crystals are precipitated, and a method in which seed crystals are inoculated in the above temperature range. When seed crystals are added, crystals B, crystals C, crystals D or known crystals A may be used, but in order to obtain crystals B more reliably, it is preferable to use crystals B as seed crystals. In addition, it is preferable to grow the crystal by holding it at the same temperature for a certain period of time after crystal precipitation because the crystal of the present invention can be obtained more reliably.
９０〜１００℃で結晶を析出させる場合、晶析溶液を９０℃以上、晶析溶液の沸点以下、好ましくは１００〜１１０℃まで加熱した後、０．０５℃〜０．５℃／分、好ましくは０．０８〜０．３℃／分で冷却し、その後９０〜１００℃で結晶を析出させる。９０〜１００℃で結晶を析出させる方法としては、結晶が析出するまで同温度で撹拌を継続する方法、上記温度範囲で種晶を接種する方法等が例示される。種晶を添加する場合、結晶Ｂ、結晶Ｃ、結晶Ｄまたは公知の結晶Ａでも良いが、より確実に結晶Ｃを得る為には結晶Ｃを種晶として用いることが好ましい。また、結晶析出後、一定時間同温度で保持し結晶を成長させる方が、より確実に本発明の結晶が得られるため好ましい。 When the crystal is precipitated at 90 to 100 ° C., the crystallization solution is heated to 90 ° C. or more and below the boiling point of the crystallization solution, preferably 100 to 110 ° C., and then 0.05 ° C. to 0.5 ° C./min, preferably Is cooled at 0.08 to 0.3 ° C./min, and then crystals are precipitated at 90 to 100 ° C. Examples of the method for precipitating crystals at 90 to 100 ° C. include a method in which stirring is continued at the same temperature until crystals are precipitated, and a method in which seed crystals are inoculated in the above temperature range. When seed crystals are added, crystals B, crystals C, crystals D or known crystals A may be used, but in order to obtain crystals C more reliably, it is preferable to use crystals C as seed crystals. In addition, it is preferable to grow the crystal by holding it at the same temperature for a certain period of time after crystal precipitation because the crystal of the present invention can be obtained more reliably.
７０℃以下で結晶を析出させる場合、晶析溶液を７０℃以上、晶析溶液の沸点以下、好ましくは１００〜１１０℃まで加熱した後、０．５℃〜２．０℃／分、好ましくは１．０〜１．５℃／分で冷却し、その後７０℃以下で結晶を析出させる。７０℃以下で結晶を析出させる方法としては、結晶が析出するまで同温度で撹拌を継続する方法、上記温度範囲で種晶を接種する方法等が例示される。種晶を添加する場合、結晶Ｂ、結晶Ｃ、結晶Ｄまたは公知の結晶Ａでも良いが、より確実に結晶Ｄを得る為には結晶Ｄを種晶として用いることが好ましい。また、結晶析出後、一定時間同温度で保持し結晶を成長させる方が、より確実に本発明の結晶が得られるため好ましい。 When the crystal is precipitated at 70 ° C. or lower, the crystallization solution is heated to 70 ° C. or higher and lower than the boiling point of the crystallization solution, preferably 100 to 110 ° C., and then 0.5 ° C. to 2.0 ° C./min, preferably It cools at 1.0-1.5 degreeC / min, and precipitates a crystal | crystallization at 70 degrees C or less after that. Examples of the method for precipitating crystals at 70 ° C. or lower include a method in which stirring is continued at the same temperature until crystals are precipitated, a method in which seed crystals are inoculated in the above temperature range, and the like. In the case of adding a seed crystal, it may be a crystal B, a crystal C, a crystal D or a known crystal A, but in order to obtain the crystal D more reliably, it is preferable to use the crystal D as a seed crystal. In addition, it is preferable to grow the crystal by holding it at the same temperature for a certain period of time after crystal precipitation because the crystal of the present invention can be obtained more reliably.
上述の通り所定の温度範囲で結晶を析出させた後、結晶析出温度と同温度で析出した結晶を分離しても良いが、より収率良く結晶を得る為には、３０℃以下まで冷却した後、析出した結晶を分離することが好ましい。分離した結晶は必要に応じ乾燥を行い、結晶に付着した炭素数が４以上の鎖状ケトン類等を除去しても良い。 After the crystals are precipitated in the predetermined temperature range as described above, the crystals precipitated at the same temperature as the crystal precipitation temperature may be separated. However, in order to obtain crystals with higher yield, the crystals were cooled to 30 ° C. or lower. Thereafter, it is preferable to separate the precipitated crystals. The separated crystals may be dried as necessary to remove chain ketones having 4 or more carbon atoms attached to the crystals.
なお、本発明の結晶は包接体ではないため、反応・晶析工程で使用した炭素数が４以上の鎖状ケトン類等の沸点以上となる温度で乾燥することにより炭素数が４以上の鎖状ケトン類等を除去することが可能である為、結晶状態を保ちながら炭素数が４以上の鎖状ケトン類等を除去可能である。なお、公知の結晶Ａの場合、包接している芳香族炭化水素類が放出される温度と結晶の融点が略同一である為、加熱により結晶Ａから芳香族炭化水素類を除去しようとすると結晶が一旦溶融するため、芳香族炭化水素類の放出後、冷却すると結晶ではなく非晶質体となる。 In addition, since the crystal of the present invention is not a clathrate, it is dried at a temperature at which the carbon number used in the reaction / crystallization step is equal to or higher than the boiling point of a chain ketone having 4 or more carbon atoms. Since chain ketones and the like can be removed, chain ketones having 4 or more carbon atoms can be removed while maintaining the crystalline state. In the case of the known crystal A, the temperature at which the encapsulated aromatic hydrocarbons are released and the melting point of the crystal are substantially the same, so that when the aromatic hydrocarbons are removed from the crystal A by heating, the crystals Is once melted, it becomes an amorphous substance instead of a crystal when cooled after releasing aromatic hydrocarbons.
こうして得られた本発明の結晶は必要に応じ、吸着、水蒸気蒸留、再結晶などの通常の精製操作を繰り返し行うこともできるが、このような操作を実施しなくとも十分に高純度であり、また、包接体でない為、ポリカーボネート、ポリエステル、ポリアクリレート、ポリウレタン、エポキシなどの樹脂材料として好適に用いられることは勿論のこと、ゲスト分子が問題となる分野、例えば医農薬用の原料（中間体）としても好適に用いることができる。 The crystals of the present invention thus obtained can be subjected to usual purification operations such as adsorption, steam distillation, recrystallization and the like, if necessary, and are sufficiently high purity without performing such operations, In addition, since it is not an inclusion body, it can be suitably used as a resin material such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy, as well as in fields where guest molecules are a problem, for example, raw materials for medical and agricultural chemicals (intermediates) ) Can also be suitably used.
以下に実施例および試験例を挙げて本発明を具体的に説明するが、本発明はこれに何ら限定されるものではない。なお、例中、各種測定は下記の方法で実施した。なお、以下実施例・比較例・参考例に記載した各成分の生成率（残存率）及び純度は下記条件で測定したＨＰＬＣの面積百分率である。 EXAMPLES The present invention will be specifically described below with reference to examples and test examples, but the present invention is not limited to these. In the examples, various measurements were performed by the following methods. In addition, the production rate (residual rate) and purity of each component described in Examples, Comparative Examples, and Reference Examples are HPLC area percentages measured under the following conditions.
（１）ＨＰＬＣ純度
装置 ：島津製作所製 ＬＣ−２０１０Ａ、
カラム：ＳＵＭＩＰＡＸ ＯＤＳ Ａ−２１１（５μｍ、４．６ｍｍφ×２５０ｍｍ）、
移動相：純水／アセトニトリル（アセトニトリル３０％→１００％）、
流量 ：１．０ｍｌ／ｍｉｎ、カラム温度：４０℃、検出波長：ＵＶ ２５４ｎｍ。
(1) HPLC purity apparatus: LC-2010A manufactured by Shimadzu Corporation,
Column: SUMPAX ODS A-211 (5 μm, 4.6 mmφ × 250 mm),
Mobile phase: pure water / acetonitrile (
Flow rate: 1.0 ml / min, column temperature: 40 ° C., detection wavelength: UV 254 nm.
