JP6809410B2 - Stabilizer compounds, liquid crystal compositions and display devices - Google Patents
Stabilizer compounds, liquid crystal compositions and display devices Download PDFInfo
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- JP6809410B2 JP6809410B2 JP2017153262A JP2017153262A JP6809410B2 JP 6809410 B2 JP6809410 B2 JP 6809410B2 JP 2017153262 A JP2017153262 A JP 2017153262A JP 2017153262 A JP2017153262 A JP 2017153262A JP 6809410 B2 JP6809410 B2 JP 6809410B2
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- 150000001875 compounds Chemical class 0.000 title claims description 208
- 239000000203 mixture Substances 0.000 title claims description 107
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 58
- 239000003381 stabilizer Substances 0.000 title description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- -1 Naphthalene-2,6-diyl group Chemical group 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims 2
- 150000001721 carbon Chemical group 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 81
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 78
- 238000004519 manufacturing process Methods 0.000 description 60
- 238000006243 chemical reaction Methods 0.000 description 51
- 238000000034 method Methods 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 30
- 239000011541 reaction mixture Substances 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 239000012044 organic layer Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 21
- 238000001816 cooling Methods 0.000 description 20
- 239000012299 nitrogen atmosphere Substances 0.000 description 20
- 238000010992 reflux Methods 0.000 description 19
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 238000001953 recrystallisation Methods 0.000 description 14
- 108700039708 galantide Proteins 0.000 description 12
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 125000000962 organic group Chemical group 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000003377 acid catalyst Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 230000002140 halogenating effect Effects 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 238000001782 photodegradation Methods 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 238000006751 Mitsunobu reaction Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 description 5
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- KRSOWIJSDPLQTH-UHFFFAOYSA-N 2,9-bis(hydroxymethyl)decane-1,10-diol Chemical compound OCC(CO)CCCCCCC(CO)CO KRSOWIJSDPLQTH-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006959 Williamson synthesis reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JKXFMUASODJEJG-UHFFFAOYSA-N tetraethyl octane-1,1,8,8-tetracarboxylate Chemical compound CCOC(=O)C(C(=O)OCC)CCCCCCC(C(=O)OCC)C(=O)OCC JKXFMUASODJEJG-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 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
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- RHYUFGNCUXTFTC-UHFFFAOYSA-N 2-pentylpropane-1,3-diol Chemical compound CCCCCC(CO)CO RHYUFGNCUXTFTC-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- YKAQAUWVYATRHU-XYPYZODXSA-N CCC[C@H]1CC[C@@H](CC1)C(CO)CO Chemical compound CCC[C@H]1CC[C@@H](CC1)C(CO)CO YKAQAUWVYATRHU-XYPYZODXSA-N 0.000 description 1
- GISRWBROCYNDME-PELMWDNLSA-N F[C@H]1[C@H]([C@H](NC1=O)COC1=NC=CC2=CC(=C(C=C12)OC)C(=O)N)C Chemical compound F[C@H]1[C@H]([C@H](NC1=O)COC1=NC=CC2=CC(=C(C=C12)OC)C(=O)N)C GISRWBROCYNDME-PELMWDNLSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 101000701286 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Alkanesulfonate monooxygenase Proteins 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 101000983349 Solanum commersonii Osmotin-like protein OSML13 Proteins 0.000 description 1
- JEDZLBFUGJTJGQ-UHFFFAOYSA-N [Na].COCCO[AlH]OCCOC Chemical compound [Na].COCCO[AlH]OCCOC JEDZLBFUGJTJGQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000007514 bases Chemical class 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012419 sodium bis(2-methoxyethoxy)aluminum hydride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MYXJYAIKMQJHIB-UHFFFAOYSA-M sodium;benzenesulfinate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)C1=CC=CC=C1 MYXJYAIKMQJHIB-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Description
本発明は安定剤化合物に関する。 The present invention relates to stabilizer compounds.
