CN106278895B - Carboxylic acid compound, method for producing same, and liquid crystal composition using same - Google Patents
Carboxylic acid compound, method for producing same, and liquid crystal composition using same Download PDFInfo
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- CN106278895B CN106278895B CN201510250660.XA CN201510250660A CN106278895B CN 106278895 B CN106278895 B CN 106278895B CN 201510250660 A CN201510250660 A CN 201510250660A CN 106278895 B CN106278895 B CN 106278895B
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- -1 Carboxylic acid compound Chemical class 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title abstract description 68
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 312
- 125000004432 carbon atom Chemical group C* 0.000 claims description 49
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 33
- 125000001424 substituent group Chemical group 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- 125000001153 fluoro group Chemical group F* 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 6
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 141
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 138
- 238000006243 chemical reaction Methods 0.000 description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 71
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 66
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 64
- 239000000243 solution Substances 0.000 description 58
- 238000004440 column chromatography Methods 0.000 description 48
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- 239000000706 filtrate Substances 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 238000000746 purification Methods 0.000 description 31
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 29
- 239000012267 brine Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 28
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 238000001953 recrystallisation Methods 0.000 description 26
- 238000001816 cooling Methods 0.000 description 24
- 239000000741 silica gel Substances 0.000 description 24
- 229910002027 silica gel Inorganic materials 0.000 description 24
- 239000010408 film Substances 0.000 description 20
- 239000002244 precipitate Substances 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 239000002585 base Substances 0.000 description 14
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 12
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000007810 chemical reaction solvent Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- SMBBZHGTZJNSRQ-UHFFFAOYSA-N n'-(6,6-dichlorohexyl)methanediimine Chemical compound ClC(Cl)CCCCCN=C=N SMBBZHGTZJNSRQ-UHFFFAOYSA-N 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- FCYRSDMGOLYDHL-UHFFFAOYSA-N chloromethoxyethane Chemical compound CCOCCl FCYRSDMGOLYDHL-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 3
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000005997 bromomethyl group Chemical group 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 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 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003509 tertiary alcohols Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- BAYAKMPRFGNNFW-UHFFFAOYSA-N 2,4-dimethylpentan-3-ol Chemical compound CC(C)C(O)C(C)C BAYAKMPRFGNNFW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920001219 Polysorbate 40 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 125000006351 ethylthiomethyl group Chemical group [H]C([H])([H])C([H])([H])SC([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrane Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Medicinal Preparation (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Furan Compounds (AREA)
- Cosmetics (AREA)
- Indole Compounds (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention provides a carboxylic acid compound, a method for producing the same, and a liquid crystal composition using the same. The present invention addresses the problem of providing a method for producing an alicyclic hydrocarbon compound having a carboxyl group, a compound produced from the compound obtained by the production method, and a composition containing the compound. The present invention provides a method for producing a compound represented by general formula (I-E), which comprises derivatizing a compound represented by general formula (I-D) to produce a compound represented by general formula (I-E), a compound produced from the compound obtained by the production method, and a composition containing the compound. [ formula 1]
[ chemical formula 2)]
Description
Technical Field
The present invention relates to a method for producing an alicyclic hydrocarbon compound having 1 carboxyl group and 1 ester structure, a compound produced using the compound, a polymerizable composition containing the compound, a polymerizable liquid crystal composition, and an optically anisotropic body using the polymerizable liquid crystal composition.
Background
Compounds having a polymerizable group (polymerizable compounds) are used for various optical materials. For example, a polymerizable composition containing a polymerizable compound is aligned in a liquid crystal state and then polymerized, whereby a polymer having a uniform orientation can be produced. Such a polymer can be used for a polarizing plate, a retardation plate, and the like required for a display. In many cases, a polymerizable composition containing 2 or more polymerizable compounds is used in order to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, transparency, mechanical strength, surface hardness, heat resistance and light resistance of the polymer. In this case, it is necessary for the polymerizable compound to be used to impart good physical properties to the polymerizable composition without adversely affecting other properties.
The compound used for electronic materials and optical materials is preferably high in purity. An alicyclic hydrocarbon compound having 1 carboxyl group and 1 ester structure is an important intermediate in the production of a compound used in a liquid crystal material. Various methods have been reported for producing the intermediate (patent documents 1,2, and 3). However, these production methods have a problem of producing a large amount of by-products (patent document 3), a problem of complicated purification operations (patent document 1), and a problem of requiring the use of an expensive noble metal catalyst (patent document 2).
In addition, in a retardation plate used for optical compensation of a liquid crystal display or the like, when a polymerizable composition to which a polymerizable compound is added is applied to a substrate and polymerized to produce a film-shaped polymer, it is necessary that haze and unevenness are not generated. However, a film produced using a polymerizable compound produced using an alicyclic hydrocarbon compound having 1 carboxyl group and 1 ester structure produced by a method reported so far as an intermediate contains a small amount of impurities, and thus has a problem that haze or unevenness is likely to occur (patent documents 1,2, and 3). Since these impurities are extremely small in amount, it is difficult to directly quantify them by a common analytical method. However, since even a very small amount of the catalyst causes adverse effects on the film quality, reaction conditions under which these impurity by-products are not produced as much as possible are preferred. Therefore, it is necessary to develop a method for producing an alicyclic hydrocarbon compound having 1 carboxyl group and 1 ester structure, which is less likely to cause haze and unevenness when used in a film.
Documents of the prior art
Patent document
Patent document 1: WO2011/068138A1 publication
Patent document 2: WO2009/116657A1 publication
Patent document 3: japanese laid-open patent publication No. 62-289545
Disclosure of Invention
Problems to be solved by the invention
The invention provides a method for producing an alicyclic hydrocarbon compound having a carboxyl group, a compound produced from the compound obtained by the production method, and a composition containing the compound. Also disclosed is a polymerizable composition which is less likely to cause haze or unevenness when a film-shaped polymer is produced by polymerizing a polymerizable composition containing a polymerizable compound produced from a compound obtained by the production method. Further, a polymer obtained by polymerizing a polymerizable composition containing the compound obtained by the production method, and an optically anisotropic body using the polymer are also provided.
Means for solving the problems
As a result of intensive studies to solve the above problems, the present inventors have developed a method for producing a compound represented by the following general formula (I-E). That is, the present invention provides a process for producing a compound represented by the general formula (I-E), which comprises derivatizing a compound represented by the general formula (I-D) to produce a compound represented by the general formula (I-E), also disclosed are a polymerizable composition containing such a compound, a resin additive, an oil, a filter, an adhesive, a pressure-sensitive adhesive, a fat or oil, an ink, a pharmaceutical product, a cosmetic product, a detergent, a building material, a packaging material, a liquid crystal material, an organic EL material, an organic semiconductor material, an electronic material, a display element, an electronic device, a communication device, an automobile part, an aircraft part, a mechanical part, an agricultural chemical, a food, a product using such a material, a polymerizable liquid crystal composition, a polymer obtained by polymerizing such a polymerizable liquid crystal composition, and an optically anisotropic body using such a polymer.
ADVANTAGEOUS EFFECTS OF INVENTION
The optically anisotropic body using the polymerizable liquid crystal composition containing the compound produced by the production method of the present invention has small haze and little unevenness, and therefore the compound produced by the production method of the present invention is useful for optical material applications such as optical compensation films.
Detailed Description
The present invention provides a method for producing an alicyclic hydrocarbon compound having a carboxyl group, a compound produced from the compound obtained by the production method, a composition containing the compound, a resin additive, an oil, a filter, an adhesive, a binder, a grease, an ink, a pharmaceutical product, a cosmetic product, a detergent, a building material, a packaging material, a liquid crystal material, an organic EL material, an organic semiconductor material, an electronic material, a display element, an electronic device, a communication device, an automobile part, an airplane part, a mechanical part, an agricultural chemical, and a food each using the compound, a polymerizable liquid crystal composition, a polymer obtained by polymerizing the polymerizable liquid crystal composition, and an optically anisotropic body using the polymer.
In the general formula (I-D), R1Represents a group selected from methyl, unsubstituted or 2-position may have 1 or more L1Ethyl group as a substituent represented by the formula, or may have 1 or more L11A group of silyl groups of the substituents represented by, L1Represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or 1-CH group2-or non-adjacent 2 or more-CH2-a linear or branched alkyl group having 1 to 20 carbon atoms which may be independently substituted by-O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH ═ CH-, -CF ≡ CF-or-C ≡ C-, wherein any hydrogen atom in the alkyl group may be substituted by a fluorine atom, and L is a fluorine atom11Represents a silyl group substituted with a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aromatic group having 5 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 20 carbon atoms. From the viewpoints of ease of synthesis, ease of obtaining raw materials, and cost, R1Preferably represents a methyl group, unsubstituted or may have 1 or more L in the 2-position1The ethyl group of the substituent(s) represents, more preferably, a methyl group or the 2-position may be substituted by 1-CH2-or non-adjacent 2 or more-CH2-an ethyl group which is independently substituted by an-O-substituted linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, or a linear alkyl group having 3 to 22 carbon atoms which is substituted at the 2-position by a linear alkyl group having 1 to 20 carbon atoms, still more preferably a methyl group, an ethyl group or a propyl group, and particularly preferably a methyl group or an ethyl group.