（２）残存溶媒量、包接溶媒量の分析
溶媒の残存量、または上記式（１）で表されるフルオレン骨格を有するアルコールに包接されているゲスト分子（芳香族炭化水素類等）の含量については下記条件に基づくガスクロマトグラフィーにより定量を行った。
装置 ：島津製作所製 ＧＣ−２０１４、
カラム：ＤＢ−１（０．２５μｍ、０．２５ｍｍＩＤ×３０ｍ）、
昇温：４０℃（５分保持）→２０℃／ｍｉｎ→２５０℃（１０分保持）、
Ｉｎｊ温度：２５０℃、Ｄｅｔ温度：３００℃、スプリット比 １：１０、
キャリアー：窒素５４．４ｋＰａ（一定）、
サンプル調製方法：十分に乾燥させた上記式（１）で表されるフルオレン骨格を有するアルコールの結晶１００ｍｇを１０ｍｌメスフラスコに量り取り、そこへあらかじめ調製していた１，２−ジメトキシエタンのアセトニトリル溶液(１，２−ジメトキシエタン４００ｍｇをアセトニトリル２００ｍｌに溶解したもの)をホールピペットで５ｍｌ加え、アセトニトリルでメスアップさせ溶解したものを試料溶液とした。
一方、残存量（包接量）を測定したい化合物１０ｍｇを１０ｍｌメスフラスコに量り取り、上述と同量の１，２−ジメトキシエタンのアセトニトリル溶液を加え、アセトニトリルでメスアップさせ溶解したものを標準溶液とした。
試料溶液及び標準溶液を上述の条件にて分析し、得られた各成分のピーク面積をデータ処理装置で求め、各成分の含量(重量％)を算出した。（内部標準法）
(2) Analysis of residual solvent amount and clathrate solvent amount Residual amount of solvent, or guest molecules (aromatic hydrocarbons, etc.) clathrated with alcohol having a fluorene skeleton represented by the above formula (1) The content was determined by gas chromatography based on the following conditions.
Apparatus: GC-2014 manufactured by Shimadzu Corporation
Column: DB-1 (0.25 μm, 0.25 mm ID × 30 m),
Temperature rise: 40 ° C. (hold for 5 minutes) → 20 ° C./min→250° C. (hold for 10 minutes)
Inj temperature: 250 ° C., Det temperature: 300 ° C., split ratio 1:10,
Carrier: nitrogen 54.4 kPa (constant),
Sample preparation method: 100 mg of alcohol crystals having a fluorene skeleton represented by the above formula (1), which had been sufficiently dried, were weighed into a 10 ml volumetric flask and prepared in advance in acetonitrile solution of 1,2-dimethoxyethane. A sample solution was prepared by adding 5 ml of (1,2-dimethoxyethane dissolved in 200 ml of acetonitrile) with a whole pipette and making up with acetonitrile and dissolving.
On the other hand, 10 mg of the compound whose residual amount (inclusion amount) is to be measured is weighed into a 10 ml volumetric flask, and the same amount of 1,2-dimethoxyethane in acetonitrile as above is added, and the solution is made up with acetonitrile and dissolved. It was.
The sample solution and the standard solution were analyzed under the above conditions, the peak areas of the obtained components were obtained with a data processor, and the content (% by weight) of each component was calculated. (Internal standard method)
（３）包接体であることの確認のための分析
上記式（１）で表されるフルオレン骨格を有するアルコールの結晶５ｍｇをアルミパンに精密に秤取し、（株）リガク社製示差熱天秤 ＴＧ−ＤＴＡ８１２１を用い、下記操作条件で測定した。
（操作条件）
昇温速度：１０℃／ｍｉｎ、
測定範囲：３０−２５０℃、
雰囲気 ：開放、窒素２５０ｍｌ／ｍｉｎ。
(3) Analysis for Confirmation of Inclusion Body 5 mg of an alcohol crystal having a fluorene skeleton represented by the above formula (1) was accurately weighed in an aluminum pan, and differential heat manufactured by Rigaku Corporation. Measurement was performed under the following operating conditions using a balance TG-DTA811.
(Operating conditions)
Temperature increase rate: 10 ° C./min,
Measurement range: 30-250 ° C.
Atmosphere: Open, nitrogen 250 ml / min.
（４）示差走査熱量測定（ＤＳＣ）
上記式（１）で表されるフルオレン骨格を有するアルコールの結晶５ｍｇをアルミパンに精密に秤取し、示差走査熱量計（エスアイアイ・ナノテクノロジー株式会社：ＤＳＣ７０２０）を用い、酸化アルミニウムを対照として下記操作条件で測定した。
（操作条件）
昇温速度：１０℃／ｍｉｎ、
測定範囲：３０−２５０℃、
雰囲気 ：開放、窒素４０ｍｌ／ｍｉｎ。
(4) Differential scanning calorimetry (DSC)
Precisely weigh 5 mg of an alcohol crystal having a fluorene skeleton represented by the above formula (1) in an aluminum pan, and use a differential scanning calorimeter (SII Nanotechnology Inc .: DSC7020), with aluminum oxide as a control. The measurement was performed under the following operating conditions.
(Operating conditions)
Temperature increase rate: 10 ° C./min,
Measurement range: 30-250 ° C.
Atmosphere: Open,
（５）粉末Ｘ線回折
上記式（１）で表されるフルオレン骨格を有するアルコールの結晶１５０ｍｇをガラス試験板の試料充填部に充填し、粉末Ｘ線回折装置（スペクトリス社製：Ｘ’ＰｅｒｔＰＲＯ）を用いて下記の条件で測定した。
Ｘ線源 ：ＣｕＫα、
出力 ：１．８ｋＷ（４５ｋＶ−４０ｍＡ）、
測定範囲 ：２θ＝５°〜７０°、
スキャン速度：２θ＝２°／ｍｉｎ、
スリット ：ＤＳ＝１°、マスク＝１５ｍｍ、ＲＳ＝可変（０．１ｍｍ〜）。
(5) Powder X-ray diffraction 150 mg of alcohol crystals having a fluorene skeleton represented by the above formula (1) are filled in a sample filling portion of a glass test plate, and a powder X-ray diffractometer (Spectris: X'PertPRO) Was measured under the following conditions.
X-ray source: CuKα,
Output: 1.8 kW (45 kV-40 mA),
Measurement range: 2θ = 5 ° to 70 °,
Scan speed: 2θ = 2 ° / min,
Slit: DS = 1 °, mask = 15 mm, RS = variable (from 0.1 mm).
（６）ＹＩ値
上記式（１）で表されるフルオレン骨格を有するアルコールの結晶１２ｇを、純度９９重量％以上のＮ，Ｎ―ジメチルホルムアミド３０ｍｌに溶解させ、以下の条件で得られたＮ，Ｎ―ジメチルホルムアミド溶液のＹＩ値（黄色度）を測定した。
装置 ：色差計（日本電色工業社製，ＳＥ６０００）、
使用セル：光路長３３ｍｍ 石英セル。
なお、測定に使用するＮ，Ｎ−ジメチルホルムアミド自身の着色が測定値に影響を与えないよう、事前にＮ，Ｎ−ジメチルホルムアミドの色相を測定して補正した。(ブランク測定)。
上述のブランク測定を実施したうえで、サンプルを測定した値を本発明におけるＹＩ値とする。
(6) YI value 12 g of an alcohol crystal having a fluorene skeleton represented by the above formula (1) was dissolved in 30 ml of N, N-dimethylformamide having a purity of 99% by weight or more. The YI value (yellowness) of the N-dimethylformamide solution was measured.
Apparatus: Color difference meter (Nippon Denshoku Industries Co., Ltd. SE6000),
Cell used: Optical path length 33 mm Quartz cell.
In addition, the hue of N, N-dimethylformamide was measured and corrected in advance so that the coloration of N, N-dimethylformamide itself used for the measurement did not affect the measurement value. (Blank measurement).
A value obtained by measuring the sample after performing the above-described blank measurement is defined as a YI value in the present invention.
