JP2020093995A - Polymerizable cinnamate ester derivative manufacturing method - Google Patents
Polymerizable cinnamate ester derivative manufacturing method Download PDFInfo
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- JP2020093995A JP2020093995A JP2018232586A JP2018232586A JP2020093995A JP 2020093995 A JP2020093995 A JP 2020093995A JP 2018232586 A JP2018232586 A JP 2018232586A JP 2018232586 A JP2018232586 A JP 2018232586A JP 2020093995 A JP2020093995 A JP 2020093995A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 68
- -1 cinnamate ester Chemical class 0.000 title claims abstract description 58
- 229940114081 cinnamate Drugs 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 361
- 239000000203 mixture Substances 0.000 claims abstract description 98
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 47
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 63
- 125000001153 fluoro group Chemical group F* 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 13
- 125000006239 protecting group Chemical group 0.000 claims description 11
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 6
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 6
- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims description 5
- 125000006850 spacer group Chemical group 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000003821 2-(trimethylsilyl)ethoxymethyl group Chemical group [H]C([H])([H])[Si](C([H])([H])[H])(C([H])([H])[H])C([H])([H])C(OC([H])([H])[*])([H])[H] 0.000 claims description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 333
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 186
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 108
- 238000006243 chemical reaction Methods 0.000 description 107
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 69
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 66
- 238000004440 column chromatography Methods 0.000 description 63
- 239000012267 brine Substances 0.000 description 59
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 59
- 238000000746 purification Methods 0.000 description 58
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 53
- 239000000243 solution Substances 0.000 description 49
- 238000001816 cooling Methods 0.000 description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 42
- 239000012299 nitrogen atmosphere Substances 0.000 description 41
- 238000001953 recrystallisation Methods 0.000 description 37
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 28
- 238000001914 filtration Methods 0.000 description 27
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- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
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- 125000003367 polycyclic group Chemical group 0.000 description 10
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- 238000003786 synthesis reaction Methods 0.000 description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229930016911 cinnamic acid Natural products 0.000 description 9
- 235000013985 cinnamic acid Nutrition 0.000 description 9
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 8
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
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- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
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- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
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- GXHFUVWIGNLZSC-UHFFFAOYSA-N meldrum's acid Chemical compound CC1(C)OC(=O)CC(=O)O1 GXHFUVWIGNLZSC-UHFFFAOYSA-N 0.000 description 1
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- 229910052753 mercury Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
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- IDVWLLCLTVBSCS-UHFFFAOYSA-N n,n'-ditert-butylmethanediimine Chemical compound CC(C)(C)N=C=NC(C)(C)C IDVWLLCLTVBSCS-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
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- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Liquid Crystal (AREA)
Abstract
Description
本発明は重合性ケイ皮酸エステル誘導体の製造方法、当該重合性化合物を使用して製造される重合性組成物及び当該重合性組成物を用いた液晶表示素子に関する。 The present invention relates to a method for producing a polymerizable cinnamic acid ester derivative, a polymerizable composition produced using the polymerizable compound, and a liquid crystal display device using the polymerizable composition.
ＴＦＴ液晶材料に使用される液晶化合物及び重合性化合物は、ディスプレイに焼き付きを引き起こす不純物を含有しないことは元より、なるべく高純度であることが好ましいとされている。 It is said that the liquid crystal compound and the polymerizable compound used for the TFT liquid crystal material preferably have a high purity as much as possible because they do not contain impurities that cause image sticking to the display.
ＴＦＴ液晶表示素子の種類の一つであるＰＳＡ（Ｐｏｌｙｍｅｒ Ｓｕｓｔａｉｎｅｄ Ａｌｉｇｎｍｅｎｔ）型液晶表示素子は、セル内にプレチルト角を制御するためのポリマー構造を有しており、高コントラスト表示及び高速応答が可能である。この素子は、重合性化合物を添加した液晶組成物をセル内に注入し、電圧を印加した状態でＵＶ照射を行い、重合性化合物を重合させることによって作製される。従って、この素子に使用される液晶化合物及び重合性化合物には、特にＵＶ照射によってパネルに焼き付き等の悪影響を及ぼす不純物を含有しないことが求められる。 A PSA (Polymer Sustained Alignment) liquid crystal display device, which is one of the types of TFT liquid crystal display devices, has a polymer structure for controlling the pretilt angle in the cell, and is capable of high contrast display and high-speed response. is there. This device is manufactured by injecting a liquid crystal composition to which a polymerizable compound is added into a cell, and irradiating with UV while a voltage is applied to polymerize the polymerizable compound. Therefore, it is required that the liquid crystal compound and the polymerizable compound used in this device do not contain impurities that adversely affect the panel such as image sticking due to UV irradiation.
重合性ケイ皮酸エステル誘導体の製造方法としては、フェノール部位を有するメソゲン構造を先に製造し、最終工程においてアクリル基又はメタクリル基を導入する方法が一般的に用いられてきた（特許文献１）。これは、先にアクリル基又はメタクリル基等の重合性基を導入してしまうと、その後の加熱工程、濃縮工程及び乾燥工程等において、それらの重合性基が反応しオリゴマーが生成してしまい、純度が低下することが懸念されるからであった。特に重合性ケイ皮酸エステル誘導体においては、ケイ皮酸部位がオリゴマー等の種々の不純物の生成を促進してしまうため、上記の製造方法が採られてきた。しかしながら、上記の製造方法によって製造された重合性ケイ皮酸エステル誘導体は、液晶組成物に添加しＴＦＴ液晶表示素子を作製した場合に、表示素子に焼き付きを起こしやすい問題があった。そのため、そのような表示素子に焼き付きを起こしやすい不純物を生じにくい、重合性ケイ皮酸エステル誘導体の製造方法の開発が求められていた。 As a method for producing a polymerizable cinnamic acid ester derivative, a method of first producing a mesogenic structure having a phenol moiety and introducing an acrylic group or a methacrylic group in the final step has been generally used (Patent Document 1). .. This is because if a polymerizable group such as an acrylic group or a methacrylic group is introduced in advance, then in the subsequent heating step, concentration step and drying step, those polymerizable groups react to form an oligomer, This is because there is a concern that the purity will decrease. Especially in the case of a polymerizable cinnamic acid ester derivative, the above-mentioned production method has been adopted because the cinnamic acid site promotes the production of various impurities such as oligomers. However, the polymerizable cinnamic acid ester derivative produced by the above-mentioned production method has a problem that when a TFT liquid crystal display element is produced by adding it to a liquid crystal composition, burn-in is likely to occur in the display element. Therefore, there has been a demand for development of a method for producing a polymerizable cinnamic acid ester derivative, in which impurities that easily cause image sticking to such a display element are less likely to occur.
本発明が解決しようとする課題は、液晶組成物に添加しＴＦＴ液晶表示素子を作製した場合に、表示素子に焼き付きを起こしにくい、重合性ケイ皮酸エステル誘導体の製造方法を提供することである。また、当該重合性ケイ皮酸エステル誘導体を含有する重合性組成物の製造方法及び当該重合性組成物を重合させることで得られる液晶表示素子の製造方法を提供することである。 The problem to be solved by the present invention is to provide a method for producing a polymerizable cinnamic acid ester derivative, which is less likely to cause burn-in to a display element when added to a liquid crystal composition to produce a TFT liquid crystal display element. .. Another object is to provide a method for producing a polymerizable composition containing the polymerizable cinnamic acid ester derivative and a method for producing a liquid crystal display device obtained by polymerizing the polymerizable composition.
本発明者らは、上記課題を解決すべく、鋭意研究を行った結果、従来から行われてきたフェノール部位を有するメソゲン構造を先に製造し、最終工程においてアクリル基又はメタクリル基を導入する方法によると、中間体として使用したフェノール部位を有するメソゲン構造において、当該構造に含まれるエステル結合が交換反応を起こすことによって、多環性の微量不純物が生じ、この多環性の微量不純物が焼き付きを引き起こしていることが原因と推測した。そこで、本発明者らは、下記の一般式（Ｉ） As a result of intensive studies to solve the above problems, the present inventors have previously produced a mesogen structure having a phenol moiety, which has been conventionally performed, and a method of introducing an acrylic group or a methacrylic group in the final step. According to the above, in the mesogenic structure having a phenol moiety used as an intermediate, an ester bond contained in the structure causes an exchange reaction to generate a polycyclic trace impurity, and this polycyclic trace impurity causes seizure. I suspected that the cause was the cause. Therefore, the present inventors have made the following general formula (I)
で表される化合物と、下記の一般式（ＩＩ） And a compound represented by the following general formula (II)
で表される化合物とを反応させる工程を含む、下記の一般式（ＩＩＩ） The compound represented by the following general formula (III) including a step of reacting with a compound represented by
で表される化合物の製造方法を提供する。併せて一般式（ＩＩＩ）で表される化合物を含有する重合性組成物の製造方法及び当該重合性組成物を重合させることで得られる液晶表示素子の製造方法を提供する。 A method for producing the compound represented by Also provided are a method for producing a polymerizable composition containing a compound represented by formula (III) and a method for producing a liquid crystal display device obtained by polymerizing the polymerizable composition.
本願発明の製造方法は、従来の方法と比較し、液晶組成物に添加しＴＦＴ液晶表示素子を作製した場合に、表示素子に焼き付きを起こしにくいことから、重合性ケイ皮酸エステル誘導体の製造方法として有用である。 The production method of the present invention is a method for producing a polymerizable cinnamic acid ester derivative, as compared with a conventional method, when a TFT liquid crystal display element is produced by adding it to a liquid crystal composition, the display element is less likely to cause burn-in. Is useful as
本願発明は、一般式（Ｉ）で表される化合物と一般式（ＩＩ）で表される化合物とを反応させる工程を含む一般式（ＩＩＩ）で表される化合物の製造方法を提供する。併せて一般式（ＩＩＩ）で表される化合物を含有する重合性組成物の製造方法及び当該重合性組成物を重合させることで得られる液晶表示素子の製造方法を提供する。 The present invention provides a process for producing a compound represented by general formula (III), which comprises a step of reacting a compound represented by general formula (I) with a compound represented by general formula (II). Also provided are a method for producing a polymerizable composition containing a compound represented by formula (III) and a method for producing a liquid crystal display device obtained by polymerizing the polymerizable composition.
一般式（Ｉ）及び一般式（ＩＩ）において、Ｐ１及びＰ２は各々独立してラジカル重合、カチオン重合又はアニオン重合により重合する基を表す。合成の容易さ、液晶組成物との相溶性、液晶表示素子を作製した場合の焼き付きの生じにくさの観点から、Ｐ１及びＰ２が各々独立して下記の式（Ｐ−１）から式（Ｐ−２０） In the general formula (I) and the general formula (II), P 1 and P 2 each independently represent a group polymerized by radical polymerization, cationic polymerization or anionic polymerization. From the viewpoints of ease of synthesis, compatibility with a liquid crystal composition, and resistance to image sticking when a liquid crystal display device is manufactured, P 1 and P 2 are each independently a formula from the following formula (P-1): (P-20)
（式中、破線は結合位置を表す。）から選ばれる基を表すことが好ましく、Ｐ１及びＰ２は各々独立して式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）、式（Ｐ−４）、式（Ｐ−５）、式（Ｐ−７）、式（Ｐ−１１）、式（Ｐ−１３）、式（Ｐ−１５）及び式（Ｐ−１８）から選ばれる基を表すことがより好ましく、Ｐ１及びＰ２は各々独立して式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）、式（Ｐ−７）、式（Ｐ−１１）、式（Ｐ−１３）及び式（Ｐ−１８）から選ばれる基を表すことがさらに好ましく、Ｐ１及びＰ２は各々独立して式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）及び式（Ｐ−１８）から選ばれる基を表すことがさらにより好ましく、Ｐ１及びＰ２は各々独立して式（Ｐ−１）及び式（Ｐ−２）から選ばれる基を表すことが特に好ましい。 (In the formula, a broken line represents a bonding position.), and P 1 and P 2 are each independently a formula (P-1), a formula (P-2), or a formula (P- 3), formula (P-4), formula (P-5), formula (P-7), formula (P-11), formula (P-13), formula (P-15) and formula (P-18). ) Is more preferable, and P 1 and P 2 are each independently formula (P-1), formula (P-2), formula (P-3), formula (P-7), It is more preferable to represent a group selected from formula (P-11), formula (P-13) and formula (P-18), and P 1 and P 2 are each independently formula (P-1) or formula (P-1). Even more preferably, it represents a group selected from P-2), formula (P-3) and formula (P-18), and P 1 and P 2 are each independently formula (P-1) and formula (P). It is particularly preferable to represent a group selected from -2).
一般式（Ｉ）において、Ａ１は１，４−フェニレン基、１，４−シクロヘキシレン基、ビシクロ［２．２．２］オクタン−１，４−ジイル基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ナフタレン−１，４−ジイル基、テトラヒドロナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基、テトラヒドロピラン−２，５−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表すが、これらの基は無置換であるか又は１つ以上の置換基Ｌ１によって置換されても良い。合成の容易さ、液晶組成物との相溶性、液晶表示素子を作製した場合の焼き付きの生じにくさの観点から、Ａ１は無置換であるか又は１つ以上の置換基Ｌ１によって置換されても良い１，４−フェニレン基、１，４−シクロヘキシレン基又はナフタレン−１，４−ジイル基を表すことが好ましく、Ａ１は下記の式（Ａ１−１）から式（Ａ１−９） In the general formula (I), A 1 is a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo[2.2.2]octane-1,4-diyl group, a pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, tetrahydropyran-2,5-diyl group or Represents a 1,3-dioxane-2,5-diyl group, which groups may be unsubstituted or substituted by one or more substituents L 1 . From the viewpoint of ease of synthesis, compatibility with a liquid crystal composition, and resistance to image sticking when a liquid crystal display device is produced, A 1 is unsubstituted or substituted with one or more substituents L 1 . And preferably represents a 1,4-phenylene group, a 1,4-cyclohexylene group or a naphthalene-1,4-diyl group, and A 1 is represented by the following formula (A1-1) to formula (A1-9).
（式中、破線は結合位置を表し、Ｌ１が複数存在する場合それらは同一であっても異なっていても良い。）から選ばれる基を表すことがより好ましく、Ａ１は式（Ａ１−１）から式（Ａ１−８）から選ばれる基を表すことがさらに好ましく、Ａ１は式（Ａ１−１）、式（Ａ１−２）、式（Ａ１−６）及び式（Ａ１−８）から選ばれる基を表すことがさらにより好ましく、Ａ１及びＡ２は複数存在する場合それらは同一であっても異なっていても良く、各々独立して式（Ａ１−１）で表される基を表すことが特に好ましい。 (In the formula, a broken line represents a bonding position, and when a plurality of L 1's are present, they may be the same or different.) It is more preferable to represent a group selected from, and A 1 is a formula (A1- It is more preferable to represent a group selected from 1) to formula (A1-8), wherein A 1 is formula (A1-1), formula (A1-2), formula (A1-6) and formula (A1-8). It is even more preferable to represent a group selected from the following, and when a plurality of A 1 and A 2 are present, they may be the same or different and each is independently a group represented by formula (A1-1). Is particularly preferably represented.
一般式（Ｉ）及び一般式（ＩＩ）において、Ｌ１及びＬ２はハロゲン原子、シアノ基、ニトロ基、ペンタフルオロスルファニル基、置換されていても良いアミノ基、置換されていても良いシリル基、任意の水素原子がフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−によって置換されても良い炭素原子数１から２０のアルキル基、若しくは、ＰＬ−ＳｐＬ−で表される基（式中、ＰＬはラジカル重合、カチオン重合又はアニオン重合により重合する基を表し、ＳｐＬはスペーサー基又は単結合を表す。）を表すが、Ｌ１及びＬ２が複数存在する場合それらは同一であっても異なっていても良い。合成の容易さ、液晶組成物との相溶性、液晶表示素子を作製した場合の焼き付きの生じにくさの観点から、Ｌ１及びＬ２は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、塩素原子、シアノ基、ニトロ基、任意の水素原子がフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−によって置換されても良い炭素原子数１から２０のアルキル基、若しくは、ＰＬ−ＳｐＬ−で表される基を表すことが好ましく、Ｌ１及びＬ２は、複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から２０のアルキル基、炭素原子数１から１９のアルコキシ基、炭素原子数２から２０のアルケニル基又は炭素原子数２から１９のアルケニルオキシ基を表すことがより好ましく、Ｌ１及びＬ２は、複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から１２のアルキル基又は炭素原子数１から１１のアルコキシ基を表すことがさらに好ましく、Ｌ１及びＬ２は、複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から６のアルキル基又は炭素原子数１から５のアルコキシ基を表すことがさらにより好ましく、Ｌ１及びＬ２は、複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、メチル基、エチル基、プロピル基又はメトキシ基を表すことが特に好ましい。 In formulas (I) and (II), L 1 and L 2 are a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, or an optionally substituted silyl group. , Any hydrogen atom may be replaced by a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO. -, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, Number of carbon atoms which may be substituted by -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-. 1 to 20 alkyl group, or, P L -Sp L - group (wherein represented by, P L is radical polymerization, represents a polymerized group by cationic polymerization or anionic polymerization, Sp L is a spacer group or a single bond When there are a plurality of L 1 and L 2, they may be the same or different. From the viewpoint of ease of synthesis, compatibility with a liquid crystal composition, and resistance to image sticking when a liquid crystal display device is produced, when a plurality of L 1 and L 2 are present, they may be the same or different. It may be a fluorine atom, a chlorine atom, a cyano group, a nitro group, even if any of the hydrogen atoms substituted by fluorine atoms may, one -CH 2 - or nonadjacent two or more -CH 2 - is Each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C. ≡C- alkyl group having 20 good 1 -C be replaced by, or, P L -Sp L - preferably represents a group represented by, L 1 and L 2, which if there are a plurality of May be the same or different, and may be a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 carbon atoms. It is more preferable to represent 19 alkenyloxy groups, and when L 1 and L 2 are present in plurality, they may be the same or different, and are a fluorine atom, an alkyl group having 1 to 12 carbon atoms or a carbon atom. More preferably, it represents an alkoxy group having 1 to 11 atoms, and when a plurality of L 1 and L 2 are present, they may be the same or different, and a fluorine atom, an alkyl having 1 to 6 carbon atoms More preferably, it represents a group or an alkoxy group having 1 to 5 carbon atoms, and when a plurality of L 1 and L 2 are present, they may be the same or different, and a fluorine atom, a methyl group, an ethyl group It is particularly preferred to represent a radical, a propyl radical or a methoxy radical.
一般式（Ｉ）及び一般式（ＩＩ）において、Ｌ１又はＬ２がＰＬ−ＳｐＬ−で表される基を表す場合、ＰＬ及びＳｐＬの好ましい構造は各々Ｐ１及びＳｐ１の好ましい構造と同様である。 In General Formula (I) and General Formula (II), when L 1 or L 2 represents a group represented by P L —Sp L —, preferred structures of P L and Sp L are respectively P 1 and Sp 1 . It is similar to the preferred structure.
一般式（ＩＩ）において、Ｓｐ１はスペーサー基又は単結合を表す。合成の容易さ、液晶組成物との相溶性、液晶表示素子を作製した場合の焼き付きの生じにくさの観点から、Ｓｐ１は基中の任意の水素原子がフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−に置き換えられても良い炭素原子数１から２０の直鎖状又は分岐状アルキレン基又は単結合を表すことが好ましく、Ｓｐ１は１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−ＣＯＯ−、−ＯＣＯ−又は−Ｏ−ＣＯ−Ｏ−によって置換されても良い炭素原子数２から１２の直鎖状又は分岐状アルキレン基又は単結合を表すことがより好ましく、Ｓｐ１は１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−によって置換されても良い炭素原子数２から８の直鎖状アルキレン基又は単結合を表すことがさらに好ましく、Ｓｐ１は１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−によって置換されても良い炭素原子数２から８の直鎖状アルキレン基又は単結合を表すことがさらにより好ましく、Ｓｐ１は単結合を表すことが特に好ましい。 In the general formula (II), Sp 1 represents a spacer group or a single bond. From the viewpoint of easiness of synthesis, compatibility with a liquid crystal composition, and resistance to image sticking when a liquid crystal display device is produced, Sp 1 may have any hydrogen atom in the group substituted with a fluorine atom, One —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—. , -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C-. It is preferable that a linear or branched alkylene group having 1 to 20 carbon atoms or a single bond is represented, and in Sp 1 , one —CH 2 — or two or more non-adjacent —CH 2 — are independently. And more preferably represents a linear or branched alkylene group having 2 to 12 carbon atoms which may be substituted by -O-, -COO-, -OCO- or -O-CO-O-, or a single bond. Preferably, Sp 1 is the number of carbon atoms in which one —CH 2 — or two or more non-adjacent —CH 2 — may be independently substituted by —O—, —COO— or —OCO—. It is more preferred that 2 to 8 represent a linear alkylene group or a single bond, and Sp 1 is one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—. Even more preferably, it represents a linear alkylene group having 2 to 8 carbon atoms which may be substituted by or a single bond, and Sp 1 particularly preferably represents a single bond.