When R is1Indicating 2 bits with more than 1L1In the case of an ethyl group as the substituent, L is L from the viewpoint of easiness of synthesis and easiness of availability of raw materials1Preferably represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or 1-CH2-or non-adjacent 2 or more-CH2-carbon each independently of the others being optionally substituted by-O-or-S-, any hydrogen atom being optionally substituted by a fluorine atomThe linear or branched alkyl group having 1 to 20 atoms more preferably represents a fluorine atom, a chlorine atom or 1-CH2-or non-adjacent 2 or more-CH2-a linear or branched alkyl group having 1 to 10 carbon atoms, each of which is independently optionally substituted by-O-or-S-, more preferably a linear alkyl group having 1 to 10 carbon atoms, and particularly preferably a methyl group.
In addition, when R is1Denotes a group having 1 or more L11In the case of the silyl group as the substituent represented, L is L from the viewpoints of ease of synthesis and ease of availability of raw materials11Preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aromatic group having 5 to 20 carbon atoms, more preferably represents a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a phenyl group, and still more preferably represents a methyl group, an isopropyl group or a tert-butyl group. More specifically, when R1The representation may have L11In the silyl group of the substituent represented by (A), R1Preferably represents a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a t-butyldiphenylsilyl group, an isopropyldimethylsilyl group, a phenyldimethylsilyl group, a di-t-butylmethylsilyl group, a triisopropylsilyl group, a tris (2, 6-diphenylbenzyl) silyl group, more preferably represents a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, an isopropyldimethylsilyl group, a di-t-butylmethylsilyl group, a triisopropylsilyl group, still more preferably represents a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group, and still more preferably represents a trimethylsilyl group.
In the general formula (I-D), R2Represents a group selected from an alkoxymethyl group having 2 to 20 carbon atoms, an alkyl p-aminobenzenesulfonylmethyl group having 2 to 20 carbon atoms, a secondary alkyl group having 3 to 20 carbon atoms, a tertiary alkyl group having 4 to 20 carbon atoms, a 2-tetrahydropyranyl group having 5 to 20 carbon atoms, a 2-tetrahydrothiopyranyl group having 5 to 20 carbon atoms, a 2-tetrahydrofuranyl group having 4 to 20 carbon atoms, a 2-tetrahydrothiofuranyl group having 4 to 20 carbon atoms, these groups being unsubstituted or may be substituted by 1 or more substituents L2Substituted, L2Represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, a phenyl group, or 1-CH2-or non-adjacent 2 or more-CH2-a linear or branched alkyl group having 1 to 20 carbon atoms which may be independently substituted by-O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH ═ CH-, -CF ≡ CF-, or-C ≡ C-, wherein any hydrogen atom in the alkyl group may be substituted by a fluorine atom, or represents a phenyl group which may be substituted by the above. L from the viewpoints of ease of synthesis, ease of obtaining raw materials, and yield2Preferably represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a trimethylsilyl group, a dimethylsilyl group, a phenyl group, or 1-CH in which any hydrogen atom may be substituted by a fluorine atom2-or non-adjacent 2 or more-CH2-a linear or branched alkyl group having 1 to 20 carbon atoms which may be independently substituted with-O-, -S-, -CO-S-, -CH ═ CH-, and more preferably represents a chlorine atom, a bromine atom, a nitro group, a phenyl group, or 1-CH2-or non-adjacent 2 or more-CH2-a linear or branched alkyl group having 1 to 10 carbon atoms which may be independently substituted with-O-, -S-, -CH ═ CH-, more preferably represents a linear alkyl group having 1 to 10 carbon atoms or a phenyl group, and still more preferably represents a linear alkyl group having 1 to 3 carbon atoms.
In the general formula (I-D), R is R from the viewpoints of ease of synthesis, ease of obtaining raw materials, and yield2Preferably represents a substituent selected from the group consisting of L which is unsubstituted or may be substituted by 1 or more2A substituted alkoxymethyl group having 2 to 20 carbon atoms, a tertiary alkyl group having 4 to 20 carbon atoms, or a 2-tetrahydropyranyl group having 5 to 20 carbon atoms. More specifically, the substituent L is unsubstituted or may be substituted by 1 or more2The substituted alkoxymethyl group having 2 to 20 carbon atoms preferably represents a group selected from the group consisting of methoxymethyl, ethoxymethyl, t-butoxymethyl, methoxyethoxymethyl, 4-methoxybenzyloxymethyl, 2-methoxybenzyloxymethylGroups based on benzyloxymethyl, 4-nitrobenzyloxymethyl, 2- (trimethylsilyl) ethoxymethyl, benzyloxymethyl, pivaloyloxymethyl, as unsubstituted or optionally substituted by 1 or more substituents L2The substituted alkyl p-aminobenzenesulfonylmethyl group having 2 to 20 carbon atoms preferably represents a methylthiomethyl group, an ethylthiomethyl group or a tert-butylthiomethyl group, and is unsubstituted or may be substituted by 1 or more substituents L2The substituted secondary alkyl group having 3 to 20 carbon atoms preferably represents a group selected from the group consisting of 2-propyl, 2-butyl, 3-pentyl, 2-methyl-3-pentyl, 2, 4-dimethyl-3-pentyl and diphenylmethyl, as unsubstituted or 1 or more substituents L2The substituted tertiary alkyl group having 4 to 20 carbon atoms preferably represents a group selected from the group consisting of a tertiary butyl group, a 3-methyl-3-pentyl group, a triphenylmethyl group and a 2-chlorophenyldiphenylmethyl group, as an unsubstituted or 1 or more substituents L2The substituted 2-tetrahydropyranyl group having 5 to 20 carbon atoms preferably represents a group selected from the group consisting of 2-tetrahydropyranyl group and 3-bromo-2-tetrahydropyranyl group, as the substituent L which may be unsubstituted or substituted by 1 or more2The substituted 2-tetrahydrothiopyranyl group having 5 to 20 carbon atoms preferably represents a 2-tetrahydrothiopyranyl group as the unsubstituted or 1 or more substituents L2The substituted 2-tetrahydrofuryl group having 4 to 20 carbon atoms preferably represents a 2-tetrahydrofuryl group as the unsubstituted or 1 or more substituents L2The substituted 2-tetrahydrothiofuryl group having 4 to 20 carbon atoms preferably represents a 2-tetrahydrothiofuryl group. From the viewpoint of easiness of obtaining raw materials and yield, R2More preferably represents a group selected from the group consisting of t-butyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl and 2-tetrahydropyranyl.
In the general formula (I-D), M represents an unsubstituted or 1 or more substituents LMA substituted 2-valent group comprising at least 1 alicyclic hydrocarbon group.
From the viewpoints of ease of synthesis, ease of starting materials, and reduction in haze and unevenness in film production, M preferably represents a group represented by the following formula (I-M),
[ solution 8]
(in the formula, A)1And A2Represents a compound selected from the following formulae (A-1) to (A-9)
[ solution 9]
(in the formula, an arbitrary position may have an atomic bond, and an arbitrary-CH2Each independently may be substituted by-O-, -S-, -NR-0- (in the formula, R0Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ) -CS-or-CO-but does not include an-O-O-bond. Here, the arbitrary position may have an atomic bond means, for example, A1And A2Since it is a 2-valent group, an arbitrary position has 2 atomic bonds (hereinafter, in the present invention, it is indicated that any position may have the same meaning as an atomic bond). Furthermore, these radicals are unsubstituted or may be substituted by 1 or more substituents LMAnd (4) substitution. ) When a plurality of A's are present1When they are the same or different, Z1represents-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-, or a single bond, when there are more than one Z1When used, they may be the same or different, and m1 represents an integer of 0 to 6. ).
From synthesized volumesIn the formula (I-M), A is represented by the formula (I-M)1And A2More preferably represents an unsubstituted or a1 or more substituent LMThe substituted groups represented by the above formulae (A-1) to (A-10) are more preferably unsubstituted or substituted by 1 or more substituents LMThe substituted group represented by the formula (A-1) or the formula (A-2) is more preferably an unsubstituted group represented by the formula (A-1), and particularly preferably an unsubstituted trans-1, 4-cyclohexylene group.
In the formula (I-M), Z is in the range of Z from the viewpoints of ease of synthesis, ease of starting materials, and reduction in haze and unevenness in film production1More preferably represents-OCH2-、-CH2O-、-CH2CH2-、-COO-、-OCO-、-CO-S-、-S-CO-、-CO-NH-、-NH-CO-、-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-, -CH ═ CH-, -N ═ N-, -CH ═ N-, -N ═ CH-, -CH ═ N-N ═ CH-, -CF ═ CF-, -C ≡ C-, or a single bond, and more preferably-CH-, -CH ≡ CH-, -C ≡ C-, or a single bond2CH2-, -CH ═ CH-, -N ═ N-, -CH ═ N-, -N ═ CH-, -CH ═ N-N ═ CH-, -CF ═ CF-, -C ≡ C-, or a single bond, and more preferably represents-CH ═ CH-, -CF ≡ CF-, -C ≡ C-, or a single bond2CH2-or a single bond, particularly preferably a single bond.
In the formula (I-M), M1 more preferably represents an integer of 0 to 3, further preferably represents an integer of 0 to 2, further preferably represents 0 or 1, and particularly preferably represents 0, from the viewpoint of ease of synthesis, ease of starting materials, and reduced haze and unevenness in film production.