（７）嵩密度
実施例及び比較例で得られた結晶を１０ｍｌのメスシリンダーに５ｍｌまで入れ、メスシリンダーに入った結晶の重量から嵩密度を算出した。
(7) Bulk density
The crystals obtained in Examples and Comparative Examples were placed in a 10 ml graduated cylinder up to 5 ml, and the bulk density was calculated from the weight of the crystals in the graduated cylinder.
＜実施例１＞
攪拌器、加熱冷却器、および温度計を備えたガラス製反応器に、上記式（２）で表されるフルオレン骨格を有するフェノール化合物（９，９’−ビス（４−ヒドロキシー３−フェニルフェニル）フルオレン）１２０ｇ（０．２３９ｍｏｌ）、炭酸カリウム２．８ｇ（０．０２０ｍｏｌ）、エチレンカーボネート４８ｇ（０．５４５ｍｏｌ）、メチルイソブチルケトン（以下、ＭＩＢＫと称することもある）１８０ｇを仕込み、１２０℃まで昇温し、同温度で６時間撹拌後、ＨＰＬＣにて原料が消失していることを確認した。
得られた反応液を８０℃まで冷却した後、ＭＩＢＫ１８０ｇ、水１８０ｇを加え、８０〜８５℃で１時間撹拌し、静置後、水層を分離した。同じ操作を３回繰り返した後、ＭＩＢＫ１３０ｇ、ヘプタン２１０ｇを添加し、晶析溶液を得た。
得られた晶析溶液を１００℃まで昇温し、３０分間撹拌して結晶を完溶させた後、該晶析溶液を０．８℃／分で冷却することにより８０℃で結晶を析出させ、同温度で２時間撹拌した。撹拌後、更に２５℃まで冷却し、結晶を得た。
得られた結晶を内圧０．４ｋＰａの減圧下、内温８５〜９０℃で９時間乾燥した所、ＭＩＢＫ及びヘプタンの合計含有量が０．２重量％となった為、乾燥終了とした。
<Example 1>
A phenol compound (9,9′-bis (4-hydroxy-3-phenylphenyl) having a fluorene skeleton represented by the above formula (2) is added to a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer. Fluorene (120 g, 0.239 mol), potassium carbonate (2.8 g, 0.020 mol), ethylene carbonate (48 g, 0.545 mol), methyl isobutyl ketone (hereinafter sometimes referred to as MIBK) (180 g) was charged and the temperature was raised to 120 ° C. After stirring for 6 hours at the same temperature, it was confirmed by HPLC that the raw materials had disappeared.
After cooling the obtained reaction liquid to 80 ° C., 180 g of MIBK and 180 g of water were added, stirred at 80 to 85 ° C. for 1 hour, and allowed to stand, and then the aqueous layer was separated. After repeating the same operation three times, 130 g MIBK and 210 g heptane were added to obtain a crystallization solution.
The obtained crystallization solution was heated to 100 ° C. and stirred for 30 minutes to completely dissolve the crystals, and then the crystallization solution was cooled at 0.8 ° C./min to precipitate crystals at 80 ° C. The mixture was stirred at the same temperature for 2 hours. After stirring, the mixture was further cooled to 25 ° C. to obtain crystals.
The obtained crystals were dried at an internal temperature of 85 to 90 ° C. for 9 hours under a reduced pressure of 0.4 kPa, and the total content of MIBK and heptane was 0.2% by weight.
得られた上記式（１）で表されるフルオレン骨格を有するアルコールの結晶の各分析値は以下の通り。
得られた結晶の重さ：１２５ｇ（収率：８２％）
ＨＰＬＣ純度：９８．６％
１０１．３ｋＰａにおける沸点が１５０℃以下の有機溶媒の含有量（ＭＩＢＫ及びヘプタンの含有量を含む）：０．２４重量％
ＹＩ値：５．２
ＤＳＣ融解吸熱最大温度：１７５℃
嵩密度：０．５ｇ／ｃｍ３
Each analytical value of the crystal | crystallization of the alcohol which has the fluorene skeleton represented by the said Formula (1) obtained is as follows.
Weight of the obtained crystal: 125 g (yield: 82%)
HPLC purity: 98.6%
Content of organic solvent whose boiling point at 101.3 kPa is 150 ° C. or lower (including MIBK and heptane content): 0.24% by weight
YI value: 5.2
DSC melting endotherm maximum temperature: 175 ° C
Bulk density: 0.5 g / cm 3
ＤＳＣ分析チャートを図１に、粉末Ｘ線のパターンを図４に、粉末Ｘ線の主なピーク（５％を超える相対強度を有するもの）を表１に列挙する。表１に示す通り、本実施例で得られた上記式（１）で表されるフルオレン骨格を有するアルコールは、回折角２θ＝７．７±０．２°、１７．２±０．２°、１８．３±０．２°、１９．６±０．２°、２０．８±０．２°および２１．４±０．２°に特徴的な回折ピークを示した。（以下、本パターンと同様のＸ線ピークを有するものを「パターンＢ」と称することがある。） The DSC analysis chart is shown in FIG. 1, the pattern of the powder X-ray is shown in FIG. 4, and the main peak of the powder X-ray (having a relative intensity exceeding 5%) is listed in Table 1. As shown in Table 1, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this example has diffraction angles 2θ = 7.7 ± 0.2 °, 17.2 ± 0.2 °. 18.3 ± 0.2 °, 19.6 ± 0.2 °, 20.8 ± 0.2 ° and 21.4 ± 0.2 °, characteristic diffraction peaks. (Hereinafter, a pattern having the same X-ray peak as the present pattern may be referred to as “pattern B”.)
＜実施例２＞
攪拌器、加熱冷却器、および温度計を備えたガラス製反応器に、上記式（２）で表されるフルオレン骨格を有するフェノール化合物（９，９’−ビス（４−ヒドロキシー３−フェニルフェニル）フルオレン）１３８ｇ（０．２７５ｍｏｌ）、炭酸カリウム３．１ｇ（０．０２２ｍｏｌ）、エチレンカーボネート５０．８ｇ（０．５７７ｍｏｌ）、ＭＩＢＫ１３８ｇを仕込み、１２０℃まで昇温し、同温度で９時間撹拌後、ＨＰＬＣにて原料が消失していることを確認した。
得られた反応液を８０℃まで冷却した後、ＭＩＢＫ２７６ｇ、水２０７ｇを加え、７０〜７５℃で２時間撹拌し、静置後、水層を分離した。同じ操作を３回繰り返した後、ＭＩＢＫ５５ｇ、ヘプタン１９８ｇを添加し、晶析溶液を得た。
得られた晶析溶液を１０５℃まで昇温し、３０分間撹拌して結晶を完溶させた後、該晶析溶液を０．１℃／分で冷却することにより９５℃で結晶を析出させ、同温度で２時間撹拌した。その後、２５℃まで冷却、濾過し、結晶を得た。
得られた結晶を内圧１．３ｋＰａの減圧下、内温８０〜９０℃で３時間乾燥した所、ＭＩＢＫの含有量が０．０６重量％となった為、乾燥終了とした。
<Example 2>
A phenol compound (9,9′-bis (4-hydroxy-3-phenylphenyl) having a fluorene skeleton represented by the above formula (2) is added to a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer. Fluorene) 138 g (0.275 mol), potassium carbonate 3.1 g (0.022 mol), ethylene carbonate 50.8 g (0.577 mol) and MIBK 138 g were charged, heated to 120 ° C., stirred at the same temperature for 9 hours, It was confirmed by HPLC that the raw material had disappeared.
After cooling the obtained reaction liquid to 80 ° C., 276 g of MIBK and 207 g of water were added, stirred at 70 to 75 ° C. for 2 hours, and allowed to stand, and then the aqueous layer was separated. After repeating the same operation three times, 55 g MIBK and 198 g heptane were added to obtain a crystallization solution.
The obtained crystallization solution was heated to 105 ° C. and stirred for 30 minutes to completely dissolve the crystals, and then the crystallization solution was cooled at 0.1 ° C./min to precipitate crystals at 95 ° C. The mixture was stirred at the same temperature for 2 hours. Then, it cooled to 25 degreeC and filtered and the crystal | crystallization was obtained.