一般式（ＩＩ）において、Ａ２及びＡ３は各々独立して１，４−フェニレン基、１，４−シクロヘキシレン基、ビシクロ［２．２．２］オクタン−１，４−ジイル基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ナフタレン−２，６−ジイル基、ナフタレン−１，４−ジイル基、テトラヒドロナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基、テトラヒドロピラン−２，５−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表すが、これらの基は無置換であるか又は１つ以上の置換基Ｌによって置換されても良く、Ａ３が複数存在する場合それらは同一であっても異なっていても良い。合成の容易さ、液晶組成物との相溶性、液晶表示素子を作製した場合の焼き付きの生じにくさの観点から、Ａ２及びＡ３は、Ａ３が複数存在する場合それらは同一であっても異なっていても良く、各々独立して無置換であるか又は１つ以上の置換基Ｌによって置換されても良い１，４−フェニレン基、１，４−シクロヘキシレン基、ナフタレン−２，６−ジイル基、ナフタレン−１，４−ジイル基、テトラヒドロピラン−２，５−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表すことが好ましく、Ａ２及びＡ３は、Ａ３が複数存在する場合それらは同一であっても異なっていても良く、各々独立して下記の式（Ａ２−１）から式（Ａ２−１４） In the general formula (II), A 2 and A 3 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo[2.2.2]octane-1,4-diyl group, pyridine. -2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2 , 6-diyl group, tetrahydropyran-2,5-diyl group or 1,3-dioxane-2,5-diyl group, which groups are unsubstituted or substituted by one or more substituents L. They may be substituted, and when there are a plurality of A 3, they may be the same or different. From the viewpoints of ease of synthesis, compatibility with a liquid crystal composition, and resistance to image sticking when a liquid crystal display device is produced, A 2 and A 3 are the same when a plurality of A 3 are present. 1,4-phenylene group, 1,4-cyclohexylene group, naphthalene-2,6, each of which may independently be unsubstituted or may be substituted by one or more substituents L. -Diyl group, naphthalene-1,4-diyl group, tetrahydropyran-2,5-diyl group or 1,3-dioxane-2,5-diyl group is preferable, and A 2 and A 3 are A 3 When there are a plurality of groups, they may be the same or different and each independently represents the following formula (A2-1) to formula (A2-14).
（式中、破線は結合位置を表し、Ｌ２が複数存在する場合それらは同一であっても異なっていても良い。）から選ばれる基を表すことがより好ましく、Ａ２及びＡ３は、Ａ３が複数存在する場合それらは同一であっても異なっていても良く、各々独立して式（Ａ２−１）から式（Ａ２−９）から選ばれる基を表すことがさらに好ましく、Ａ２及びＡ３は、Ａ３が複数存在する場合それらは同一であっても異なっていても良く、各々独立して式（Ａ２−１）から式（Ａ２−７）から選ばれる基を表すことがさらにより好ましく、Ａ２及びＡ３は、Ａ３が複数存在する場合それらは同一であっても異なっていても良く、各々独立して式（Ａ２−１）から式（Ａ２−６）から選ばれる基を表すことが特に好ましい。 (In the formula, the broken line represents a bonding position, and when there are a plurality of L 2's, they may be the same or different, and it is more preferable that they represent a group selected from the following. A 2 and A 3 are If a 3 there are a plurality of them may be the same or different and more preferably represents a group selected each independently from formula (A2-1) from the formula (A2-9), a 2 And A 3 may be the same or different when a plurality of A 3 are present, and each independently represent a group selected from formula (A2-1) to formula (A2-7). Even more preferably, A 2 and A 3 may be the same or different when a plurality of A 3 are present, each independently selected from formula (A2-1) to formula (A2-6). It is particularly preferred to represent a group represented by
一般式（ＩＩ）において、Ｚ１は−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＯＣＯ−ＮＨ−、−ＮＨ−ＣＯＯ−、−ＮＨ−ＣＯ−ＮＨ−、−ＮＨ−Ｏ−、−Ｏ−ＮＨ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表すが、Ｚ１が複数存在する場合それらは同一であっても異なっていても良い。合成の容易さ、液晶組成物との相溶性、液晶表示素子を作製した場合の焼き付きの生じにくさの観点から、Ｚ１は複数存在する場合それらは同一であっても異なっていても良く、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表すことが好ましく、Ｚ１は複数存在する場合それらは同一であっても異なっていても良く、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表すことがより好ましく、Ｚ１は複数存在する場合それらは同一であっても異なっていても良く、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は単結合を表すことがさらに好ましく、Ｚ１は複数存在する場合それらは同一であっても異なっていても良く、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−又は単結合を表すことがさらにより好ましく、Ｚ１は単結合を表すことが特に好ましい。 In the general formula (II), Z 1 is —O—, —S—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —CO—, —COO—, —OCO—, —CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O -, - O- NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH- COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N - , - N = CH -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond, if Z 1 there are a plurality of They may be the same or different. From the viewpoint of ease of synthesis, compatibility with a liquid crystal composition, and resistance to image sticking when a liquid crystal display device is produced, when a plurality of Z 1's are present, they may be the same or different, -OCH 2 -, - CH 2 O -, - CH 2 CH 2 -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, -CH=CH-, -CF=CF-, -C≡C- or a single bond is preferable, and when a plurality of Z 1's are present, they may be the same or different. , -OCH 2 -, - CH 2 O -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - OCO-CH = CH -, - CH = CH -, - CF = CF - , - C≡C- or is more preferably a single bond, Z 1 is them if there are a plurality may be different even in the same, -COO -, - OCO -, -CH=CH-COO-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or more preferably represents a single bond, and when Z 1 is present in plural numbers, they are the same. may be different even, -COO -, - OCO -, - CH = CH-COO -, - even more preferably represent a OCO-CH = CH- or a single bond, Z 1 represents a single bond Is particularly preferable.
一般式（ＩＩ）において、ｍ１は０から６の整数を表す。合成の容易さ、液晶組成物との相溶性、液晶表示素子を作製した場合の焼き付きの生じにくさの観点から、ｍ１は０から４の整数を表すことが好ましく、ｍ１は０から３の整数を表すことがより好ましく、ｍ１は０、１又は２を表すことがさらに好ましく、ｍ１は０又は１を表すことがさらにより好ましく、ｍ１は０を表すことが特に好ましい。 In the general formula (II), m1 represents an integer of 0 to 6. From the viewpoint of ease of synthesis, compatibility with a liquid crystal composition, and resistance to image sticking when a liquid crystal display device is manufactured, m1 is preferably an integer of 0 to 4, and m1 is an integer of 0 to 3. Is more preferable, m1 is further preferably 0, 1 or 2, m1 is even more preferably 0 or 1, and m1 is particularly preferably 0.
一般式（Ｉ）で表される化合物は、下記の一般式（Ｉ−ｉ） The compound represented by the general formula (I) has the following general formula (Ii).
（式中、Ｐ１１は式（Ｐ−１）から式（Ｐ−２０）から選ばれる基を表し、Ａ１１は無置換であるか又は１つ以上の置換基Ｌ１１によって置換されても良い１，４−フェニレン基、１，４−シクロヘキシレン基又はナフタレン−１，４−ジイル基を表し、Ｌ１１は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、塩素原子、シアノ基、ニトロ基、任意の水素原子がフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−によって置換されても良い炭素原子数１から２０のアルキル基、若しくは、ＰＬ−ＳｐＬ−で表される基を表す。）で表される化合物であることが好ましく、下記の一般式（Ｉ−ｉ−１） (In the formula, P 11 represents a group selected from formula (P-1) to formula (P-20), and A 11 may be unsubstituted or substituted by one or more substituents L 11 . It represents a 1,4-phenylene group, a 1,4-cyclohexylene group or a naphthalene-1,4-diyl group, and when a plurality of L 11's are present, they may be the same or different and may be a fluorine atom or chlorine. An atom, a cyano group, a nitro group, or any hydrogen atom may be replaced by a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—. , -S-, -CO-, -COO-, -OCO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C-. alkyl group from which may 1 to 20 carbon atoms, or, P L -Sp L -. that in a group represented preferably be a compound represented by), the general formula (I-i-1 )
（式中、Ｐ１１１は式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）、式（Ｐ−４）、式（Ｐ−５）、式（Ｐ−７）、式（Ｐ−１１）、式（Ｐ−１３）、式（Ｐ−１５）及び式（Ｐ−１８）から選ばれる基を表し、Ａ１１１は式（Ａ１−１）から式（Ａ１−９）から選ばれる基を表すが、式（Ａ１−１）から式（Ａ１−９）において存在するＬ１はＬ１１１を表し、Ｌ１１１は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から２０のアルキル基、炭素原子数１から１９のアルコキシ基、炭素原子数２から２０のアルケニル基又は炭素原子数２から１９のアルケニルオキシ基を表す。）で表される化合物であることがより好ましく、下記の一般式（Ｉ−ｉ−２） (In formula, P111 is Formula (P-1), Formula (P-2), Formula (P-3), Formula (P-4), Formula (P-5), Formula (P-7), Formula. Represents a group selected from (P-11), formula (P-13), formula (P-15) and formula (P-18), and A 111 represents formula (A1-1) to formula (A1-9) Representing a group selected, L 1 present in formulas (A1-1) to (A1-9) represents L 111, and when a plurality of L 111 are present, they may be the same or different. , A fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkenyloxy group having 2 to 19 carbon atoms). Are more preferably compounds represented by the following general formula (Ii-2)
（式中、Ｐ１１２は式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）、式（Ｐ−７）、式（Ｐ−１１）、式（Ｐ−１３）及び式（Ｐ−１８）から選ばれる基を表し、Ａ１１２は式（Ａ１−１）から式（Ａ１−８）から選ばれる基を表すが、式（Ａ１−１）から式（Ａ１−８）において存在するＬ１はＬ１１２を表し、Ｌ１１２は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から１２のアルキル基又は炭素原子数１から１１のアルコキシ基を表す。）で表される化合物であることがさらに好ましく、下記の一般式（Ｉ−ｉ−３） (In formula, P112 is Formula (P-1), Formula (P-2), Formula (P-3), Formula (P-7), Formula (P-11), Formula (P-13) and Formula. Represents a group selected from (P-18), A 112 represents a group selected from formula (A1-1) to formula (A1-8), and in formula (A1-1) to formula (A1-8) L 1 which is present represents L 112, and when a plurality of L 112 are present, they may be the same or different, and they may be a fluorine atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 11 carbon atoms. A compound represented by the following general formula (I-i-3) is more preferable.
（式中、Ｐ１１３は式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）及び式（Ｐ−１８）から選ばれる基を表し、Ａ１１３は式（Ａ１−１）、式（Ａ１−２）、式（Ａ１−６）及び式（Ａ１−８）から選ばれる基を表すが、式（Ａ１−１）、式（Ａ１−２）、式（Ａ１−６）及び式（Ａ１−８）において存在するＬ１はＬ１１３を表し、Ｌ１１３は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から６のアルキル基又は炭素原子数１から５のアルコキシ基を表す。）で表される化合物であることがさらにより好ましく、下記の一般式（Ｉ−ｉ−４） (In the formula, P 113 represents a group selected from formula (P-1), formula (P-2), formula (P-3) and formula (P-18), and A 113 represents formula (A1-1). Represents a group selected from formula (A1-2), formula (A1-6) and formula (A1-8), and is represented by formula (A1-1), formula (A1-2), formula (A1-6) and L 1 present in formula (A1-8) represents L 113, and when a plurality of L 113 are present, they may be the same or different, and a fluorine atom, an alkyl group having 1 to 6 carbon atoms or The compound represented by the formula (I-i-4) represents an alkoxy group having 1 to 5 carbon atoms.
（式中、Ｐ１１４は式（Ｐ−１）及び式（Ｐ−２）から選ばれる基を表す。）で表される化合物であることが特に好ましい。 (In the formula, P 114 represents a group selected from the formula (P-1) and the formula (P-2).) A compound represented by the formula is particularly preferable.
一般式（Ｉ）で表される化合物として具体的には、下記の式（Ｉ−１）から式（Ｉ−１９） Specific examples of the compound represented by the general formula (I) include the following formulas (I-1) to (I-19).
で表される化合物が挙げられる。 The compound represented by
一般式（Ｉ）で表される化合物は下記製法によって製造することができる。
（製法１）一般式（Ｉ）で表される化合物の製造
The compound represented by the general formula (I) can be produced by the following production method.
(Production Method 1) Production of Compound Represented by General Formula (I)
（式中、Ｐ１及びＡ１は各々一般式（Ｉ）におけるＰ１及びＡ１と同じ意味を表し、Ｘ１はハロゲン原子又はハロゲン等価体を表し、Ｐｇ１は保護基を表す。）
一般式（Ｉａ）で表される化合物と一般式（Ｉｂ）で表される化合物とをヘック反応によって反応させることによって、一般式（Ｉｃ）で表される化合物を得ることができる。パラジウム触媒としては例えば酢酸パラジウム（ＩＩ）が挙げられる。一般式（Ｉｃ）で表される化合物は下記製法によっても製造することができる。
(In the formula, P 1 and A 1 each have the same meaning as P 1 and A 1 in the general formula (I), X 1 represents a halogen atom or a halogen equivalent, and Pg 1 represents a protecting group.)
The compound represented by the general formula (Ic) can be obtained by reacting the compound represented by the general formula (Ia) with the compound represented by the general formula (Ib) by a Heck reaction. Examples of the palladium catalyst include palladium (II) acetate. The compound represented by the general formula (Ic) can also be produced by the following production method.
（式中、Ｒ１及びＲ２は各々独立して水素原子又は炭素原子数１から２０の炭化水素基を表すが、Ｒ１及びＲ２とが環を形成していても良い。）一般式（Ｉｅ）で表される化合物を一般式（Ｉｇ）で表される化合物存在下、一般式（Ｉｆ）で表される化合物とクネーフェナーゲル縮合によって反応させることによって、一般式（Ｉｃ）で表される化合物を得ることができる。また、一般式（Ｉｃ）で表される化合物は下記製法によっても製造することができる。 (In the formula, R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, but R 1 and R 2 may form a ring.) General formula The compound represented by the general formula (Ic) is reacted with the compound represented by the general formula (If) by Knoevenagel condensation in the presence of the compound represented by the general formula (Ig) to give the compound represented by the general formula (Ic). The compounds represented can be obtained. The compound represented by the general formula (Ic) can also be produced by the following production method.
（式中、Ｒ１及びＲ２は各々独立して水素原子又は炭素原子数１から２０の炭化水素基を表すが、Ｒ１及びＲ２とが環を形成していても良い。）一般式（Ｉｅ）で表される化合物を一般式（Ｉｈ）で表される化合物と反応させることによって、一般式（Ｉｃ）で表される化合物を得ることができる。 (In the formula, R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, but R 1 and R 2 may form a ring.) General formula The compound represented by general formula (Ic) can be obtained by reacting the compound represented by (Ie) with the compound represented by general formula (Ih).
一般式（Ｉｃ）で表される化合物に重合性基Ｐ１を導入することによって、一般式（Ｉｄ）で表される化合物を得ることができる。 By introducing the polymerizable group P 1 into the compound represented by the general formula (Ic), the compound represented by the general formula (Id) can be obtained.
一般式（Ｉｄ）で表される化合物の保護基Ｐｇ１を脱保護することによって、一般式（Ｉ）で表される化合物を得ることができる。反応条件としては例えばＧＲＥＥＮＥ’Ｓ ＰＲＯＴＥＣＴＩＶＥ ＧＲＯＵＰＳ ＩＮ ＯＲＧＡＮＩＣ ＳＹＮＴＨＥＳＩＳ（（Ｆｏｕｒｔｈ Ｅｄｉｔｉｏｎ）、ＰＥＴＥＲ Ｇ．Ｍ．ＷＵＴＳ、ＴＨＥＯＤＯＲＡ Ｗ．ＧＲＥＥＮＥ共著、Ａ Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，Ｉｎｃ．，Ｐｕｂｌｉｃａｔｉｏｎ）に記載の条件が挙げられる。 The compound represented by the general formula (I) can be obtained by deprotecting the protecting group Pg 1 of the compound represented by the general formula (Id). Examples of the reaction conditions include those described in Green's PROTECTIVE GROUPS IN ORGANIC SYNTHESIS ((Fourth Edition), PETER GM WUTS, THEODORA W. GREENE, co-authored by A John Wiley & c., Sons, Inc., Sons, Inc.). ..
一般式（ＩＩ）で表される化合物は、下記の一般式（ＩＩ−ｉ） The compound represented by the general formula (II) has the following general formula (II-i).
（式中、Ｐ２１は式（Ｐ−１）から式（Ｐ−２０）から選ばれる基を表し、Ｓｐ１１は基中の任意の水素原子がフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−に置き換えられても良い炭素原子数１から２０の直鎖状又は分岐状アルキレン基又は単結合を表し、Ａ２１及びＡ３１は、Ａ３１が複数存在する場合それらは同一であっても異なっていても良く、各々独立して無置換であるか又は１つ以上の置換基Ｌ２１によって置換されても良い１，４−フェニレン基、１，４−シクロヘキシレン基、ナフタレン−２，６−ジイル基、ナフタレン−１，４−ジイル基、テトラヒドロピラン−２，５−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表し、Ｌ２１は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、塩素原子、シアノ基、ニトロ基、任意の水素原子がフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−によって置換されても良い炭素原子数１から２０のアルキル基、若しくは、ＰＬ−ＳｐＬ−で表される基を表し、Ｚ１１は複数存在する場合それらは同一であっても異なっていても良く、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表し、ｍ１１は０から４の整数を表す。）で表される化合物であることが好ましく、下記の一般式（ＩＩ−ｉ−１） (In the formula, P 21 represents a group selected from the formula (P-1) to the formula (P-20), and Sp 11 may have any hydrogen atom in the group substituted with a fluorine atom. —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S. Number of carbon atoms which may be replaced with -CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C-. 1 to 20 represents a straight-chain or branched alkylene group or a single bond, and A 21 and A 31 may be the same or different when a plurality of A 31 are present, each independently being absent. 1,4-phenylene group, 1,4-cyclohexylene group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl which may be substituted or substituted by one or more substituents L 21 Group, a tetrahydropyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group, and when a plurality of L 21's are present, they may be the same or different, a fluorine atom, A chlorine atom, a cyano group, a nitro group, or any hydrogen atom may be replaced by a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — are independently —O. Substituted by -, -S-, -CO-, -COO-, -OCO-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C-. alkyl group with 1 to 20 carbon atoms be, or, P L -Sp L - represents a group represented by, Z 11 is them if there are a plurality may be the same or different and - OCH 2 -, - CH 2 O -, - CH 2 CH 2 -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, -CH=CH-, -CF=CF-, -C≡C- or a single bond, and m11 represents an integer of 0 to 4). Of the general formula (II-i-1)
（式中、Ｐ２１１は式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）、式（Ｐ−４）、式（Ｐ−５）、式（Ｐ−７）、式（Ｐ−１１）、式（Ｐ−１３）、式（Ｐ−１５）及び式（Ｐ−１８）から選ばれる基を表し、Ｓｐ１１１は１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−ＣＯＯ−、−ＯＣＯ−又は−Ｏ−ＣＯ−Ｏ−によって置換されても良い炭素原子数２から１２の直鎖状又は分岐状アルキレン基又は単結合を表し、Ａ２１１及びＡ３１１は、Ａ３１１が複数存在する場合それらは同一であっても異なっていても良く、各々独立して式（Ａ２−１）から式（Ａ２−１４）から選ばれる基を表すが、式（Ａ２−１）から式（Ａ２−１４）において存在するＬ２はＬ２１１を表し、Ｌ２１１は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から２０のアルキル基、炭素原子数１から１９のアルコキシ基、炭素原子数２から２０のアルケニル基又は炭素原子数２から１９のアルケニルオキシ基を表し、Ｚ１１１は複数存在する場合それらは同一であっても異なっていても良く、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表し、ｍ１１１は０から３の整数を表す。）で表される化合物であることがより好ましく、下記の一般式（ＩＩ−ｉ−２） (In the formula, P 211 is formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P-7), formula Represents a group selected from (P-11), formula (P-13), formula (P-15) and formula (P-18), and Sp 111 represents one —CH 2 — or two non-adjacent groups. more -CH 2 - are each independently -O -, - COO -, - OCO- or -O-CO-O-2 good carbon atoms be replaced by the 12 linear or branched alkylene Represents a group or a single bond, and A 211 and A 311 may be the same or different when a plurality of A 311 are present, and are independently the formula (A2-1) to the formula (A2-14). Group represented by formula (A2-1) to formula (A2-14), L 2 in formula (A2-1) to (A2-14) represents L 211, and when plural L 211 are present, they may be the same or different. And a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 19 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an alkenyloxy group having 2 to 19 carbon atoms, Z 111 they if there exist a plurality may be different even in the same, -OCH 2 -, - CH 2 O -, - COO -, - OCO -, - CF 2 O -, - OCF 2 -, - CH=CH-COO-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, -C≡C- or a single bond, and m111 represents an integer of 0 to 3). A compound represented by the following general formula (II-i-2) is more preferable.