In the general formula (I-D), LMRepresents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethyl groupSilyl, dimethylsilyl, thioisocyano, or 1-CH2-or non-adjacent 2 or more-CH2A linear or branched alkyl group having 1 to 20 carbon atoms which may be independently substituted with-O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH-, -CF-or-C.ident.C-, and any hydrogen atom may be substituted with a fluorine atom. L is from the viewpoints of ease of synthesis, ease of starting materials, and reduction in haze and unevenness in film productionMMore preferably represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, or 1-CH2-or non-adjacent 2 or more-CH2-a linear or branched alkyl group having 1 to 20 carbon atoms which may be independently substituted with-O-and any hydrogen atom may be substituted with a fluorine atom, and further preferably represents a fluorine atom, a chlorine atom, or 1-CH2-or non-adjacent 2 or more-CH2-a linear alkyl group having 1 to 10 carbon atoms, each independently being optionally substituted with-O-.
Specific embodiments are described below.
In the step of derivatizing the compound represented by the general formula (I-D) to produce the compound represented by the general formula (I-E), the reaction conditions for the reaction in the presence of a base or a basic group are preferred. From the viewpoint of yield and ease of purification, the reaction in the presence of an alkali is more preferable. Examples of the base include ammonia, calcium hydroxide, lithium hydroxide, magnesium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. From the viewpoints of easiness of post-treatment and reaction rate, the alkali is preferably calcium hydroxide, lithium hydroxide, potassium hydroxide or sodium hydroxide, more preferably potassium hydroxide or sodium hydroxide.
The reaction temperature is preferably from-100 ℃ to 200 ℃, more preferably from-20 ℃ to 150 ℃, further preferably from 0 ℃ to 120 ℃, further preferably from 5 ℃ to 100 ℃, and particularly preferably from room temperature to 80 ℃ from the viewpoint of yield and reaction rate.
The reaction solvent may be an organic solvent, water, an ionic liquid, or a supercritical fluid, or may be a mixture of two or more of them, and may be a two-phase system or a solvent-free reaction. Examples of the organic solvent include isopropanol, 2-methoxyethanol, ethylene glycol, methanol, ethanol, propanol, chloroform, dichloromethane, 1, 2-dichloroethane, acetone, acetonitrile, N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, hexane, pentane, methyl isobutyl ketone, and methyl ethyl ketone. From the viewpoint of solubility of the compound represented by the general formula (I-D) and the base or the basic group, the organic solvent is preferably an alcohol, more specifically, isopropanol, 2-methoxyethanol, ethylene glycol, methanol, ethanol, or propanol, and more preferably methanol or ethanol from the viewpoint of easiness of post-treatment.
When the reaction is carried out in a two-phase system of an organic solvent and water, a phase transfer catalyst may also be added. Examples of the phase transfer catalyst include benzalkonium chloride, benzyltrimethylammonium bromide, polyoxyethylene (10) octylphenyl ether [ Triton X-100], polyoxyethylene (20) sorbitan monolaurate [ Tween 20], polyoxyethylene (20) sorbitan monopalmitate [ Tween 40], polyoxyethylene (20) sorbitan monostearate [ Tween 60] polyoxyethylene (23) lauryl ether [ Brij35], and sorbitan monopalmitate [ Span 40 ].
The amount of the reaction solvent is not particularly limited as long as it is an amount that can sufficiently dissipate the heat of reaction generated by the reaction, but if the amount of the solvent is too small, the heat of reaction accumulates in the reaction system and by-products are easily generated. On the other hand, if the amount of the solvent is too large, the concentration of the reactant decreases, and the reaction rate decreases significantly. From the above viewpoint, the amount of the solvent is preferably 0.01 ml to 1 l with respect to 1g of the compound represented by the general formula (I-D), more preferably 0.1 ml to 100ml with respect to 1g of the compound represented by the general formula (I-D), more preferably 0.2 ml to 50ml with respect to 1g of the compound represented by the general formula (I-D), more preferably 1ml to 20ml with respect to 1g of the compound represented by the general formula (I-D), and particularly preferably 2ml to 10ml with respect to 1g of the compound represented by the general formula (I-D).
Further, purification may be carried out after the reaction, if necessary. Examples of the purification method include chromatography, filtration, recrystallization, distillation, sublimation, reprecipitation, adsorption, centrifugal separation, and liquid separation. When a refining agent is used, examples of the refining agent include silica gel, alumina, activated carbon, activated clay, diatomaceous earth, zeolite, mesoporous silica, carbon nanotubes, carbon nanohorns, binchous carbon, charcoal, graphene, ion exchange resins, acid clay, silica, diatomaceous earth, perlite, cellulose, organic polymers, and porous gels.
As the method for producing the compound represented by the general formula (I-D), it is preferable to derive it into the following general formula (I-C)
[ solution 10]
(wherein M and R1The same meanings as described above are shown. ) The compounds represented by the general formula (I-D). For introducing the aforementioned R into a compound represented by the general formula (I-C)2Reagents and reaction conditions for the groups represented are according to R2The kind of the group is preferably selected as appropriate, more preferably Greene's PROTECTIVE GROUPS in ORGANIC SYNTHESIS (Fourth Edition), PETER G.M.WUTS, THEODORA W.GREENE, A John Wiley&Sons, inc., Publication), etc. When R is used from the viewpoints of ease of synthesis, ease of obtaining raw materials, and yield2Represents a substituent selected from the group consisting of L which is unsubstituted or substituted by 1 or more2When the group of the substituted alkoxymethyl group having 2 to 20 carbon atoms or the alkyl p-aminobenzenesulfonylmethyl group having 2 to 20 carbon atoms is substituted, it is preferable that R is not bonded to R1Reaction of the group represented by (a) with the corresponding chloromethyl, bromomethyl, iodomethyl, chloromethyl, bromomethyl or iodomethyl alkyl sulfide in the presence of a base or a base having low reactivity. In this case, the base is preferably the aforementioned base, and more preferably sodium bicarbonate, sodium carbonate, calcium carbonate, potassium acetate, and potassium carbonatePotassium hydrogen carbonate and cesium carbonate, and sodium carbonate and potassium carbonate are more preferable. The base is preferably ammonia, a primary amine, a secondary amine, a tertiary amine, an aromatic amine, or a salt thereof, more preferably a secondary amine, a tertiary amine, or an aromatic amine, and still more preferably a tertiary amine, from the viewpoint of yield. More specifically, N-dimethylethylamine, triethylamine, N-ethyldiisopropylamine, pyridine, piperidine, and N, N-dimethylaminopyridine are preferable, and triethylamine and N-ethyldiisopropylamine are more preferable.
The reaction temperature is preferably from-100 ℃ to 200 ℃, more preferably from-50 ℃ to 150 ℃, even more preferably from-20 ℃ to 120 ℃, and even more preferably from 0 ℃ to 80 ℃ from the viewpoint of yield and reaction rate. The kind and amount of the reaction solvent may be the same as those of the reaction solvent.
Further, when R is introduced into the compound represented by the general formula (I-C)2Represents a substituent selected from the group consisting of L which is unsubstituted or substituted by 1 or more2Examples of the substituted C3-20 secondary alkyl group and C4-20 tertiary alkyl group include, for example, those obtained by converting a compound represented by the general formula (I-C) into an acid chloride, a mixed acid anhydride or a carboxylic acid anhydride, and then reacting the acid chloride, the mixed acid anhydride or the carboxylic acid anhydride with R1The reaction of the group represented by (a) with a corresponding secondary or tertiary alcohol in the presence of a base or base having low reactivity, or the reaction with a corresponding secondary or tertiary alcohol in the presence of a condensing agent. Examples of the condensing agent include N, N '-dichlorohexylcarbodiimide, N' -diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and N- [3- (dimethylamino) propyl ] carbodiimide]-N' -ethylcarbodiimide and the like. The reaction temperature and the type and amount of the reaction solvent may be the same as those described above.
Further, R introduced when the compound represented by the general formula (I-C)2Represents unsubstituted or may be substituted by 1 or more substituents L2Examples of the substituted 2-tetrahydropyranyl group having 5 to 20 carbon atoms include conditions for reacting with 3, 4-dihydro-2H-pyran. Among the above, aprotic solvents are preferable as the reaction solvent, and chloroform, dichloromethane, 1, 2-dichloroethane, and the like are more preferable from the viewpoint of easiness of the post-treatment,Ethyl acetate, butyl acetate, tetrahydrofuran, toluene, hexane, pentane, heptane, and further preferably chloroform, dichloromethane, toluene, hexane, heptane. The reaction temperature and the type and amount of the reaction solvent may be the same as those described above.
As the method for producing the compound represented by the general formula (I-C), it is preferable to derive it into the following general formula (I-B)
[ solution 11]
(wherein M and R1The same meanings as described above are shown. ) The compounds represented by the general formula (I-C). For reacting one R in the compound represented by the general formula (I-B)1The reagents and reaction conditions for the elimination of the groups represented are preferably in accordance with R1The kind of the group is suitably selected, and more preferably Greene's PROTECTIVE GROUPS in ORGANIC SYNTHESIS (Fourth Edition), PETER G.M.WUTS, THEODORA W.GREENE, A John Wiley&Sons, inc., Publication), etc. From the viewpoints of ease of synthesis, ease of obtaining raw materials, and yield, the same conditions as those in the step of derivatizing the compound represented by the general formula (I-D) to produce the compound represented by the general formula (I-E) are preferred. The equivalent of the base is preferably 0.01 to 5 equivalents, more preferably 0.1 to 2.5 equivalents, further preferably 0.5 to 1.5 equivalents, further preferably 0.75 to 1.25 equivalents, and particularly preferably 0.9 to 1.1 equivalents, relative to the compound represented by the general formula (I-B), from the viewpoints of easiness of post-treatment and purification, and yield.