The obtained crystals were dried at an internal temperature of 80 to 90 ° C. for 3 hours under a reduced pressure of 1.3 kPa, and the content of MIBK was 0.06% by weight.
得られた上記式（１）で表されるフルオレン骨格を有するアルコールの結晶の各分析値は以下の通り。
得られた結晶の重さ：１２７ｇ（収率：７８％）
ＨＰＬＣ純度：９８．７％
１０１．３ｋＰａにおける沸点が１５０℃以下の有機溶媒の含有量（ＭＩＢＫ及びヘプタンの含有量を含む）：０．０７重量％
ＹＩ値：７．０
ＤＳＣ融解吸熱最大温度：１９５℃
嵩密度：０．６ｇ／ｃｍ３
Each analytical value of the crystal | crystallization of the alcohol which has the fluorene skeleton represented by the said Formula (1) obtained is as follows.
Weight of crystals obtained: 127 g (yield: 78%)
HPLC purity: 98.7%
Content of organic solvent whose boiling point at 101.3 kPa is 150 ° C. or lower (including MIBK and heptane content): 0.07% by weight
YI value: 7.0
DSC melting endotherm maximum temperature: 195 ° C
Bulk density: 0.6 g / cm 3
ＤＳＣ分析チャートを図２に、粉末Ｘ線のパターンを図５に、粉末Ｘ線の主なピーク（５％を超える相対強度を有するもの）を表２に列挙する。表２に示す通り、本実施例で得られた上記式（１）で表されるフルオレン骨格を有するアルコールは、回折角２θ＝１４．９±０．２°、１７．８±０．２°、１８．９±０．２°、１９．７±０．２°、２０．０±０．２°および２１．０±０．２°に特徴的な回折ピークを示した。
（以下、本パターンと同様のＸ線ピークを有するものを「パターンＣ」と称することがある。）
FIG. 2 shows the DSC analysis chart, FIG. 5 shows the pattern of the powder X-ray, and Table 2 lists the main peaks of the powder X-ray (having a relative intensity exceeding 5%). As shown in Table 2, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this example has a diffraction angle 2θ = 14.9 ± 0.2 °, 17.8 ± 0.2 °. , 18.9 ± 0.2 °, 19.7 ± 0.2 °, 20.0 ± 0.2 ° and 21.0 ± 0.2 °.
(Hereinafter, a pattern having the same X-ray peak as the present pattern may be referred to as “pattern C”.)
＜実施例３＞
攪拌器、加熱冷却器、および温度計を備えたガラス製反応器に、上記式（２）で表されるフルオレン骨格を有するフェノール化合物（９，９’−ビス（４−ヒドロキシー３−フェニルフェニル）フルオレン）１５０ｇ（０．２９８ｍｏｌ）、炭酸カリウム３．４ｇ（０．０２５ｍｏｌ）、エチレンカーボネート６５．７ｇ（０．７４７ｍｏｌ）、メチルイソアミルケトン（以下、ＭＩＡＫと称することもある）１５０ｇを仕込み、１２０℃まで昇温し、同温度で７時間撹拌後、ＨＰＬＣにて原料が消失していることを確認した。
得られた反応液を９０℃まで冷却した後、水１５０ｇを加え、８５〜９０℃で３０分撹拌し、静置後、水層を分離した。同じ操作を３回繰り返した後、ＭＩＡＫ２５０ｇを添加し、晶析溶液を得た。
得られた晶析溶液を１１０℃まで昇温し、３０分間撹拌して結晶を完溶させた後、該晶析溶液を０．３℃／分で９８℃まで冷却し、同温度で、実施例２で得られた結晶２０ｍｇを種晶として接種し、１０分撹拌した所、結晶が析出し始めた為、同温度で１時間撹拌した。撹拌後、更に２２℃まで冷却した後、濾過し、結晶を得た。
得られた結晶を内圧１．３ｋＰａの減圧下、内温８０〜９０℃で３時間乾燥した所、ＭＩＡＫの含有量が０．０７重量％となった為、乾燥終了とした。
<Example 3>
A phenol compound (9,9′-bis (4-hydroxy-3-phenylphenyl) having a fluorene skeleton represented by the above formula (2) is added to a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer. Fluorene (150 g, 0.298 mol), potassium carbonate (3.4 g, 0.025 mol), ethylene carbonate (65.7 g, 0.747 mol), methyl isoamyl ketone (hereinafter sometimes referred to as MIAK) (150 g), 120 ° C. The mixture was stirred for 7 hours at the same temperature, and it was confirmed by HPLC that the raw materials had disappeared.
After cooling the obtained reaction liquid to 90 degreeC, 150 g of water was added, it stirred at 85-90 degreeC for 30 minutes, and after standing still, the water layer was isolate | separated. After repeating the same operation three times, 250 g of MIAK was added to obtain a crystallization solution.
The obtained crystallization solution was heated to 110 ° C. and stirred for 30 minutes to completely dissolve the crystals. Then, the crystallization solution was cooled to 98 ° C. at 0.3 ° C./min and carried out at the same temperature. When 20 mg of the crystal obtained in Example 2 was inoculated as a seed crystal and stirred for 10 minutes, the crystal started to precipitate, and thus stirred at the same temperature for 1 hour. After stirring, the mixture was further cooled to 22 ° C. and then filtered to obtain crystals.
The obtained crystals were dried at an internal temperature of 80 to 90 ° C. for 3 hours under a reduced pressure of 1.3 kPa, and the content of MIAK was 0.07% by weight.
得られた上記式（１）で表されるフルオレン骨格を有するアルコールの結晶の各分析値は以下の通り。
得られた結晶の重さ：１１２ｇ（収率：６４％）
ＨＰＬＣ純度：９８．１％
１０１．３ｋＰａにおける沸点が１５０℃以下の有機溶媒の含有量（ＭＩＡＫを含む）：０．０８重量％
ＹＩ値：１．７
ＤＳＣ融解吸熱最大温度：１９５℃
嵩密度：０．８ｇ／ｃｍ３
Ｘ線回折パターン：パターンＣ
Each analytical value of the crystal | crystallization of the alcohol which has the fluorene skeleton represented by the said Formula (1) obtained is as follows.
Weight of the obtained crystal: 112 g (yield: 64%)
HPLC purity: 98.1%
Content of organic solvent whose boiling point at 101.3 kPa is 150 ° C. or less (including MIAK): 0.08% by weight
YI value: 1.7
DSC melting endotherm maximum temperature: 195 ° C
Bulk density: 0.8 g / cm 3
X-ray diffraction pattern: Pattern C
＜実施例４＞
実施例１と同じスケール、同様の方法にて反応工程、水洗工程を行った後、得られた水洗工程後の反応液にＭＩＢＫ２４０ｇ、ヘプタン２４０ｇを添加し、晶析溶液を得た。
得られた晶析溶液を１００℃まで昇温し、３０分間撹拌して結晶を完溶させた後、該晶析溶液を１．５℃／分で冷却することにより６９℃で結晶を析出させ、同温度で２時間撹拌した。撹拌後、更に２０℃まで冷却した後、濾過し、結晶を得た。
得られた結晶を内圧１．３ｋＰａの減圧下、内温８０〜８５℃で３時間乾燥した所、ＭＩＢＫ及びヘプタンの合計含有量が０．８重量％となった為、乾燥終了とした。
得られた上記式（１）で表されるフルオレン骨格を有するアルコールの結晶の各分析値は以下の通り。
得られた結晶の重さ：１０７ｇ（収率：７６％）
ＨＰＬＣ純度：９８．３％
１０１．３ｋＰａにおける沸点が１５０℃以下の有機溶媒の含有量（ＭＩＢＫ及びヘプタンの含有量を含む）：０．８重量％
ＹＩ値：４．５
ＤＳＣ融解吸熱最大温度：１６９℃
嵩密度：１．５ｇ／ｃｍ３
<Example 4>
After performing the reaction step and the water washing step in the same manner and in the same manner as in Example 1, 240 g MIBK and 240 g heptane were added to the reaction solution obtained after the water washing step to obtain a crystallization solution.