（式中、Ｐ２１２は式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）、式（Ｐ−７）、式（Ｐ−１１）、式（Ｐ−１３）及び式（Ｐ−１８）から選ばれる基を表し、Ｓｐ１１２は１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−によって置換されても良い炭素原子数２から８の直鎖状アルキレン基又は単結合を表し、Ａ２１２及びＡ３１２は、Ａ３１２が複数存在する場合それらは同一であっても異なっていても良く、各々独立して式（Ａ２−１）から式（Ａ２−９）から選ばれる基を表すが、式（Ａ２−１）から式（Ａ２−９）において存在するＬ２はＬ２１２を表し、Ｌ２１２は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から１２のアルキル基又は炭素原子数１から１１のアルコキシ基を表し、Ｚ１１２は複数存在する場合それらは同一であっても異なっていても良く、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は単結合を表し、ｍ１１２は０、１又は２を表す。）で表される化合物であることがさらに好ましく、下記の一般式（ＩＩ−ｉ−３） (In formula, P212 is Formula (P-1), Formula (P-2), Formula (P-3), Formula (P-7), Formula (P-11), Formula (P-13), and Formula. Represents a group selected from (P-18), and Sp 112 represents one —CH 2 — or two or more non-adjacent —CH 2 — each independently —O—, —COO— or —OCO. Represents a linear alkylene group having 2 to 8 carbon atoms or a single bond which may be substituted by -, and A 212 and A 312 may be the same or different when a plurality of A 312 are present. Well, each independently represents a group selected from formula (A2-1) to formula (A2-9), but L 2 present in formula (A2-1) to formula (A2-9) represents L 212 . , L 212 , when present in plural numbers, may be the same or different and each represents a fluorine atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 11 carbon atoms, and Z 112 is plural. When present, they may be the same or different and are -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -CH=CH-, -CF=CF. -Or a single bond, m112 represents 0, 1 or 2), and a compound represented by the following general formula (II-i-3) is more preferable.
（式中、Ｐ２１３は式（Ｐ−１）、式（Ｐ−２）、式（Ｐ−３）及び式（Ｐ−１８）から選ばれる基を表し、Ｓｐ１１３は１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−によって置換されても良い炭素原子数２から８の直鎖状アルキレン基又は単結合を表し、Ａ２１３及びＡ３１３は、Ａ３１３が複数存在する場合それらは同一であっても異なっていても良く、各々独立して式（Ａ２−１）から式（Ａ２−７）から選ばれる基から選ばれる基を表すが、式（Ａ２−１）から式（Ａ２−７）において存在するＬ２はＬ２１３を表し、Ｌ２１３は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から６のアルキル基又は炭素原子数１から５のアルコキシ基を表し、Ｚ１１３は複数存在する場合それらは同一であっても異なっていても良く、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−又は単結合を表し、ｍ１１３は０又は１を表す。）で表される化合物であることがさらにより好ましく、下記の一般式（ＩＩ−ｉ−４） (In the formula, P 213 represents a group selected from the formula (P-1), the formula (P-2), the formula (P-3), and the formula (P-18), and Sp 113 represents one —CH 2 group. —Or two or more non-adjacent —CH 2 — each independently represent a linear alkylene group having 2 to 8 carbon atoms which may be substituted by —O— or a single bond, A 213 and A When a plurality of A 313 are present, they may be the same or different and each independently represents a group selected from the groups selected from formula (A2-1) to formula (A2-7). In the formulas (A2-1) to (A2-7), L 2 represents L 213, and when a plurality of L 213 are present, they may be the same or different, and may be a fluorine atom or a carbon atom. Represents an alkyl group having 1 to 6 atoms or an alkoxy group having 1 to 5 carbon atoms, and when a plurality of Z 113 are present, they may be the same or different, and -COO-, -OCO-,- CH=CH-COO-, -OCO-CH=CH- or a single bond, and m113 represents 0 or 1.) Even more preferably, the compound is represented by the following general formula (II-i). -4)
（式中、Ｐ２１４は式（Ｐ−１）及び式（Ｐ−２）から選ばれる基を表し、Ａ２１４は式（Ａ２−１）から式（Ａ２−６）から選ばれる基から選ばれる基を表すが、式（Ａ２−１）から式（Ａ２−６）において存在するＬ２はＬ２１４を表し、Ｌ２１４は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、メチル基、エチル基、プロピル基又はメトキシ基を表す。）で表される化合物であることが特に好ましい。 (In the formula, P 214 represents a group selected from formula (P-1) and formula (P-2), and A 214 is selected from a group selected from formula (A2-1) to formula (A2-6). The group represents a group, and L 2 present in formulas (A2-1) to (A2-6) represents L 214, and when a plurality of L 214 are present, they may be the same or different, and are fluorine. An atom, a methyl group, an ethyl group, a propyl group, or a methoxy group) is particularly preferable.
また、一般式（ＩＩ）で表される化合物は、下記の一般式（ＩＩ−ｉ−５） The compound represented by the general formula (II) has the following general formula (II-i-5).
（式中、Ｐ２１５は式（Ｐ−１）及び式（Ｐ−２）から選ばれる基を表し、Ｓｐ１１５は１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−によって置換されても良い炭素原子数２から８の直鎖状アルキレン基又は単結合を表し、Ａ２１５及びＡ３１５は、Ａ３１５が複数存在する場合それらは同一であっても異なっていても良く、各々独立して式（Ａ２−１）から式（Ａ２−７）から選ばれる基から選ばれる基を表すが、式（Ａ２−１）から式（Ａ２−７）において存在するＬ２はＬ２１５を表し、存在するＡ２１５及びＡ３１５のうち少なくとも１つは式（Ａ２−２）から式（Ａ２−７）から選ばれる基から選ばれる基を表し、Ｌ２１５は複数存在する場合それらは同一であっても異なっていても良く、フッ素原子、炭素原子数１から６のアルキル基又は炭素原子数１から５のアルコキシ基を表すが、存在するＬ２１５のうち少なくとも１つは炭素原子数１から６のアルキル基又は炭素原子数１から５のアルコキシ基を表し、ｍ１１５は１から６の整数を表す。）で表される化合物であることも好ましい。 (In the formula, P 215 represents a group selected from formula (P-1) and formula (P-2), and Sp 115 represents one —CH 2 — or two or more non-adjacent —CH 2 —. Each independently represent a linear alkylene group having 2 to 8 carbon atoms which may be substituted by -O- or a single bond, and A 215 and A 315 are the same when a plurality of A 315 are present. Which may be present or different, each independently represent a group selected from the group selected from the formula (A2-1) to the formula (A2-7), and the formula (A2-1) to the formula (A2-7) present in) L 2 represents L 215, at least one of the existing a 215 and a 315 represents a group selected from the group selected from the formula (A2-7) from the formula (A2-2), L When a plurality of 215 are present, they may be the same or different and each represents a fluorine atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 5 carbon atoms . It is also preferable that at least one of them represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and m115 represents an integer of 1 to 6.).
一般式（ＩＩ）で表される化合物として具体的には、下記の式（ＩＩ−１）から式（ＩＩ−４５） Specific examples of the compound represented by the general formula (II) include the following formula (II-1) to formula (II-45).
で表される化合物が挙げられる。 The compound represented by
一般式（ＩＩ）で表される化合物は下記製法によって製造することができる。
（製法２）一般式（ＩＩ）で表される化合物の製造
The compound represented by the general formula (II) can be produced by the following production method.
(Production method 2) Production of compound represented by general formula (II)
（式中、Ｐ２、Ｓｐ１、Ａ２、Ａ３、Ｚ１及びｍ１は各々一般式（ＩＩ）におけるＰ２、Ｓｐ１、Ａ２、Ａ３、Ｚ１及びｍ１と同じ意味を表し、Ｘ２はハロゲン原子、ハロゲン等価体又は水酸基を表し、Ｐｇ２は保護基を表す。）
一般式（ＩＩａ）で表される化合物と一般式（ＩＩｂ）で表される化合物と反応させることによって、一般式（ＩＩｃ）で表される化合物を得ることができる。Ｘ２がハロゲン原子又はハロゲン等価体を表す場合、塩基存在下反応させることができる。また、Ｘ２が水酸基を表す場合、光延反応によって反応させることができる。一般式（ＩＩｃ）で表される化合物は下記製法によっても製造することができる。
(Wherein, P 2, Sp 1, A 2, A 3, Z 1 and m1 each represent the same meaning as P 2, Sp 1, A 2 , A 3, Z 1 and m1 in formula (II), (X 2 represents a halogen atom, a halogen equivalent or a hydroxyl group, and Pg 2 represents a protective group.)
The compound represented by the general formula (IIc) can be obtained by reacting the compound represented by the general formula (IIa) with the compound represented by the general formula (IIb). When X 2 represents a halogen atom or a halogen equivalent, the reaction can be performed in the presence of a base. When X 2 represents a hydroxyl group, it can be reacted by the Mitsunobu reaction. The compound represented by the general formula (IIc) can also be produced by the following production method.
一般式（ＩＩｄ）で表される化合物に重合性基Ｐ２を導入することによって、一般式（ＩＩｃ）で表される化合物を得ることができる。 The compound represented by the general formula (IIc) can be obtained by introducing the polymerizable group P 2 into the compound represented by the general formula (IId).
一般式（ＩＩｃ）で表される化合物の保護基Ｐｇ２を脱保護することによって、一般式（ＩＩ）で表される化合物を得ることができる。反応条件としては例えば前記文献に記載の条件が挙げられる。保護基Ｐｇ２はエトキシメチル基、メトキシメチル基、ベンジルオキシメチル基、メトキシエトキシメチル基、２−（トリメチルシリル）エトキシメチル基、テトラヒドロピラニル基、エトキシエチル基、ｔｅｒｔ−ブチル基、置換されていても良いベンジル基及び置換されていても良いシリル基から選ばれる基を表すことが好ましく、保護基Ｐｇ２はエトキシメチル基、メトキシメチル基、メトキシエトキシメチル基、テトラヒドロピラニル基、置換されていても良いベンジル基及び置換されていても良いシリル基から選ばれる基を表すことがより好ましく、保護基Ｐｇ２はエトキシメチル基、メトキシメチル基、メトキシエトキシメチル基及びテトラヒドロピラニル基から選ばれる基を表すことがさらに好ましく、保護基Ｐｇ２はエトキシメチル基及びテトラヒドロピラニル基から選ばれる基を表すことがさらにより好ましく、保護基Ｐｇ２はテトラヒドロピラニル基を表すことが特に好ましい。 The compound represented by the general formula (II) can be obtained by deprotecting the protecting group Pg 2 of the compound represented by the general formula (IIc). Examples of the reaction conditions include the conditions described in the above literature. The protecting group Pg 2 is substituted with ethoxymethyl group, methoxymethyl group, benzyloxymethyl group, methoxyethoxymethyl group, 2-(trimethylsilyl)ethoxymethyl group, tetrahydropyranyl group, ethoxyethyl group, tert-butyl group, Is preferably a benzyl group or an optionally substituted silyl group, and the protective group Pg 2 is an ethoxymethyl group, a methoxymethyl group, a methoxyethoxymethyl group, a tetrahydropyranyl group, or a substituted group. More preferably represents a group selected from a benzyl group and an optionally substituted silyl group, and the protective group Pg 2 is a group selected from an ethoxymethyl group, a methoxymethyl group, a methoxyethoxymethyl group and a tetrahydropyranyl group. Is more preferable, the protective group Pg 2 is even more preferably a group selected from an ethoxymethyl group and a tetrahydropyranyl group, and the protective group Pg 2 is particularly preferably a tetrahydropyranyl group.
一般式（ＩＩＩ）で表される化合物は、下記の一般式（ＩＩＩ−ｉ） The compound represented by the general formula (III) has the following general formula (III-i).
（式中、Ｐ１１、Ｐ２１、Ｓｐ１１、Ａ１１、Ａ２１、Ａ３１、Ｚ１１及びｍ１１は各々一般式（Ｉ−ｉ）及び一般式（ＩＩ−ｉ）におけるＰ１１、Ｐ２１、Ｓｐ１１、Ａ１１、Ａ２１、Ａ３１、Ｚ１１及びｍ１１と同じ意味を表す。）で表される化合物であることが好ましく、下記の一般式（ＩＩＩ−ｉ−１） (Wherein, P 11, P 21, Sp 11, A 11, A 21, A 31, Z 11 and m11 are each the general formula (I-i) and P 11, P 21 in the general formula (II-i), Sp 11 , A 11 , A 21 , A 31 , Z 11, and m11 have the same meanings), and a compound represented by the following general formula (III-i-1) is preferable.
（式中、Ｐ１１１、Ｐ２１１、Ｓｐ１１１、Ａ１１１、Ａ２１１、Ａ３１１、Ｚ１１１及びｍ１１１は各々一般式（Ｉ−ｉ−１）及び一般式（ＩＩ−ｉ−１）におけるＰ１１１、Ｐ２１１、Ｓｐ１１１、Ａ１１１、Ａ２１１、Ａ３１１、Ｚ１１１及びｍ１１１と同じ意味を表す。）で表される化合物であることがより好ましく、下記の一般式（ＩＩＩ−ｉ−２） (In the formula, P 111 , P 211 , Sp 111 , A 111 , A 211 , A 311 , Z 111 and m 111 are respectively P 111 in general formula (I-i-1) and general formula (II-i-1). , P 211, Sp 111, a 111, a 211, a 311, Z 111 and more preferably a compound represented by the representative.) the same meaning as m111, the following general formula (III-i-2)
（式中、Ｐ１１２、Ｐ２１２、Ｓｐ１１２、Ａ１１２、Ａ２１２、Ａ３１２、Ｚ１１２及びｍ１１２は各々一般式（Ｉ−ｉ−２）及び一般式（ＩＩ−ｉ−２）におけるＰ１１２、Ｐ２１２、Ｓｐ１１２、Ａ１１２、Ａ２１２、Ａ３１２、Ｚ１１２及びｍ１１２と同じ意味を表す。）で表される化合物であることがさらに好ましく、下記の一般式（ＩＩＩ−ｉ−３） (Wherein, P 112, P 212, Sp 112, A 112, A 212, A 312, Z 112 and m112 are each formula (I-i-2) and P 112 in the general formula (II-i-2) , P 212, Sp 112, a 112, a 212, a 312, represents the same meaning as Z 112, and M112. more preferably a compound represented by), the following general formula (III-i-3)
（式中、Ｐ１１３、Ｐ２１３、Ｓｐ１１３、Ａ１１３、Ａ２１３、Ａ３１３、Ｚ１１３及びｍ１１３は各々一般式（Ｉ−ｉ−３）及び一般式（ＩＩ−ｉ−３）におけるＰ１１３、Ｐ２１３、Ｓｐ１１３、Ａ１１３、Ａ２１３、Ａ３１３、Ｚ１１３及びｍ１１３と同じ意味を表す。）で表される化合物であることがさらにより好ましく、下記の一般式（ＩＩＩ−ｉ−４） (In the formula, P 113 , P 213 , Sp 113 , A 113 , A 213 , A 313 , Z 113 and m 113 are respectively P 113 in the general formula (I-i-3) and the general formula (II-i-3). , P 213, Sp 113, a 113, a 213, a 313, Z 113 and still more preferably a compound represented by the representative.) the same meanings as M113, the following general formula (III-i-4 )
（式中、Ｐ１１４、Ｐ２１４及びＡ２１４は各々一般式（Ｉ−ｉ−４）及び一般式（ＩＩ−ｉ−４）におけるＰ１１４、Ｐ２１４及びＡ２１４と同じ意味を表す。）で表される化合物であることが特に好ましい。 (In the formula, P 114 , P 214, and A 214 have the same meanings as P 114 , P 214, and A 214 in formula (Ii-4) and formula (II-i-4), respectively). Particularly preferred are the compounds represented.
一般式（ＩＩＩ）で表される化合物として具体的には、下記の式（ＩＩＩ−１）から式（ＩＩＩ−２０） Specific examples of the compound represented by the general formula (III) include the following formula (III-1) to formula (III-20).
で表される化合物が挙げられる。 The compound represented by
一般式（ＩＩＩ）で表される化合物は下記製法によって製造することができる。
（製法３）一般式（ＩＩＩ）で表される化合物の製造
The compound represented by the general formula (III) can be produced by the following production method.
(Production method 3) Production of compound represented by general formula (III)
一般式（Ｉ）で表される化合物を一般式（ＩＩ）で表される化合物と反応させることによって、式（ＩＩＩ）で表される化合物を得ることができる。反応条件としては例えば縮合剤を用いる方法又は一般式（Ｉ）で表される化合物を酸クロリド、混合酸無水物又はカルボン酸無水物とした後、一般式（ＩＩ）で表される化合物と塩基存在下反応させる方法が挙げられる。反応後に得られる粗体の着色の少なさを重視する場合、縮合剤を用いる方法が好ましく、コストを重視する場合、一般式（Ｉ）で表される化合物を酸クロリド、混合酸無水物又はカルボン酸無水物とする方法が好ましい。 The compound represented by formula (III) can be obtained by reacting the compound represented by formula (I) with the compound represented by formula (II). The reaction conditions include, for example, a method using a condensing agent or a compound represented by the general formula (I) is converted to an acid chloride, a mixed acid anhydride or a carboxylic acid anhydride, and then the compound represented by the general formula (II) and a base are used. A method of reacting in the presence can be mentioned. When importance is attached to the degree of coloring of the crude product obtained after the reaction, a method using a condensing agent is preferred, and when importance is attached to cost, the compound represented by the general formula (I) is converted into an acid chloride, a mixed acid anhydride or a carvone. The method of using an acid anhydride is preferable.