As the method for producing the compound represented by the general formula (I-B), it is preferable to derive it to the following general formula (I-A)
[ solution 12]
(wherein M represents the same meaning as described above) to a compound represented by the general formula (I-B). For introducing R into a compound represented by the general formula (I-A)1The reagents and reaction conditions for the radicals indicated are preferably in accordance with R1The kind of the group is suitably selected, and more preferably Greene's PROTECTIVE GROUPS in ORGANIC SYNTHESIS (Fourth Edition), PETER G.M.WUTS, THEODORA W.GREENE, A John Wiley&Sons, inc., Publication), etc. When R is used from the viewpoints of ease of synthesis, ease of obtaining raw materials, and yield1Representing a methyl group or may have L in position 21Examples of the ethyl group as the substituent include conditions in which the compound represented by the general formula (I-A) is converted into an acid chloride, a mixed acid anhydride or a carboxylic acid anhydride, and then reacted with the corresponding alcohol in the presence of a base or a basic group, conditions in which the compound is reacted with the corresponding alcohol in the presence of a condensing agent, and conditions in which the compound is dehydrated with the corresponding alcohol in the presence of an acid catalyst. Examples of the acid catalyst include p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, pyridinium p-toluenesulfonate, oxalic acid, hydrochloric acid, sulfuric acid, and the like. The kind of the condensing agent, the reaction temperature, and the kind and amount of the reaction solvent include the kind of the condensing agent, the reaction temperature, and the kind and amount of the reaction solvent. In addition, when R is1The representation may have L11The silyl group as the substituent(s) is exemplified by the conditions for reacting with the corresponding silyl halide in the presence of a basic group. Examples of the base include the above-mentioned bases.
[ examples ]
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the compositions of examples and comparative examples below, "%" means "% by mass". In each step, when a substance unstable in oxygen and/or water is handled, it is preferable to perform the operation in an inert gas such as nitrogen or argon. The usual post-treatment is an operation carried out for obtaining a target compound from a reaction solution, and is an operation usually carried out by those skilled in the art, such as quenching, liquid separation-extraction, neutralization, washing, drying, and concentration of a reaction.
(GC analysis conditions)
Column: agilent Technologies, J & W Column DB-1HT, 15m × 0.25mm × 0.10 μm
Temperature program: 100 deg.C (1 min) - (20 deg.C/min) -250 deg.C- (10 deg.C/min) -380 deg.C- (7 deg.C/min) -400 deg.C (2.64 min)
Injection port temperature: 350 deg.C
Detector temperature: 400 deg.C
(UPLC analysis conditions)
Column: waters ACQUITY UPLC BEH C18，2.1×100mm，1.7μm
Eluting solvent: acetonitrile/water (90:10)
Flow rate: 0.5mL/min
A detector: UV, 210nm
Column oven: 40 deg.C
Example 1 production of Compound represented by formula (I-1)
[ solution 13]
5.0g of the compound represented by the formula (I-1-1), 20mL of methanol and 1mL of concentrated sulfuric acid were placed in a reaction vessel and heated under reflux for 8 hours. After addition of water, the methanol was distilled off. Extracted with toluene and washed with brine. After the solvent was distilled off, 4.9g of the compound represented by the formula (I-1-2) was obtained by recrystallization from methanol.
4.9g of the compound represented by the formula (I-1-2) and 20mL of methanol were charged in a reaction vessel. 4.9mL of 20% aqueous sodium hydroxide solution was added dropwise with stirring. 10% hydrochloric acid was added dropwise to adjust the pH to 3.5. After addition of 10mL of water, the methanol was distilled off. Further, 20mL of water was added to the reaction solution, and the precipitated solid was filtered. Dichloroethane was added to the solid, dispersion washed and filtered. The filtrate was concentrated, and 1.8g of the compound represented by the formula (I-1-3) was obtained by recrystallization from toluene.
A reaction vessel was charged with 10.0g of the compound represented by the formula (I-1-3), 4.0g of t-butyl alcohol, 0.7g of N, N-dimethylaminopyridine and 40mL of methylene chloride. While cooling with ice, 8.1g of diisopropylcarbodiimide was added dropwise and stirred. After the precipitate was filtered, the filtrate was washed with 5% hydrochloric acid, water and a salt solution, and the solvent was distilled off. Dissolved in methylene chloride/hexane (1:1) and purified by column chromatography (silica gel) to give 9.9g of the compound represented by the formula (I-1-4).
9.9g of the compound represented by the formula (I-1-4) and 40mL of methanol were charged in a reaction vessel. While cooling with ice, 6.5mL of a 25% aqueous solution of sodium hydroxide was added dropwise, followed by stirring at room temperature. After methanol was distilled off, 100mL of water was added to dissolve the mixture. After insoluble matter was filtered, 10% hydrochloric acid was added to the filtrate to adjust the pH to 4. Dichloromethane was added and the mixture was washed with water and brine. Purification by column chromatography (alumina) and drying gave 8.4g of the compound represented by the formula (I-1).
Example 2 production of Compound represented by formula (I-2)
[ solution 14]
5.0g of the compound represented by the formula (I-2-1), 25mL of ethanol and 1mL of concentrated sulfuric acid were placed in a reaction vessel and heated under reflux for 8 hours. After addition of water, the ethanol was distilled off. Extracted with toluene and washed with brine. After the solvent was distilled off, 5.0g of the compound represented by the formula (I-2-2) was obtained by recrystallization from ethanol.
5.0g of the compound represented by the formula (I-2-2), 20mL of tetrahydrofuran and 20mL of ethanol were charged in a reaction vessel. 3.2mL of 20% aqueous potassium hydroxide solution was added dropwise with stirring. 10% hydrochloric acid was added dropwise to adjust the pH to 3.5. After addition of 10mL of water, the methanol was distilled off. Further, 20mL of water was added to the reaction solution, and the precipitated solid was filtered. Dichloroethane was added to the solid, dispersion washed and filtered. The filtrate was concentrated, and 1.8g of the compound represented by the formula (I-2-3) was obtained by recrystallization from toluene.
8.0g of the compound represented by the formula (I-2-3), 0.4g of pyridinium p-toluenesulfonate, and 80mL of methylene chloride were charged in a reaction vessel. 2.9g of 3, 4-dihydro-2H-pyran are added dropwise with stirring. After washing with an aqueous sodium hydrogencarbonate solution and brine, the mixture was purified by column chromatography (alumina) to give 10.0g of a compound represented by the formula (I-2-4).
10.0g of the compound represented by the formula (I-2-4) and 40mL of ethanol were charged in a reaction vessel. While cooling with ice, 6.5mL of a 25% aqueous solution of sodium hydroxide was added dropwise, followed by stirring at 50 ℃. After adjusting the pH to 4 by adding 10% hydrochloric acid, dichloromethane was added, and the mixture was washed with water and brine. Purification by column chromatography (alumina) and drying gave 8.2g of the compound represented by the formula (I-2).
Example 3 production of Compound represented by formula (I-3)
[ solution 15]
A compound represented by the formula (I-3-1), 1-octanol, toluene and sulfuric acid were charged into a reaction vessel and heated under reflux. After washing with water or brine, the solvent was distilled off, and the compound represented by the formula (I-3-2) was obtained by recrystallization from methanol.
A compound represented by the formula (I-3-2) and methanol were charged into a reaction vessel. 20% aqueous sodium hydroxide solution was added dropwise with stirring. The pH was adjusted to 4 by addition of 10% hydrochloric acid. After addition of water, the methanol was distilled off. Further, water was added to the reaction solution, and the precipitated solid was filtered. Dichloroethane was added to the solid, dispersion washed and filtered. The filtrate was concentrated and recrystallized from toluene to obtain a compound represented by the formula (I-3-3).
A compound represented by the formula (I-3-3), chloromethyl methyl ether, triethylamine and N, N-dimethylformamide were added to a reaction vessel and stirred. Toluene was added thereto, and the mixture was washed with water and brine. Purifying by column chromatography to obtain compound represented by formula (I-3-4).
A compound represented by the formula (I-3-4) and tetrahydrofuran are charged into a reaction vessel. After a 25% aqueous solution of sodium hydroxide was added dropwise thereto, the mixture was stirred at 60 ℃. After tetrahydrofuran was distilled off, water was added to dissolve. After insoluble matter was filtered, 10% hydrochloric acid was added to the filtrate to adjust the pH to 4. Dichloromethane was added and the mixture was washed with water and brine. Purification by column chromatography and drying gave a compound represented by the formula (I-3).
Example 4 production of Compound represented by formula (I-4)
[ solution 16]
A compound represented by the formula (I-4-1), chloromethyl ethyl ether, triethylamine and N, N-dimethylformamide were charged into a reaction vessel and stirred. Toluene was added thereto, and the mixture was washed with water and brine. Purifying by column chromatography to obtain the compound represented by formula (I-4-2).
A compound represented by the formula (I-4-2) and 2-propanol were charged into a reaction vessel. After a 15% aqueous solution of sodium hydroxide was added dropwise thereto, the mixture was stirred at 55 ℃. After the 2-propanol was distilled off, water was added to dissolve it. After insoluble matter was filtered, 5% hydrochloric acid was added to the filtrate to adjust pH 4. Dichloromethane was added and the mixture was washed with water and brine. Purification by column chromatography and drying gave the compound represented by the formula (I-4).
Example 5 production of Compound represented by formula (I-5)
[ solution 17]
A compound represented by the formula (I-5-1), pyridine and tetrahydrofuran were charged in a reaction vessel under a nitrogen atmosphere. While cooling with ice, the compound represented by the formula (I-5-2) was added dropwise thereto, and the mixture was stirred at 50 ℃. After ordinary post-treatment, the resulting product was purified by column chromatography to obtain a compound represented by the formula (I-5-3).