The obtained crystallization solution was heated to 100 ° C. and stirred for 30 minutes to completely dissolve the crystals, and then the crystallization solution was cooled at 1.5 ° C./min to precipitate crystals at 69 ° C. The mixture was stirred at the same temperature for 2 hours. After stirring, the mixture was further cooled to 20 ° C. and then filtered to obtain crystals.
The obtained crystals were dried at an internal temperature of 80 to 85 ° C. for 3 hours under a reduced pressure of 1.3 kPa, and the total content of MIBK and heptane was 0.8% by weight.
Each analytical value of the crystal | crystallization of the alcohol which has the fluorene skeleton represented by the said Formula (1) obtained is as follows.
Weight of the obtained crystal: 107 g (yield: 76%)
HPLC purity: 98.3%
Content of organic solvent having a boiling point of 150 ° C. or lower at 101.3 kPa (including MIBK and heptane content): 0.8% by weight
YI value: 4.5
DSC melting endotherm maximum temperature: 169 ° C
Bulk density: 1.5 g / cm 3
ＤＳＣ分析チャートを図９に、粉末Ｘ線のパターンを図１０に、粉末Ｘ線の主なピーク（５％を超える相対強度を有するもの）を表６に列挙する。表６に示す通り、本実施例で得られた上記式（１）で表されるフルオレン骨格を有するアルコールは、回折角２θ＝９．８±０．２°、１４．９±０．２°、１７．６±０．２°、１８．８±０．２°、１９．４±０．２°、２０．０±０．２および２０．６±０．２°に特徴的な回折ピークを示した。（以下、本パターンと同様のＸ線ピークを有するものを「パターンＤ」と称することがある。） The DSC analysis chart is shown in FIG. 9, the powder X-ray pattern is shown in FIG. 10, and the main peaks of powder X-rays (having a relative intensity exceeding 5%) are listed in Table 6. As shown in Table 6, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this example has a diffraction angle 2θ = 9.8 ± 0.2 °, 14.9 ± 0.2 °. , 17.6 ± 0.2 °, 18.8 ± 0.2 °, 19.4 ± 0.2 °, diffraction peaks characteristic of 20.0 ± 0.2 and 20.6 ± 0.2 ° showed that. (Hereinafter, a pattern having the same X-ray peak as this pattern may be referred to as “pattern D”.)
＜比較例１＞
攪拌器、加熱冷却器、および温度計を備えたガラス製反応器に、上記式（２）で表されるフルオレン骨格を有するフェノール化合物（９，９’−ビス（４−ヒドロキシー３−フェニルフェニル）フルオレン）４０．０ｇ（０．０８０ｍｏｌ）、エチレンカーボネート１６．１ｇ（０．１８３ｍｏｌ）、炭酸カリウム０．８ｇ（０．００６ｍｏｌ）およびトルエン４０．０ｇを仕込み、１１０℃で１１時間撹拌し、ＨＰＬＣにて原料ピークが１％以下であることを確認した。
得られた反応液を８５℃まで冷却した後、水６８ｇを加え、８０〜８５℃で３０分撹拌し、静置後、水層を分離した。同じ操作を３回繰り返した後、得られた有機溶媒層をディーンスターク装置を用いて還流下で脱水し、上記式（１）で表されるフルオレン骨格を有するアルコールが溶解した晶析溶液を得た。
得られた晶析溶液を０．３℃／分で冷却した所、６５℃で結晶が析出し、同温度で２時間撹拌した。撹拌後、更に２６℃まで冷却した後、濾過し、結晶を得た。
得られた結晶を内圧１．１ｋＰａの減圧下、内温を６８℃〜７３℃で３時間乾燥したが、トルエンが４重量％含まれていた為、内温を１１０℃まで昇温し、同温度で更に３時間乾燥したが、トルエンの含量は４重量％のままであった。
<Comparative Example 1>
A phenol compound (9,9′-bis (4-hydroxy-3-phenylphenyl) having a fluorene skeleton represented by the above formula (2) is added to a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer. Fluorene) 40.0 g (0.080 mol), ethylene carbonate 16.1 g (0.183 mol), potassium carbonate 0.8 g (0.006 mol) and toluene 40.0 g were charged, and stirred at 110 ° C. for 11 hours. It was confirmed that the raw material peak was 1% or less.
After cooling the obtained reaction liquid to 85 degreeC, 68 g of water was added, it stirred at 80-85 degreeC for 30 minutes, and after standing still, the water layer was isolate | separated. After repeating the same operation three times, the obtained organic solvent layer was dehydrated under reflux using a Dean-Stark apparatus to obtain a crystallization solution in which the alcohol having the fluorene skeleton represented by the above formula (1) was dissolved. It was.
When the obtained crystallization solution was cooled at 0.3 ° C./min, crystals were precipitated at 65 ° C. and stirred at the same temperature for 2 hours. After stirring, the mixture was further cooled to 26 ° C. and then filtered to obtain crystals.
The obtained crystals were dried at an internal pressure of 1.1 kPa at an internal temperature of 68 ° C. to 73 ° C. for 3 hours. Since toluene was contained at 4% by weight, the internal temperature was raised to 110 ° C. After further drying for 3 hours at temperature, the toluene content remained at 4% by weight.
得られた上記式（１）で表されるフルオレン骨格を有するアルコールの結晶の各分析値は以下の通り。
得られた結晶の重さ：３９．３ｇ
ＨＰＬＣ純度：９７．５％
トルエン含量：４．１重量％
ＤＳＣ融解吸熱最大温度：１５１℃
嵩密度：０．３ｇ／ｃｍ３
Each analytical value of the crystal | crystallization of the alcohol which has the fluorene skeleton represented by the said Formula (1) obtained is as follows.
Weight of the obtained crystal: 39.3 g
HPLC purity: 97.5%
Toluene content: 4.1% by weight
DSC melting endotherm maximum temperature: 151 ° C
Bulk density: 0.3 g / cm 3
ＤＳＣ分析チャートを図３に、粉末Ｘ線のパターンを図６に、粉末Ｘ線の主なピーク（５％を超える相対強度を有するもの）を表３に、ＴＧ−ＤＴＡの分析チャートを図７に列挙する。表３に示す通り、本比較例で得られた上記式（１）で表されるフルオレン骨格を有するアルコールは、回折角２θ＝７．６±０．２°、１５．６±０．２°、１６．４±０．２°、１８．７±０．２°、１９．０±０．２°、２０．５±０．２°および２３．６±０．２°に特徴的な回折ピークを示した。
また、高温・減圧下で乾燥を行ってもトルエンの残量が減少しなかったため、ＴＧ−ＤＴＡ分析を行い包接体であるか否かを確認した所、図７に示す通り、トルエンの沸点以上の温度である約１３９℃で重量の減少が始まり、続いて約１５０℃に吸熱ピークが観測されたことから、本比較例で得られた上記式（１）で表されるフルオレン骨格を有するアルコールは、包接体であることが支持される。
The DSC analysis chart is shown in FIG. 3, the powder X-ray pattern is shown in FIG. 6, the main peak of the powder X-ray (having a relative intensity exceeding 5%) is shown in Table 3, and the TG-DTA analysis chart is shown in FIG. Are listed. As shown in Table 3, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this comparative example has a diffraction angle of 2θ = 7.6 ± 0.2 °, 15.6 ± 0.2 °. , 16.4 ± 0.2 °, 18.7 ± 0.2 °, 19.0 ± 0.2 °, 20.5 ± 0.2 ° and 23.6 ± 0.2 ° characteristic diffraction Showed a peak.
Moreover, since the residual amount of toluene did not decrease even after drying under high temperature and reduced pressure, a boiling point of toluene as shown in FIG. 7 was confirmed by performing TG-DTA analysis and confirming whether it was an inclusion body. Since the weight decrease started at about 139 ° C., which was the above temperature, and subsequently an endothermic peak was observed at about 150 ° C., the fluorene skeleton represented by the above formula (1) obtained in this comparative example was obtained. The alcohol is supported to be an inclusion body.