一般式（Ｉ）で表される化合物と一般式（ＩＩ）で表される化合物とを反応させ、一般式（ＩＩＩ）で表される化合物を得る工程において、縮合剤を用いる場合、縮合剤としてはカルボジイミド又はカルボジイミダゾールが好ましく、カルボジイミドとしては、１，３−ビス（２，２−ジメチル−１，３−ジオキソラン−４−イルメチル）カルボジイミド、１−シクロヘキシル−３−（２−モルホリノエチル）カルボジイミドメト−ｐ−トルエンスルホナート、Ｎ，Ｎ’−ジイソプロピルカルボジイミド、Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド、１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩、１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド、Ｎ，Ｎ’−ジ−ｔｅｒｔ−ブチルカルボジイミドが好ましく、カルボジイミダゾールとしては、１，１’−カルボニルジイミダゾール、１，１’−カルボニルジ（１，２，４−トリアゾール）、１，１’−オキサリルジイミダゾールが好ましい。収率の観点から、縮合剤としてはカルボジイミドがより好ましく、Ｎ，Ｎ’−ジイソプロピルカルボジイミド、１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩、１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミドが特に好ましい。 When a condensing agent is used in the step of reacting the compound represented by the general formula (I) with the compound represented by the general formula (II) to obtain the compound represented by the general formula (III), Is preferably carbodiimide or carbodiimidazole, and as carbodiimide, 1,3-bis(2,2-dimethyl-1,3-dioxolan-4-ylmethyl)carbodiimide, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide Meto-p-toluenesulfonate, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-(3-dimethylaminopropyl) -3-Ethylcarbodiimide and N,N'-di-tert-butylcarbodiimide are preferable, and as carbodiimidazole, 1,1'-carbonyldiimidazole and 1,1'-carbonyldi(1,2,4-triazole are included. ), 1,1'-oxalyldiimidazole are preferred. From the viewpoint of yield, carbodiimide is more preferable as the condensing agent, and N,N′-diisopropylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1-(3-dimethylaminopropyl)- 3-ethylcarbodiimide is particularly preferred.
一般式（Ｉ）で表される化合物と一般式（ＩＩ）で表される化合物とを反応させ、一般式（ＩＩＩ）で表される化合物を得る工程において、縮合剤を用いる場合、縮合反応の触媒として、芳香族アミン又は芳香族アミン塩を使用することがより好ましい。具体的にはピリジン、Ｎ−メチルピリジン、２−クロロピリジン、２−ブロモピリジン、ピペリジン、ピリミジン、キノリン、アクリジン、Ｎ，Ｎ−ジメチル−４−アミノピリジン、ピコリン、ビピリジン、２，６−ルチジン、クロロクロム酸ピリジニウム、ピリジニウムパラトルエンスルホナートが挙げられる。 When a condensing agent is used in the step of reacting the compound represented by the general formula (I) with the compound represented by the general formula (II) to obtain the compound represented by the general formula (III), It is more preferred to use aromatic amines or aromatic amine salts as catalysts. Specifically, pyridine, N-methylpyridine, 2-chloropyridine, 2-bromopyridine, piperidine, pyrimidine, quinoline, acridine, N,N-dimethyl-4-aminopyridine, picoline, bipyridine, 2,6-lutidine, Examples include pyridinium chlorochromate and pyridinium paratoluene sulfonate.
一般式（Ｉ）で表される化合物と一般式（ＩＩ）で表される化合物とを反応させ、一般式（ＩＩＩ）で表される化合物を得る工程において、縮合剤を用いる場合、反応溶媒としては、脂肪族炭化水素、芳香族炭化水素、エーテル、アミン、エステル、ハロゲン化炭化水素、ケトン、ニトリル、アミド、スルホキシドが好ましく、エーテル、エステル、ハロゲン化炭化水素、ケトンがより好ましく、エーテル又はハロゲン化炭化水素が特に好ましい。具体的には、クロロホルム、四塩化炭素、ジクロロメタン、１，２−ジクロロエタン、１，２−ジクロロエチレン、１，１，２，２−テトラクロロエタン、トリクロロエチレン、１−クロロブタン、二硫化炭素、アセトン、アセトニトリル、ベンゾニトリル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、ジエチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテル、ジエチレングリコールジエチルエーテル、ｏ−ジクロロベンゼン、キシレン、クロロベンゼン、酢酸イソブチル、酢酸イソプロピル、酢酸イソアミル、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸ペンチル、酢酸メチル、酢酸２−メトキシエチル、シクロヘキサノン、１，４−ジオキサン、ジクロロメタン、スチレン、テトラクロロエチレン、テトラヒドロフラン、ピリジン、１−メチル−２−ピロリジノン、１，１，１−トリクロロエタン、トルエン、ヘキサン、ペンタン、シクロヘキサン、シクロペンタン、ヘプタン、ベンゼン、メチルイソブチルケトン、ｔｅｒｔ−ブチルメチルエーテル、メチルエチルケトン、メチルシクロヘキサノン、メチルブチルケトン、ジエチルケトンが挙げられる。 In the step of reacting the compound represented by the general formula (I) with the compound represented by the general formula (II) to obtain the compound represented by the general formula (III), when a condensing agent is used, as a reaction solvent Is preferably an aliphatic hydrocarbon, aromatic hydrocarbon, ether, amine, ester, halogenated hydrocarbon, ketone, nitrile, amide or sulfoxide, more preferably ether, ester, halogenated hydrocarbon or ketone, ether or halogen. Chemical hydrocarbons are particularly preferred. Specifically, chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2,2-tetrachloroethane, trichloroethylene, 1-chlorobutane, carbon disulfide, acetone, acetonitrile, Benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, diethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol diethyl ether, o-dichlorobenzene, xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl acetate, 2-methoxyethyl acetate, cyclohexanone, 1,4-dioxane, dichloromethane, styrene , Tetrachloroethylene, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, 1,1,1-trichloroethane, toluene, hexane, pentane, cyclohexane, cyclopentane, heptane, benzene, methyl isobutyl ketone, tert-butyl methyl ether, methyl ethyl ketone, Methyl cyclohexanone, methyl butyl ketone, and diethyl ketone are mentioned.
一般式（Ｉ）で表される化合物と一般式（ＩＩ）で表される化合物とを反応させ、一般式（ＩＩＩ）で表される化合物を得る工程において、縮合剤を用いる場合、反応温度としては、−７０℃から１８０℃であることが好ましく、−２０℃から１２０℃であることがより好ましく、−１０℃から８０℃であることがさらに好ましく、０℃から５０℃であることが特に好ましい。 In the step of reacting the compound represented by the general formula (I) with the compound represented by the general formula (II) to obtain the compound represented by the general formula (III), when a condensing agent is used, the reaction temperature is Is preferably −70° C. to 180° C., more preferably −20° C. to 120° C., further preferably −10° C. to 80° C., particularly preferably 0° C. to 50° C. preferable.
製法１から製法３において記載した以外の反応条件として、例えば実験化学講座（日本化学会編、丸善株式会社発行）、Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｅｓ（Ａ Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，Ｉｎｃ．，Ｐｕｂｌｉｃａｔｉｏｎ）、Ｂｅｉｌｓｔｅｉｎ Ｈａｎｄｂｏｏｋ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ（Ｂｅｉｌｓｔｅｉｎ−Ｉｎｓｔｉｔｕｔ ｆｕｅｒ Ｌｉｔｅｒａｔｕｒ ｄｅｒ Ｏｒｇａｎｉｓｃｈｅｎ Ｃｈｅｍｉｅ、Ｓｐｒｉｎｇｅｒ−Ｖｅｒｌａｇ Ｂｅｒｌｉｎ ａｎｄ Ｈｅｉｄｅｌｂｅｒｇ ＧｍｂＨ ＆ Ｃｏ．Ｋ）、Ｆｉｅｓｅｒｓ’ Ｒｅａｇｅｎｔｓ ｆｏｒ Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｉｓ（Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，Ｉｎｃ．）等の文献に記載の条件又はＳｃｉＦｉｎｄｅｒ（Ｃｈｅｍｉｃａｌ Ａｂｓｔｒａｃｔｓ Ｓｅｒｖｉｃｅ，Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ）又はＲｅａｘｙｓ（Ｅｌｓｅｖｉｅｒ Ｌｔｄ．）等のオンライン検索サービスから提供される条件が挙げられる。 As reaction conditions other than those described in the production methods 1 to 3, for example, experimental chemistry course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Syntheses (A John Wiley & Sons, Inc., Publication), Beilstein Handbook of Organics. (Beilstein-Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) conditions described in literature etc. or SciFinder (Chemical Abstracts Examples include conditions provided by online search services such as Service, American Chemical Society, and Reaxys (Elsevier Ltd.).
また、各工程において適宜反応溶媒を用いることができる。溶媒としては目的の化合物を与えるものであれば制限は無いが、例えばイソプロピルアルコール、シクロヘキサノール、１−ブタノール、２−ブタノール、２−メトキシエタノール、エチレングリコール、ジエチレングリコール、メタノール、エタノール、プロパノール、クロロホルム、ジクロロメタン、１，２−ジクロロエタン、アセトン、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、ジエチルエーテル、エチレングリコールモノエチルエーテル、キシレン、酢酸エチル、１，４−ジオキサン、テトラヒドロフラン、ピリジン、１−メチル−２−ピロリジノン、トルエン、ヘキサン、シクロヘキサン、ヘプタン、メチルイソブチルケトン、メチルエチルケトン等が挙げられる。有機溶媒及び水の二相系で反応を行う場合、相間移動触媒を添加することも可能である。相間移動触媒としては、例えば、ベンジルトリメチルアンモニウムクロリド、ポリオキシエチレン（２０）ソルビタンモノラウラート［Ｔｗｅｅｎ ２０］、ソルビタンモノオレアート［Ｓｐａｎ ８０］等が挙げられる。 Moreover, a reaction solvent can be appropriately used in each step. The solvent is not limited as long as it gives the target compound, for example, isopropyl alcohol, cyclohexanol, 1-butanol, 2-butanol, 2-methoxyethanol, ethylene glycol, diethylene glycol, methanol, ethanol, propanol, chloroform, Dichloromethane, 1,2-dichloroethane, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, diethyl ether, ethylene glycol monoethyl ether, xylene, ethyl acetate, 1,4-dioxane, tetrahydrofuran , Pyridine, 1-methyl-2-pyrrolidinone, toluene, hexane, cyclohexane, heptane, methyl isobutyl ketone, methyl ethyl ketone and the like. When the reaction is carried out in a two-phase system of organic solvent and water, it is possible to add a phase transfer catalyst. Examples of the phase transfer catalyst include benzyltrimethylammonium chloride, polyoxyethylene (20) sorbitan monolaurate [Tween 20], sorbitan monooleate [Span 80] and the like.
また、各工程において必要に応じて精製を行うことができる。精製方法としてはクロマトグラフィー、再結晶、蒸留、昇華、再沈殿、吸着、分液処理等が挙げられる。精製剤を用いる場合、精製剤としてシリカゲル、アルミナ、活性炭、活性白土、セライト、ゼオライト、メソポーラスシリカ、カーボンナノチューブ、カーボンナノホーン、備長炭、木炭、グラフェン、イオン交換樹脂、酸性白土、二酸化ケイ素、珪藻土、パーライト、セルロース、有機ポリマー、多孔質ゲル等が挙げられる。 In addition, purification can be performed in each step as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a refining agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotubes, carbon nanohorns, bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, as a refining agent. Examples include perlite, cellulose, organic polymers, porous gels and the like.
本願発明において、１，４−シクロヘキシレン基、デカヒドロナフタレン−２，６−ジイル基及び１，３−ジオキサン−２，５−ジイル基に含まれる環構造は、各々トランス体及びシス体のいずれであっても良いが、液晶性の観点から、各々トランス体の含有率がシス体の含有率よりも多いことが好ましく、環構造におけるトランス体の含有率が８０％以上であることがより好ましく、環構造におけるトランス体の含有率が９０％以上であることがさらに好ましく、環構造におけるトランス体の含有率が９５％以上であることがさらにより好ましく、環構造におけるトランス体の含有率が９８％以上であることが特に好ましい。また、本願発明において下記の表記（ＣＹ−１） In the present invention, the ring structure contained in the 1,4-cyclohexylene group, decahydronaphthalene-2,6-diyl group and 1,3-dioxane-2,5-diyl group is either trans or cis. From the viewpoint of liquid crystallinity, the content of the trans isomer is preferably higher than the content of the cis isomer, and the content of the trans isomer in the ring structure is more preferably 80% or more. The content of the trans isomer in the ring structure is more preferably 90% or more, more preferably the content of the trans isomer in the ring structure is 95% or more, and the content of the trans isomer in the ring structure is 98% or more. % Or more is particularly preferable. In the present invention, the following notation (CY-1)
（式中、破線は結合位置を表す。）は１，４−シクロヘキシレン基のトランス体及び／又はシス体を意味し、下記の表記（ＣＹ−２）及び表記（ＣＹ−３） (In the formula, a broken line represents a bonding position.) means a trans isomer and/or a cis isomer of a 1,4-cyclohexylene group, and the following notation (CY-2) and notation (CY-3).
（式中、破線は結合位置を表す。）は各々１，４−シクロヘキシレン基のトランス体及びシス体を意味する。 (In the formula, a broken line represents a bonding position.) means a trans isomer and a cis isomer of a 1,4-cyclohexylene group, respectively.
また、本願発明において、各元素は同じ元素の同位体に置き換えられていても良い。 Further, in the present invention, each element may be replaced with an isotope of the same element.
以下、実施例を挙げて本発明を更に記述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「％」は『質量％』を意味する。各工程において酸素及び／又は水分に不安定な物質を取り扱う際は、窒素ガス、アルゴンガス等の不活性ガス中で作業を行うことが好ましい。各化合物の純度はＵＰＬＣ（Ｗａｔｅｒｓ ＡＣＱＵＩＴＹ ＵＰＬＣ、ＢＥＨ Ｃ１８（１００×２．１ｍｍ×１．７μｍ）、アセトニトリル／水又は０．１％ギ酸含有アセトニトリル／水、ＰＤＡ、カラム温度４０℃）、ＧＰＣ（島津製作所 ＨＰＬＣ Ｐｒｏｍｉｎｅｎｃｅ、Ｓｈｏｄｅｘ ＫＦ−８０１（３００ｍｍ×８ｍｍ×６μｍ）＋ＫＦ−８０２（３００ｍｍ×８ｍｍ×６μｍ）、テトラヒドロフラン、ＲＩ、ＵＶ（２５４ｎｍ）、カラム温度４０℃）、ＧＣ（Ａｇｉｌｅｎｔ ６８９０Ａ、Ｊ＆Ｗ ＤＢ−１、３０ｍ×０．２５ｍｍ×０．２５μｍ、キャリアガス Ｈｅ、ＦＩＤ、１００℃（１分）→昇温１０℃／分→３００℃（１２分））又は１Ｈ ＮＭＲ（ＪＥＯＬ、４００ＭＨｚ）によって決定した。
（実施例１）式（ＩＩＩ−１）で表される化合物の製造
Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Moreover, "%" in the compositions of the following Examples and Comparative Examples means "mass %". When handling a substance unstable to oxygen and/or water in each step, it is preferable to work in an inert gas such as nitrogen gas or argon gas. The purity of each compound is UPLC (Waters ACQUITY UPLC, BEH C 18 (100×2.1 mm×1.7 μm), acetonitrile/water or acetonitrile/water containing 0.1% formic acid, PDA, column temperature 40° C.), GPC ( Shimadzu HPLC Prominence, Shodex KF-801 (300 mm×8 mm×6 μm)+KF-802 (300 mm×8 mm×6 μm), tetrahydrofuran, RI, UV (254 nm), column temperature 40° C., GC (Agilent 6890A, J&W DB-). 1, 30 m×0.25 mm×0.25 μm, carrier gas He, FID, 100° C. (1 min)→temperature rise 10° C./min→300° C. (12 min)) or 1 H NMR (JEOL, 400 MHz) did.
(Example 1) Production of compound represented by formula (III-1)
窒素雰囲気下、反応容器に式（ＩＩＩ−１−１）で表される化合物１０．０ｇ、アクリル酸ｔｅｒｔ−ブチル８．９ｇ、炭酸カリウム１２．０ｇ、Ｎ，Ｎ−ジメチルアセトアミド１００ｍＬ、酢酸パラジウム（ＩＩ）０．０１０ｇを加え、１２０℃で５時間加熱撹拌した。室温に冷却し、反応液を５％塩酸に注いだ。酢酸エチルで抽出し、有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行うことによって、式（ＩＩＩ−１−２）で表される化合物１０．２ｇを得た。 In a nitrogen atmosphere, 10.0 g of a compound represented by the formula (III-1-1), tert-butyl acrylate 8.9 g, potassium carbonate 12.0 g, N,N-dimethylacetamide 100 mL, palladium acetate ( II) 0.010 g was added, and the mixture was heated with stirring at 120° C. for 5 hours. After cooling to room temperature, the reaction solution was poured into 5% hydrochloric acid. It was extracted with ethyl acetate, and the organic layer was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) gave 10.2 g of the compound represented by the formula (III-1-2).
窒素雰囲気下、反応容器に式（ＩＩＩ−１−２）で表される化合物１０．２ｇ、メタクリル酸４．４ｇ、４−ジメチルアミノピリジン０．６ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド７．０ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行うことによって、式（ＩＩＩ−１−３）で表される化合物１０．７ｇを得た。 Under a nitrogen atmosphere, 10.2 g of the compound represented by the formula (III-1-2), 4.4 g of methacrylic acid, 0.6 g of 4-dimethylaminopyridine, and 100 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 7.0 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane/hexane) gave 10.7 g of a compound represented by the formula (III-1-3).
反応容器に式（ＩＩＩ−１−３）で表される化合物１０．７ｇ、ジクロロメタン３０ｍＬ、ギ酸６０ｍＬを加え、４０℃で６時間加熱撹拌した。溶媒を減圧留去した後、得られた固体を水で洗浄した。乾燥させることによって、式（ＩＩＩ−１−４）で表される化合物８．２ｇを得た。 10.7 g of the compound represented by formula (III-1-3), 30 mL of dichloromethane, and 60 mL of formic acid were added to a reaction vessel, and the mixture was heated with stirring at 40° C. for 6 hours. After evaporating the solvent under reduced pressure, the obtained solid was washed with water. By drying, 8.2 g of the compound represented by the formula (III-1-4) was obtained.
反応容器に式（ＩＩＩ−１−５）で表される化合物１０．０ｇ、ピリジニウムｐ−トルエンスルホナート１．３ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、３，４−ジヒドロ−２Ｈ−ピラン５．０ｇを滴下し、室温で８時間撹拌した。反応液を飽和炭酸水素ナトリウム水溶液及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−１−６）で表される化合物１２．８ｇを得た。 To the reaction container, 10.0 g of the compound represented by the formula (III-1-5), 1.3 g of pyridinium p-toluenesulfonate, and 100 mL of dichloromethane were added. While cooling with ice, 5.0 g of 3,4-dihydro-2H-pyran was added dropwise, and the mixture was stirred at room temperature for 8 hours. The reaction solution was washed successively with saturated aqueous sodium hydrogen carbonate solution and brine. By refining by column chromatography (alumina, dichloromethane), 12.8 g of the compound represented by the formula (III-1-6) was obtained.
耐圧反応容器に式（ＩＩＩ−１−６）で表される化合物１２．８ｇ、テトラヒドロフラン５０ｍＬ、エタノール５０ｍＬ、パラジウム触媒（エボニック社製、Ｅ １０６ Ｏ／Ｗ ５％Ｐｄ）を加えた。水素圧０．５ＭＰａ、５０℃で８時間加熱撹拌した。触媒をろ過により除去し、ろ液を減圧留去した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行うことによって、式（ＩＩＩ−１−７）で表される化合物８．３ｇを得た。 12.8 g of the compound represented by the formula (III-1-6), 50 mL of tetrahydrofuran, 50 mL of ethanol, and a palladium catalyst (E 106 O/W 5% Pd, manufactured by Evonik Ltd.) were added to a pressure resistant reactor. The mixture was heated and stirred at a hydrogen pressure of 0.5 MPa and 50° C. for 8 hours. The catalyst was removed by filtration, and the filtrate was evaporated under reduced pressure. Purification by column chromatography (alumina, ethyl acetate) yielded 8.3 g of a compound represented by the formula (III-1-7).
窒素雰囲気下、反応容器に式（ＩＩＩ−１−７）で表される化合物８．３ｇ、メタクリル酸４．０ｇ、４−ジメチルアミノピリジン０．５ｇ、ジクロロメタン９０ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド６．５ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−１−８）で表される化合物９．０ｇを得た。 Under a nitrogen atmosphere, 8.3 g of the compound represented by the formula (III-1-7), 4.0 g of methacrylic acid, 0.5 g of 4-dimethylaminopyridine and 90 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 6.5 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (alumina, dichloromethane) gave 9.0 g of a compound represented by the formula (III-1-8).