A reaction vessel was charged with the compound represented by the formula (I-5-3), triethylamine and tetrahydrofuran. The compound represented by the formula (I-5-4) was added dropwise thereto and stirred with heating at 50 ℃. After usual post-treatment, purification was carried out by column chromatography to obtain the compound represented by the formula (I-5-5).
A compound represented by the formula (I-5-5), methanol and potassium carbonate were charged into a reaction vessel and stirred. The solid material was filtered and the filtrate was concentrated. Dichloromethane was added, and the mixture was washed with 1% hydrochloric acid, water and brine. Purification by column chromatography gave the compound represented by the formula (I-5).
Example 6 production of Compound represented by formula (I-6)
[ solution 18]
The compound represented by the formula (I-6-1) was obtained by the method described in Journal of Organic Chemistry, 2005, volume 70, No. 20, page 7799-7809. A reaction vessel was charged with the compound represented by the formula (I-6-1), 2, 4-dimethyl-3-pentanol, N-dimethylaminopyridine and dichloromethane under a nitrogen atmosphere. Dichlorohexylcarbodiimide was added dropwise and stirred. After ordinary post-treatment, the resulting product was purified by column chromatography to obtain a compound represented by the formula (I-6-2).
A compound represented by the formula (I-6-2) and propanol were charged into a reaction vessel. An aqueous lithium hydroxide solution was added dropwise and heated with stirring at 40 ℃. After the propanol was distilled off, water was added to dissolve it. After insoluble matter was filtered, 1% hydrochloric acid was added to the filtrate to adjust the pH to 4. Dichloromethane was added and the mixture was washed with water and brine. Purification by column chromatography and drying gave the compound represented by the formula (I-6).
Example 7 production of Compound represented by the formula (I-7)
[ solution 19]
A compound represented by the formula (I-7-1), methanol and concentrated sulfuric acid are charged into a reaction vessel and heated under reflux. After addition of water, the methanol was distilled off. Extracted with toluene and washed with brine. The solvent was distilled off and dried to obtain a compound represented by the formula (I-7-2).
A compound represented by the formula (I-7-2) and methanol were charged into a reaction vessel. 10% aqueous sodium hydroxide solution was added dropwise with stirring. 5% hydrochloric acid was added dropwise to adjust the pH to 3.5. After addition of water, the methanol was distilled off. Further, water was added to the reaction solution, and the precipitated solid was filtered. Dichloroethane was added to the solid, dispersion washed and filtered. The filtrate was concentrated and recrystallized from toluene to obtain a compound represented by the formula (I-7-3).
A compound represented by the formula (I-7-3), chloromethyl ethyl ether, triethylamine and N, N-dimethylformamide were charged into a reaction vessel and stirred. Toluene was added thereto, and the mixture was washed with water and brine. Purifying by column chromatography to obtain the compound represented by formula (I-7-4).
A reaction vessel was charged with a compound represented by the formula (I-7-4), methanol and acetonitrile. While cooling with ice, a 25% aqueous solution of sodium hydroxide was added dropwise, followed by stirring at room temperature. After methanol and acetonitrile were distilled off, water was added to dissolve them. After insoluble matter was filtered, 10% hydrochloric acid was added to the filtrate to adjust the pH to 4. Dichloromethane was added and the mixture was washed with water and brine. The resulting extract was purified by column chromatography (alumina) and dried to obtain a compound represented by the formula (I-7).
Example 8 production of Compound represented by formula (I-8)
[ solution 20]
The compound represented by the formula (I-8-1) is obtained by the method described in Japanese patent application laid-open No. 2002-508345. A reaction vessel was charged with the compound represented by the formula (I-8-1), tetrahydrofuran and triethylamine. The compound represented by the formula (I-8-2) was added dropwise with stirring at 50 ℃. After ordinary post-treatment, purification was carried out by column chromatography to obtain the compound represented by the formula (I-8-3).
A reaction vessel was charged with the compound represented by the formula (I-8-3), and methylene chloride was added. Aqueous potassium hydroxide solution and heated at 40 ℃ with stirring. The pH of the aqueous layer was adjusted to 4 by adding 10% hydrochloric acid. The aqueous layer was washed with water and brine. The resulting extract was purified by column chromatography (alumina) and dried to obtain a compound represented by the formula (I-8).
Example 9 production of Compound represented by the formula (I-9)
[ solution 21]
The compound represented by the formula (I-9-1) was obtained by the method described in Journal of Organic Chemistry, 2013, volume 78, No. 21, page 10737-10746. A reaction vessel was charged with the compound represented by the formula (I-9-1), tert-butyl alcohol, N-dimethylaminopyridine and methylene chloride. Diisopropylcarbodiimide was added dropwise with stirring while cooling with ice. After the precipitate was filtered, the filtrate was washed with 5% hydrochloric acid, water and a salt solution, and the solvent was distilled off. Purification by column chromatography (silica gel) gave the compound represented by the formula (I-9-2).
A compound represented by the formula (I-9-2) and methanol were charged into a reaction vessel. While cooling with ice, a 25% aqueous solution of sodium hydroxide was added dropwise, followed by stirring at 35 ℃. After methanol was distilled off, water was added to dissolve it. After insoluble matter was filtered, 10% hydrochloric acid was added to the filtrate to adjust the pH to 4. Dichloromethane was added and the mixture was washed with water and brine. The resulting extract was purified by column chromatography (alumina) and dried to obtain a compound represented by the formula (I-9).
The following compounds were produced using the compounds produced by the production method of the present invention as intermediates.
Example 10 production of Compound represented by formula (I-10)
[ solution 22]
A reaction vessel was charged with the compound represented by the formula (I-10-1) obtained in example 1, the compound represented by the formula (I-10-2), N-dimethylaminopyridine and methylene chloride. Diisopropylcarbodiimide was added dropwise with stirring while cooling with ice. After the precipitate was filtered, the filtrate was washed with 5% hydrochloric acid, water and a salt solution, and the solvent was distilled off. Purification was performed by column chromatography (silica gel) and recrystallization to obtain the compound represented by the formula (I-10-3).
A reaction vessel was charged with the compound represented by the formula (I-10-3) and methylene chloride. While cooling with ice, trifluoroacetic acid was added dropwise and stirred at room temperature. Methylene chloride was distilled off, and diisopropyl ether was added to precipitate. The precipitated solid was filtered and washed with diisopropyl ether. Drying to obtain the compound represented by the formula (I-10-4).
The compound represented by the formula (I-10-4), the compound represented by the formula (I-10-5), N-dimethylaminopyridine and methylene chloride are added. Diisopropylcarbodiimide was added dropwise with stirring while cooling with ice. After the precipitate was filtered, the filtrate was washed with 5% hydrochloric acid, water and a salt solution, and the solvent was distilled off. Purification was performed by column chromatography (silica gel) and recrystallization to obtain the compound represented by the formula (I-10).
Purity: 99.97 percent
Example 11 production of Compound represented by formula (I-11)
[ solution 23]
A compound represented by the formula (I-11-2) was obtained by the method described in patent document 1. 36.5g of the compound represented by the formula (I-11-1) obtained in example 1, 42.3g of the compound represented by the formula (I-11-2), 2.0g of N, N-dimethylaminopyridine and 211mL of methylene chloride were charged in a reaction vessel. While cooling with ice, 24.2g of diisopropylcarbodiimide was added dropwise and stirred. After the precipitate was filtered, the filtrate was washed with 5% hydrochloric acid, water and a salt solution, and the solvent was distilled off. Dissolved in methylene chloride, and subjected to column chromatography (silica gel) and recrystallization using methylene chloride/methanol to give 44.2g of the compound represented by the formula (I-11-3).
44.2g of the compound represented by the formula (I-11-3), 177mL of methylene chloride, and 177mL of formic acid were charged in a reaction vessel and stirred with heating at 40 ℃. 200mL of methylene chloride was added, and the mixture was washed with a 5% aqueous solution of sodium hydrogencarbonate and brine and purified by column chromatography (alumina) to give 36.9g of the compound represented by the formula (I-11-4).
6.1g of the compound represented by the formula (I-11-4), 1.0g of the compound represented by the formula (I-11-5), 0.1g of N, N-dimethylaminopyridine and 20mL of methylene chloride were charged in a reaction vessel. While cooling with ice, 2.0g of diisopropylcarbodiimide was added dropwise and stirred. After the precipitate was filtered, the filtrate was washed with 5% hydrochloric acid, water and a salt solution, and the solvent was distilled off. Dissolved in methylene chloride, and subjected to column chromatography (silica gel) and recrystallization using methylene chloride/methanol to give 5.1g of the compound represented by the formula (I-11-6).
The compound represented by the formula (I-11-7) was obtained by the method described in WO2014/010325A 1. 5.1g of the compound represented by the formula (I-11-6), (+ -) -10-camphorsulfonic acid 0.02g, 1.4g of the compound represented by the formula (I-11-7), 10mL of tetrahydrofuran and 10mL of ethanol were charged into a reaction vessel and stirred. After the solvent was distilled off, methanol was added to conduct crystallization. Drying, purification by column chromatography (silica gel) and recrystallization gave 2.7g of the compound represented by the formula (I-11).