＜比較例２＞
攪拌器、加熱冷却器、および温度計を備えたガラス製反応器に、上記式（２）で表されるフルオレン骨格を有するフェノール化合物（９，９’−ビス（４−ヒドロキシー３−フェニルフェニル）フルオレン）３０．０ｇ（０．０６０ｍｏｌ）、エチレンカーボネート１２．０ｇ（０．１３６ｍｏｌ）、炭酸カリウム０．７ｇ（０．００５ｍｏｌ）、およびシクロヘキサノン３０．０ｇを仕込み、１４０℃で７時間撹拌し、ＨＰＬＣにて原料ピークが１％以下であることを確認した。
得られた反応液を９０℃まで冷却した後、シクロヘキサノン２３ｇ、ヘプタン２７ｇを加え、有機溶媒層を９０℃に保ちながら洗浄水が中性となるまで水洗を行った。水洗後、得られた有機溶媒層をディーンスターク装置を用いて還流下で脱水し、上記式（１）で表されるフルオレン骨格を有するアルコールが溶解した晶析溶液を得た。
その後、７０℃まで冷却し、７０℃で１時間保温することで結晶を析出させた後、同温度で２時間撹拌した。撹拌後、更に１９℃まで冷却した後、濾過し、結晶を得た。
得られた結晶を内圧１．１ｋＰａの減圧下、内温を９０℃で３時間乾燥したが、シクロヘキサノンが１４重量％含まれていた為、内温を１１０℃まで昇温し、同温度で更に３時間乾燥したが、シクロヘキサノン含量は１４重量％のままであった。
<Comparative example 2>
A phenol compound (9,9′-bis (4-hydroxy-3-phenylphenyl) having a fluorene skeleton represented by the above formula (2) is added to a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer. Fluorene) 30.0 g (0.060 mol), ethylene carbonate 12.0 g (0.136 mol), potassium carbonate 0.7 g (0.005 mol), and cyclohexanone 30.0 g were charged and stirred at 140 ° C. for 7 hours. It was confirmed that the raw material peak was 1% or less.
After cooling the obtained reaction liquid to 90 ° C., 23 g of cyclohexanone and 27 g of heptane were added, and the organic solvent layer was kept at 90 ° C. and washed with water until the washing water became neutral. After washing with water, the obtained organic solvent layer was dehydrated under reflux using a Dean-Stark apparatus to obtain a crystallization solution in which the alcohol having a fluorene skeleton represented by the above formula (1) was dissolved.
Then, after cooling to 70 degreeC and keeping at 70 degreeC for 1 hour, the crystal | crystallization was deposited, Then, it stirred at the same temperature for 2 hours. After stirring, the mixture was further cooled to 19 ° C. and then filtered to obtain crystals.
The obtained crystal was dried under an internal pressure of 1.1 kPa at an internal temperature of 90 ° C. for 3 hours. Since 14% by weight of cyclohexanone was contained, the internal temperature was increased to 110 ° C. After drying for 3 hours, the cyclohexanone content remained at 14% by weight.
得られた上記式（１）で表されるフルオレン骨格を有するアルコールの結晶の各分析値は以下の通り。
得られた結晶の重さ：３３．０ｇ
ＨＰＬＣ純度：９７．８％
シクロヘキサノン含量：１４重量％
ＤＳＣ融解吸熱最大温度：１１４℃
嵩密度：０．４ｇ／ｃｍ３
Each analytical value of the crystal | crystallization of the alcohol which has the fluorene skeleton represented by the said Formula (1) obtained is as follows.
Weight of the obtained crystal: 33.0 g
HPLC purity: 97.8%
Cyclohexanone content: 14% by weight
DSC melting endotherm maximum temperature: 114 ° C
Bulk density: 0.4 g / cm 3
また、高温・減圧下で乾燥を行ってもシクロヘキサノンの残量が減少しなかったため、ＴＧ−ＤＴＡ分析を行い包接体であるか否かを確認した。ＴＧ−ＤＴＡの分析チャートを図８に示す。該チャートに示される通り、約１１４℃で重量の減少が始まり、併せて同温度で吸熱ピークが観測されたことから、本比較例２で得られた上記式（１）で表されるフルオレン骨格を有するアルコールは、包接体であることが支持される。 Moreover, since the residual amount of cyclohexanone did not decrease even after drying under high temperature and reduced pressure, TG-DTA analysis was performed to confirm whether it was an inclusion body. An analysis chart of TG-DTA is shown in FIG. As shown in the chart, the weight began to decrease at about 114 ° C., and an endothermic peak was observed at the same temperature. Therefore, the fluorene skeleton represented by the above formula (1) obtained in Comparative Example 2 was obtained. It is supported that the alcohol having a clathrate.
＜比較例３＞
スケールを１０分の１とする以外は特開２００１−２０６８６３号の実施例６に記載されている方法で仕込・反応を行い、６５℃で１時間撹拌した段階で反応液を高速液体クロマトグラフィーで分析したが、上記式（２）で表されるフルオレン骨格を有するアルコールは殆ど生成しておらず、原料の９−フルオレノンが９８％残存していた。そこで更に同温度で７時間撹拌を継続し、反応液を高速液体クロマトグラフィーで分析したが同様に反応は殆ど進行しておらず、原料の９−フルオレノンが９７％残存していた。
そこで特開２００１−２０６８６３号〔００１９〕の記載に基づき、反応温度を６５℃から１００℃へと変更し同温度で撹拌を継続したところ、原料である９−フルオレノンの消失までに７３時間必要であった。
該文献記載に基づく後処理を実施するため、得られた反応液を２分割し、一方にメタノール１０ｇ、もう一方にイソプロピルアルコール１０ｇを加え６０℃まで加温し、１時間撹拌を継続した後、それぞれ純水３０ｇを加え、３０℃まで冷却したが両方とも結晶は析出せず、それぞれ水と分離したタール状の液体が得られた。
<Comparative Example 3>
The reaction solution was charged and reacted by the method described in Example 6 of JP-A-2001-206863, except that the scale was reduced to 1/10, and the reaction solution was stirred at 65 ° C. for 1 hour by high performance liquid chromatography. As a result of analysis, almost no alcohol having a fluorene skeleton represented by the above formula (2) was produced, and 98% of the raw material 9-fluorenone remained. Therefore, stirring was further continued at the same temperature for 7 hours, and the reaction solution was analyzed by high performance liquid chromatography. Similarly, the reaction hardly proceeded and 97% of the starting material 9-fluorenone remained.
Therefore, based on the description of JP 2001-206863 [0019], when the reaction temperature was changed from 65 ° C. to 100 ° C. and stirring was continued at the same temperature, 73 hours were required until the disappearance of 9-fluorenone as a raw material. there were.
In order to carry out post-treatment based on the literature description, the obtained reaction solution was divided into two, 10 g of methanol was added to one side, 10 g of isopropyl alcohol was added to the other side, the mixture was heated to 60 ° C., and stirring was continued for 1 hour. In each case, 30 g of pure water was added and cooled to 30 ° C., but in both cases, crystals did not precipitate, and tar-like liquids separated from water were obtained.
＜比較例４＞
９−フルオレノンの使用量を１８ｇとして特開２００９−２５６３４２号の実施例４記載の方法を追試した所、上記式（１）で表されるフルオレン骨格を有するアルコール２０．７ｇ（純度８８．６％）を得た。得られた上記式（１）で表されるフルオレン骨格を有するアルコールの結晶の各分析値は以下の通り。
<Comparative Example 4>
When the amount of 9-fluorenone used was 18 g and the method described in Example 4 of JP-A-2009-256342 was further tested, 20.7 g of alcohol having a fluorene skeleton represented by the above formula (1) (purity: 88.6%) ) Each analytical value of the crystal | crystallization of the alcohol which has the fluorene skeleton represented by the said Formula (1) obtained is as follows.