反応容器に式（ＩＩＩ−１−８）で表される化合物９．０ｇ、テトラヒドロフラン７０ｍＬ、メタノール７０ｍＬ、濃塩酸０．１ｍＬを加え、室温で６時間撹拌した。反応液に酢酸エチルを加え、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−１−９）で表される化合物５．５ｇを得た。 9.0 g of the compound represented by the formula (III-1-8), 70 mL of tetrahydrofuran, 70 mL of methanol, and 0.1 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) yielded 5.5 g of a compound represented by the formula (III-1-9).
窒素雰囲気下、反応容器に式（ＩＩＩ−１−９）で表される化合物５．５ｇ、式（ＩＩＩ−１−４）で表される化合物７．１ｇ、４−ジメチルアミノピリジン０．４ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド４．７ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−１）で表される化合物９．７ｇを得た。
相転移温度：Ｃ １６１ Ｉ
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ ２．０８（ｍ，６Ｈ），５．７８（ｄ，２Ｈ），６．３７（ｄ，２Ｈ），６．５９（ｄ，１Ｈ），７．１６−７．２２（ｍ，６Ｈ），７．６３（ｄ，２Ｈ），７．８６（ｄ，１Ｈ）ｐｐｍ
ＬＣ−ＭＳ：３９３［Ｍ＋１］
（実施例２）式（ＩＩＩ−２）で表される化合物の製造
Under a nitrogen atmosphere, 5.5 g of a compound represented by the formula (III-1-9), 7.1 g of a compound represented by the formula (III-1-4), 0.4 g of 4-dimethylaminopyridine in a reaction vessel, 100 mL of dichloromethane was added. While cooling with ice, 4.7 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 9.7 g of a compound represented by the formula (III-1).
Phase transition temperature: C 161 I
1 H NMR (CDCl 3 ) δ 2.08 (m, 6H), 5.78 (d, 2H), 6.37 (d, 2H), 6.59 (d, 1H), 7.16-7. 22 (m, 6H), 7.63 (d, 2H), 7.86 (d, 1H) ppm
LC-MS: 393 [M+1]
(Example 2) Production of compound represented by formula (III-2)
窒素雰囲気下、反応容器に式（ＩＩＩ−２−１）で表される化合物１０．０ｇ、アクリル酸ｔｅｒｔ−ブチル８．２ｇ、炭酸カリウム１１．１ｇ、Ｎ，Ｎ−ジメチルアセトアミド１００ｍＬ、酢酸パラジウム（ＩＩ）０．００９６ｇを加え、１２０℃で１２時間加熱撹拌した。室温に冷却し、反応液を５％塩酸に注いだ。酢酸エチルで抽出し、有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行うことによって、式（ＩＩＩ−２−２）で表される化合物１０．０ｇを得た。 In a nitrogen atmosphere, 10.0 g of a compound represented by the formula (III-2-1), tert-butyl acrylate 8.2 g, potassium carbonate 11.1 g, N,N-dimethylacetamide 100 mL, palladium acetate ( II) 0.0096 g was added, and the mixture was heated with stirring at 120° C. for 12 hours. After cooling to room temperature, the reaction solution was poured into 5% hydrochloric acid. It was extracted with ethyl acetate, and the organic layer was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) gave 10.0 g of the compound represented by the formula (III-2-2).
窒素雰囲気下、反応容器に式（ＩＩＩ−２−２）で表される化合物１０．０ｇ、メタクリル酸４．１ｇ、４−ジメチルアミノピリジン０．５ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド６．５ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行うことによって、式（ＩＩＩ−２−３）で表される化合物１０．３ｇを得た。 Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (III-2-2), 4.1 g of methacrylic acid, 0.5 g of 4-dimethylaminopyridine and 100 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 6.5 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane/hexane) gave 10.3 g of the compound represented by the formula (III-2-3).
反応容器に式（ＩＩＩ−２−３）で表される化合物１０．３ｇ、ジクロロメタン３０ｍＬ、ギ酸６０ｍＬを加え、４０℃で６時間加熱撹拌した。溶媒を減圧留去した後、得られた固体を水で洗浄した。乾燥させることによって、式（ＩＩＩ−２−４）で表される化合物７．６ｇを得た。 To the reaction vessel, 10.3 g of the compound represented by the formula (III-2-3), 30 mL of dichloromethane and 60 mL of formic acid were added, and the mixture was heated with stirring at 40° C. for 6 hours. After evaporating the solvent under reduced pressure, the obtained solid was washed with water. By drying, 7.6 g of a compound represented by the formula (III-2-4) was obtained.
窒素雰囲気下、反応容器に式（ＩＩＩ−２−４）で表される化合物７．６ｇ、式（ＩＩＩ−２−５）で表される化合物５．５ｇ、４−ジメチルアミノピリジン０．４ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド４．７ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−２）で表される化合物１０．０ｇを得た。
相転移温度：Ｃ １１７ Ｉ
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ ２．０７（ｓ，６Ｈ），２．４８（ｓ，３Ｈ），５．７７（ｍ，２Ｈ），６．３６（ｓ，２Ｈ），６．５２（ｄ，１Ｈ），７．０４（ｍ，２Ｈ），７．１６−７．２２（ｍ，４Ｈ），７．６６（ｄ，１Ｈ），８．１１（ｄ，１Ｈ）ｐｐｍ
ＬＣ−ＭＳ：４０７［Ｍ＋１］
（実施例３）式（ＩＩＩ−３）で表される化合物の製造
In a nitrogen atmosphere, in a reaction vessel, 7.6 g of a compound represented by the formula (III-2-4), 5.5 g of a compound represented by the formula (III-2-5), 0.4 g of 4-dimethylaminopyridine, 100 mL of dichloromethane was added. While cooling with ice, 4.7 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) yielded 10.0 g of a compound represented by the formula (III-2).
Phase transition temperature: C 117 I
1 H NMR (CDCl 3 ) δ 2.07 (s, 6H), 2.48 (s, 3H), 5.77 (m, 2H), 6.36 (s, 2H), 6.52 (d, 1H), 7.04 (m, 2H), 7.16-7.22 (m, 4H), 7.66 (d, 1H), 8.11 (d, 1H) ppm
LC-MS: 407 [M+1]
(Example 3) Production of compound represented by formula (III-3)
反応容器に式（ＩＩＩ−３−１）で表される化合物１０．０ｇ、ピリジニウムｐ−トルエンスルホナート１．３ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、３，４−ジヒドロ−２Ｈ−ピラン５．３ｇを滴下し、室温で８時間撹拌した。反応液を飽和炭酸水素ナトリウム水溶液及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−３−２）で表される化合物１３．０ｇを得た。 To a reaction vessel, 10.0 g of the compound represented by the formula (III-3-1), 1.3 g of pyridinium p-toluenesulfonate, and 100 mL of dichloromethane were added. While cooling with ice, 5.3 g of 3,4-dihydro-2H-pyran was added dropwise, and the mixture was stirred at room temperature for 8 hours. The reaction solution was washed successively with saturated aqueous sodium hydrogen carbonate solution and brine. Purification by column chromatography (alumina, dichloromethane) gave 13.0 g of the compound represented by the formula (III-3-2).
窒素雰囲気下、反応容器に式（ＩＩＩ−３−２）で表される化合物１３．０ｇ、ビス（ピナコラト）ジボロン１３．２ｇ、酢酸カリウム６．９ｇ、［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（ＩＩ）ジクロリド・ジクロロメタン付加物０．４ｇ、ジメチルスルホキシド１００ｍＬを加え、１００℃で８時間加熱撹拌した。室温に冷却し、反応液を水に注いだ。ジクロロメタンで抽出し、有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−３−３）で表される化合物１２．１ｇを得た。 In a reaction vessel under a nitrogen atmosphere, 13.0 g of a compound represented by the formula (III-3-2), 13.2 g of bis(pinacolato)diboron, 6.9 g of potassium acetate, [1,1′-bis(diphenylphosphino). ) Ferrocene]palladium(II) dichloride/dichloromethane adduct 0.4 g and dimethyl sulfoxide 100 mL were added, and the mixture was heated with stirring at 100° C. for 8 hours. After cooling to room temperature, the reaction solution was poured into water. It was extracted with dichloromethane, and the organic layer was washed successively with water and brine. Purification by column chromatography (alumina, dichloromethane) gave 12.1 g of the compound represented by the formula (III-3-3).
反応容器に式（ＩＩＩ−３−３）で表される化合物１２．１ｇ、テトラヒドロフラン１００ｍＬ、飽和炭酸水素ナトリウム水溶液５ｍＬを加えた。３０％過酸化水素水２０ｍＬを滴下し、室温で８時間撹拌した。反応液を水に注ぎ、酢酸エチルで抽出した。有機層を水、亜硫酸水素ナトリウム水溶液、食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行うことによって、式（ＩＩＩ−３−４）で表される化合物７．２ｇを得た。 12.1 g of the compound represented by the formula (III-3-3), 100 mL of tetrahydrofuran, and 5 mL of a saturated aqueous sodium hydrogen carbonate solution were added to a reaction vessel. 20 mL of 30% hydrogen peroxide solution was added dropwise, and the mixture was stirred at room temperature for 8 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water, aqueous sodium hydrogen sulfite solution, and brine. By purifying by column chromatography (alumina, ethyl acetate), 7.2 g of the compound represented by the formula (III-3-4) was obtained.
窒素雰囲気下、反応容器に式（ＩＩＩ−３−４）で表される化合物７．２ｇ、メタクリル酸３．２ｇ、４−ジメチルアミノピリジン０．４ｇ、ジクロロメタン９０ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド５．１ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−３−５）で表される化合物７．６ｇを得た。 Under a nitrogen atmosphere, 7.2 g of the compound represented by the formula (III-3-4), 3.2 g of methacrylic acid, 0.4 g of 4-dimethylaminopyridine and 90 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 5.1 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (alumina, dichloromethane) yielded 7.6 g of a compound represented by the formula (III-3-5).
反応容器に式（ＩＩＩ−３−５）で表される化合物７．６ｇ、テトラヒドロフラン７０ｍＬ、メタノール７０ｍＬ、濃塩酸０．１ｍＬを加え、室温で６時間撹拌した。反応液に酢酸エチルを加え、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−３−６）で表される化合物４．８ｇを得た。 7.6 g of the compound represented by the formula (III-3-5), 70 mL of tetrahydrofuran, 70 mL of methanol, and 0.1 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) yielded 4.8 g of a compound represented by the formula (III-3-6).
反応容器に式（ＩＩＩ−３−７）で表される化合物６．０ｇ、ジクロロメタン６０ｍＬ、Ｎ，Ｎ−ジメチルホルムアミド０．１ｍＬを加えた。塩化オキサリル４．７ｇを滴下し、４０℃で８時間加熱撹拌した。溶媒を減圧留去することによって、式（ＩＩＩ−３−７）で表される化合物の酸クロリドを得た。反応容器に式（ＩＩＩ−３−６）で表される化合物４．８ｇ、ジクロロメタン５０ｍＬ、ピリジン３．９ｇを加えた。氷冷しながら、式（ＩＩＩ−３−７）で表される化合物の酸クロリドをジクロロメタン２５ｍＬに溶解させた溶液を滴下し、室温で６時間撹拌した。反応液を飽和炭酸水素ナトリウム水溶液に注ぎ、ジクロロメタンで抽出した。有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−３）で表される化合物８．３ｇを得た。
ＬＣ−ＭＳ：４２５［Ｍ＋１］
（実施例４）式（ＩＩＩ−４）で表される化合物の製造
6.0 g of the compound represented by the formula (III-3-7), 60 mL of dichloromethane, and 0.1 mL of N,N-dimethylformamide were added to the reaction vessel. 4.7 g of oxalyl chloride was added dropwise, and the mixture was heated with stirring at 40° C. for 8 hours. The solvent was distilled off under reduced pressure to obtain an acid chloride of the compound represented by the formula (III-3-7). To the reaction vessel, 4.8 g of the compound represented by the formula (III-3-6), 50 mL of dichloromethane, and 3.9 g of pyridine were added. A solution prepared by dissolving the acid chloride of the compound represented by formula (III-3-7) in 25 mL of dichloromethane was added dropwise with ice cooling, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution and extracted with dichloromethane. The organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 8.3 g of a compound represented by the formula (III-3).
LC-MS: 425 [M+1]
(Example 4) Production of compound represented by formula (III-4)
実施例１において式（ＩＩＩ−１−１）で表される化合物を式（ＩＩＩ−４−１）で表される化合物に置き換えた以外は同様の方法によって、式（ＩＩＩ−４−４）で表される化合物を製造した。 A compound of the formula (III-4-4) was prepared in the same manner as in Example 1 except that the compound of the formula (III-1-1) was replaced with the compound of the formula (III-4-1). The compound represented was prepared.
窒素雰囲気下反応容器に式（ＩＩＩ−４−５）で表される化合物１０．０ｇ、式（ＩＩＩ−４−６）で表される化合物１１．０ｇ、炭酸カリウム１０．３ｇ、エタノール９０ｍＬ、水５０ｍＬ、ジクロロビス［ジ−ｔｅｒｔ−ブチル（ｐ−ジメチルアミノフェニル）ホスフィノ］パラジウム（ＩＩ）０．４ｇを加え、６時間加熱還流させた。室温に冷却し、反応液を水に注いだ。水層をｐＨ４に調整し、酢酸エチルで抽出した。有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−４−７）で表される化合物１１．９ｇを得た。 In a reaction vessel under a nitrogen atmosphere, 10.0 g of a compound represented by formula (III-4-5), 11.0 g of a compound represented by formula (III-4-6), 10.3 g of potassium carbonate, 90 mL of ethanol, water. 50 mL and 0.4 g of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II) were added, and the mixture was heated under reflux for 6 hours. After cooling to room temperature, the reaction solution was poured into water. The aqueous layer was adjusted to pH 4 and extracted with ethyl acetate. The organic layer was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) gave 11.9 g of the compound represented by the formula (III-4-7).
窒素雰囲気下、反応容器に式（ＩＩＩ−４−７）で表される化合物１１．９ｇ、メタクリル酸３．８ｇ、４−ジメチルアミノピリジン０．５ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド６．０ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−４−８）で表される化合物１１．７ｇを得た。 Under a nitrogen atmosphere, 11.9 g of the compound represented by the formula (III-4-7), 3.8 g of methacrylic acid, 0.5 g of 4-dimethylaminopyridine, and 100 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 6.0 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. By refining by column chromatography (alumina, dichloromethane), 11.7 g of the compound represented by the formula (III-4-8) was obtained.
反応容器に式（ＩＩＩ−４−８）で表される化合物１１．７ｇ、テトラヒドロフラン７０ｍＬ、メタノール７０ｍＬ、濃塩酸０．１ｍＬを加え、室温で６時間撹拌した。反応液に酢酸エチルを加え、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−４−９）で表される化合物８．１ｇを得た。 11.7 g of the compound represented by formula (III-4-8), 70 mL of tetrahydrofuran, 70 mL of methanol, and 0.1 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) yielded 8.1 g of a compound represented by the formula (III-4-9).
窒素雰囲気下、反応容器に式（ＩＩＩ−４−９）で表される化合物８．１ｇ、式（ＩＩＩ−４−４）で表される化合物７．６ｇ、４−ジメチルアミノピリジン０．３ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド４．３ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−４）で表される化合物１２．１ｇを得た。
ＬＣ−ＭＳ：５２９［Ｍ＋１］
（実施例５）式（ＩＩＩ−５）で表される化合物の製造
In a nitrogen atmosphere, 8.1 g of the compound represented by the formula (III-4-9), 7.6 g of the compound represented by the formula (III-4-4) and 0.3 g of 4-dimethylaminopyridine in a reaction vessel. 100 mL of dichloromethane was added. While cooling with ice, 4.3 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 12.1 g of a compound represented by the formula (III-4).
LC-MS: 529 [M+1]
(Example 5) Production of compound represented by formula (III-5)
実施例１において式（ＩＩＩ−１−１）で表される化合物を式（ＩＩＩ−５−１）で表される化合物に置き換えた以外は同様の方法によって、式（ＩＩＩ−５−４）で表される化合物を製造した。実施例４において式（ＩＩＩ−４−５）で表される化合物を式（ＩＩＩ−５−５）で表される化合物に、式（ＩＩＩ−４−４）で表される化合物を式（ＩＩＩ−５−４）で表される化合物に置き換えた以外は同様の方法によって、式（ＩＩＩ−５）で表される化合物を製造した。
ＬＣ−ＭＳ：５１９［Ｍ＋１］
（実施例６）式（ＩＩＩ−６）で表される化合物の製造
A compound of the formula (III-5-4) was prepared in the same manner as in Example 1 except that the compound of the formula (III-1-1) was replaced with the compound of the formula (III-5-1). The compound represented was prepared. In Example 4, the compound represented by the formula (III-4-5) is converted into the compound represented by the formula (III-5-5), and the compound represented by the formula (III-4-4) is converted into the compound represented by the formula (III). A compound represented by the formula (III-5) was produced by the same method except that the compound represented by the formula (5-4) was replaced.
LC-MS: 519 [M+1]
(Example 6) Production of compound represented by formula (III-6)
実施例１において式（ＩＩＩ−１−１）で表される化合物を式（ＩＩＩ−６−１）で表される化合物に置き換えた以外は同様の方法によって、式（ＩＩＩ−６−４）で表される化合物を製造した。 A compound of the formula (III-6-4) was prepared in the same manner as in Example 1 except that the compound of the formula (III-1-1) was replaced with the compound of the formula (III-6-1). The compound represented was prepared.
反応容器に式（ＩＩＩ−６−５）で表される化合物１０．０ｇ、ピリジニウムｐ−トルエンスルホナート１．３ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、３，４−ジヒドロ−２Ｈ−ピラン５．３ｇを滴下し、室温で８時間撹拌した。反応液を飽和炭酸水素ナトリウム水溶液及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−６−６）で表される化合物１３．０ｇを得た。 To the reaction vessel, 10.0 g of the compound represented by the formula (III-6-5), 1.3 g of pyridinium p-toluenesulfonate, and 100 mL of dichloromethane were added. While cooling with ice, 5.3 g of 3,4-dihydro-2H-pyran was added dropwise, and the mixture was stirred at room temperature for 8 hours. The reaction solution was washed successively with saturated aqueous sodium hydrogen carbonate solution and brine. Purification by column chromatography (alumina, dichloromethane) gave 13.0 g of the compound represented by the formula (III-6-6).
窒素雰囲気下反応容器に式（ＩＩＩ−６−６）で表される化合物１３．０ｇ、式（ＩＩＩ−６−７）で表される化合物１２．４ｇ、炭酸カリウム９．８ｇ、１，２−ジメトキシエタン１２０ｍＬ、ジクロロビス［ジ−ｔｅｒｔ−ブチル（ｐ−ジメチルアミノフェニル）ホスフィノ］パラジウム（ＩＩ）０．３ｇを加え、８時間加熱還流させた。室温に冷却し、反応液を水に注いだ。ジクロロメタンで抽出し、有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−６−８）で表される化合物１２．５ｇを得た。 In a reaction vessel under a nitrogen atmosphere, 13.0 g of a compound represented by formula (III-6-6), 12.4 g of a compound represented by formula (III-6-7), 9.8 g of potassium carbonate, 1,2- 120 mL of dimethoxyethane and 0.3 g of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II) were added, and the mixture was heated under reflux for 8 hours. After cooling to room temperature, the reaction solution was poured into water. It was extracted with dichloromethane, and the organic layer was washed successively with water and brine. Purification by column chromatography (alumina, dichloromethane) gave 12.5 g of the compound represented by the formula (III-6-8).
窒素雰囲気下、反応容器に式（ＩＩＩ−６−８）で表される化合物１２．５ｇ、メタクリル酸３．６ｇ、４−ジメチルアミノピリジン０．５ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド５．７ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−６−９）で表される化合物１２．１ｇを得た。 Under a nitrogen atmosphere, 12.5 g of the compound represented by the formula (III-6-8), 3.6 g of methacrylic acid, 0.5 g of 4-dimethylaminopyridine, and 100 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 5.7 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (alumina, dichloromethane) gave 12.1 g of the compound represented by the formula (III-6-9).