Purity: 98.20 percent
Example 12 production of Compound represented by formula (I-12)
[ solution 24]
7.0g of the compound represented by the formula (I-12-1), 1.0g of p-toluenesulfonic acid monohydrate, and 65mL of ethyl acetate were charged in a reaction vessel equipped with a dean-Stark apparatus. While the reaction solvent was removed, fresh ethyl acetate was added thereto, and the mixture was refluxed for 5 hours. After washing with an aqueous sodium hydrogencarbonate solution and brine, purification was performed by column chromatography (alumina) to give 9.0g of the compound represented by the formula (I-12-2).
9.0g of the compound represented by the formula (I-12-2), 4.6g of paraformaldehyde, 7.2g of magnesium chloride, 36mL of acetonitrile and 18mL of triethylamine were charged in a reaction vessel, and the mixture was stirred with heating at 60 ℃. In the process, paraformaldehyde is added as appropriate. Diluted with ethyl acetate, washed with 5% hydrochloric acid and brine. Purification by column chromatography (alumina) gave 9.7g of the compound represented by the formula (I-12-3).
9.7g of the compound represented by the formula (I-12-3), 29mL of methanol, and 15mL of 25% aqueous sodium hydroxide solution were placed in a reaction vessel, and the mixture was stirred with heating at 60 ℃. The methanol was distilled off, dichloromethane was added, and 10% hydrochloric acid was added to adjust the pH to 3. The organic layer was washed with brine. Purification by column chromatography (alumina) gave 6.8g of the compound represented by the formula (I-12-4).
The compound represented by the formula (I-12-5) was obtained in the same manner as the compound represented by the formula (I-11-4) in example 11. 1.0g of the compound represented by the formula (I-12-4), 5.0g of the compound represented by the formula (I-11-5), 0.1g of N, N-dimethylaminopyridine and 20mL of methylene chloride were charged in a reaction vessel. While cooling with ice, 1.7g of diisopropylcarbodiimide was added dropwise and stirred. After the precipitate was filtered, the filtrate was washed with 5% hydrochloric acid, water and a salt solution, and the solvent was distilled off. Dissolved in methylene chloride, and subjected to column chromatography (silica gel) and recrystallization using methylene chloride/methanol to give 3.5g of the compound represented by the formula (I-12-6).
3.5g of the compound represented by the formula (I-12-6), (+ -) -10-camphorsulfonic acid 0.02g, the compound represented by the formula (I-12-7) 0.6g, tetrahydrofuran 8mL, and ethanol 8mL were added to a reaction vessel and stirred. After the solvent was distilled off, methanol was added to conduct crystallization. Drying, purification by column chromatography (silica gel) and recrystallization gave 1.7g of the compound represented by the formula (I-12).
Purity: 97.75 percent
Example 13 production of Compound represented by formula (I-13)
[ solution 25]
6.0g of the compound represented by the formula (I-13-1), 2.5g of paraformaldehyde, 3.9g of magnesium chloride, 36mL of acetonitrile and 18mL of triethylamine were charged in a reaction vessel, and the mixture was stirred with heating at 60 ℃. In the process, paraformaldehyde is added as appropriate. Diluted with ethyl acetate, washed with 5% hydrochloric acid and brine. Purification by column chromatography (alumina) gave 5.1g of the compound represented by the formula (I-13-2).
The compound represented by the formula (I-13-3) was obtained in the same manner as the compound represented by the formula (I-11-4) in example 11. 2.5g of the compound represented by the formula (I-13-2), 4.3g of the compound represented by the formula (I-13-3), 0.06g of N, N-dimethylaminopyridine and 40mL of methylene chloride were charged in a reaction vessel. While cooling with ice, 1.5g of diisopropylcarbodiimide was added dropwise and stirred. After the precipitate was filtered, the filtrate was washed with 5% hydrochloric acid, water and a salt solution, and the solvent was distilled off. Dissolved in methylene chloride, and purified by column chromatography (silica gel) and recrystallization (methylene chloride/methanol) to give 4.3g of the compound represented by the formula (I-13-4).
4.3g of the compound represented by the formula (I-13-4), (+ -) -10-camphorsulfonic acid 0.03g, 1.1g of the compound represented by the formula (I-13-5), tetrahydrofuran 8mL, and ethanol 8mL were added to a reaction vessel and stirred. After the solvent was distilled off, methanol was added to conduct crystallization. Drying and purification by column chromatography (silica gel) and recrystallization (dichloromethane/methanol) gave 3.1g of the compound represented by the formula (I-13).
Purity: 98.80 percent
Example 14 production of Compound represented by the formula (I-14)
[ solution 26]
A compound represented by the formula (I-14-2) was obtained by the method described in patent document 1. 5.0g of the compound represented by the formula (I-14-1), 5.7g of the compound represented by the formula (I-14-2), 0.3g of N, N-dimethylaminopyridine and 30mL of chloroform, which were obtained by the method described in example 4, were charged into a reaction vessel under a nitrogen atmosphere. While cooling with ice, a solution of 4.9g of dichlorohexylcarbodiimide dissolved in 5mL of chloroform was added dropwise and stirred. 20mL of chloroform and 20mL of heptane were added to filter the precipitate, and then the filtrate was washed with 5% hydrochloric acid, water and brine, and insoluble matter was filtered. After drying the filtrate over anhydrous sodium sulfate, the solvent was distilled off, and by drying, 10.0g of the compound represented by the formula (I-14-3) was obtained.
10.0g of the compound represented by the formula (I-14-3), 0.4g of pure water, 0.4g of p-toluenesulfonic acid monohydrate, and 20mL of tetrahydrofuran were charged in a reaction vessel under a nitrogen atmosphere, and the mixture was stirred at 50 ℃ for 3 hours. The solvent was distilled off, 20mL of heptane was added, and the precipitate was filtered, washed with pure water, and dried. Dissolved in chloroform, and purified by column chromatography (silica gel) and recrystallization (heptane), to give 6.4g of the compound represented by the formula (I-14-4).
The compound represented by the formula (I-14-5) is obtained by the method described in Japanese patent application laid-open No. 2011-207765. 9.9g of the compound represented by the formula (I-14-4), 3.5g of the compound represented by the formula (I-14-5), 0.1g of dimethylaminopyridine and 70mL of toluene were charged in a reaction vessel. While cooling with ice, 5.6g of dichlorohexylcarbodiimide was added thereto and stirred. Purification was performed by column chromatography (silica gel) and recrystallization (methanol). After dissolving in chloroform, 0.2g of activated carbon was added thereto and stirred, the activated carbon was filtered off, and purification was carried out by reprecipitation (methanol) and dispersion washing (heptane), whereby 7.4g of the compound represented by the formula (I-14) was obtained.
Purity: 98.22 percent
Example 15 production of Compound represented by formula (I-15)
[ solution 27]
The compound represented by the formula (I-15-2) is obtained by the method described in Japanese patent laid-open No. 2008-107767. The compound represented by the formula (I-15-1) was obtained in the same manner as the compound represented by the formula (I-11-4) in example 11. 3.4g of the compound represented by the formula (I-15-1), 1.0g of the compound represented by the formula (I-15-2), 0.02g of N, N-dimethylaminopyridine and 40mL of methylene chloride were charged in a reaction vessel. While cooling with ice, 1.1g of diisopropylcarbodiimide was added dropwise and stirred. After the precipitate was filtered, the filtrate was washed with 5% hydrochloric acid, water and a salt solution, and the solvent was distilled off. Dissolved in methylene chloride, and purified by column chromatography (silica gel) and recrystallization (methylene chloride/methanol) to obtain 2.1g of the compound represented by the formula (I-15).
Purity: 97.73 percent
Example 16 production of Compound represented by the formula (I-16)
[ solution 28]
The compound represented by the formula (I-16-1) was obtained by the method described in example 2. 3.0g of the compound represented by the formula (I-16-1), 1.2g of the compound represented by the formula (I-16-2), 0.05g of N, N-dimethylaminopyridine and 30mL of methylene chloride were charged in a reaction vessel. While cooling with ice, 1.3g of diisopropylcarbodiimide was added dropwise and stirred. The precipitate was filtered, and purified by column chromatography (alumina) and recrystallization (dichloromethane/methanol) to give 2.8g of the compound represented by the formula (I-16-3).
2.8g of the compound represented by the formula (I-16-3), 10mL of tetrahydrofuran, 10mL of methanol and 1mL of concentrated hydrochloric acid were put into a reaction vessel and stirred. Diluted with ethyl acetate and washed with brine. Purification was performed by column chromatography (alumina) and recrystallization (ethyl acetate/hexane) to obtain 2.1g of the compound represented by the formula (I-16-4).
The compound represented by the formula (I-16-5) is obtained by the method described in Japanese patent application laid-open No. 2010-024438. 2.1g of the compound represented by the formula (I-16-4), 1.3g of the compound represented by the formula (I-16-5), 0.03g of N, N-dimethylaminopyridine and 20mL of methylene chloride were charged in a reaction vessel. While cooling with ice, 0.9g of diisopropylcarbodiimide was added dropwise and stirred. After the precipitate was filtered, the filtrate was washed with 1% hydrochloric acid, water and a saline solution. Purification by column chromatography (silica gel) and recrystallization (dichloromethane/methanol) gave 2.0g of the compound represented by the formula (I-16).
Purity: 98.87 percent
Example 17 production of Compound represented by formula (I-17)
[ solution 29]
The compound represented by the formula (I-17-1) was obtained by the method described in example 5. A compound represented by the formula (I-17-1), benzyl bromide, potassium carbonate and N, N-dimethylformamide are added to a reaction vessel, and the mixture is stirred with heating. The mixture was diluted with toluene and washed with water and brine. Purification by column chromatography (alumina) gave the compound represented by the formula (I-17-2).
A compound represented by the formula (I-17-2), tetrahydrofuran, methanol and concentrated sulfuric acid were charged into a reaction vessel and stirred. The mixture was diluted with ethyl acetate and washed with water and brine. Purification by column chromatography (alumina) gave the compound represented by the formula (I-17-3).
A compound represented by the formula (I-17-3), methyl iodide, potassium carbonate and N, N-dimethylformamide were charged into a reaction vessel and stirred with heating. The mixture was diluted with toluene and washed with water and brine. Purification by column chromatography (silica gel) gave the compound represented by the formula (I-17).
Example 18 the following compound was produced by the same method as described above.
[ solution 30]
[ solution 31]
[ solution 32]
[ solution 33]
[ chemical 34]
[ solution 35]
[ solution 36]
[ solution 37]
[ solution 38]
[ solution 39]
[ solution 40]
Comparative example 1A compound represented by the formula (R-1-3) was produced by the method described in patent document 1, and a compound represented by the formula (R-1) using the intermediate was produced
[ solution 41]
Under a nitrogen atmosphere, 20.0g of the compound represented by the formula (R-1-1), 100mL of chloroform, and 17.6g of triethylamine were charged in a reaction vessel. While cooling with ice, 23.1g of chloromethyl ethyl ether and 17.6g of triethylamine were added dropwise with stirring. The precipitate was filtered, and the filtrate was washed with pure water and then distilled off. Heptane was added and distilled off, followed by drying, to obtain 30.4g of a compound represented by the formula (R-1-2).
Under a nitrogen atmosphere, 20.8g of the compound represented by the formula (R-1-2) and 120mL of heptane were charged into a reaction vessel. A mixture of 8.2g of trifluoroacetic acid and 37mL of heptane was added dropwise at 40 ℃ and stirred. After further stirring at room temperature, the solvent was distilled off. 80mL of chloroform and 4g of silica gel were added, and the mixture was filtered through celite. To the solid obtained, 40mL of acetone was added, and the mixture was stirred and then filtered. The filtrate was concentrated and dried to obtain 3.0g of a compound represented by the formula (R-1-3).
5.0g of the compound represented by the formula (R-1-3), 5.7g of the compound represented by the formula (R-1-4), 0.3g of N, N-dimethylaminopyridine and 30mL of chloroform were charged into a reaction vessel under a nitrogen atmosphere. While cooling with ice, a solution of 4.9g of dichlorohexylcarbodiimide dissolved in 5mL of chloroform was added dropwise and stirred. 20mL of chloroform and 20mL of heptane were added to filter the precipitate, and then the filtrate was washed with 5% hydrochloric acid, water and brine, and insoluble matter was filtered. After drying the filtrate over anhydrous sodium sulfate, the solvent was distilled off, and by drying, 10.0g of the compound represented by the formula (R-1-5) was obtained.
10.0g of the compound represented by the formula (R-1-5), 0.4g of pure water, 0.4g of p-toluenesulfonic acid monohydrate, and 20mL of tetrahydrofuran were charged in a reaction vessel under a nitrogen atmosphere, and the mixture was stirred with heating at 50 ℃ for 3 hours. The solvent was distilled off, 20mL of heptane was added, and the precipitate was filtered, washed with pure water, and dried. Dissolved in chloroform, and purified by column chromatography (silica gel) and recrystallization (heptane), to give 6.4g of a compound represented by the formula (R-1-6).
The compound represented by the formula (R-1-7) is obtained by the method described in Japanese patent application laid-open No. 2011-207765. 9.9g of the compound represented by the formula (R-1-6), 3.5g of the compound represented by the formula (R-1-7), 0.1g of dimethylaminopyridine and 70mL of toluene were charged in a reaction vessel. While cooling with ice, 5.6g of dichlorohexylcarbodiimide was added thereto and stirred. Purification was performed by column chromatography (silica gel) and recrystallization (methanol). After dissolving in chloroform, 0.2g of activated carbon was added thereto and the mixture was stirred, the activated carbon was filtered off, and the mixture was purified by reprecipitation (methanol) and dispersion washing (heptane), whereby 7.3g of the compound represented by the formula (R-1) was obtained.
Purity: 97.78 percent
Comparative example 2A compound represented by the formula (R-2-4) was produced by the method described in patent document 2, and a compound represented by the formula (R-2) using the intermediate was produced
[ solution 42]
Under a nitrogen atmosphere, 20.0g of the compound represented by the formula (R-2-1), 9.6g of potassium carbonate, 18.9g of benzyl bromide, and 60mL of N, N-dimethylacetamide were charged into a reaction vessel, and the mixture was stirred with heating at 80 ℃. The mixture was left to cool and poured into ice water. The precipitated solid was filtered, washed with a 1:1 solution of methanol and water, and then washed with water. The solid was dissolved in chloroform and purified by column chromatography (silica gel) to obtain 13.8g of a compound represented by the formula (R-2-2).
6.0g of the compound represented by the formula (R-2-2), 4.3g of chloromethyl ethyl ether, 20mL of chloroform, and 6.9g of triethylamine were charged into a reaction vessel under a nitrogen atmosphere and stirred. 60mL of toluene was added, and the precipitate was filtered. The filtrate was washed with water and then dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off and dried to obtain 7.4g of a compound represented by the formula (R-2-3).
6.4g of the compound represented by the formula (R-2-3), 25mL of tetrahydrofuran, and 0.3g of 10% palladium on carbon (containing 50% water) were charged into a reaction vessel and stirred at room temperature under normal pressure for 6 hours under a hydrogen atmosphere. After the catalyst was filtered off, the solvent was distilled off. After washing with a 1:1 solution of methanol and water, washing with water was carried out. By drying, 4.5g of the compound represented by the formula (R-2-4) was obtained.
The compounds represented by the formulae (R-2-4) to (R-2) were obtained in the same manner as in example 14 and comparative example 1.
Purity: 97.80 percent
Comparative example 3A compound represented by the formula (R-3-3) was produced by a method similar to that described in patent document 3, and a compound represented by the formula (R-3) using the intermediate was produced
[ solution 43]
A compound represented by the formula (R-3-3) was obtained as described below according to the method described in example 1 of patent document 3. 5.0g of the compound represented by the formula (R-3-1) and 50mL of toluene were charged in a reaction vessel under a nitrogen atmosphere. A mixture of 4.5g of pyridine and 12.6g of the compound represented by the formula (R-3-2) was added dropwise while stirring at 100 ℃. A mixture of 4.5g pyridine and 10mL water was added and cooled to 20 ℃. The pH was adjusted to 3 by the addition of 10% hydrochloric acid and the solid was filtered. By recrystallization from toluene, 1.50g of the compound represented by the formula (R-3-3) was obtained.
The compounds represented by the formulae (R-3-3) to (R-3) were obtained in the same manner as in example 14 and comparative example 1.
Purity: 90.11 percent
Comparative example 4A Compound represented by the formula (R-4-4) was produced by the method described in patent document 2, and a Compound represented by the formula (R-4) using the intermediate was produced
[ solution 44]
Under a nitrogen atmosphere, 20.0g of the compound represented by the formula (R-4-1), 9.6g of potassium carbonate, 18.9g of benzyl bromide, and 60mL of N, N-dimethylacetamide were charged into a reaction vessel, and the mixture was stirred with heating at 80 ℃. The mixture was left to cool and poured into ice water. The precipitated solid was filtered, washed with a 1:1 solution of methanol and water, and then washed with water. The solid was dissolved in chloroform and purified by column chromatography (silica gel) to obtain 13.8g of a compound represented by the formula (R-4-2).
6.0g of the compound represented by the formula (R-4-2), 0.04g of p-toluenesulfonic acid monohydrate, and 20mL of chloroform were charged in a reaction vessel under a nitrogen atmosphere. While cooling with ice, 3.8g of 3, 4-dihydro-2H-pyran was added dropwise thereto and stirred. 60mL of toluene was added, insoluble matter was filtered, and the filtrate was washed with 100mL of water. After drying over anhydrous sodium sulfate, the filtrate was filtered, and the filtrate was concentrated and dried to obtain 7.0g of a compound represented by the formula (R-4-3).
7.0g of the compound represented by the formula (R-2-3), 25mL of tetrahydrofuran, and 0.3g of 10% palladium on carbon (containing 50% water) were charged into a reaction vessel and stirred at room temperature under normal pressure for 6 hours under a hydrogen atmosphere. After the catalyst was filtered off, the solvent was distilled off. After washing with a 1:1 solution of methanol and water, washing with water was carried out. By drying, 2.1g of the compound represented by the formula (R-4-4) was obtained.
A compound represented by the formula (R-4-5) is obtained by the method described in patent document 1. 2.1g of the compound represented by the formula (R-4-4), 2.2g of the compound represented by the formula (R-4-5), 0.05g of N, N-dimethylaminopyridine and 20mL of methylene chloride were charged in a reaction vessel. While cooling with ice, 1.2g of diisopropylcarbodiimide was added dropwise and stirred. After the precipitate was filtered, the filtrate was washed with 1% hydrochloric acid, water and a saline solution. Purification by column chromatography (silica gel) and recrystallization (methylene chloride/methanol) gave 2.9g of the compound represented by the formula (R-4-6).