キシレン含量：５．２重量％
ＹＩ値：４６
ＤＳＣ融解吸熱最大温度：１４６℃
嵩密度：０．３ｇ／ｃｍ３
Xylene content: 5.2% by weight
YI value: 46
DSC melting endotherm maximum temperature: 146 ° C
Bulk density: 0.3 g / cm 3
粉末Ｘ線の主なピーク（５％を超える相対強度を有するもの）を表４に示す。表４に示す通り、本比較例４で得られた、キシレンを包接する上記式（１）で表されるフルオレン骨格を有するアルコールは、回折角２θ＝７．６±０．２°、１５．６±０．２°、１６．４±０．２°、１８．７±０．２°、１９．０±０．２°、２０．５±０．２°および２３．６±０．２°に特徴的な回折ピークを示した。 Table 4 shows the main peaks of powder X-rays (having a relative intensity exceeding 5%). As shown in Table 4, the alcohol having a fluorene skeleton represented by the above formula (1) and containing xylene obtained in Comparative Example 4 has a diffraction angle 2θ = 7.6 ± 0.2 °, 15. 6 ± 0.2 °, 16.4 ± 0.2 °, 18.7 ± 0.2 °, 19.0 ± 0.2 °, 20.5 ± 0.2 ° and 23.6 ± 0.2 A characteristic diffraction peak was shown at °.
＜比較例５＞
９−フルオレノンの使用量を９ｇとして特開２００９−２５６３４２号の実施例２記載の方法を追試した所、上記式（１）で表されるフルオレン骨格を有するアルコール１３．５ｇ（純度７４．７％）を得た。得られた上記式（１）で表されるフルオレン骨格を有するアルコールの結晶の各分析値は以下の通り。
<Comparative Example 5>
When the amount of 9-fluorenone used was 9 g and the method described in Example 2 of JP-A-2009-256342 was further tested, 13.5 g of an alcohol having a fluorene skeleton represented by the above formula (1) (purity: 74.7%) ) Each analytical value of the crystal | crystallization of the alcohol which has the fluorene skeleton represented by the said Formula (1) obtained is as follows.
トルエン含量：３．０重量％
ＹＩ値：８３
ＤＳＣ融解吸熱最大温度：１２６℃
嵩密度：０．２ｇ／ｃｍ３
Toluene content: 3.0% by weight
YI value: 83
DSC melting endotherm maximum temperature: 126 ° C
Bulk density: 0.2 g / cm 3
粉末Ｘ線の主なピーク（５％を超える相対強度を有するもの）を表５に示す。表５に示す通り、本比較例５で得られた、トルエンを包接する上記式（１）で表されるフルオレン骨格を有するアルコールは、回折角２θ＝７．６±０．２°、１５．６±０．２°、１６．４±０．２°、１８．７±０．２°、１９．０±０．２°、２０．５±０．２°および２３．６±０．２°に特徴的な回折ピークを示した。 Table 5 shows the main peaks of powder X-rays (having a relative intensity exceeding 5%). As shown in Table 5, the alcohol having a fluorene skeleton represented by the above formula (1) obtained by inclusion in toluene and obtained in Comparative Example 5 has a diffraction angle of 2θ = 7.6 ± 0.2 °, 15. 6 ± 0.2 °, 16.4 ± 0.2 °, 18.7 ± 0.2 °, 19.0 ± 0.2 °, 20.5 ± 0.2 ° and 23.6 ± 0.2 A characteristic diffraction peak was shown at °.
Claims (13)
（ａ）
炭素数が４以上の鎖状ケトン類存在下、下記式（２）
（ｂ）
前記反応液から、炭素数が４以上の鎖状ケトン類を含有し、かつ芳香族炭化水素類及び環状ケトン類の合計含有量が１０重量％未満である晶析溶液を調製する工程。
（ｃ）
前記晶析溶液から７５〜８５℃で結晶を析出させ、析出した結晶を分離する工程。 The manufacturing method of the alcohol which has the fluorene skeleton represented by the said Formula (1) of Claim 1 or 2 including the process of (a)-(c) in this order below.
(A)
In the presence of a chain ketone having 4 or more carbon atoms, the following formula (2)
(B)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(C)
A step of depositing crystals at 75 to 85 ° C. from the crystallization solution and separating the precipitated crystals.
（ｄ）
炭素数が４以上の鎖状ケトン類存在下、上記式（２）で表されるフルオレン骨格を有するフェノール化合物とエチレンカーボネートとを反応させ、上記式（１）で表されるフルオレン骨格を有するアルコールを含む反応液を得る工程。
（ｅ）
前記反応液から、炭素数が４以上の鎖状ケトン類を含有し、かつ芳香族炭化水素類及び環状ケトン類の合計含有量が１０重量％未満である晶析溶液を調製する工程。
（ｆ）
前記晶析溶液から９０〜１００℃で結晶を析出させ、析出した結晶を分離する工程。 The manufacturing method of the alcohol which has the fluorene skeleton represented by the said Formula (1) of Claim 3 or 4 which includes the process of (d)-(f) in this order below.
(D)
An alcohol having a fluorene skeleton represented by the above formula (1) by reacting a phenol compound having a fluorene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a chain ketone having 4 or more carbon atoms. The process of obtaining the reaction liquid containing this.
(E)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(F)
A step of depositing crystals from the crystallization solution at 90 to 100 ° C. and separating the precipitated crystals.
（ｇ）
炭素数が４以上の鎖状ケトン類存在下、上記式（２）で表されるフルオレン骨格を有するフェノール化合物とエチレンカーボネートとを反応させ、上記式（１）で表されるフルオレン骨格を有するアルコールを含む反応液を得る工程。
（ｈ）
前記反応液から、炭素数が４以上の鎖状ケトン類を含有し、かつ芳香族炭化水素類及び環状ケトン類の合計含有量が１０重量％未満である晶析溶液を調製する工程。
（ｉ）
前記晶析溶液から７０℃以下で結晶を析出させ、析出した結晶を分離する工程。 The manufacturing method of the alcohol which has the fluorene skeleton represented by the said Formula (1) of Claim 5 or 6 including the process of (g)-(i) in this order below.
(G)
An alcohol having a fluorene skeleton represented by the above formula (1) by reacting a phenol compound having a fluorene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a chain ketone having 4 or more carbon atoms. The process of obtaining the reaction liquid containing this.