反応容器に式（ＩＩＩ−６−９）で表される化合物１２．１ｇ、テトラヒドロフラン７０ｍＬ、メタノール７０ｍＬ、濃塩酸０．１ｍＬを加え、室温で６時間撹拌した。反応液に酢酸エチルを加え、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−６−１０）で表される化合物８．６ｇを得た。 12.1 g of the compound represented by the formula (III-6-9), 70 mL of tetrahydrofuran, 70 mL of methanol, and 0.1 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) yielded 8.6 g of a compound represented by the formula (III-6-10).
窒素雰囲気下、反応容器に式（ＩＩＩ−６−１０）で表される化合物８．６ｇ、式（ＩＩＩ−６−４）で表される化合物７．１ｇ、４−ジメチルアミノピリジン０．３ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド４．１ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−６）で表される化合物１２．１ｇを得た。
ＬＣ−ＭＳ：５５７［Ｍ＋１］
（実施例７）式（ＩＩＩ−７）で表される化合物の製造
In a nitrogen atmosphere, in a reaction vessel, 8.6 g of a compound represented by formula (III-6-10), 7.1 g of a compound represented by formula (III-6-4), 0.3 g of 4-dimethylaminopyridine, 100 mL of dichloromethane was added. While cooling with ice, 4.1 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 12.1 g of a compound represented by the formula (III-6).
LC-MS: 557 [M+1]
(Example 7) Production of compound represented by formula (III-7)
反応容器にメルドラム酸２３．０ｇ、ｔｅｒｔ−ブチルアルコール１２．３ｇ、トルエン２０ｍＬを加え、４時間加熱還流させた。７０℃で、式（ＩＩＩ−７−１）で表される化合物１０．０ｇ、ピリジン１２．６ｇ及びピペリジン１．４ｇを混合した溶液を滴下し、７０℃で３０時間加熱撹拌した。室温に冷却し、反応液を５％塩酸に注いだ。酢酸エチルで抽出し、有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行うことによって、式（ＩＩＩ−７−２）で表される化合物１３．２ｇを得た。 23.0 g of Meldrum's acid, 12.3 g of tert-butyl alcohol, and 20 mL of toluene were added to a reaction vessel, and the mixture was heated under reflux for 4 hours. A solution obtained by mixing 10.0 g of the compound represented by the formula (III-7-1), 12.6 g of pyridine and 1.4 g of piperidine was added dropwise at 70°C, and the mixture was heated and stirred at 70°C for 30 hours. After cooling to room temperature, the reaction solution was poured into 5% hydrochloric acid. It was extracted with ethyl acetate, and the organic layer was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) gave 13.2 g of the compound represented by the formula (III-7-2).
実施例１において式（ＩＩＩ−１−２）で表される化合物を式（ＩＩＩ−７−２）で表される化合物に置き換えた以外は同様の方法によって、式（ＩＩＩ−７−４）で表される化合物を製造した。実施例４において式（ＩＩＩ−４−５）で表される化合物を式（ＩＩＩ−７−５）で表される化合物に、式（ＩＩＩ−４−４）で表される化合物を式（ＩＩＩ−７−４）で表される化合物に置き換えた以外は同様の方法によって、式（ＩＩＩ−７）で表される化合物を製造した。
ＬＣ−ＭＳ：５１５［Ｍ＋１］
（実施例８）式（ＩＩＩ−８）で表される化合物の製造
A compound of the formula (III-7-4) was prepared in the same manner as in Example 1 except that the compound of the formula (III-1-2) was replaced with the compound of the formula (III-7-2). The compound represented was prepared. In Example 4, the compound represented by the formula (III-4-5) is replaced by the compound represented by the formula (III-7-5), and the compound represented by the formula (III-4-4) is prepared by the formula (III). A compound represented by the formula (III-7) was produced by the same method except that the compound represented by -7-4) was used.
LC-MS: 515 [M+1]
(Example 8) Production of compound represented by formula (III-8)
窒素雰囲気下、反応容器に式（ＩＩＩ−８−１）で表される化合物１０．０ｇ、ビス（ピナコラト）ジボロン１１．１ｇ、酢酸カリウム５．４ｇ、［１，１’−ビス（ジフェニルホスフィノ）フェロセン］パラジウム（ＩＩ）ジクロリド・ジクロロメタン付加物０．３ｇ、ジメチルスルホキシド１００ｍＬを加え、１００℃で８時間加熱撹拌した。室温に冷却し、反応液を水に注いだ。ジクロロメタンで抽出し、有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−８−２）で表される化合物９．４ｇを得た。 In a reaction vessel under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (III-8-1), bis(pinacolato)diboron 11.1 g, potassium acetate 5.4 g, [1,1′-bis(diphenylphosphino). ) Ferrocene]palladium(II) dichloride/dichloromethane adduct (0.3 g) and dimethyl sulfoxide (100 mL) were added, and the mixture was heated with stirring at 100°C for 8 hours. After cooling to room temperature, the reaction solution was poured into water. It was extracted with dichloromethane, and the organic layer was washed successively with water and brine. Purification by column chromatography (alumina, dichloromethane) gave 9.4 g of the compound represented by the formula (III-8-2).
窒素雰囲気下、反応容器に式（ＩＩＩ−８−３）で表される化合物１０．０ｇ、式（ＩＩＩ−８−４）で表される化合物８．４ｇ、炭酸カリウム６．７ｇ、１，２−ジメトキシエタン１００ｍＬ、テトラキス（トリフェニルホスフィン）パラジウム（０）０．４ｇを加え、８０℃で５時間加熱撹拌した。室温に冷却し、反応液を水に注いだ。酢酸エチルで抽出し、有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン／酢酸エチル）により精製を行うことによって、式（ＩＩＩ−８−５）で表される化合物８．２ｇを得た。 Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (III-8-3), 8.4 g of the compound represented by the formula (III-8-4), 6.7 g of potassium carbonate and 1,2 in a reaction vessel. -Dimethoxyethane 100mL and tetrakis (triphenylphosphine) palladium (0) 0.4g were added, and it heat-stirred at 80 degreeC for 5 hours. After cooling to room temperature, the reaction solution was poured into water. It was extracted with ethyl acetate, and the organic layer was washed successively with water and brine. Purification by column chromatography (silica gel, dichloromethane/ethyl acetate) gave 8.2 g of a compound represented by the formula (III-8-5).
実施例４において式（ＩＩＩ−４−５）で表される化合物を式（ＩＩＩ−８−５）で表される化合物に、式（ＩＩＩ−４−６）で表される化合物を式（ＩＩＩ−８−２）で表される化合物に、式（ＩＩＩ−４−４）で表される化合物を式（ＩＩＩ−８−９）で表される化合物に置き換えた以外は同様の方法によって、式（ＩＩＩ−８）で表される化合物を製造した。
ＬＣ−ＭＳ：６３３［Ｍ＋１］
（実施例９）式（ＩＩＩ−９）で表される化合物の製造
In Example 4, the compound represented by the formula (III-4-5) is replaced by the compound represented by the formula (III-8-5), and the compound represented by the formula (III-4-6) is prepared by the formula (III). A compound represented by formula (III-8-4) was replaced by a compound represented by formula (III-4-4) by a compound represented by formula (III-8-9). The compound represented by (III-8) was produced.
LC-MS: 633 [M+1]
(Example 9) Production of compound represented by formula (III-9)
実施例３において式（ＩＩＩ−３−１）で表される化合物を式（ＩＩＩ−９−１）で表される化合物に置き換えた以外は同様の方法によって、式（ＩＩＩ−９−４）で表される化合物を製造した。 A compound of the formula (III-9-4) was prepared in the same manner as in Example 3 except that the compound of the formula (III-3-1) was replaced with the compound of the formula (III-9-1). The compound represented was prepared.
窒素雰囲気下、反応容器に式（ＩＩＩ−９−４）で表される化合物１０．０ｇ、式（ＩＩＩ−９−５）で表される化合物１１．２ｇ、４−ジメチルアミノピリジン０．６ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド７．３ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−９−６）で表される化合物１６．２ｇを得た。 In a nitrogen atmosphere, 10.0 g of the compound represented by the formula (III-9-4), 11.2 g of the compound represented by the formula (III-9-5), and 0.6 g of 4-dimethylaminopyridine in a reaction vessel. 100 mL of dichloromethane was added. While cooling with ice, 7.3 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. By purifying by column chromatography (alumina, dichloromethane), 16.2 g of the compound represented by the formula (III-9-6) was obtained.
反応容器に式（ＩＩＩ−９−６）で表される化合物１６．２ｇ、テトラヒドロフラン１００ｍＬ、メタノール１００ｍＬ、濃塩酸０．２ｍＬを加え、室温で６時間撹拌した。反応液に酢酸エチルを加え、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−９−７）で表される化合物１１．７ｇを得た。 16.2 g of the compound represented by the formula (III-9-6), 100 mL of tetrahydrofuran, 100 mL of methanol, and 0.2 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) yielded 11.7 g of the compound represented by the formula (III-9-7).
窒素雰囲気下、反応容器に式（ＩＩＩ−９−７）で表される化合物１１．７ｇ、式（ＩＩＩ−９−８）で表される化合物８．０ｇ、４−ジメチルアミノピリジン０．４ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド５．２ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−９）で表される化合物１５．３ｇを得た。
ＬＣ−ＭＳ：５５３［Ｍ＋１］
（実施例１０）式（ＩＩＩ−１０）で表される化合物の製造
Under a nitrogen atmosphere, 11.7 g of the compound represented by the formula (III-9-7), 8.0 g of the compound represented by the formula (III-9-8), 0.4 g of 4-dimethylaminopyridine in a reaction vessel, 100 mL of dichloromethane was added. While cooling with ice, 5.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 15.3 g of a compound represented by the formula (III-9).
LC-MS: 553 [M+1]
(Example 10) Production of compound represented by formula (III-10)
ＷＯ２００４／００２９３５Ａ１号公報に記載の方法によって、式（ＩＩＩ−１０−１）で表される化合物を製造した。窒素雰囲気下、反応容器に式（ＩＩＩ−１０−１）で表される化合物１０．０ｇ、エチルジイソプロピルアミン７．０ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、塩化アクリロイル４．５ｇを滴下し、室温で６時間撹拌した。反応液を飽和炭酸水素ナトリウム水溶液に注ぎ、ジクロロメタンで抽出した。有機層を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−１０−２）で表される化合物９．９ｇを得た。 The compound represented by the formula (III-10-1) was produced by the method described in WO2004/002935A1. Under a nitrogen atmosphere, 10.0 g of the compound represented by the formula (III-10-1), 7.0 g of ethyldiisopropylamine, and 100 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 4.5 g of acryloyl chloride was added dropwise, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution and extracted with dichloromethane. The organic layer was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (alumina, dichloromethane) gave 9.9 g of the compound represented by the formula (III-10-2).
反応容器に式（ＩＩＩ−１０−２）で表される化合物９．９ｇ、ピリジニウムｐ−トルエンスルホン酸０．９ｇ、エタノール５０ｍＬを加え、６０℃で５時間加熱撹拌した。室温に冷却し、反応液を水に注いだ。析出した固体をろ過し、水で洗浄した。乾燥させることによって、式（ＩＩＩ−１０−３）で表される化合物７．１ｇを得た。 9.9 g of the compound represented by formula (III-10-2), 0.9 g of pyridinium p-toluenesulfonic acid, and 50 mL of ethanol were added to a reaction vessel, and the mixture was heated with stirring at 60° C. for 5 hours. After cooling to room temperature, the reaction solution was poured into water. The precipitated solid was filtered and washed with water. By drying, 7.1 g of the compound represented by the formula (III-10-3) was obtained.
実施例３において式（ＩＩＩ−３−１）で表される化合物を式（ＩＩＩ−１０−４）で表される化合物に置き換えた以外は同様の方法によって、式（ＩＩＩ−１０−７）で表される化合物を製造した。窒素雰囲気下、反応容器に式（ＩＩＩ−１０−７）で表される化合物１０．０ｇ、式（ＩＩＩ−１０−３）で表される化合物９．８ｇ、４−ジメチルアミノピリジン０．５ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド６．８ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−１０−８）で表される化合物１５．２ｇを得た。 A compound of the formula (III-10-7) was prepared in the same manner as in Example 3 except that the compound of the formula (III-3-1) was replaced with the compound of the formula (III-10-4). The compound represented was prepared. In a nitrogen atmosphere, 10.0 g of the compound represented by the formula (III-10-7), 9.8 g of the compound represented by the formula (III-10-3), and 0.5 g of 4-dimethylaminopyridine in a reaction vessel. 100 mL of dichloromethane was added. While cooling with ice, 6.8 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. By purifying by column chromatography (alumina, dichloromethane), 15.2 g of the compound represented by the formula (III-10-8) was obtained.
反応容器に式（ＩＩＩ−１０−８）で表される化合物１５．２ｇ、テトラヒドロフラン１００ｍＬ、メタノール１００ｍＬ、濃塩酸０．２ｍＬを加え、室温で６時間撹拌した。反応液に酢酸エチルを加え、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−１０−９）で表される化合物１１．０ｇを得た。 15.2 g of the compound represented by the formula (III-10-8), 100 mL of tetrahydrofuran, 100 mL of methanol, and 0.2 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) gave 11.0 g of a compound represented by the formula (III-10-9).
窒素雰囲気下、反応容器に式（ＩＩＩ−１０−９）で表される化合物１１．０ｇ、式（ＩＩＩ−１０−３）で表される化合物７．１ｇ、４−ジメチルアミノピリジン０．４ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド４．９ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−１０）で表される化合物１４．０ｇを得た。
ＬＣ−ＭＳ：５３９［Ｍ＋１］
（実施例１１）式（ＩＩＩ−１１）で表される化合物の製造
In a nitrogen atmosphere, 11.0 g of a compound represented by formula (III-10-9), 7.1 g of a compound represented by formula (III-10-3) and 0.4 g of 4-dimethylaminopyridine in a reaction vessel under a nitrogen atmosphere. 100 mL of dichloromethane was added. While cooling with ice, 4.9 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 14.0 g of a compound represented by the formula (III-10).
LC-MS: 539 [M+1]
(Example 11) Production of compound represented by formula (III-11)
窒素雰囲気下、反応容器に式（ＩＩＩ−１１−１）で表される化合物２５．０ｇ、パラトルエンスルホン酸ピリジニウム０．７ｇ、ジクロロメタン１２０ｍＬを加えた。氷冷しながら、３，４−ジヒドロ−２Ｈ−ピラン１６．８ｇを滴下し、室温で２時間撹拌した。反応液に水を注ぎ、有機層を飽和炭酸水素ナトリウム水溶液及び食塩水で順次洗浄した。カラムクロマトグラフィー（ＮＨ２シリカゲル、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−１１−２）で表される化合物３８．２ｇを得た。 Under a nitrogen atmosphere, 25.0 g of the compound represented by the formula (III-11-1), 0.7 g of pyridinium paratoluenesulfonate, and 120 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 16.8 g of 3,4-dihydro-2H-pyran was added dropwise, and the mixture was stirred at room temperature for 2 hours. Water was poured into the reaction solution, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and brine. Purification by column chromatography (NH2 silica gel, dichloromethane) gave 38.2 g of the compound represented by the formula (III-11-2).
窒素雰囲気下、反応容器に式（ＩＩＩ−１１−２）で表される化合物３８．０ｇ、ジクロロビス［ジ−ｔ−ブチル（ｐ−ジメチルアミノフェニル）ホスフィノ］パラジウム（ＩＩ）０．５ｇ、炭酸カリウム（２ｍｏｌ／Ｌ水溶液）１５０ｍＬ、テトラヒドロフラン５００ｍＬを加え、６０℃で加熱撹拌した。式（ＩＩＩ−１１−３）で表される化合物２３．１ｇのテトラヒドロフラン（１００ｍＬ）／水（２０ｍＬ）溶液を滴下し、６０℃で１０時間加熱撹拌した。室温に冷却し、反応液に水を注いだ。酢酸エチルで抽出し、有機層を食塩水で洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−１１−４）で表される化合物４５．７ｇを得た。 Under a nitrogen atmosphere, 38.0 g of the compound represented by the formula (III-11-2), dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) 0.5 g, and potassium carbonate were placed in a reaction vessel. (2 mol/L aqueous solution) 150 mL and tetrahydrofuran 500 mL were added, and the mixture was heated with stirring at 60°C. A solution of 23.1 g of the compound represented by the formula (III-11-3) in tetrahydrofuran (100 mL)/water (20 mL) was added dropwise, and the mixture was heated with stirring at 60° C. for 10 hours. After cooling to room temperature, water was poured into the reaction solution. It was extracted with ethyl acetate and the organic layer was washed with brine. Purification by column chromatography (alumina, dichloromethane) gave 45.7 g of the compound represented by the formula (III-11-4).
窒素雰囲気下、反応容器に式（ＩＩＩ−１１−４）で表される化合物４５．７ｇ、４−ジメチルアミノピリジン１．６ｇ、ジクロロメタン３００ｍＬ、メタクリル酸１４．７ｇを加えた。氷冷しながら、ジイソプロピルカルボジイミド２２．３ｇを滴下し、室温で６時間撹拌した。析出した固体をろ過により除去し、有機層を１０％塩酸、食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）、再結晶（ジクロロメタン／メタノール、−７８℃）により精製を行うことによって、式（ＩＩＩ−１１−５）で表される化合物２５．０ｇを得た。 Under a nitrogen atmosphere, 45.7 g of the compound represented by the formula (III-11-4), 1.6 g of 4-dimethylaminopyridine, 300 mL of dichloromethane, and 14.7 g of methacrylic acid were added to a reaction vessel. While cooling with ice, 22.3 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 6 hours. The precipitated solid was removed by filtration, and the organic layer was washed successively with 10% hydrochloric acid and brine. Purification by column chromatography (alumina, dichloromethane) and recrystallization (dichloromethane/methanol, -78°C) gave 25.0 g of a compound represented by the formula (III-11-5).
反応容器に式（ＩＩＩ−１１−５）で表される化合物２５．０ｇ、テトラヒドロフラン２５０ｍＬ、メタノール５０ｍＬを加えた。濃塩酸０．２ｍＬを加え、室温で２時間撹拌した。反応液を水に注ぎ、酢酸エチルで抽出し、有機層を食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）、再結晶（ヘキサン）により精製を行うことによって、式（ＩＩＩ−１１−６）で表される化合物１２．５ｇを得た。 25.0 g of the compound represented by formula (III-11-5), 250 mL of tetrahydrofuran, and 50 mL of methanol were added to a reaction vessel. 0.2 mL of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into water, extracted with ethyl acetate, and the organic layer was washed with brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (hexane) gave 12.5 g of a compound represented by the formula (III-11-6).
窒素雰囲気下、反応容器に式（ＩＩＩ−１１−６）で表される化合物３．７ｇ、式（ＩＩＩ−１１−７）で表される化合物３．２ｇ、４−ジメチルアミノピリジン０．２ｇ、ジクロロメタン５０ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド２．１ｇを滴下し、室温で４時間撹拌した。析出した固体をろ過により除去し、有機層を１０％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）、再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−１１）で表される化合物５．９ｇを得た。
相転移温度：Ｃ １６０ Ｎ ＞２２０ Ｉ
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ ２．０８（ｓ，３Ｈ），２．０９（ｓ，３Ｈ），２．２９（ｓ，３Ｈ），５．７９（ｄｔ，２Ｈ），６．３８（ｄ，２Ｈ），６．６２（ｄ，１Ｈ），７．０６（ｍ，２Ｈ），７．１６−７．３５（ｍ，７Ｈ），７．６４（ｄ，２Ｈ），７．８７（ｄ，１Ｈ）ｐｐｍ
ＬＣ−ＭＳ：４８３［Ｍ＋１］
（実施例１２）式（ＩＩＩ−１２）で表される化合物の製造
In a nitrogen atmosphere, 3.7 g of the compound represented by the formula (III-11-6), 3.2 g of the compound represented by the formula (III-11-7), and 0.2 g of 4-dimethylaminopyridine in a reaction vessel under a nitrogen atmosphere. 50 mL of dichloromethane was added. 2.1 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 4 hours. The precipitated solid was removed by filtration, and the organic layer was washed successively with 10% hydrochloric acid and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) yielded 5.9 g of a compound represented by the formula (III-11).
Phase transition temperature: C 160 N >220 I
1 H NMR (CDCl 3 ) δ 2.08 (s, 3H), 2.09 (s, 3H), 2.29 (s, 3H), 5.79 (dt, 2H), 6.38 (d, 2H), 6.62 (d, 1H), 7.06 (m, 2H), 7.16-7.35 (m, 7H), 7.64 (d, 2H), 7.87 (d, 1H). ) Ppm
LC-MS: 483 [M+1]
(Example 12) Production of compound represented by formula (III-12)
窒素雰囲気下、反応容器に式（ＩＩＩ−１２−１）で表される化合物２５．０ｇ、ジクロロビス［ジ−ｔ−ブチル（ｐ−ジメチルアミノフェニル）ホスフィノ］パラジウム（ＩＩ）０．５ｇ、炭酸カリウム（２ｍｏｌ／Ｌ水溶液）１６０ｍＬ、テトラヒドロフラン５００ｍＬを加え、６０℃で加熱撹拌した。式（ＩＩＩ−１２−２）で表される化合物３５．０ｇのテトラヒドロフラン（１００ｍＬ）／水（２０ｍＬ）溶液を滴下し、６０℃で３時間加熱撹拌した。室温に冷却し、反応液に水を注いだ。酢酸エチルで抽出し、有機層を食塩水で洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（ＩＩＩ−１２−３）で表される化合物４４．７ｇを得た。 In a nitrogen atmosphere, 25.0 g of the compound represented by the formula (III-12-1), dichlorobis[di-t-butyl(p-dimethylaminophenyl)phosphino]palladium(II) 0.5 g, potassium carbonate in a reaction vessel. (2 mol/L aqueous solution) 160 mL and tetrahydrofuran 500 mL were added, and the mixture was heated with stirring at 60°C. A solution of 35.0 g of the compound represented by the formula (III-12-2) in tetrahydrofuran (100 mL)/water (20 mL) was added dropwise, and the mixture was heated with stirring at 60° C. for 3 hours. After cooling to room temperature, water was poured into the reaction solution. It was extracted with ethyl acetate and the organic layer was washed with brine. Purification by column chromatography (alumina, dichloromethane) gave 44.7 g of the compound represented by the formula (III-12-3).
窒素雰囲気下、反応容器に式（ＩＩＩ−１２−３）で表される化合物４４．７ｇ、４−ジメチルアミノピリジン１．６ｇ、ジクロロメタン３００ｍＬ、メタクリル酸１２．７ｇを加えた。氷冷しながら、ジイソプロピルカルボジイミド２０．３ｇを滴下し、室温で２時間撹拌した。析出した固体をろ過により除去し、有機層を１０％塩酸、食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）、再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−１２−４）で表される化合物３７．０ｇを得た。 Under a nitrogen atmosphere, 44.7 g of the compound represented by the formula (III-12-3), 1.6 g of 4-dimethylaminopyridine, 300 mL of dichloromethane, and 12.7 g of methacrylic acid were added to a reaction vessel. While cooling with ice, 20.3 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 2 hours. The precipitated solid was removed by filtration, and the organic layer was washed successively with 10% hydrochloric acid and brine. By purification by column chromatography (alumina, dichloromethane) and recrystallization (dichloromethane/methanol), 37.0 g of a compound represented by the formula (III-12-4) was obtained.
反応容器に式（ＩＩＩ−１２−４）で表される化合物３７．０ｇ、テトラヒドロフラン２５０ｍＬ、メタノール５０ｍＬを加えた。濃塩酸０．２ｍＬを加え、室温で２時間撹拌した。反応液を水に注ぎ、酢酸エチルで抽出し、有機層を食塩水で洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）、再沈殿（ヘキサン）により精製を行うことによって、式（ＩＩＩ−１２−５）で表される化合物２５．３ｇを得た。 To the reaction vessel, 37.0 g of the compound represented by the formula (III-12-4), 250 mL of tetrahydrofuran, and 50 mL of methanol were added. 0.2 mL of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into water, extracted with ethyl acetate, and the organic layer was washed with brine. Purification by column chromatography (silica gel, dichloromethane) and reprecipitation (hexane) gave 25.3 g of a compound represented by the formula (III-12-5).
窒素雰囲気下、反応容器に式（ＩＩＩ−１２−５）で表される化合物３．７ｇ、式（ＩＩＩ−１２−６）で表される化合物３．２ｇ、４−ジメチルアミノピリジン０．２ｇ、ジクロロメタン５０ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド２．１ｇを滴下し、室温で５時間撹拌した。析出した固体をろ過により除去し、有機層を１０％塩酸及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）、再結晶（ジクロロメタン／メタノール）及びカラムクロマトグラフィー（シリカゲル、ジクロロメタン／ヘキサン）により精製を行うことによって、式（ＩＩＩ−１２）で表される化合物１．８ｇを得た。
相転移温度：Ｃ １６５ Ｎ ２００ ｐｏｌｙ
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ ２．０８（ｓ，６Ｈ），２．２９（ｓ，３Ｈ），５．７８（ｄｔ，２Ｈ），６．３７（ｄｔ，２Ｈ），６．６３（ｄ，１Ｈ），７．０１（ｍ，２Ｈ），７．２２（ｍ，５Ｈ），７．３５（ｍ，２Ｈ），７．６４（ｄ，２Ｈ），７．８８（ｄ，１Ｈ）ｐｐｍ
ＬＣ−ＭＳ：４８３［Ｍ＋１］
（実施例１３）式（ＩＩＩ−１３）で表される化合物の製造
In a reaction vessel under a nitrogen atmosphere, 3.7 g of the compound represented by the formula (III-12-5), 3.2 g of the compound represented by the formula (III-12-6), 0.2 g of 4-dimethylaminopyridine, 50 mL of dichloromethane was added. 2.1 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 5 hours. The precipitated solid was removed by filtration, and the organic layer was washed successively with 10% hydrochloric acid and brine. Purification by column chromatography (silica gel, dichloromethane), recrystallization (dichloromethane/methanol) and column chromatography (silica gel, dichloromethane/hexane) gave 1.8 g of a compound represented by the formula (III-12). It was
Phase transition temperature: C 165 N 200 poly
1 H NMR (CDCl 3 ) δ 2.08 (s, 6H), 2.29 (s, 3H), 5.78 (dt, 2H), 6.37 (dt, 2H), 6.63 (d, 1H), 7.01 (m, 2H), 7.22 (m, 5H), 7.35 (m, 2H), 7.64 (d, 2H), 7.88 (d, 1H) ppm
LC-MS: 483 [M+1]
(Example 13) Production of compound represented by formula (III-13)
ディーンスターク装置を備えた反応容器に式（ＩＩＩ−１３−１）で表される化合物１３．８ｇ、ｐ−トルエンスルホン酸一水和物１．４ｇ、酢酸エチル１５０ｍＬを加えた。溶媒を除去しながら、新たに酢酸エチルを追加しながら、５時間加熱還流させた。冷却した後、反応液を飽和炭酸水素ナトリウム水溶液及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−１３−２）で表される化合物１３．９ｇを得た。 To a reaction vessel equipped with a Dean-Stark apparatus, 13.8 g of the compound represented by the formula (III-13-1), 1.4 g of p-toluenesulfonic acid monohydrate and 150 mL of ethyl acetate were added. While the solvent was removed, new ethyl acetate was added, and the mixture was heated under reflux for 5 hours. After cooling, the reaction solution was washed successively with saturated aqueous sodium hydrogen carbonate solution and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) gave 13.9 g of the compound represented by the formula (III-13-2).
窒素雰囲気下、反応容器に式（ＩＩＩ−１３−２）で表される化合物１３．９ｇ、ピリジニウムｐ−トルエンスルホン酸０．３ｇ、ジクロロメタン６０ｍＬを加えた。氷冷しながら、３，４−ジヒドロ−２Ｈ−ピラン７．５ｇを滴下し、室温で１０時間撹拌した。反応液を飽和炭酸水素ナトリウム水溶液及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−１３−３）で表される化合物１６．６ｇを得た。 Under a nitrogen atmosphere, 13.9 g of the compound represented by the formula (III-13-2), 0.3 g of pyridinium p-toluenesulfonic acid, and 60 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 7.5 g of 3,4-dihydro-2H-pyran was added dropwise, and the mixture was stirred at room temperature for 10 hours. The reaction solution was washed successively with saturated aqueous sodium hydrogen carbonate solution and brine. Purification by column chromatography (alumina, dichloromethane) and recrystallization (dichloromethane/methanol) gave 16.6 g of a compound represented by the formula (III-13-3).
反応容器に式（ＩＩＩ−１３−３）で表される化合物１６．６ｇ、メタノール３００ｍＬを加えた。室温で５０％水酸化ナトリウム水溶液８．４ｍＬを加え、５０℃で４時間加熱撹拌した。反応液を水に注いだ。水層をｐＨ７に調整した後、酢酸エチルで抽出した。有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−１３−４）で表される化合物１２．７ｇを得た。 To the reaction vessel, 16.6 g of the compound represented by the formula (III-13-3) and 300 mL of methanol were added. 8.4 mL of 50% sodium hydroxide aqueous solution was added at room temperature, and the mixture was heated with stirring at 50° C. for 4 hours. The reaction solution was poured into water. The aqueous layer was adjusted to pH 7 and then extracted with ethyl acetate. The organic layer was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) yielded 12.7 g of the compound represented by the formula (III-13-4).
窒素雰囲気下、反応容器に式（ＩＩＩ−１３−４）で表される化合物１２．４ｇ、４−ジメチルアミノピリジン０．６ｇ、ジクロロメタン９９ｍＬ、メタクリル酸４．６ｇを加えた。氷冷しながら、ジイソプロピルカルボジイミド６．８ｇを滴下し、室温で１０時間撹拌した。析出した固体をろ過により除去し、溶媒を減圧留去した。再結晶（メタノール）を行った。カラムクロマトグラフィー（ＮＨ２シリカゲル、ジクロロメタン／ヘキサン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−１３−５）で表される化合物５．４ｇを得た。 Under a nitrogen atmosphere, 12.4 g of the compound represented by the formula (III-13-4), 0.6 g of 4-dimethylaminopyridine, 99 mL of dichloromethane, and 4.6 g of methacrylic acid were added to a reaction vessel. While cooling with ice, 6.8 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 10 hours. The precipitated solid was removed by filtration, and the solvent was evaporated under reduced pressure. Recrystallization (methanol) was performed. Purification by column chromatography (NH2 silica gel, dichloromethane/hexane) and recrystallization (dichloromethane/methanol) yielded 5.4 g of a compound represented by the formula (III-13-5).
反応容器に式（ＩＩＩ−１３−５）で表される化合物５．４ｇ、テトラヒドロフラン５０ｍＬ、メタノール５０ｍＬを加えた。濃塩酸０．２ｍＬを加え、室温で３時間撹拌した。反応液を水に注ぎ、酢酸エチルで抽出した。有機層を食塩水で洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（ＩＩＩ−１３−６）で表される化合物４．０ｇを得た。 To the reaction vessel, 5.4 g of the compound represented by the formula (III-13-5), 50 mL of tetrahydrofuran, and 50 mL of methanol were added. 0.2 mL of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) yielded 4.0 g of a compound represented by the formula (III-13-6).
窒素雰囲気下、反応容器に式（ＩＩＩ−１３−６）で表される化合物４．０ｇ、式（ＩＩＩ−１３−７）で表される化合物３．５ｇ、４−ジメチルアミノピリジン０．２ｇ、ジクロロメタン５０ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド２．３ｇを滴下し、室温で１０時間撹拌した。析出した固体をろ過により除去し、溶媒を減圧留去した。再結晶（メタノール）を行った。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（ＩＩＩ−１３）で表される化合物５．９ｇを得た。
相転移温度：Ｃ １７９ Ｎ ＞２２０ Ｉ
１Ｈ ＮＭＲ（ＣＤＣｌ３）δ １．５４−１．６７（ｍ，４Ｈ），１．９５−２．０１（ｍ，５Ｈ），２．０７（ｓ，３Ｈ），２．１４−２．１４（ｍ，２Ｈ），２．５７（ｍ，１Ｈ），４．８５（ｍ，１Ｈ），５．５５（ｍ，１Ｈ），５．７９（ｍ，１Ｈ），６．１１（ｓ，１Ｈ），６．３７（ｓ，１Ｈ），６．５９（ｄ，１Ｈ），７．０９（ｄ，２Ｈ），７．２０（ｄ，２Ｈ），７．２４（ｄ，２Ｈ），７．６２（ｄ，２Ｈ），７．８５（ｄ，１Ｈ）ｐｐｍ
ＬＣ−ＭＳ：４７５［Ｍ＋１］
（比較例１）式（Ｒ−１）で表される化合物の製造
In a reaction vessel under a nitrogen atmosphere, 4.0 g of a compound represented by the formula (III-13-6), 3.5 g of a compound represented by the formula (III-13-7), 0.2 g of 4-dimethylaminopyridine, 50 mL of dichloromethane was added. 2.3 g of diisopropylcarbodiimide was added dropwise while cooling with ice, and the mixture was stirred at room temperature for 10 hours. The precipitated solid was removed by filtration, and the solvent was evaporated under reduced pressure. Recrystallization (methanol) was performed. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 5.9 g of a compound represented by the formula (III-13).
Phase transition temperature: C179N>220I
1 H NMR(CDCl 3 ) δ 1.54-1.67 (m, 4H), 1.95-2.01 (m, 5H), 2.07 (s, 3H), 2.14-2.14. (M, 2H), 2.57 (m, 1H), 4.85 (m, 1H), 5.55 (m, 1H), 5.79 (m, 1H), 6.11 (s, 1H) , 6.37 (s, 1H), 6.59 (d, 1H), 7.09 (d, 2H), 7.20 (d, 2H), 7.24 (d, 2H), 7.62( d, 2H), 7.85 (d, 1H) ppm
LC-MS: 475 [M+1]
(Comparative Example 1) Production of compound represented by formula (R-1)
窒素雰囲気下、反応容器に式（Ｒ−１−１）で表される化合物２．０ｇ、式（Ｒ−１−２）で表される化合物８．０ｇ、４−ジメチルアミノピリジン０．４ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド４．９ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（Ｒ−１−３）で表される化合物７．５ｇを得た。 In a nitrogen atmosphere, 2.0 g of the compound represented by the formula (R-1-1), 8.0 g of the compound represented by the formula (R-1-2), 0.4 g of 4-dimethylaminopyridine in a reaction vessel, 100 mL of dichloromethane was added. While cooling with ice, 4.9 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (alumina, dichloromethane) and recrystallization (dichloromethane/methanol) yielded 7.5 g of a compound represented by the formula (R-1-3).
反応容器に式（Ｒ−１−３）で表される化合物７．５ｇ、テトラヒドロフラン１００ｍＬ、メタノール１００ｍＬ、濃塩酸０．２ｍＬを加え、室温で６時間撹拌した。反応液に酢酸エチルを加え、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（Ｒ−１−４）で表される化合物４．８ｇを得た。 7.5 g of the compound represented by the formula (R-1-3), 100 mL of tetrahydrofuran, 100 mL of methanol, and 0.2 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) gave 4.8 g of the compound represented by the formula (R-1-4).
窒素雰囲気下、反応容器に式（Ｒ−１−４）で表される化合物４．８ｇ、メタクリル酸２．２ｇ、４−ジメチルアミノピリジン０．３ｇ、ジクロロメタン７０ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド３．５ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（Ｒ−１）で表される化合物５．１ｇを得た。
ＬＣ−ＭＳ：５５３［Ｍ＋１］
（比較例２）式（Ｒ−２）で表される化合物の製造
Under a nitrogen atmosphere, 4.8 g of the compound represented by the formula (R-1-4), 2.2 g of methacrylic acid, 0.3 g of 4-dimethylaminopyridine and 70 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 3.5 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 5.1 g of a compound represented by the formula (R-1).
LC-MS: 553 [M+1]
(Comparative Example 2) Production of compound represented by formula (R-2)
反応容器に式（Ｒ−２−１）で表される化合物１０．０ｇ、ピリジニウムｐ−トルエンスルホナート１．４ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、３，４−ジヒドロ−２Ｈ−ピラン５．７ｇを滴下し、室温で１０時間撹拌した。反応液を水に注ぎ、ジクロロメタンで抽出した。有機層を飽和炭酸水素ナトリウム水溶液及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（Ｒ−２−２）で表される化合物１３．２ｇを得た。 To the reaction vessel, 10.0 g of the compound represented by the formula (R-2-1), 1.4 g of pyridinium p-toluenesulfonate, and 100 mL of dichloromethane were added. While cooling with ice, 5.7 g of 3,4-dihydro-2H-pyran was added dropwise, and the mixture was stirred at room temperature for 10 hours. The reaction solution was poured into water and extracted with dichloromethane. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and brine. By purifying by column chromatography (alumina, dichloromethane), 13.2 g of the compound represented by the formula (R-2-2) was obtained.
反応容器に式（Ｒ−２−２）で表される化合物１３．２ｇ、メタノール１５０ｍＬを加えた。室温で５０％水酸化ナトリウム水溶液１２ｍＬを滴下し、５０℃で４時間加熱撹拌した。反応液を水に注ぎ、水層をｐＨ４．５に調整した。酢酸エチルで抽出し、有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（Ｒ−２−３）で表される化合物１１．３ｇを得た。 13.2 g of the compound represented by the formula (R-2-2) and 150 mL of methanol were added to the reaction vessel. 12 mL of 50% sodium hydroxide aqueous solution was added dropwise at room temperature, and the mixture was heated with stirring at 50° C. for 4 hours. The reaction solution was poured into water and the aqueous layer was adjusted to pH 4.5. It was extracted with ethyl acetate, and the organic layer was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) gave 11.3 g of the compound represented by the formula (R-2-3).
窒素雰囲気下、反応容器に式（Ｒ−２−４）で表される化合物３．１ｇ、式（Ｒ−２−３）で表される化合物１１．３ｇ、４−ジメチルアミノピリジン０．６ｇ、ジクロロメタン１００ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド６．９ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（Ｒ−２−５）で表される化合物１０．９ｇを得た。 Under a nitrogen atmosphere, 3.1 g of the compound represented by the formula (R-2-4), 11.3 g of the compound represented by the formula (R-2-3) and 0.6 g of 4-dimethylaminopyridine in a reaction vessel. 100 mL of dichloromethane was added. While cooling with ice, 6.9 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (alumina, dichloromethane) and recrystallization (dichloromethane/methanol) gave 10.9 g of a compound represented by the formula (R-2-5).
反応容器に式（Ｒ−２−５）で表される化合物１０．９ｇ、テトラヒドロフラン１００ｍＬ、メタノール１００ｍＬ、濃塩酸０．２ｍＬを加え、室温で６時間撹拌した。反応液に酢酸エチルを加え、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（Ｒ−２−６）で表される化合物７．０ｇを得た。 10.9 g of the compound represented by the formula (R-2-5), 100 mL of tetrahydrofuran, 100 mL of methanol, and 0.2 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) gave 7.0 g of a compound represented by the formula (R-2-6).
窒素雰囲気下、反応容器に式（Ｒ−２−６）で表される化合物７．０ｇ、アクリル酸２．６ｇ、４−ジメチルアミノピリジン０．４ｇ、ジクロロメタン７０ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド５．０ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（Ｒ−２）で表される化合物７．１ｇを得た。
ＬＣ−ＭＳ：５３９［Ｍ＋１］
（比較例３）式（Ｒ−３）で表される化合物の製造
Under a nitrogen atmosphere, 7.0 g of the compound represented by the formula (R-2-6), 2.6 g of acrylic acid, 0.4 g of 4-dimethylaminopyridine, and 70 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 5.0 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 7.1 g of a compound represented by the formula (R-2).
LC-MS: 539 [M+1]
(Comparative Example 3) Production of compound represented by formula (R-3)
窒素雰囲気下、反応容器に式（Ｒ−３−１）で表される化合物５．０ｇ、式（Ｒ−３−２）で表される化合物３．９ｇ、４−ジメチルアミノピリジン０．２ｇ、ジクロロメタン５０ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド３．０ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、ジクロロメタン）により精製を行うことによって、式（Ｒ−３−３）で表される化合物６．９ｇを得た。 In a nitrogen atmosphere, 5.0 g of the compound represented by the formula (R-3-1), 3.9 g of the compound represented by the formula (R-3-2), and 0.2 g of 4-dimethylaminopyridine in a reaction vessel. 50 mL of dichloromethane was added. While cooling with ice, 3.0 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (alumina, dichloromethane) gave the compound of the formula (R-3-3) 6.9 g.
反応容器に式（Ｒ−３−３）で表される化合物６．９ｇ、テトラヒドロフラン１００ｍＬ、メタノール１００ｍＬ、濃塩酸０．２ｍＬを加え、室温で６時間撹拌した。反応液に酢酸エチルを加え、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）及び再結晶（酢酸エチル／ヘキサン）により精製を行うことによって、式（Ｒ−３−４）で表される化合物３．９ｇを得た。 6.9 g of the compound represented by formula (R-3-3), 100 mL of tetrahydrofuran, 100 mL of methanol, and 0.2 mL of concentrated hydrochloric acid were added to a reaction vessel, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) and recrystallization (ethyl acetate/hexane) yielded 3.9 g of a compound represented by the formula (R-3-4).
窒素雰囲気下、反応容器に式（Ｒ−３−４）で表される化合物３．９ｇ、メタクリル酸２．９ｇ、４−ジメチルアミノピリジン０．４ｇ、ジクロロメタン７０ｍＬを加えた。氷冷しながら、ジイソプロピルカルボジイミド４．２ｇを滴下し、室温で７時間撹拌した。析出物をろ過により除去し、ろ液を５％塩酸、水及び食塩水で順次洗浄した。カラムクロマトグラフィー（シリカゲル、ジクロロメタン）及び再結晶（ジクロロメタン／メタノール）により精製を行うことによって、式（Ｒ−３）で表される化合物４．２ｇを得た。
ＬＣ−ＭＳ：３９３［Ｍ＋１］
（比較例４）式（Ｒ−４）で表される化合物の製造
Under a nitrogen atmosphere, 3.9 g of the compound represented by the formula (R-3-4), 2.9 g of methacrylic acid, 0.4 g of 4-dimethylaminopyridine and 70 mL of dichloromethane were added to a reaction vessel. While cooling with ice, 4.2 g of diisopropylcarbodiimide was added dropwise, and the mixture was stirred at room temperature for 7 hours. The precipitate was removed by filtration, and the filtrate was washed successively with 5% hydrochloric acid, water and brine. Purification by column chromatography (silica gel, dichloromethane) and recrystallization (dichloromethane/methanol) gave 4.2 g of the compound represented by the formula (R-3).
LC-MS: 393 [M+1]
(Comparative Example 4) Production of compound represented by formula (R-4)
窒素雰囲気下、反応容器に式（Ｒ−４−１）で表される化合物１０．０ｇ、アクリル酸エチル５．９ｇ、炭酸カリウム１０．０ｇ、Ｎ，Ｎ−ジメチルアセトアミド１００ｍＬ、酢酸パラジウム（ＩＩ）０．００８８ｇを加え、１２０℃で８時間加熱撹拌した。室温に冷却し、反応液を５％塩酸に注いだ。酢酸エチルで抽出し、有機層を水及び食塩水で順次洗浄した。カラムクロマトグラフィー（アルミナ、酢酸エチル）により精製を行うことによって、式（Ｒ−４−２）で表される化合物８．７ｇを得た。 In a nitrogen atmosphere, 10.0 g of a compound represented by the formula (R-4-1), 5.9 g of ethyl acrylate, 10.0 g of potassium carbonate, 100 mL of N,N-dimethylacetamide, and palladium (II) acetate were placed in a reaction vessel. 0.0088 g was added, and the mixture was heated with stirring at 120° C. for 8 hours. After cooling to room temperature, the reaction solution was poured into 5% hydrochloric acid. It was extracted with ethyl acetate, and the organic layer was washed successively with water and brine. Purification by column chromatography (alumina, ethyl acetate) gave 8.7 g of a compound represented by the formula (R-4-2).
比較例２において、式（Ｒ−２−１）で表される化合物を式（Ｒ−４−２）で表される化合物に置き換えた以外は同様の方法によって、式（Ｒ−４−４）で表される化合物を製造した。実施例６において、式（ＩＩＩ−６−５）で表される化合物を式（Ｒ−４−５）で表される化合物に、式（ＩＩＩ−６−７）で表される化合物を式（Ｒ−４−７）で表される化合物に置き換えた以外は同様の方法によって、式（Ｒ−４−８）で表される化合物を製造した。比較例３において、式（Ｒ−３−１）で表される化合物を式（Ｒ−４−４）で表される化合物に、式（Ｒ−３−２）で表される化合物を式（Ｒ−４−８）で表される化合物に置き換えた以外は同様の方法によって、式（Ｒ−４）で表される化合物を製造した。
ＬＣ−ＭＳ：５２９［Ｍ＋１］
上記の実施例１から実施例１３及び比較例１から比較例４において製造した式（ＩＩＩ−１）から式（ＩＩＩ−１３）で表される化合物及び式（Ｒ−１）から式（Ｒ−４）で表される化合物に含まれるオリゴマーの含有率及び多環性不純物の含有率の分析値を下表に示す。
A compound of the formula (R-4-4) was prepared in the same manner as in Comparative Example 2 except that the compound of the formula (R-2-1) was replaced with the compound of the formula (R-4-2). A compound represented by In Example 6, the compound represented by the formula (III-6-5) is converted into the compound represented by the formula (R-4-5), and the compound represented by the formula (III-6-7) is represented by the formula (III A compound represented by the formula (R-4-8) was produced by the same method except that the compound represented by R-4-7) was substituted. In Comparative Example 3, the compound represented by the formula (R-3-1) was added to the compound represented by the formula (R-4-4), and the compound represented by the formula (R-3-2) was replaced with the compound represented by the formula (R-3-2). A compound represented by the formula (R-4) was produced by the same method except that the compound represented by R-4-8) was used.
LC-MS: 529 [M+1]
Compounds represented by Formulas (III-1) to (III-13) and Formulas (R-1) to (R-) produced in Examples 1 to 13 and Comparative Examples 1 to 4 described above. The analysis values of the content of the oligomer and the content of the polycyclic impurity contained in the compound represented by 4) are shown in the table below.
前記の結果から、本願発明の製造方法によって製造された化合物はいずれも比較例の製造方法によって製造された化合物と比較して、オリゴマーの含有率は高いが、多環性不純物の含有率が低いことがわかる。比較例の製造方法では、例えば中間体である式（Ｒ−１−４）で表される化合物を製造した際に、エステル交換反応が起こり、式（Ｒ−１−４−ｉ）等で表される種々の微量の副生成物が生じてしまう。これらの副生成物がその後の反応によって誘導化され、多環性不純物として残留したと考えられる。 From the above results, all the compounds produced by the production method of the present invention have a high oligomer content but a low polycyclic impurity content as compared with the compound produced by the comparative production method. I understand. In the production method of Comparative Example, for example, when a compound represented by the formula (R-1-4), which is an intermediate, is produced, a transesterification reaction occurs, and the compound represented by the formula (R-1-4-i) or the like Various trace amounts of by-products are generated. It is considered that these by-products were derivatized by the subsequent reaction and remained as polycyclic impurities.
その他の比較例においても同様に、エステル交換反応が起こり、多環性不純物を生じてしまうと考えられる。 It is considered that the transesterification reaction similarly occurs in the other comparative examples to generate polycyclic impurities.
一方、本願発明の製造方法では、例えば中間体である式（ＩＩＩ−９−７）で表される化合物を製造した際に、エステル交換反応が起こると、式（ＩＩＩ−９−７−ｉ）で表される副生成物が生じる可能性がある。式（ＩＩＩ−９−７）で表される化合物は、分子内にフェノール性水酸基を１つのみ有するため、比較例のような多環性不純物が生じにくいと考えられる。 On the other hand, in the production method of the present invention, for example, when a transesterification reaction occurs when a compound represented by the formula (III-9-7) which is an intermediate is produced, the formula (III-9-7-i) There is a possibility that a by-product represented by Since the compound represented by the formula (III-9-7) has only one phenolic hydroxyl group in the molecule, it is considered that polycyclic impurities as in Comparative Example are unlikely to occur.
その他の実施例においても同様に、本願発明の製造方法では、エステル交換反応によって多環性不純物が生じにくいと考えられる。
（実施例１４から実施例２６、比較例５から比較例８）
実施例１から実施例１３に記載の式（ＩＩＩ−１）から式（ＩＩＩ−１３）で表される化合物及び比較例１から比較例４に記載の式（Ｒ−１）から及び式（Ｒ−４）で表される化合物を評価対象の化合物とした。また、下記成分によって構成される組成物を母体液晶とした。
Similarly in other examples, it is considered that the production method of the present invention is unlikely to cause polycyclic impurities due to the transesterification reaction.
(Examples 14 to 26, Comparative Examples 5 to 8)
Compounds represented by formula (III-1) to formula (III-13) described in Examples 1 to 13 and formula (R-1) described in Comparative Examples 1 to 4 and formula (R) The compound represented by -4) was used as a compound to be evaluated. A composition composed of the following components was used as a base liquid crystal.
母体液晶に評価対象の各化合物を０．３％添加し溶解させ重合性液晶組成物を調製し、評価対象の重合性液晶組成物とした。この評価対象の重合性液晶組成物を、セルギャップ３．５μｍでホメオトロピック配向を誘起するポリイミド配向膜を塗布したＩＴＯ付きセルに真空注入法で注入した。周波数１ｋＨｚで１．８Ｖの矩形波を印加しながら、高圧水銀灯を用いて３２０ｎｍ以上のＵＶを１０ｍＷ／ｃｍ２で６００秒間照射することにより、評価対象のＰＳＡ型垂直配向性液晶表示素子を作製した。 0.3% of each compound to be evaluated was added to the matrix liquid crystal and dissolved to prepare a polymerizable liquid crystal composition, which was used as the evaluation target polymerizable liquid crystal composition. The polymerizable liquid crystal composition to be evaluated was injected by a vacuum injection method into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. A PSA-type vertical alignment liquid crystal display element to be evaluated was produced by irradiating UV of 320 nm or more at 10 mW/cm 2 for 600 seconds using a high-pressure mercury lamp while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. ..
評価対象の液晶表示素子の焼き付きの生じにくさを比較するために、７０℃で７．５Ｖの電圧を印加し経過時間ごとに目視によって評価を行った。目視によって焼き付きが無ければＡ、表示素子の一部に僅かに焼き付きが見られる場合はＢ、表示素子の全体に僅かに焼き付きが見られる場合はＣ、焼き付きが強く見られる場合はＤとした。結果を下記表に示す。 In order to compare the occurrence of image sticking of the liquid crystal display element to be evaluated, a voltage of 7.5 V was applied at 70° C. and visual evaluation was performed at each elapsed time. When there was no burn-in by visual observation, it was A, when slight burn-in was observed in a part of the display element, C when slight burn-in was observed in the entire display element, and D when strong burn-in was observed. The results are shown in the table below.
このように、本願発明の製造方法によって製造された化合物を添加して作製した液晶表示素子はいずれも焼き付きが生じにくいことがわかる。一方、比較例の製造方法によって製造された化合物を添加して作製した液晶表示素子は長時間の電圧印加によって焼き付きが生じやすいことがわかる。比較例の液晶表示素子では、重合性化合物に含まれる多環性不純物が、ポリマーの剛性を低下させてしまったため、焼き付きが起こりやすくなったと考えられる。一方で、本願発明の液晶表示素子では、多環性不純物が少ないことから、焼き付きが起こりにくいと考えられる。以上の結果から、本願発明の製造方法は、従来の方法と比較し、液晶組成物に添加しＴＦＴ液晶表示素子を作製した場合に、表示素子に焼き付きを起こしにくいことから、重合性ケイ皮酸エステル誘導体の製造方法として有用である。 As described above, it is understood that the liquid crystal display element manufactured by adding the compound manufactured by the manufacturing method of the present invention hardly causes image sticking. On the other hand, it can be seen that the liquid crystal display element manufactured by adding the compound manufactured by the manufacturing method of the comparative example is apt to cause burn-in by long-term voltage application. In the liquid crystal display element of the comparative example, it is considered that the polycyclic impurities contained in the polymerizable compound decreased the rigidity of the polymer, so that the image sticking easily occurred. On the other hand, in the liquid crystal display device of the present invention, since the polycyclic impurities are small, it is considered that the image sticking is unlikely to occur. From the above results, the production method of the present invention is less likely to cause burn-in to the display element when added to the liquid crystal composition to produce a TFT liquid crystal display element, as compared with the conventional method. It is useful as a method for producing an ester derivative.
Claims (15)
Ａ１は１，４−フェニレン基、１，４−シクロヘキシレン基、ビシクロ［２．２．２］オクタン−１，４−ジイル基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ナフタレン−１，４−ジイル基、テトラヒドロナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基、テトラヒドロピラン−２，５−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表すが、これらの基は無置換であるか又は１つ以上の置換基Ｌ１によって置換されても良く、
Ｌ１はハロゲン原子、シアノ基、ニトロ基、ペンタフルオロスルファニル基、置換されていても良いアミノ基、置換されていても良いシリル基、任意の水素原子がフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−によって置換されても良い炭素原子数１から２０のアルキル基、若しくは、ＰＬ−ＳｐＬ−で表される基（式中、ＰＬはラジカル重合、カチオン重合又はアニオン重合により重合する基を表し、ＳｐＬはスペーサー基又は単結合を表す。）を表すが、Ｌ１が複数存在する場合それらは同一であっても異なっていても良い。）で表される化合物と、下記の一般式（ＩＩ）
Ｓｐ１はスペーサー基又は単結合を表し、
Ａ２及びＡ３は各々独立して１，４−フェニレン基、１，４−シクロヘキシレン基、ビシクロ［２．２．２］オクタン−１，４−ジイル基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ナフタレン−２，６−ジイル基、ナフタレン−１，４−ジイル基、テトラヒドロナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基、テトラヒドロピラン−２，５−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表すが、これらの基は無置換であるか又は１つ以上の置換基Ｌ２によって置換されても良く、Ａ３が複数存在する場合それらは同一であっても異なっていても良く、
Ｌ２はハロゲン原子、シアノ基、ニトロ基、ペンタフルオロスルファニル基、置換されていても良いアミノ基、置換されていても良いシリル基、任意の水素原子がフッ素原子に置換されても良く、１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−が各々独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−又は−Ｃ≡Ｃ−によって置換されても良い炭素原子数１から２０のアルキル基、若しくは、ＰＬ−ＳｐＬ−で表される基（式中、ＰＬはラジカル重合、カチオン重合又はアニオン重合により重合する基を表し、ＳｐＬはスペーサー基又は単結合を表す。）を表すが、Ｌ２が複数存在する場合それらは同一であっても異なっていても良く、
Ｚ１は−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ２ＣＨ２−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＯＣＯ−ＮＨ−、−ＮＨ−ＣＯＯ−、−ＮＨ−ＣＯ−ＮＨ−、−ＮＨ−Ｏ−、−Ｏ−ＮＨ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｓ−、−ＳＣＦ２−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＣＯＯ−ＣＨ２−、−ＯＣＯ−ＣＨ２−、−ＣＨ２−ＣＯＯ−、−ＣＨ２−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−又は単結合を表すが、Ｚ１が複数存在する場合それらは同一であっても異なっていても良く、
ｍ１は０から６の整数を表す。）で表される化合物とを反応させる工程を含む、下記の一般式（ＩＩＩ）
A 1 is 1,4-phenylene group, 1,4-cyclohexylene group, bicyclo[2.2.2]octane-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5- Diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, tetrahydropyran-2,5-diyl group or 1,3-dioxane-2 ,5-diyl group, which may be unsubstituted or substituted by one or more substituents L 1 .
L 1 is a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, an optionally substituted silyl group, or an arbitrary hydrogen atom may be substituted with a fluorine atom, 1 number of -CH 2 - or nonadjacent two or more -CH 2 - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH = CH -, - CH = CH -, - CF = CF- or an alkyl group of 20 good 1 -C be replaced by -C≡C-, or, P L -Sp L - in a group represented by (wherein, P L represents a group of polymerization by radical polymerization, cationic polymerization or anionic polymerization, Sp L represents. a spacer group or a single bond) represents a, those case where L 1 there are a plurality May be the same or different. ) And a compound represented by the following general formula (II)
Sp 1 represents a spacer group or a single bond,
A 2 and A 3 are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a bicyclo[2.2.2]octane-1,4-diyl group, a pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, tetrahydro Represents a pyran-2,5-diyl group or a 1,3-dioxane-2,5-diyl group, which may be unsubstituted or substituted by one or more substituents L 2 . When there are a plurality of A 3, they may be the same or different,
L 2 is a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group, an optionally substituted amino group, an optionally substituted silyl group, or an arbitrary hydrogen atom may be substituted with a fluorine atom, 1 number of -CH 2 - or nonadjacent two or more -CH 2 - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH = CH -, - CH = CH -, - CF = CF- or an alkyl group of 20 good 1 -C be replaced by -C≡C-, or, P L -Sp L - in a group represented by (wherein, P L represents a group of polymerization by radical polymerization, cationic polymerization or anionic polymerization, Sp L represents. a spacer group or a single bond) represents a, those case where L 2 there are a plurality May be the same or different,
Z 1 is -O -, - S -, - OCH 2 -, - CH 2 O -, - CH 2 CH 2 -, - CO -, - COO -, - OCO -, - CO-S -, - S- CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -. O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH -OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO- CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, -N=CH-, -CH=NN-CH-, -CF=CF-, -C≡C- or represents a single bond, but when a plurality of Z 1's are present, they may be the same. Can be different,
m1 represents an integer of 0 to 6. ) And a compound represented by the following general formula (III):
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| JP (1) | JP2020093995A (en) |
| CN (1) | CN111302933A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014148471A1 (en) * | 2013-03-21 | 2014-09-25 | Dic株式会社 | Polymerizable compound, and liquid crystal composition produced using same |
| WO2017188001A1 (en) * | 2016-04-27 | 2017-11-02 | Dic株式会社 | Polymerizable compound and liquid crystal composition using same |
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| ATE263746T1 (en) * | 1998-07-24 | 2004-04-15 | Rolic Ag | CROSS-LINKABLE LIQUID CRYSTALLINE COMPOUNDS |
| JP4200195B2 (en) * | 1998-10-09 | 2008-12-24 | Ｄｉｃ株式会社 | Liquid crystalline (meth) acrylate compound, liquid crystal composition containing the compound, and optical anisotropic body using the same |
| JP2002156668A (en) * | 2000-11-17 | 2002-05-31 | Fuji Photo Film Co Ltd | Nonlinear optical material |
| JP5545519B2 (en) * | 2009-10-27 | 2014-07-09 | Ｄｉｃ株式会社 | Polymerizable compound |
| US9157027B2 (en) * | 2012-04-24 | 2015-10-13 | Jnc Corporation | Compound having four polymerizable groups, liquid crystal composition and liquid crystal display device |
| JP2016011346A (en) * | 2014-06-27 | 2016-01-21 | Jnc株式会社 | Polymerizable compound, polymerizable composition, and liquid crystal display element |
| US20180321560A1 (en) * | 2015-09-29 | 2018-11-08 | Sharp Kabushiki Kaisha | Liquid crystal display device and method for producing same |
| EP3390570B1 (en) * | 2015-12-17 | 2020-03-18 | Merck Patent GmbH | Liquid crystal mixture and liquid crystal display |
| WO2017154588A1 (en) * | 2016-03-10 | 2017-09-14 | Dic株式会社 | Method for producing compound having ester group |
| JP7271896B2 (en) * | 2018-10-02 | 2023-05-12 | Dic株式会社 | Polymerizable compound, liquid crystal composition and liquid crystal display element using the same |
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- 2018-12-12 JP JP2018232586A patent/JP2020093995A/en active Pending
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014148471A1 (en) * | 2013-03-21 | 2014-09-25 | Dic株式会社 | Polymerizable compound, and liquid crystal composition produced using same |
| WO2017188001A1 (en) * | 2016-04-27 | 2017-11-02 | Dic株式会社 | Polymerizable compound and liquid crystal composition using same |
Non-Patent Citations (1)
| Title |
|---|
| MOLECULAR CRYSTALS AND LIQUID CRYSTALS, vol. 470, JPN6022031383, 2007, pages 19 - 29, ISSN: 0004982117 * |
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