2.9g of the compound represented by the formula (R-4-6), 0.3g of pure water, 0.3g of p-toluenesulfonic acid monohydrate, and 15mL of tetrahydrofuran were charged in a reaction vessel under a nitrogen atmosphere, and the mixture was stirred at 50 ℃ for 3 hours. The solvent was distilled off, 15mL of heptane was added, and the precipitate was filtered, washed with pure water, and dried. Dissolved in chloroform, and purified by column chromatography (silica gel) and recrystallization (heptane), to give 2.2g of a compound represented by the formula (R-4-7).
The compounds represented by the formulae (R-4-7) to (R-4) were obtained in the same manner as in example 15.
Purity: 97.43 percent
Comparative example 5A Compound represented by the formula (R-5-3) was produced by the method described in patent document 1, and a Compound represented by the formula (R-5) using the intermediate was produced
[ solution 45]
The compound represented by the formula (R-5-1) to the compound represented by the formula (R-5-6) were obtained in the same manner as in comparative example 1.
The compound represented by the formula (R-5-6) to the compound represented by the formula (R-5) were obtained in the same manner as in example 11.
Purity: 98.17 percent
(examples 19 to 25 and comparative examples 6 to 10) production of film
For producing the film, a liquid crystal composition containing 30% of the compound (X-1) described in WO2012/002140A1, 30% of the compound (X-2) described in Japanese patent application laid-open No. 2002-542219, and 40% of the compound (X-3) described in Japanese patent laid-open No. 2005-015473 was used as the matrix liquid crystal (X).
[ solution 46]
Each composition prepared by adding 30% of a compound to be evaluated to a mother liquid crystal (X) was added with 3% of a photopolymerization initiator Irgacure907 (manufactured by Ciba Specialty Chemicals), and then dissolved in cyclopentanone to prepare a 25% solution. The solution was coated on the glass with polyimide subjected to rubbing treatment by spin coating and dried at 70 ℃ for 3 minutes. The resulting coating film was placed on a hot plate at 70 ℃ under 20mW/cm2Ultraviolet rays were irradiated at an intensity of (1) for 60 seconds. The correspondence between the film example number and the evaluation target compound is shown in the following table.
[ Table 1]
| Film | Evaluation Compound used |
| Example 19 | Compound (I-10) of the invention of the present application |
| Example 20 | Compound (I-11) of the invention of the present application |
| Example 21 | Compound (I-12) of the invention of the present application |
| Example 22 | Compound (I-13) of the invention of the present application |
| Example 23 | Compound (I-14) of the invention of the present application |
| Example 24 | Compound (I-15) of the invention of the present application |
| Example 25 | Compound (I-16) of the invention of the present application |
| Comparative example 6 | Comparative Compound (R-1) |
| Comparative example 7 | Comparative Compound (R-2) |
| Comparative example 8 | Comparative Compound (R-3) |
| Comparative example 9 | Comparative Compound (R-4) |
| Comparative example 10 | Comparative Compound (R-5) |
The haze value and unevenness of the produced film were evaluated. The haze value is represented by the following formula,
haze (%). Td/Tt.times.100
(in the formula, Td represents a diffuse transmittance and Tt represents a total light transmittance.) the measurement was carried out at the center of the substrate using a haze measuring device (NHD 2000, manufactured by Nippon Denshoku industries Co., Ltd.). Further, the film was regarded as "excellent" when observed with a polarizing microscope, if the film had no unevenness and was uniform as a whole; when a small amount of unevenness is found at 1-2 points, it is determined as O; when a small amount of unevenness is found at 3-5 positions, setting as delta; when an infinite unevenness is found, it is set to X. The evaluation results are shown in the following table.
[ Table 2]
| Haze degree | Unevenness of the flow of water | |
| Example 19 | 1.2 | ○ |
| Example 20 | 0.6 | ◎ |
| Example 21 | 1.0 | ◎ |
| Example 22 | 0.9 | ◎ |
| Example 23 | 1.0 | ◎ |
| Example 24 | 0.7 | ◎ |
| Example 25 | 1.3 | ○ |
| Comparative example 6 | 3.5 | ○ |
| Comparative example 7 | 1.5 | × |
| Comparative example 8 | 5.1 | × |
| Comparative example 9 | 1.6 | × |
| Comparative example 10 | 3.6 | ○ |
As is clear from table 2, the films containing the compounds produced by the production methods of the present invention in examples 19 to 25 have low haze values and less unevenness. On the other hand, it is found that the film haze values of comparative examples 6 and 10 containing the compound produced by the method described in patent document 1 are large. This is considered to be because, in the production of the compounds represented by the formulae (R-1-3) and (R-5-3) as intermediates, dicarboxylic acids are formed as by-products, and high-molecular-weight impurities induced in the subsequent steps are mixed in a slight amount, which leads to an increase in the haze value. Further, it is found that the films containing the compounds produced by the method described in patent document 2 in comparative examples 7 and 9 have many variations. This is presumably because the palladium contained in the palladium carbon used in the production of the compounds represented by the formulae (R-2-4) and (R-4-4) as intermediates elutes, is mixed in a trace amount, and is not removed in the subsequent step, and thus the variation is increased. Further, it is found that the film of comparative example 8 containing the compound produced by the method described in patent document 3 has a high haze value and many variations. This is presumably because a large amount of by-products such as acid anhydride, methyl ester, and high molecular weight product are produced when the compound represented by the formula (R-3-3) is produced as an intermediate, and these by-products are not removed in the subsequent step and remain.
Therefore, the compound produced by the production method of the present invention is useful as a component of a polymerizable composition. Further, an optically anisotropic body using a composition containing the compound of the present invention is useful for applications such as an optical film.
Claims (7)
1. A process for producing a compound represented by the general formula (I-E), which comprises reacting a compound represented by the general formula (I-D) with a base or a base to thereby obtain a compound represented by the general formula (I-E),
wherein M represents a group represented by the following formula (I-M),
in the formula, A1And A2A group represented by the following formula (A-1),
wherein any position may have an atomic bond, and any-CH2Each independently may be substituted by-O-, -S-, -NR-0-, -CS-or-CO-substituted but not comprising-O-bonds, of the formula-NR0In (A) R0Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; furthermore, these radicals are unsubstituted or may be substituted by 1 or more substituents LMSubstitution; when there are a plurality of A1When they are used, they may be the same or different; z1represents-O-, -S-, -OCH2-、-CH2O-、-CH2CH2-、-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-, -CH ═ CH-, -N ═ N-, -CF ═ CF-, -C ≡ C-, or a single bond; when there are a plurality of Z1When they are used, they may be the same or different; m1 represents an integer of 0 to 6,
R1represents a methyl group, unsubstituted or may have 1 or more L at the 2-position1Ethyl of the substituents, L1Represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or 1-CH group2-or non-adjacent 2 or more-CH2-a linear or branched alkyl group having 1 to 20 carbon atoms which may be independently substituted by-O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH-, -CF-or-C.ident.C-, wherein any hydrogen atom in the alkyl group may be substituted by a fluorine atom,
R2represents a group selected from an alkoxymethyl group having 2 to 20 carbon atoms, a tertiary alkyl group having 4 to 20 carbon atoms, and a 2-tetrahydropyranyl group having 5 to 20 carbon atoms, these groups being unsubstituted or substituted by 1 or more substituents L2Substituted, L2Represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or a trimethylsilaneA group of dimethylsilyl, thioisocyano, phenyl, or 1-CH2-or non-adjacent 2 or more-CH2-a linear or branched alkyl group having 1 to 20 carbon atoms which may be independently substituted by-O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH-, -CF-or-C.ident.C-, wherein any hydrogen atom in the alkyl group may be substituted by a fluorine atom,
LMrepresents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or 1-CH group2-or non-adjacent 2 or more-CH2-a linear or branched alkyl group having 1 to 20 carbon atoms which may be independently substituted by-O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH ═ CH-, -CF ≡ CF-or-C ≡ C-, wherein any hydrogen atom in the alkyl group may be substituted by a fluorine atom, and when a plurality of L' S are present in the compoundMThey may be the same or different,
in the formula, M and R2The same meanings as described above are shown.
2. The production process according to claim 1, wherein the compound represented by the following general formula (I-C) is derivatized to produce a compound represented by the general formula (I-D),
in the formula, M and R1The same meanings as described above are shown.
3. The production process according to claim 1 or 2, wherein the compound represented by the following general formula (I-A) is derivatized to produce a compound represented by the general formula (I-B), and the compound represented by the general formula (I-B) is derivatized to produce a compound represented by the general formula (I-C),
wherein M has the same meaning as described above,
in the formula, M and R1The same meanings as described above are shown.
4. The production process according to claim 1 or 2, wherein in the general formulae (I-A) to (I-E), M represents a1, 4-cyclohexylene group.
5. The production process according to claim 1 or 2, wherein in the general formulae (I-A) to (I-E), M represents a trans-1, 4-cyclohexylene group.
6. The process according to claim 1 or 2, wherein R in the general formulae (I-B) to (I-D)1Represents a methyl group.
7. The process according to claim 1 or 2, wherein R in the general formulae (I-D) and (I-E)2Represents a tert-butyl group.
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| JP6970828B2 (en) * | 2018-07-25 | 2021-11-24 | 富士フイルム株式会社 | Liquid crystal composition, optically anisotropic film, optical film, polarizing plate and image display device |
| WO2020067391A1 (en) * | 2018-09-27 | 2020-04-02 | 富士フイルム株式会社 | Production method for dicarboxylic acid monoester |
| CN109796479B (en) * | 2019-01-11 | 2020-07-14 | 大连理工大学 | Fluoroboropyrrole liquid crystal compound containing 8- (diphenylethnyl) -ester flexible polycyclic ring, and preparation method and application thereof |
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