(H)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(I)
A step of depositing crystals from the crystallization solution at 70 ° C. or lower and separating the precipitated crystals.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015144187 | 2015-07-21 | ||
| JP2015144187 | 2015-07-21 | ||
| JP2016089742 | 2016-04-27 | ||
| JP2016089742 | 2016-04-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017200901A true JP2017200901A (en) | 2017-11-09 |
| JP6739137B2 JP6739137B2 (en) | 2020-08-12 |
Family
ID=57833962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016132178A Active JP6739137B2 (en) | 2015-07-21 | 2016-07-04 | Crystal of alcohol having fluorene skeleton and method for producing the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6739137B2 (en) |
| KR (1) | KR102614834B1 (en) |
| CN (2) | CN111848370A (en) |
| TW (1) | TWI658034B (en) |
| WO (1) | WO2017014141A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019108408A (en) * | 2019-04-16 | 2019-07-04 | 田岡化学工業株式会社 | Crystal of alcohol compound having fluorene skeleton and method for producing the same |
| WO2020059710A1 (en) * | 2018-09-19 | 2020-03-26 | 本州化学工業株式会社 | Crystal of bisfluorene compound |
| WO2020059709A1 (en) * | 2018-09-19 | 2020-03-26 | 本州化学工業株式会社 | Crystal mixture of bisfluorene compound |
| JP2020117460A (en) * | 2019-01-24 | 2020-08-06 | 田岡化学工業株式会社 | Method of producing bisphenol compound with fluorene skeleton |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI707839B (en) * | 2016-05-30 | 2020-10-21 | 日商田岡化學工業股份有限公司 | Manufacturing method of alcohols having fluorene skeleton |
| CN114890877B (en) * | 2022-01-28 | 2024-03-26 | 江苏永星化工股份有限公司 | 9, 9-bis [ 3-phenyl-4- (2-hydroxyethoxy) phenyl ] fluorene and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09255609A (en) * | 1996-03-21 | 1997-09-30 | Taoka Chem Co Ltd | Production of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene |
| JP2001206863A (en) * | 2000-01-25 | 2001-07-31 | Osaka Gas Co Ltd | Fluorene compound and method for the same |
| JP2007197368A (en) * | 2006-01-26 | 2007-08-09 | Taoka Chem Co Ltd | Method for producing fluorene derivative |
| JP2008222708A (en) * | 2007-02-15 | 2008-09-25 | Taoka Chem Co Ltd | Crystal polymorph of fluorene derivative and method for producing the same |
| JP2009173647A (en) * | 2007-12-26 | 2009-08-06 | Osaka Gas Co Ltd | Bifunctional (meth)acrylate having fluorene skeleton |
| JP2009256342A (en) * | 2008-03-27 | 2009-11-05 | Osaka Gas Co Ltd | Method for producing alcohol having fluorene skeleton |
| WO2013133106A1 (en) * | 2012-03-09 | 2013-09-12 | 本州化学工業株式会社 | Method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, crystal of said compound, and method for producing said crystal |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2977714B2 (en) | 1993-10-04 | 1999-11-15 | 鐘紡株式会社 | Polyester molding |
| JPH1045655A (en) * | 1996-07-30 | 1998-02-17 | Taoka Chem Co Ltd | Production of fluorene derivative |
| JPH11158106A (en) * | 1997-12-01 | 1999-06-15 | Osaka Gas Co Ltd | Production of 9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene |
| JP2001122828A (en) | 1999-10-27 | 2001-05-08 | Shinnakamura Kagaku Kogyo Kk | Bifunctional (meth)acrylic ester composition and dihydric alcohol therefor |
| JP5285561B2 (en) * | 2009-09-30 | 2013-09-11 | 大阪瓦斯株式会社 | Polyester resin having a fluorene skeleton |
| JP5501790B2 (en) * | 2010-02-19 | 2014-05-28 | 大阪ガスケミカル株式会社 | Polyester resin having a fluorene skeleton |
| JP5437106B2 (en) * | 2010-02-19 | 2014-03-12 | 大阪ガスケミカル株式会社 | Polyester resin having a fluorene skeleton |
| JP6210555B2 (en) * | 2014-04-03 | 2017-10-11 | 田岡化学工業株式会社 | Method for recovering bisphenolfluorenes from a polyester resin having a fluorene structure |
| JP2016138071A (en) * | 2015-01-29 | 2016-08-04 | 田岡化学工業株式会社 | Method for producing bis hydroxyethyl ether of bisphenols |
-
2016
- 2016-07-04 JP JP2016132178A patent/JP6739137B2/en active Active
- 2016-07-14 KR KR1020187002468A patent/KR102614834B1/en active IP Right Grant
- 2016-07-14 CN CN202010806494.8A patent/CN111848370A/en active Pending
- 2016-07-14 WO PCT/JP2016/070819 patent/WO2017014141A1/en active Application Filing
- 2016-07-14 CN CN201680042171.8A patent/CN107848933B/en active Active
- 2016-07-20 TW TW105122933A patent/TWI658034B/en active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09255609A (en) * | 1996-03-21 | 1997-09-30 | Taoka Chem Co Ltd | Production of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene |
| JP2001206863A (en) * | 2000-01-25 | 2001-07-31 | Osaka Gas Co Ltd | Fluorene compound and method for the same |
| JP2007197368A (en) * | 2006-01-26 | 2007-08-09 | Taoka Chem Co Ltd | Method for producing fluorene derivative |
| JP2008222708A (en) * | 2007-02-15 | 2008-09-25 | Taoka Chem Co Ltd | Crystal polymorph of fluorene derivative and method for producing the same |
| JP2009173647A (en) * | 2007-12-26 | 2009-08-06 | Osaka Gas Co Ltd | Bifunctional (meth)acrylate having fluorene skeleton |
| JP2009256342A (en) * | 2008-03-27 | 2009-11-05 | Osaka Gas Co Ltd | Method for producing alcohol having fluorene skeleton |
| WO2013133106A1 (en) * | 2012-03-09 | 2013-09-12 | 本州化学工業株式会社 | Method for producing 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, crystal of said compound, and method for producing said crystal |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020059710A1 (en) * | 2018-09-19 | 2020-03-26 | 本州化学工業株式会社 | Crystal of bisfluorene compound |
| WO2020059709A1 (en) * | 2018-09-19 | 2020-03-26 | 本州化学工業株式会社 | Crystal mixture of bisfluorene compound |
| CN112638852A (en) * | 2018-09-19 | 2021-04-09 | 本州化学工业株式会社 | Crystal of bifluorene compound |
| KR20210060453A (en) | 2018-09-19 | 2021-05-26 | 혼슈우 카가쿠고교 가부시키가이샤 | Crystal mixture of bisfluorene compounds |
| KR20210063323A (en) | 2018-09-19 | 2021-06-01 | 혼슈우 카가쿠고교 가부시키가이샤 | Crystals of Bisfluorene Compounds |
| JP7358696B2 (en) | 2018-09-19 | 2023-10-11 | 本州化学工業株式会社 | Crystalline mixture of bisfluorene compounds |
| JP7379770B2 (en) | 2018-09-19 | 2023-11-15 | 本州化学工業株式会社 | Crystalline form of bisfluorene compound |
| JP2020117460A (en) * | 2019-01-24 | 2020-08-06 | 田岡化学工業株式会社 | Method of producing bisphenol compound with fluorene skeleton |
| JP7134579B2 (en) | 2019-01-24 | 2022-09-12 | 田岡化学工業株式会社 | Method for producing bisphenol compound having fluorene skeleton |
| JP2019108408A (en) * | 2019-04-16 | 2019-07-04 | 田岡化学工業株式会社 | Crystal of alcohol compound having fluorene skeleton and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201710231A (en) | 2017-03-16 |
| JP6739137B2 (en) | 2020-08-12 |
| WO2017014141A1 (en) | 2017-01-26 |
| CN111848370A (en) | 2020-10-30 |
| KR102614834B1 (en) | 2023-12-15 |
| CN107848933A (en) | 2018-03-27 |
| KR20180030851A (en) | 2018-03-26 |
| CN107848933B (en) | 2020-11-17 |
| TWI658034B (en) | 2019-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6739137B2 (en) | Crystal of alcohol having fluorene skeleton and method for producing the same | |
| JP6739136B2 (en) | Crystal of alcohol having fluorene skeleton and method for producing the same | |
| EP3805195B1 (en) | Crystal of 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl | |
| JP6484465B2 (en) | Crystalline polymorph of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene and process for producing the same | |
| TWI596083B (en) | Crystallization polymorphs of 2,2'-bis (2-hydroxyethoxy) -1,1'-bis-naphthalene and methods for producing the same | |
| JP6830304B2 (en) | Method for Purifying Dihydroxy Compound with Fluorene Skeleton | |
| JP6931984B2 (en) | Crystals of alcohol compounds having a fluorene skeleton and methods for producing them | |
| JP6241977B2 (en) | Method for producing alcohol compound having fluorene skeleton | |
| JP6537388B2 (en) | Inclusion compound using alcohols having a fluorene skeleton | |
| JP2017214364A (en) | Method for producing alcohols having fluorene skeleton | |
| JP6994299B2 (en) | A method for purifying a dihydroxy compound having a fluorene skeleton | |
| TW202110779A (en) | Hexamethyl-substituted/dimethyl-substituted-4,4'-bis(2-propene-1-ylosy)-1,1'-biphenyl crystal body | |
| JP2020158401A (en) | Method for producing crystal of diol compound having fluorene skeleton | |
| JP2019108408A (en) | Crystal of alcohol compound having fluorene skeleton and method for producing the same | |
| JP2024056627A (en) | Crystal of 9,9-bis(6-hydroxy-2-naphthyl)fluorene and method for producing same | |
| WO2020004207A1 (en) | Crystalline body of 9,9-bis(4-hydroxyphenyl)-2,3-benzofluorene | |
| TW202344494A (en) | Biphenanthrene compound or alkali metal salt thereof | |
| JP2020075866A (en) | Bisphenol compound having fluorene skeleton |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190507 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200130 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200228 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20200407 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200602 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200720 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200720 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6739137 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |