JP6760075B2 - Butyrolactone compound and manufacturing method - Google Patents
Butyrolactone compound and manufacturing method Download PDFInfo
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- JP6760075B2 JP6760075B2 JP2016557748A JP2016557748A JP6760075B2 JP 6760075 B2 JP6760075 B2 JP 6760075B2 JP 2016557748 A JP2016557748 A JP 2016557748A JP 2016557748 A JP2016557748 A JP 2016557748A JP 6760075 B2 JP6760075 B2 JP 6760075B2
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- -1 Butyrolactone compound Chemical class 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- YEJRWHAVMIAJKC-UHFFFAOYSA-N gamma-butyrolactone Natural products O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 title description 3
- 229930188620 butyrolactone Natural products 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 99
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- MTCMFVTVXAOHNQ-UHFFFAOYSA-N ethyl 2-(bromomethyl)prop-2-enoate Chemical compound CCOC(=O)C(=C)CBr MTCMFVTVXAOHNQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- NOOYFQLPKUQDNE-UHFFFAOYSA-N 2-(bromomethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)CBr NOOYFQLPKUQDNE-UHFFFAOYSA-N 0.000 claims description 2
- AMNGVFRKAFUEHP-UHFFFAOYSA-N 2-(chloromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)CCl AMNGVFRKAFUEHP-UHFFFAOYSA-N 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 27
- 239000004973 liquid crystal related substance Substances 0.000 description 26
- 150000002430 hydrocarbons Chemical group 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 23
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 20
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 20
- 229930195733 hydrocarbon Natural products 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 150000002170 ethers Chemical class 0.000 description 10
- 150000002367 halogens Chemical group 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000001502 aryl halides Chemical class 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 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 6
- 238000005406 washing Methods 0.000 description 6
- NLWKSLBQYKEGGS-UHFFFAOYSA-N 5-(4-hydroxybutyl)-3-methylideneoxolan-2-one Chemical compound OCCCCC1CC(C(O1)=O)=C NLWKSLBQYKEGGS-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 239000003495 polar organic solvent Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 235000011181 potassium carbonates Nutrition 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 229940117389 dichlorobenzene Drugs 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229940017219 methyl propionate Drugs 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- GSLDEZOOOSBFGP-UHFFFAOYSA-N alpha-methylene gamma-butyrolactone Chemical group C=C1CCOC1=O GSLDEZOOOSBFGP-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- WXFUESXUGJESGK-UHFFFAOYSA-N 5-(4-iodobutyl)-3-methylideneoxolan-2-one Chemical compound ICCCCC1CC(C(O1)=O)=C WXFUESXUGJESGK-UHFFFAOYSA-N 0.000 description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229930008407 benzylideneacetone Natural products 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- NDGDRYSROJEHNM-UHFFFAOYSA-N ethyl 3-bromo-2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=CBr NDGDRYSROJEHNM-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- YJBKVPRVZAQTPY-UHFFFAOYSA-J tetrachlorostannane;dihydrate Chemical compound O.O.Cl[Sn](Cl)(Cl)Cl YJBKVPRVZAQTPY-UHFFFAOYSA-J 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000000825 ultraviolet detection Methods 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 1
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- QVQNAAFDYYJACI-UHFFFAOYSA-N 2-fluoro-4-(4-hydroxyphenyl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C(F)=C1 QVQNAAFDYYJACI-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VBFMBKSMWWSLKU-UHFFFAOYSA-N C(CCC)C1(C)CC=C(C=C1)S(=O)(=O)O Chemical compound C(CCC)C1(C)CC=C(C=C1)S(=O)(=O)O VBFMBKSMWWSLKU-UHFFFAOYSA-N 0.000 description 1
- 0 CC1C(O)OC(*)C1 Chemical compound CC1C(O)OC(*)C1 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- PWUBONDMIMDOQY-UHFFFAOYSA-N acetonitrile;hydrochloride Chemical compound Cl.CC#N PWUBONDMIMDOQY-UHFFFAOYSA-N 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- XXECWTBMGGXMKP-UHFFFAOYSA-L dichloronickel;2-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 XXECWTBMGGXMKP-UHFFFAOYSA-L 0.000 description 1
- ZBQUMMFUJLOTQC-UHFFFAOYSA-L dichloronickel;3-diphenylphosphanylpropyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-L 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- WRKSFOCSVUCYGJ-UHFFFAOYSA-N ethene;triphenylphosphane Chemical compound C=C.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WRKSFOCSVUCYGJ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CFTUQSLVERGMHL-UHFFFAOYSA-N methyl 2-(bromomethyl)prop-2-enoate Chemical compound COC(=O)C(=C)CBr CFTUQSLVERGMHL-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal (AREA)
- Furan Compounds (AREA)
Description
本発明は、ブチロラクトン環を有する化合物の製造方法、及びそこで使用される新規な中間体化合物に関する。 The present invention relates to a method for producing a compound having a butyrolactone ring, and a novel intermediate compound used therein.
基板に対して垂直に配向している液晶分子を、電界によって応答させる方式（垂直配向（ＶＡ）方式ともいう）の液晶表示素子の中には、その製造過程において、液晶分子に電圧を印加しながら紫外線を照射する工程を含むものがある。
このような垂直配向方式の液晶表示素子では、あらかじめ液晶組成物中に光重合性化合物を添加し、ポリイミド等の垂直配向膜と共に用いて、液晶セルに電圧を印加しながら紫外線を照射することで、液晶の応答速度を速くするＰＳＡ（（Polymer sustained Alignment）型液晶ディスプレイ）が知られている。（特許文献１及び非特許文献１参照）In the liquid crystal display element of the method (also called the vertical orientation (VA) method) in which liquid crystal molecules oriented perpendicular to the substrate are made to respond by an electric field, a voltage is applied to the liquid crystal molecules in the manufacturing process. However, some include the step of irradiating ultraviolet rays.
In such a vertically oriented liquid crystal display element, a photopolymerizable compound is added to the liquid crystal composition in advance, and the liquid crystal display element is used together with a vertically oriented film such as polyimide to irradiate the liquid crystal cell with ultraviolet rays while applying a voltage. , PSA ((Polymer sustained Alignment) type liquid crystal display) that increases the response speed of the liquid crystal is known. (See Patent Document 1 and Non-Patent Document 1)
通常、電界に応答した液晶分子の傾く方向は、基板上に設けられた突起や表示用電極に設けられたスリットなどによって制御されているが、液晶組成物中に光重合性化合物を添加し、液晶セルに電圧を印加しながら紫外線を照射することにより、液晶分子の傾いていた方向が記憶されたポリマー構造物が液晶配向膜上に形成されるので、突起やスリットのみで液晶分子の傾き方向を制御する方法と比べて、液晶表示素子の応答速度が速くなるといわれている。
また、光重合性化合物を液晶組成物中ではなく液晶配向膜中に添加することによっても、液晶表示素子の応答速度が速くなることが報告されている（ＳＣ−ＰＶＡ型液晶ディスプレイ）（非特許文献２参照）。
上記の添加光重合性化合物としては、幾つかの重合性化合物が知られている（特許文献２〜６参照）。Normally, the tilting direction of the liquid crystal molecules in response to the electric field is controlled by protrusions provided on the substrate or slits provided in the display electrode, but a photopolymerizable compound is added to the liquid crystal composition. By irradiating the liquid crystal cell with ultraviolet rays while applying a voltage, a polymer structure in which the tilted direction of the liquid crystal molecules is memorized is formed on the liquid crystal alignment film, so that the tilting direction of the liquid crystal molecules is formed only by protrusions and slits. It is said that the response speed of the liquid crystal display element is faster than that of the method of controlling.
It has also been reported that the response speed of the liquid crystal display element is increased by adding the photopolymerizable compound not in the liquid crystal composition but in the liquid crystal alignment film (SC-PVA type liquid crystal display) (non-patented). Reference 2).
As the above-mentioned added photopolymerizable compound, some polymerizable compounds are known (see Patent Documents 2 to 6).
光重合性化合物は、従来、高価な化合物を原料として製造されてきた。そのため、コスト削減が要求される電子機器の原料としては、その供給性に課題があった。そこで、光重合性化合物を安価に製造しうる、新規な製造方法が求められている。 Conventionally, photopolymerizable compounds have been produced using expensive compounds as raw materials. Therefore, as a raw material for electronic devices that are required to reduce costs, there is a problem in its supplyability. Therefore, there is a demand for a novel production method capable of producing a photopolymerizable compound at low cost.
本発明の目的は、上述した従来技術の問題点を解決することにある。
具体的には、本発明の目的は、液晶表示素子に用いられる光重合性化合物を、安価に、収率よく製造するための新規な製造方法及び新規な中間体を提供することにある。An object of the present invention is to solve the above-mentioned problems of the prior art.
Specifically, an object of the present invention is to provide a novel production method and a novel intermediate for producing a photopolymerizable compound used in a liquid crystal display device at low cost and in high yield.
本発明者らは、上記目的を達成すべく、ヒドロキシアルキル基で置換されたγ−ブチロラクトン化合物を中間体として用いることにより、ヒドロキシフェニル基及びヒドロキシナフチル基から選ばれる高価な原料を最終工程に用いることが可能となると考え、検討を重ねた。
その結果、当該中間体が、安価な不飽和へテロ環化合物から１段階で収率よく得られるとともに、当該中間体の保存安定性も良いことから、工業的にも極めて有利であることを見いだした。また、当該中間体を用いて、液晶表示素子において有用な光重合性化合物を製造しうることを見いだした。In order to achieve the above object, the present inventors use an expensive raw material selected from a hydroxyphenyl group and a hydroxynaphthyl group as an intermediate by using a γ-butyrolactone compound substituted with a hydroxyalkyl group in the final step. We thought that it would be possible, and repeated studies.
As a result, it was found that the intermediate is industrially extremely advantageous because it can be obtained from an inexpensive unsaturated heterocyclic compound in a high yield in one step and the storage stability of the intermediate is also good. It was. It has also been found that the intermediate can be used to produce a photopolymerizable compound useful in a liquid crystal display device.
本発明はかかる知見に基づくもので、以下の要旨を有する。
１．下記式（Ａ）で表される化合物と、下記式（Ｃ）で表される化合物とを金属錫又は錫含有化合物の存在下に、酸性条件で反応させることを特徴とする式（１）で表される化合物の製造方法。
1. 1. The formula (1) is characterized in that the compound represented by the following formula (A) and the compound represented by the following formula (C) are reacted in the presence of metallic tin or a tin-containing compound under acidic conditions. Method for producing the represented compound.
２．下記式（１）で表される化合物と、下記式（Ｄ）で表される化合物とを、塩基存在下で反応させ、次いで、式（２）におけるＲ１がハロゲン原子の場合は、得られる反応生成物を金属ハロゲン化物と反応させる下記式（２）で表される化合物の製造方法。
３．下記式（２）で表される化合物を、下記式（Ｅ）で表される化合物と反応させることによる、下記式（３）で表される化合物の製造方法。
（式（４）、（５）又は（６）中、Ｘは、各々独立に、ハロゲン原子、炭素原子数１〜６のアルコキシ基、炭素原子数１〜６のハロアルキル基、炭素原子数１〜６のハロアルコキシ基及びシアノ基から選ばれる置換基を表し、ｍ１〜ｍ６は、各々独立に、０〜４の整数であり、ｍ7及びｍ８は、各々独立に、０〜３の整数であり、Ｘの数が２以上となる場合は、Ｘ同士は同一でも異なっていてもよい。）
４．下記式（１）で表される化合物。
５．下記式（２）で表される化合物。
本発明によれば、ハロゲン置換基を少なくとも１つ有する芳香族環を有する二価の有機基と、２個のα−メチレン−γ−ブチロラクトン基を有する式（３）で表される化合物を、安価に、収率よく製造するための新規な製造方法、及び該製造方法などに使用される、式（１）で表される化合物、及び式（２）で表される化合物の新規な中間体化合物が提供される。
本発明の製造方法で得られる式（３）で表される化合物は、液晶表示素子における重合性化合物として、特に、液晶配向膜材料に添加される重合性化合物として用いた場合には、高い配向固定化能力を有し、且つ、ワニス中での保存安定性が向上し、さらには液晶への溶解性が向上する。According to the present invention, a compound represented by the formula (3) having a divalent organic group having an aromatic ring having at least one halogen substituent and two α-methylene-γ-butyrolactone groups is used. A novel production method for inexpensive and high-yield production, a compound represented by the formula (1), and a novel intermediate of the compound represented by the formula (2) used in the production method and the like. Compounds are provided.
The compound represented by the formula (3) obtained by the production method of the present invention has a high orientation when used as a polymerizable compound in a liquid crystal display element, particularly as a polymerizable compound added to a liquid crystal alignment film material. It has an immobilization ability, improves storage stability in varnish, and further improves solubility in liquid crystal.
＜式（１）で表される化合物＞
本発明は、下記スキームで表されるとおり、下記式（Ａ）で表される不飽和ヘテロ環化合物と、下記式（Ｃ）で表される化合物とを金属錫又は錫含有化合物の存在下に酸性条件で反応させることによる、式（１）で表される化合物の製造方法である。<Compound represented by formula (1)>
In the present invention, as represented by the following scheme, an unsaturated heterocyclic compound represented by the following formula (A) and a compound represented by the following formula (C) are mixed in the presence of metallic tin or a tin-containing compound. This is a method for producing a compound represented by the formula (1) by reacting under acidic conditions.
Ｊ１は、塩素、臭素、ヨウ素が好ましく、塩素又は臭素が好ましい。
Ｒとしては、炭素原子数が１〜５のアルキル基が好ましく、直鎖状でも分岐状でもよいが、直鎖状が好ましい。特に、メチル基又はエチル基が好ましい。
J 1 is chlorine, bromine and iodine are preferred, and chlorine or bromine is preferred.
As R, an alkyl group having 1 to 5 carbon atoms is preferable, and it may be linear or branched, but linear is preferable. In particular, a methyl group or an ethyl group is preferable.
式（Ａ）で表される化合物は、公知化合物であり、商業的に入手することが可能である。式（Ｃ）で表される化合物も公知化合物であり、商業的に入手することが可能である。 The compound represented by the formula (A) is a known compound and is commercially available. The compound represented by the formula (C) is also a known compound and is commercially available.
金属錫又は錫含有化合物の例としては、錫粉末、無水塩化錫、塩化錫二水和物、塩化錫五水和物などの錫系化合物が使用できる。特に、無水塩化錫又は塩化錫二水和物が好ましい。 As examples of metallic tin or tin-containing compounds, tin-based compounds such as tin powder, anhydrous tin chloride, tin chloride dihydrate, and tin chloride pentahydrate can be used. In particular, anhydrous tin chloride or tin chloride dihydrate is preferable.
酸としては、塩酸、硫酸、リン酸などの無機酸水溶液、Ａｍｂｅｒｌｙｓｔ １５などの酸性樹脂、p-トルエンスルホン酸、酢酸、蟻酸などの有機酸が使用できる。特に塩酸、硫酸又は酢酸が好ましい。 As the acid, an aqueous inorganic acid solution such as hydrochloric acid, sulfuric acid or phosphoric acid, an acidic resin such as Amberlyst 15, or an organic acid such as p-toluenesulfonic acid, acetic acid or formic acid can be used. Particularly, hydrochloric acid, sulfuric acid or acetic acid is preferable.
上記化合物（Ｃ）である、アクリル酸誘導体としては、２-(クロロメチル)アクリル酸、２-(クロロメチル)アクリル酸メチル、２-(クロロメチル)アクリル酸エチル、２-(ブロモメチル)アクリル酸、２-(ブロモメチル)アクリル酸メチル、２-(ブロモメチル)アクリル酸エチルなどが好ましく、特に、２-(ブロモメチル)アクリル酸又は２-(ブロモメチル)アクリル酸エチルが好ましい。 Examples of the acrylic acid derivative of the compound (C) include 2- (chloromethyl) acrylic acid, 2- (chloromethyl) methyl acrylate, 2- (chloromethyl) ethyl acrylate, and 2- (bromomethyl) acrylic acid. Methyl 2- (bromomethyl) acrylate, ethyl 2- (bromomethyl) acrylate and the like are preferable, and ethyl 2- (bromomethyl) acrylate or 2- (bromomethyl) acrylate is particularly preferable.
化合物（Ｃ）の使用量は、式（Ａ）で表される化合物である、不飽和ヘテロ環化合物の１当量に対して、１．０〜１．２当量が好ましく、１．１〜１．２当量がより好ましい。 The amount of the compound (C) to be used is preferably 1.0 to 1.2 equivalents, preferably 1.1 to 1 equivalents, relative to 1 equivalent of the unsaturated heterocyclic compound which is the compound represented by the formula (A). 2 equivalents are more preferred.
上記反応は酸性条件で行なわれ、反応におけるｐＨが、好ましくは１〜３、より好ましくは１〜２で行なわれる。 The above reaction is carried out under acidic conditions, and the pH in the reaction is preferably 1-3, more preferably 1-2.
上記反応は、溶媒の使用が好ましく、安定で不活性であり、反応を妨げない溶媒が好ましい。例えば、水、エーテル類（Ｅｔ２Ｏ、 ｉ−Ｐｒ２Ｏ）、 ＴＢＭＥ（ｔｅｒｔ−ブチルメチルエーテル）、 ＣＰＭＥ（シクロペンチルメチルエーテル）、 テトラヒドロフラン、 ジオキサンなど）が使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができ、１種単独でも、２種以上混合しても用いることができる。好ましくは、テトラヒドロフラン又は水である。For the above reaction, the use of a solvent is preferable, and a solvent that is stable and inert and does not interfere with the reaction is preferable. For example, water, ethers (Et 2 O, i-Pr 2 O), TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), tetrahydrofuran, dioxane, etc. can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and can be used alone or in combination of two or more. Preferably, it is tetrahydrofuran or water.
反応温度は、特に限定されないが、通常、０〜１００℃、好ましくは２０〜７０℃である。
反応時間は、通常、１〜１００時間、好ましくは１〜１２時間である。The reaction temperature is not particularly limited, but is usually 0 to 100 ° C, preferably 20 to 70 ° C.
The reaction time is usually 1 to 100 hours, preferably 1 to 12 hours.
上記のようにして得られる化合物（１）である、α−メチレン−γ−ブチロラクトン化合物は、反応後に、反応液に塩基を加えて過剰の酸を除去した後、シリカゲルカラムクロマトグラフィーなどで精製することにより高純度化することができる。 After the reaction, the α-methylene-γ-butyrolactone compound, which is the compound (1) obtained as described above, is purified by silica gel column chromatography or the like after adding a base to the reaction solution to remove excess acid. As a result, high purity can be achieved.
精製に使用されるシリカゲルカラムクロマトグラフィーに用いる溶媒としては、特に限定されないが、例えば、ヘキサン、ヘプタン、トルエンなどの炭化水素類；クロロホルム、１，２−ジクロロエタン、クロロベンゼンなどのハロゲン系炭化水素類；ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサンなどのエーテル類；酢酸エチルなどのエステル類；これらの混溶液；などが挙げられる。好ましくは、酢酸エチルなどのエステル類とヘキサン又はヘプタンなどの炭化水素類との混合液である。 The solvent used for silica gel column chromatography used for purification is not particularly limited, but for example, hydrocarbons such as hexane, heptane, and toluene; halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane, and chlorobenzene; Ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate; mixed solutions thereof; and the like can be mentioned. Preferably, it is a mixed solution of esters such as ethyl acetate and hydrocarbons such as hexane or heptane.
＜式（２）で表される化合物＞
上記で得られた式（１）で表される化合物と、式（Ｄ）で表される化合物とを、塩基存在下で反応させ、次いで、式（２）におけるＲ１がハロゲン原子の場合は、得られる反応生成物を金属ハロゲン化物と反応させることにより、式（３）で表される化合物が製造される。
When the compound represented by the formula (1) obtained above and the compound represented by the formula (D) are reacted in the presence of a base, and then R 1 in the formula (2) is a halogen atom, By reacting the obtained reaction product with a metal halide, the compound represented by the formula (3) is produced.
以下にこれについて説明すると、上記で得られた式（１）で表される化合物の有するヒドロキシ基は、下記スキームに示すように、式（Ｄ）で表される化合物であるスルホン酸ハロゲン化物と反応させることにより、脱離基に変換することができる。
Ｒ２における炭化水素基としては、直鎖状又は分岐状のＣ１-１２アルキル基、Ｃ３-１２シクロアルキル基、Ｃ２-１２ハロアルキル基、Ｒａで置換されていてもよいベンジル基又はＲａで置換されていてもよいフェニル基が挙げられる。
Ｒａとしては、ハロゲン、Ｃ1-6アルキル基、Ｃ1-6ハロアルキル基、Ｃ3-6シクロアルキル基、Ｃ1-6アルコキシ基、Ｃ1-6アルコキシＣ1-6アルキル基、Ｃ1-6ハロアルコキシ基、ＮＯ２、ＣＮ、ホルミル基、及びフェニル基から選ばれる置換基が挙げられる。好ましくはメチル基又はエチル基である。The hydrocarbon group in R 2 includes a linear or branched C 1-12 alkyl group, a C 3-12 cycloalkyl group, a C 2-12 haloalkyl group, a benzyl group which may be substituted with Ra , or a benzyl group. Examples include phenyl groups which may be substituted with Ra .
The R a, halogen, C 1-6 alkyl, C 1-6 haloalkyl group, C 3-6 cycloalkyl group, C 1-6 alkoxy groups, C 1-6 alkoxy C 1-6 alkyl group, C 1 -6 Substituents selected from haloalkoxy groups, NO 2 , CN, formyl groups, and phenyl groups can be mentioned. It is preferably a methyl group or an ethyl group.
化合物（１）と化合物（Ｄ）との反応は、塩基の存在下で行うことが好ましい。塩基は、化合物（１）に対して、好ましくは１．２〜１０当量、より好ましくは１．２〜３当量使用される。
塩基としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸水素ナトリウム、炭酸水素カリウム、水素化ナトリウム等の無機塩基類；ピリジン、４−ジメチルアミノピリジン、トリエチルアミン、トリブチルアミン、Ｎ，Ｎ−ジメチルアニリン、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン等の有機塩基類；等が挙げられる。中でも、４−ジメチルアミノピリジン、ピリジン、トリエチルアミン等の塩基類が使用できる。好ましくは、ピリジン又はトリエチルアミンである。The reaction between compound (1) and compound (D) is preferably carried out in the presence of a base. The base is preferably used in an amount of 1.2 to 10 equivalents, more preferably 1.2 to 3 equivalents, relative to compound (1).
Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydride, etc .; pyridine, 4-dimethylaminopyridine, triethylamine, tributylamine. , N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene and other organic bases; and the like. Among them, bases such as 4-dimethylaminopyridine, pyridine, and triethylamine can be used. Pyridine or triethylamine is preferred.
上記反応においては、溶媒の使用が好ましく、安定で不活性であり、反応を妨げない溶媒が用いられる。例えば、アセトン、メチルエチルケトンなどのケトン類；非プロトン性極性有機溶媒（ＤＭＦ, ＤＭＳＯ, ＤＭＡｃ, ＮＭＰなど）；エーテル類（Ｅｔ２Ｏ, ｉ−Ｐｒ２Ｏ, ＴＢＭＥ, ＣＰＭＥ, テトラヒドロフラン, ジオキサンなど）；芳香族炭化水素類（ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど）；ハロゲン系炭化水素類（クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど）；低級脂肪酸エステル類（酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等）；などが使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができ、１種単独でも、２種以上混合しても用いることができる。好ましくは、テトラヒドロフランである。In the above reaction, the use of a solvent is preferable, and a solvent that is stable, inert, and does not interfere with the reaction is used. For example, ketones such as acetone and methyl ethyl ketone; aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et 2 O, i-Pr 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); Halogen hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); Lower fatty acid esters (methyl acetate) , Ethyl acetate, butyl acetate, methyl propionate, etc.); etc. can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and can be used alone or in combination of two or more. Tetrahydrofuran is preferred.
反応温度は、特に限定されないが、通常、０〜１００℃であり、好ましくは４０〜７０℃である。反応時間は、通常、１〜１００時間であり、好ましくは１〜１２時間である。 The reaction temperature is not particularly limited, but is usually 0 to 100 ° C, preferably 40 to 70 ° C. The reaction time is usually 1 to 100 hours, preferably 1 to 12 hours.
上記で得られた化合物（２−Ａ）は、反応後に、シリカゲルカラムクロマトグラフィーなどで精製することにより高純度化することができる。 The compound (2-A) obtained above can be highly purified by purification by silica gel column chromatography or the like after the reaction.
シリカゲルカラムクロマトグラフィーに用いる溶媒としては、特に限定されないが、例えば、ヘキサン、ヘプタン、トルエンなどの炭化水素類；クロロホルム、１，２−ジクロロエタン、クロロベンゼンなどのハロゲン系炭化水素類；ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサンなどのエーテル類；酢酸エチルなどのエステル類；これらの混溶液；などが挙げられ、好ましくは、酢酸エチルなどのエステル類とヘキサン又はヘプタンなどの炭化水素類との混合液である。 The solvent used for silica gel column chromatography is not particularly limited, but for example, hydrocarbons such as hexane, heptane, and toluene; halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane, and chlorobenzene; diethyl ether, tetrahydrofuran, and the like. Ethers such as 1,4-dioxane; esters such as ethyl acetate; mixed solutions thereof; and the like, preferably in a mixed solution of esters such as ethyl acetate and hydrocarbons such as hexane or heptane. is there.
式（２）におけるＲ１がハロゲン原子である式（２）の化合物を得る場合には、上記で得られた式（２−Ａ）で表される化合物を、好ましくは溶媒中、金属ハロゲン化物と反応させることにより、―ＯＹ１をハロゲンに変換した、式（２−Ｂ）で表される化合物を得ることができる。
上記金属ハロゲン化物としては、ヨウ化ナトリウム、ヨウ化カリウム、臭化ナトリウム、臭化カリウム等が使用できる。金属ハロゲン化物の使用量としては、化合物（２−Ａ）の１モルに対して、１〜２モルが好ましく、１〜１．２モルがさらに好ましい。 As the metal halide, sodium iodide, potassium iodide, sodium bromide, potassium bromide and the like can be used. The amount of the metal halide used is preferably 1 to 2 mol, more preferably 1 to 1.2 mol, based on 1 mol of the compound (2-A).
この反応の溶媒としては、反応条件下に安定であり不活性で、反応を妨げない溶媒が用いられる。例えば、アセトン、メチルエチルケトンなどのケトン類；非プロトン性極性有機溶媒（ＤＭＦ, ＤＭＳＯ, ＤＭＡｃ, ＮＭＰなど）；エーテル類（Ｅｔ２Ｏ, ｉ−Ｐｒ２Ｏ, ＴＢＭＥ, ＣＰＭＥ, テトラヒドロフラン, ジオキサンなど）；芳香族炭化水素類（ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど）；ハロゲン系炭化水素類（クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど）；低級脂肪酸エステル類（酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等）；などが使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができ、１種単独でも、２種以上混合しても用いることができる。好ましくは、アセトンである。As the solvent for this reaction, a solvent that is stable under the reaction conditions, is inert, and does not interfere with the reaction is used. For example, ketones such as acetone and methyl ethyl ketone; aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et 2 O, i-Pr 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); Halogen hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); Lower fatty acid esters (methyl acetate) , Ethyl acetate, butyl acetate, methyl propionate, etc.); etc. can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and can be used alone or in combination of two or more. Acetone is preferred.
反応温度は、特に限定されないが、通常、０〜１００℃であり、好ましくは３０〜４５℃である。反応時間は、通常、１〜１００時間であり、好ましくは１〜１２時間である。 The reaction temperature is not particularly limited, but is usually 0 to 100 ° C, preferably 30 to 45 ° C. The reaction time is usually 1 to 100 hours, preferably 1 to 12 hours.
上記のようにして式（２−Ｂ）で表される化合物は、反応後に、シリカゲルカラムクロマトグラフィーなどで精製することにより高純度化することができる。 The compound represented by the formula (2-B) as described above can be highly purified by purification by silica gel column chromatography or the like after the reaction.
上記の化合物（２−Ａ）から化合物（２−Ｂ）を得る反応において、フェノール性水酸基との反応が特に純度良く進行するという点で、化合物（２−Ａ）におけるＯＹ１におけるＹ１が-ＳＯ２-Ｒ２であり、Ｒ２が上記Ｒａで置換されていてもよいフェニル基である化合物が好ましい。In the reaction for obtaining the compound (2-B) from the above compound (2-A), Y 1 in OY 1 in the compound (2-A) is-in that the reaction with the phenolic hydroxyl group proceeds with particularly high purity. A compound which is SO 2- R 2 and is a phenyl group in which R 2 may be substituted with Ra is preferable.
＜式（３）で表される化合物＞
上記で得られた式（２）で表される化合物は、下記のスキームに示すように、式（Ｅ）で表されるフェノール性水酸基を有する芳香族化合物と、塩基の存在下で反応させることにより、式（３）で表される重合性化合物を得ることができる。<Compound represented by formula (3)>
As shown in the scheme below, the compound represented by the formula (2) obtained above is reacted with the aromatic compound having a phenolic hydroxyl group represented by the formula (E) in the presence of a base. Therefore, the polymerizable compound represented by the formula (3) can be obtained.
上記式中、Ａｒ1は、下記式（４）、（５）又は（６）で表される２価の基である。式（４）、（５）又は（６）中、Ｘは、各々独立に、ハロゲン原子、炭素原子数１〜６のアルコキシ基、炭素原子数１〜６のハロアルキル基、炭素原子数１〜６のハロアルコキシ基及びシアノ基から選ばれる置換基を表し、ｍ１〜ｍ６は、各々独立に、０〜４の整数であり、ｍ7及びｍ８は、各々独立に、０〜３の整数であり、Ｘの数が２以上となる場合は、Ｘ同士は同一でも異なっていてもよい。ハロゲン原子としては、フッ素、塩素、臭素等が挙げられる。
Ｘとしては、メトキシ基、トリフルオロメチル基、トリフロオロメトキシ基等が好ましい。ｍ１〜ｍ６は、０〜１が好ましい。ｍ7、ｍ８は、０〜１が好ましい。In the above formula, Ar 1 is a divalent group represented by the following formula (4), (5) or (6). In formulas (4), (5) or (6), X is independently a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. Represents a substituent selected from the haloalkoxy group and the cyano group of, m 1 to m 6 are each independently an integer of 0 to 4, and m 7 and m 8 are each independently an integer of 0 to 3. When the number of Xs is 2 or more, the Xs may be the same or different. Examples of the halogen atom include fluorine, chlorine, bromine and the like.
As X, a methoxy group, a trifluoromethyl group, a trifluoroolomethoxy group and the like are preferable. The values of m 1 to m 6 are preferably 0 to 1 . M 7 and m 8 are preferably 0 to 1.
塩基としては、水素化ナトリウム、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、燐酸ナトリウム、燐酸カリウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸セシウムなどの無機塩基などが使用できる。好ましくは、炭酸ナトリウム又は炭酸カリウムである。 As the base, inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate can be used. Preferably, it is sodium carbonate or potassium carbonate.
反応速度を促進する目的で、更に添加剤を使用することができる。添加剤としては、ヨウ化カリウム、ヨウ化ナトリウム、第４級アンモニウム塩、クラウンエーテルなどが使用できる。 Further additives can be used for the purpose of accelerating the reaction rate. As the additive, potassium iodide, sodium iodide, quaternary ammonium salt, crown ether and the like can be used.
上記反応においては、溶媒の使用が好ましく、安定で、不活性な、反応を妨げない溶媒が用いられる。例えば、アセトン、メチルエチルケトンなどのケトン類；非プロトン性極性有機溶媒（ＤＭＦ, ＤＭＳＯ, ＤＭＡｃ, ＮＭＰなど）；エーテル類（Ｅｔ２Ｏ, ｉ−Ｐｒ２Ｏ, ＴＢＭＥ, ＣＰＭＥ, テトラヒドロフラン, ジオキサンなど）、芳香族炭化水素類（ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど）；ハロゲン系炭化水素類（クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど）；低級脂肪酸エステル類（酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等）；ニトリル類（アセトニトリル、プロピオニトリル、ブチロニトリル等）；などが使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができ、１種単独でも、２種以上混合しても用いることができる。好ましくは、非プロトン性極性有機溶媒（ＤＭＦ, ＤＭＳＯ, ＤＭＡｃ, ＮＭＰなど）である。In the above reaction, the use of a solvent is preferable, and a stable, inert solvent that does not interfere with the reaction is used. For example, ketones such as acetone and methyl ethyl ketone; aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et 2 O, i-Pr 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.), Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetraline, etc.); Halogen hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); Lower fatty acid esters (methyl acetate) , Ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.); and the like can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and can be used alone or in combination of two or more. Preferably, it is an aprotic polar organic solvent (DMF, DMSO, DMAc, NMP, etc.).
反応温度は、特に限定されないが、通常４０〜２００℃であり、好ましくは４０〜１５０℃である。反応時間は、通常、２０〜１００時間であり、好ましくは２０〜６０時間である。 The reaction temperature is not particularly limited, but is usually 40 to 200 ° C, preferably 40 to 150 ° C. The reaction time is usually 20 to 100 hours, preferably 20 to 60 hours.
上記のようにして得られた化合物（３）は、反応後にスラリー洗浄、再結晶、シリカゲルカラムクロマトグラフィーなどで精製することにより高純度化することができる。 The compound (3) obtained as described above can be purified by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction.
洗浄に用いる溶媒としては、特に限定されないが、例えば、ヘキサン、ヘプタン、トルエンなどの炭化水素類；クロロホルム、１，２−ジクロロエタン、クロロベンゼンなどのハロゲン系炭化水素類；ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサンなどのエーテル類；酢酸エチルなどのエステル類、アセトン又はメチルエチルケトンなどのケトン類、メタノール又はエタノール、２−プロパノール等のアルコール類；これらの混合物；などが挙げられる。好ましくは、メタノール、エタノール、２−プロパノール等のアルコール類である。 The solvent used for washing is not particularly limited, but for example, hydrocarbons such as hexane, heptane, and toluene; halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane, and chlorobenzene; diethyl ether, tetrahydrofuran, 1,4. -Ethers such as dioxane; esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, alcohols such as methanol or ethanol, 2-propanol; mixtures thereof; and the like. Alcohols such as methanol, ethanol and 2-propanol are preferable.
再結晶に用いる溶媒としては、化合物（３）が加熱時に溶解し、冷却時に析出すれば特に限定されない。例えば、ヘキサン、ヘプタン、トルエンなどの炭化水素類；クロロホルム、１，２−ジクロロエタン、クロロベンゼンなどのハロゲン系炭化水素類；ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサンなどのエーテル類；酢酸エチルなどのエステル類；アセトン、メチルエチルケトンなどのケトン類；メタノール、エタノール、２−プロパノール等のアルコール類；これらの混合物；などが挙げられる。好ましくは、テトラヒドロフラン、トルエン、メタノール、エタノール、２−プロパノール、ヘキサン、ヘプタン又はこれらの混合物である。 The solvent used for recrystallization is not particularly limited as long as compound (3) dissolves during heating and precipitates during cooling. For example, hydrocarbons such as hexane, heptane, toluene; halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane, chlorobenzene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane; esters such as ethyl acetate. Classes; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and 2-propanol; mixtures thereof; and the like. Preferably, it is tetrahydrofuran, toluene, methanol, ethanol, 2-propanol, hexane, heptane or a mixture thereof.
＜式（Ｅ）で表される化合物＞
原料である式（Ｅ）で表される化合物は、市販品の入手も可能であるが、下記に示すように、ハロゲン化アリール［２−Ａ］と有機金属試薬［３−Ａ］とを、塩基の存在下に、金属触媒を用いるクロスカップリング反応（鈴木-宮浦反応）させることにより得ることができる。<Compound represented by formula (E)>
The compound represented by the formula (E) as a raw material can be commercially available, but as shown below, an aryl halide [2-A] and an organometallic reagent [3-A] are used. It can be obtained by performing a cross-coupling reaction (Suzuki-Miyaura reaction) using a metal catalyst in the presence of a base.
上記式中、Ｘ、ｍ１及びｍ２は前記の意味を表し、ＨａｌはＢｒ、Ｉ又はＯＴｆ（Ｔｆはパラトルエンスルホニル基）を表し、ＭはＢ（ＯＨ）２又は４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イルを表す。In the above formula, X, m 1 and m 2 represent the above meanings, Hall represents Br, I or OTf (Tf is a paratoluenesulfonyl group), and M is B (OH) 2 or 4,4,5,5. It represents 5-tetramethyl-1,3,2-dioxaborolan-2-yl.
上記クロスカップリング反応に用いるハロゲン化アリール［２−Ａ］とボロン酸誘導体［３−Ａ］の使用量は特に限定されないが、ハロゲン化アリール［２−Ａ］１当量に対して、ボロン酸誘導体［３−Ａ］を１．０〜１．５当量使用することが好ましい。また、ボロン酸誘導体［３−Ａ］１当量に対して、ハロゲン化アリール［２−Ａ］を１．０〜１．５当量使用してもよい。 The amount of the aryl halide [2-A] and the boronic acid derivative [3-A] used in the cross-coupling reaction is not particularly limited, but the boronic acid derivative is based on 1 equivalent of the aryl halide [2-A]. It is preferable to use 1.0 to 1.5 equivalents of [3-A]. Further, 1.0 to 1.5 equivalents of aryl halide [2-A] may be used with respect to 1 equivalent of the boronic acid derivative [3-A].
上記カップリング反応応で用いられる金属触媒としては、金属錯体と配位子とを使用することが好ましいが、配位子なしでも反応が進行する場合は、配位子を用いなくてもよい。金属錯体としては、種々の構造のものを用いることができるが、パラジウム錯体やニッケル錯体が好ましく使用される。金属錯体としては、低原子価のパラジウム錯体又はニッケル錯体を用いることが好ましく、特に３級ホスフィンや３級ホスファイトを配位子とするゼロ価錯体が好ましい。また、反応系中で容易にゼロ価錯体に変換される適当な前駆体を用いることもできる。 As the metal catalyst used in the coupling reaction, it is preferable to use a metal complex and a ligand, but if the reaction proceeds without the ligand, the ligand may not be used. As the metal complex, those having various structures can be used, but a palladium complex and a nickel complex are preferably used. As the metal complex, a low valence palladium complex or a nickel complex is preferably used, and a zero-valent complex having a tertiary phosphine or a tertiary phosphite as a ligand is particularly preferable. It is also possible to use a suitable precursor that is easily converted to a zero-valent complex in the reaction system.
さらに、反応系中で、３級ホスフィンや３級ホスファイトを配位子として含まない錯体と、３級ホスフィンや３級ホスファイトとを混合し、３級ホスフィンや３級ホスファイトを配位子とする低原子価錯体を発生させることもできる。３級ホスフィン又は３級ホスファイトとしては、例えば、トリフェニルホスフィン、トリ-o-トリルホスフィン、ジフェニルメチルホスフィン、フェニルジメチルホスフィン、1,2-ビス（ジフェニルホスフィノ）エタン、1,3-ビス（ジフェニルホスフィノ）プロパン、1,4-ビス（ジフェニルホスフィノ）ブタン、1,1’-ビス（ジフェニルホスフィノ）フェロセン、トリメチルホスファイト、トリエチルホスファイト、トリフェニルホスファイト等が挙げられる。これらの配位子の２種以上を混合して含む錯体も好適に用いられる。 Furthermore, in the reaction system, a complex that does not contain tertiary phosphine or tertiary phosphine as a ligand is mixed with tertiary phosphine or tertiary phosphite, and tertiary phosphine or tertiary phosphite is used as a ligand. It is also possible to generate a low valence complex. Examples of the tertiary phosphine or tertiary phosphine include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, and 1,3-bis ( Examples thereof include diphenylphosphine) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethylphosphite, triethylphosphite, and triphenylphosphine. A complex containing a mixture of two or more of these ligands is also preferably used.
金属触媒としては、３級ホスフィンや３級ホスファイトを含まないパラジウム錯体やニッケル錯体、及び３級ホスフィンや３級ホスファイトを含む錯体と、前記した配位子と、を組み合わせて用いることも好ましい態様である。組み合わせて用いられる、上記３級ホスフィンや３級ホスファイトを含まないパラジウム錯体やニッケル錯体としては、ビス（ベンジリデンアセトン）パラジウム、トリス（ベンジリデンアセトン）ジパラジウム、ビス（アセトニトリル）ジクロロパラジウム、ビス（ベンゾニトリル）ジクロロパラジウム、酢酸パラジウム、塩化パラジウム、塩化パラジウム-アセトニトリル錯体、パラジウム−活性炭、塩化ニッケル、ヨウ化ニッケル等が挙げられる。また、上記３級ホスフィンや３級ホスファイトを含む錯体としては、ジメチルビス（トリフェニルホスフィン）パラジウム、ジメチルビス（ジフェニルメチルホスフィン）パラジウム、（エチレン）ビス（トリフェニルホスフィン）パラジウム、テトラキス（トリフェニルホスフィン）パラジウム、ビス（トリフェニルホスフィン）ジクロロパラジウム、[1,3-ビス(ジフェニルホスフィノ)プロパン]ニッケル(ＩＩ)ジクロリド、[1,2-ビス(ジフェニルホスフィノ)エタン]ニッケル(ＩＩ)ジクロリド等が挙げられる。これらは、上記したものに限定されるものではない。
これらパラジウム錯体及びニッケル錯体の使用量は、いわゆる触媒量で良く、一般的には、基質に対して20モル%以下で十分であり、通常１０モル％以下である。As the metal catalyst, it is also preferable to use a palladium complex or nickel complex containing no tertiary phosphine or tertiary phosphine, a complex containing tertiary phosphine or tertiary phosphine, and the above-mentioned ligand in combination. It is an aspect. Examples of the palladium complex and nickel complex containing no tertiary phosphine or tertiary phosphite used in combination include bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, and bis (benzo). Nitrile) Dichloropalladium, palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated coal, nickel chloride, nickel iodide and the like can be mentioned. Examples of the complex containing the tertiary phosphine and tertiary phosphine include dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, (ethylene) bis (triphenylphosphine) palladium, and tetrakis (triphenyl). Phosphine) palladium, bis (triphenylphosphine) dichloropalladium, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride And so on. These are not limited to those described above.
The amount of these palladium complex and nickel complex used may be a so-called catalytic amount, and in general, 20 mol% or less with respect to the substrate is sufficient, and usually 10 mol% or less.
塩基としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸水素ナトリウム、炭酸水素カリウム、燐酸ナトリウム、燐酸カリウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸セシウムなどの無機塩基；メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、プロピルアミン、ジプロピルアミン、トリプロピルアミン、イソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、ブチルアミン、ジブチルアミン、トリブチルアミン、ジイソプロピルエチルアミン、ピリジン、イミダゾール、キノリン、コリジンなどのアミン類；酢酸ナトリウム、酢酸カリウム、酢酸リチウム；なども使用できる。 Bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; methylamine, dimethyl. Amine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, colisine, etc. Amines; sodium acetate, potassium acetate, lithium acetate; etc. can also be used.
上記反応においては、溶媒の使用が好ましく、安定で、不活性な、反応を妨げない溶媒が用いられる。例えば、水、アルコール類、アミン類、非プロトン性極性有機溶媒（ＤＭＦ, ＤＭＳＯ, ＤＭＡｃ, ＮＭＰなど）、エーテル類（Ｅｔ２Ｏ, ｉ−Ｐｒ２Ｏ, ＴＢＭＥ, ＣＰＭＥ, テトラヒドロフラン, ジオキサンなど）、脂肪族炭化水素類（ペンタン、へキサン、ヘプタン、石油エーテルなど）、芳香族炭化水素類（ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど）、ハロゲン系炭化水素類（クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど）、低級脂肪酸エステル類（酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等）、ニトリル類（アセトニトリル、プロピオニトリル、ブチロニトリル等）などが使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができるが、上記溶媒は１種単独でも２種以上混合しても用いることができる。In the above reaction, the use of a solvent is preferable, and a stable, inert solvent that does not interfere with the reaction is used. For example, water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et 2 O, i-Pr 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.), Aliper hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetraline, etc.), halogen-based hydrocarbons (chloroform) , Dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetohydrate, propionitrile, butyronitrile, etc.) and the like can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and the above-mentioned solvents can be used alone or in combination of two or more.
反応温度は、特に限定されないが、通常、−９０〜２００℃であり、好ましくは−５０〜１５０℃、より好ましくは４０〜１２０℃である。反応時間は、通常、０．０５〜１００時間、好ましくは０．５〜４０時間であり、より好ましくは０．５〜２４時間である。 The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably −50 to 150 ° C., and more preferably 40 to 120 ° C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, and more preferably 0.5 to 24 hours.
上記のようにして得られたビフェニル化合物［４−Ａ］は、反応後にスラリー洗浄、再結晶、シリカゲルカラムクロマトグラフィーなどで精製することにより、高純度化することができる。 The biphenyl compound [4-A] obtained as described above can be purified by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction.
スラリー洗浄に用いる溶媒としては、特に限定されないが、例えば、ヘキサン、ヘプタン、トルエンなどの炭化水素類；クロロホルム、１，２−ジクロロエタン、クロロベンゼンなどのハロゲン系炭化水素類；ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサンなどのエーテル類；酢酸エチルなどのエステル類；アセトン、メチルエチルケトンなどのケトン類；アセトニトリル又、プロピオニトリル等のニトリル類；メタノール、エタノール、２−プロパノール等のアルコール類；これらの混合物；などが挙げられる。 The solvent used for washing the slurry is not particularly limited, but for example, hydrocarbons such as hexane, heptane and toluene; halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene; diethyl ether, tetrahydrofuran, 1, Ethers such as 4-dioxane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol and 2-propanol; mixtures thereof; And so on.
再結晶に用いる溶媒としては、ビフェニル化合物［４−Ａ］が加熱時に溶解し、冷却時に析出すれば特に限定されない。例えば、ヘキサン、ヘプタン、トルエンなどの炭化水素類；クロロホルム、１，２−ジクロロエタン、クロロベンゼンなどのハロゲン系炭化水素類；ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサンなどのエーテル類；酢酸エチルなどのエステル類；アセトン、メチルエチルケトンなどのケトン類；アセトニトリル、プロピオニトリル等のニトリル類；メタノール、エタノール、２−プロパノール等のアルコール類；これらの混合物；などが挙げられる。好ましくは、酢酸エチル、テトラヒドロフラン、トルエン又はヘキサンである。このような方法により、各種の化合物（Ｅ）を製造することができる。 The solvent used for recrystallization is not particularly limited as long as the biphenyl compound [4-A] dissolves during heating and precipitates during cooling. For example, hydrocarbons such as hexane, heptane, toluene; halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane, chlorobenzene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane; esters such as ethyl acetate. Classes; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol and 2-propanol; mixtures thereof; and the like. Preferably, it is ethyl acetate, tetrahydrofuran, toluene or hexane. By such a method, various compounds (E) can be produced.
以下、本発明を実施例によりさらに具体的に説明するが、これらの実施例によって本発明の解釈が限定されるものではない。なお、実施例にて採用した分析装置及び分析条件は、下記のとおりである。
ＨＰＬＣ分析
装置：ＬＣ−２０Ａシステム（島津製作所社製）
カラム：Ｉｎｅｒｔｓｉｌ ＯＤＳ−３（４．６ｍｍΦ×２５０ｍｍ、ジーエルサイエンス社製）
検出器：ＵＶ検出（波長２２０ｎｍ）
溶離液：アセトニトリル／０．１ｗｔ％リン酸水溶液（３０／７０、ｖ／ｖ、０−１０ｍｉｎ）→（８０／２０、ｖ／ｖ、１５−２５ｍｉｎ）Hereinafter, the present invention will be described in more detail with reference to Examples, but the interpretation of the present invention is not limited by these Examples. The analyzer and analysis conditions adopted in the examples are as follows.
HPLC analyzer: LC-20A system (manufactured by Shimadzu Corporation)
Column: Inertsil ODS-3 (4.6 mmΦ x 250 mm, manufactured by GL Sciences)
Detector: UV detection (wavelength 220 nm)
Eluent: Acetonitrile / 0.1 wt% aqueous phosphate solution (30/70, v / v, 0-10 min) → (80/20, v / v, 15-25 min)
実施例１：
ＴＨＦ(テトラヒドロフラン)（３００．０ｇ）、１Ｎ塩酸（３３．９ｇ）及びブロモメタクリル酸エチルエステル（７５．７ｇ、３９２ｍｍｏｌ）の混合溶液に、塩化第一スズ−２水和物（８８．５ｇ、３９２ｍｍｏｌ）を溶解した後、３，４−ジヒドロ−２Ｈ−ピラン（３０．０ｇ、３５７ｍｍｏｌ）を、２５−３０℃で３０分かけて滴下した。その後、６４℃まで昇温し、７時間撹拌して、５−（４−ヒドロキシブチル）−３−メチレンジヒドロフラン−２（３Ｈ）−オンを含む反応混合物を得た。 Stannous chloride-2-hydrate (88.5 g, 392 mmol) in a mixed solution of THF (tetrahydrofuran) (300.0 g), 1N hydrochloric acid (33.9 g) and bromomethacrylate ethyl ester (75.7 g, 392 mmol). ) Was dissolved, and then 3,4-dihydro-2H-pyran (30.0 g, 357 mmol) was added dropwise at 25-30 ° C. over 30 minutes. Then, the temperature was raised to 64 ° C. and the mixture was stirred for 7 hours to obtain a reaction mixture containing 5- (4-hydroxybutyl) -3-methylenedihydrofuran-2 (3H) -one.
次に、得られた反応液を２５℃まで冷却し、トリエチルアミン（１２０．０ｇ、１１８６ｍｍｏｌ）を加え、生成した白色の塩をろ過により除去した。続いて、得られたろ液を濃縮して、５−（４−ヒドロキシブチル）−３−メチレンジヒドロフラン−２（３Ｈ）−オンを得た。（５８．８ｇ、収率９６．９％） Next, the obtained reaction solution was cooled to 25 ° C., triethylamine (120.0 g, 1186 mmol) was added, and the white salt produced was removed by filtration. Subsequently, the obtained filtrate was concentrated to obtain 5- (4-hydroxybutyl) -3-methylenedihydrofuran-2 (3H) -one. (58.8 g, yield 96.9%)
実施例２
ＴＨＦ（３００．０ｇ）、１Ｎ塩酸（３３．９ｇ）及びブロモメタクリル酸エチルエステル（９０．９ｇ、４７１ｍｍｏｌ）の混合溶液に、塩化第一スズ−２水和物（１０６．２ｇ、４７１ｍｍｏｌ）を溶解した後、２，３−ジヒドロフラン（３０．０ｇ、４２８ｍｍｏｌ）を、２５−３０℃で３０分かけて滴下した。その後、６４℃まで昇温し、６時間撹拌して、５−（３−ヒドロキプロピル）−３−メチレンジヒドロフラン−２（３Ｈ）−オンを含む反応混合物を得た。
次に、得られた反応液を２５℃まで冷却し、トリエチルアミン（１４２．８ｇ、１４１１ｍｍｏｌ）を加え、生成した白色の塩をろ過により除去した。続いて、得られたろ液を濃縮して、５−（３−ヒドロキプロピル）−３−メチレンジヒドロフラン−２（３Ｈ）−オンを得た。（４３．５ｇ、収率６５．１％）Stannous chloride-2-hydrate (106.2 g, 471 mmol) is dissolved in a mixed solution of THF (300.0 g), 1N hydrochloric acid (33.9 g) and bromomethacrylate ethyl ester (90.9 g, 471 mmol). After that, 2,3-dihydrofuran (30.0 g, 428 mmol) was added dropwise at 25-30 ° C. over 30 minutes. Then, the temperature was raised to 64 ° C. and the mixture was stirred for 6 hours to obtain a reaction mixture containing 5- (3-hydrokipropyl) -3-methylenedihydrofuran-2 (3H) -one.
Next, the obtained reaction solution was cooled to 25 ° C., triethylamine (142.8 g, 1411 mmol) was added, and the white salt produced was removed by filtration. Subsequently, the obtained filtrate was concentrated to obtain 5- (3-hydrokipropyl) -3-methylenedihydrofuran-2 (3H) -one. (43.5 g, yield 65.1%)
実施例1で得られた化合物を出発原料として用いた際は、例えば、以下の化合物へ誘導することが可能である。下記式中、Ｍｓはメタンスルホニル基を、Ｉはヨウ素原子を、Ｔｓはｐ−トルエンスルホニル基をそれぞれ表す。 When the compound obtained in Example 1 is used as a starting material, for example, it is possible to induce the following compounds. In the following formula, Ms represents a methanesulfonyl group, I represents an iodine atom, and Ts represents a p-toluenesulfonyl group.
実施例３
ＴＨＦ（３０３．５ｇ）、トリエチルアミン（２１．７ｇ、２１４ｍｍｏｌ）及び５−（４−ヒドロキシブチル）−３−メチレンジヒドロフラン−２（３Ｈ）−オン（３０．４ｇ、１７８ｍｍｏｌ）の混合溶液に、メタンスルホニルクロリド（２４．５ｇ、２１３ｍｍｏｌ）を、０℃で３０分かけて滴下した。その後、５時間撹拌して、４−（４−メチレン−５−オキソテトラヒドロフラン−２−イル）ブチルメタンスルホナートを含む反応混合物を得た。
次に、得られた反応液を２５℃まで昇温し、生成した白色の塩をろ過により除去した。続いて、得られたろ液を濃縮して、４−（４−メチレン−５−オキソテトラヒドロフラン−２−イル）ブチルメタンスルホナートを得た。（４１．１ｇ、収率９２．８％）Methane in a mixed solution of THF (303.5 g), triethylamine (21.7 g, 214 mmol) and 5- (4-hydroxybutyl) -3-methylenedihydrofuran-2 (3H) -one (30.4 g, 178 mmol). Sulfonyl chloride (24.5 g, 213 mmol) was added dropwise at 0 ° C. over 30 minutes. Then, the mixture was stirred for 5 hours to obtain a reaction mixture containing 4- (4-methylene-5-oxotetrahydrofuran-2-yl) butylmethanesulfonate.
Next, the temperature of the obtained reaction solution was raised to 25 ° C., and the produced white salt was removed by filtration. Subsequently, the obtained filtrate was concentrated to obtain 4- (4-methylene-5-oxotetrahydrofuran-2-yl) butylmethanesulfonate. (41.1 g, yield 92.8%)
実施例４：
アセトン（１００．０ｇ）、ヨウ化ナトリウム（７．２ｇ、４８ｍｍｏｌ）及び４−（４−メチレン−５−オキソテトラヒドロフラン−２−イル）ブチルメタンスルホナート（１０．０ｇ、４０ｍｍｏｌ）を２５〜３０℃で混合して仕込み、４５℃で６時間撹拌して、５−（４−ヨードブチル）−３−メチレンジヒドロフラン−２（３Ｈ）−オンを含む反応混合物を得た。
次に、得られた反応混合物を濃縮し、酢酸エチル（１００．０ｇ）で希釈し、１０ｗｔ％亜硫酸ナトリウム水溶液（１００．０ｇ）で２回洗浄した。次いで、水（１００．０ｇ）で洗浄し、有機層を濃縮して、５−（４−ヨードブチル）−３−メチレンジヒドロフラン−２（３Ｈ）−オンを得た。（４１．１ｇ、収率７１．０％）Acetone (100.0 g), sodium iodide (7.2 g, 48 mmol) and 4- (4-methylene-5-oxotetrahydrofuran-2-yl) butylmethanesulfonate (10.0 g, 40 mmol) at 25-30 ° C. The mixture was charged at 45 ° C. and stirred at 45 ° C. for 6 hours to obtain a reaction mixture containing 5- (4-iodobutyl) -3-methylenedihydrofuran-2 (3H) -one.
The resulting reaction mixture was then concentrated, diluted with ethyl acetate (100.0 g) and washed twice with a 10 wt% aqueous sodium sulfite solution (100.0 g). It was then washed with water (100.0 g) and the organic layer was concentrated to give 5- (4-iodobutyl) -3-methylenedihydrofuran-2 (3H) -one. (41.1 g, yield 71.0%)
実施例５：
ｐ−トルエンスルホニルクロリド（３３．６ｇ、１７６ｍｍｏｌ）及びピリジン（２００．０ｇ）の混合溶液に、５−（４−ヒドロキシブチル）−３−メチレンジヒドロフラン−２（３Ｈ）−オン（２０．０ｇ、１１８ｍｍｏｌ）を、２０〜３０℃で１０分かけて滴下した。その後、２時間撹拌して、４−（４−メチレン−５−オキソテトラヒドロフラン−２−イル）ブチル−４−メチルベンゼンスルホナートを含む反応混合物を得た。
次に、得られた反応混合物に、ジエチルエーテル（２００．０ｇ）及び水（２００．０ｇ）を加えて水洗を行った後、水層を分離、廃棄した。その後、１Ｎ塩酸（２００．０ｇ）を加えて３回洗浄を行った後、有機層を濃縮して、４−（４−メチレン−５−オキソテトラヒドロフラン−２−イル）ブチル−４−メチルベンゼンスルホナートを得た。（１４．５ｇ、収率３８．０％）In a mixed solution of p-toluenesulfonyl chloride (33.6 g, 176 mmol) and pyridine (200.0 g), 5- (4-hydroxybutyl) -3-methylenedihydrofuran-2 (3H) -one (20.0 g, 118 mmol) was added dropwise at 20-30 ° C. over 10 minutes. Then, the mixture was stirred for 2 hours to obtain a reaction mixture containing 4- (4-methylene-5-oxotetrahydrofuran-2-yl) butyl-4-methylbenzenesulfonate.
Next, diethyl ether (200.0 g) and water (200.0 g) were added to the obtained reaction mixture for washing with water, and then the aqueous layer was separated and discarded. Then, 1N hydrochloric acid (200.0 g) was added for washing three times, and then the organic layer was concentrated to concentrate 4- (4-methylene-5-oxotetrahydrofuran-2-yl) butyl-4-methylbenzenesulfon. Got nat. (14.5 g, yield 38.0%)
実施例５で得られた化合物を出発原料として用い、実施例６で示す反応により、下記化合物を合成した。
なお、実施例６で採用した分析装置及び分析条件は、検出器としてＵＶ検出（波長２６５ｎｍ）を使用し、また、溶離液として、アセトニトリル／０．２ｗｔ％酢酸アンモニウム水溶液（７０／３０（０−５ｍｉｎ）→８５／１５（１０−３０ｍｉｎ））［ｖ／ｖ］を使用した以外は、上記したＨＰＬＣ分析を使用した。Using the compound obtained in Example 5 as a starting material, the following compound was synthesized by the reaction shown in Example 6.
The analyzer and analytical conditions adopted in Example 6 used UV detection (wavelength 265 nm) as a detector, and acetonitrile / 0.2 wt% ammonium acetate aqueous solution (70/30 (0-)) as an eluent. The HPLC analysis described above was used, except that 5 min) → 85/15 (10-30 min)) [v / v] was used.
実施例６：
ジメチルホルムアミド（１００．０ｇ）、３−フルオロ［１，１‘−ビフェニル］−４，４’−ジオール（５．０ｇ、２５ｍｍｏｌ）及び炭酸カリウム（７．５ｇ、５４ｍｍｏｌ）の混合溶液に、４−（４−メチレン−５−オキソテトラヒドロフラン−２−イル）ブチル−４−メチルベンゼンスルホナート（１９．１ｇ、５９ｍｍｏｌ）を、２０〜３０℃で１０分かけて滴下した。その後、６０℃で２０時間、８０℃で２７時間撹拌して、４，４‘−ビス（４−（３−メチレンテトラヒドロフラン−２（３Ｈ）−オン−５−イル）ブトキシ）−３−フルオロ−ビフェニルを含む反応混合物を得た。 In a mixed solution of dimethylformamide (100.0 g), 3-fluoro [1,1'-biphenyl] -4,4'-diol (5.0 g, 25 mmol) and potassium carbonate (7.5 g, 54 mmol), 4- Butyl-4-methylbenzenesulfonate (19.1 g, 59 mmol) (4-methylene-5-oxotetra-2-yl) was added dropwise at 20-30 ° C. over 10 minutes. Then, the mixture was stirred at 60 ° C. for 20 hours and 80 ° C. for 27 hours to 4,4'-bis (4- (3-methylenetetrahydrofuran-2 (3H) -on-5-yl) butoxy) -3-fluoro-. A reaction mixture containing biphenyl was obtained.
次に、得られた反応混合物に水（１６７．０ｇ）を加え、ろ過を行った後で、ろ物を回収した。次いで、ろ物にＴＨＦ（１６７．０ｇ）を加えて溶解させた後、再度、ろ過により不溶物を除去した。その後、ろ液にヘプタン（６７．０ｇ）を加え、結晶を析出させた。析出した結晶をろ過し、乾燥して、４，４‘−ビス（４−（３−メチレンテトラヒドロフラン−２（３Ｈ）−オン−５−イル）ブトキシ）−３−フルオロ−ビフェニルを得た。（６．７ｇ、収率５３．５％）（ＨＰＬＣ純度；９１％） Next, water (167.0 g) was added to the obtained reaction mixture, filtration was performed, and then the filtrate was recovered. Then, THF (167.0 g) was added to the filtrate to dissolve it, and then the insoluble matter was removed by filtration again. Then, heptane (67.0 g) was added to the filtrate to precipitate crystals. The precipitated crystals were filtered and dried to give 4,4'-bis (4- (3-methylene tetrahydrofuran-2 (3H) -one-5-yl) butoxy) -3-fluoro-biphenyl. (6.7 g, yield 53.5%) (HPLC purity; 91%)
本発明の製造方法により得られる、式（３）で表されるα−メチレン−γ−ブチロラクトン基を有する化合物は、液晶表示素子に用いられる光重合性化合物などして広範な分野に使用される。また、式（１）で表される化合物、及び式（２）で表される化合物は、式（３）で表される化合物の中間体などして使用される。 The compound having an α-methylene-γ-butyrolactone group represented by the formula (3) obtained by the production method of the present invention is used in a wide range of fields such as a photopolymerizable compound used in a liquid crystal display device. .. Further, the compound represented by the formula (1) and the compound represented by the formula (2) are used as an intermediate of the compound represented by the formula (3).
なお、２０１４年１１月４日に出願された日本特許出願２０１４−２２４５１１号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2014-224511 filed on November 4, 2014 are cited here and incorporated as disclosure of the specification of the present invention. It is a thing.
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| TW201623270A (en) | 2016-07-01 |
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