液晶表示素子は、時計、電卓をはじめとして、各種測定機器、自動車用パネル、ワードプロセッサー、電子手帳、プリンター、コンピューター、テレビ、時計、広告表示板等に用いられるようになっている。液晶表示方式としては、その代表的なものにＴＮ（ツイステッド・ネマチック）型、ＳＴＮ（スーパー・ツイステッド・ネマチック）型、ＴＦＴ（薄膜トランジスタ）を用いたＶＡ（垂直配向）型やＩＰＳ（イン・プレーン・スイッチング）型またはＦＦＳ（フリンジ・フィールド・スイッチング）型等がある。液晶組成物に求められる主な特性としては、（１）水分、空気、熱、光などの外的刺激に対して安定であること、（２）室温を中心としてできるだけ広い温度範囲で液晶相を示していること、（３）低粘性であること、および（４）駆動電圧が低いことの４つが挙げられ、個々の表示素子にとって誘電率異方性（Δε）や屈折率異方性（Δｎ）等を最適な値とするために、液晶組成物は数種類から数十種類の化合物から構成されていることが一般的である。 Liquid crystal display elements have come to be used in various measuring instruments such as clocks and calculators, automobile panels, word processors, electronic organizers, printers, computers, televisions, clocks, advertisement display boards and the like. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, VA (vertical orientation) type using TFT (thin film transistor), and IPS (in-plane). There are switching) type and FFS (fringe field switching) type. The main characteristics required of the liquid crystal composition are (1) stability to external stimuli such as moisture, air, heat, and light, and (2) the liquid crystal phase in the widest possible temperature range centered on room temperature. There are four things that are shown, (3) low viscosity, and (4) low drive voltage. For each display element, dielectric anisotropy (Δε) and refractive index anisotropy (Δn) can be mentioned. ) Etc. are generally set in the liquid crystal composition to be composed of several to several tens of kinds of compounds.
上記の液晶組成物の特性のうち、Δεについては、正の値である組成物と負の値である組成物が各々使い分けられている。これらのうち、Δεが正の値を示す液晶材料を用いる表示方式としては、ＴＮ型、ＳＴＮ型、ＩＰＳ型、更にＦＦＳ型などが挙げられる。Δεが負の値を示す液晶材料を用いる表示方式としては、ＥＣＢ型、ＶＡ型、更にＦＦＳ型などが挙げられる。一方、全ての駆動方式において低電圧駆動、高速応答、広い動作温度範囲が求められている。すなわち、Δεの絶対値が大きく、粘度（η）が小さく、高いネマチック相−等方性液体相転移温度（Ｔｎｉ）が要求されている。また、Δｎとセルギャップ（ｄ）との積であるΔｎ×ｄの設定から、液晶組成物のΔｎをセルギャップに合わせて適当な範囲に調節する必要がある。加えて液晶表示素子をテレビ等へ応用する場合においては高速応答性が重視されるため、γ１の小さい液晶組成物が要求される。 Among the characteristics of the above liquid crystal composition, for Δε, a composition having a positive value and a composition having a negative value are used properly. Among these, as a display method using a liquid crystal material in which Δε shows a positive value, TN type, STN type, IPS type, FFS type and the like can be mentioned. Examples of the display method using a liquid crystal material in which Δε shows a negative value include ECB type, VA type, and FFS type. On the other hand, all drive methods are required to have low voltage drive, high-speed response, and a wide operating temperature range. That is, a large absolute value of Δε, a small viscosity (η), and a high nematic phase-isotropic liquid phase transition temperature (T ni ) are required. Further, from the setting of Δn × d, which is the product of Δn and the cell gap (d), it is necessary to adjust Δn of the liquid crystal composition to an appropriate range according to the cell gap. In addition, when a liquid crystal display element is applied to a television or the like, high-speed response is important, so a liquid crystal composition having a small γ 1 is required.
これら液晶組成物の物性における要求に加え、（１）の外的刺激に対する安定性についても更なる改善が求められている（特許文献１参照）。 In addition to the requirements for the physical characteristics of these liquid crystal compositions, further improvement in stability to external stimuli (1) is required (see Patent Document 1).
本願発明が解決しようとする課題は、液晶組成物に添加することにより液晶組成物の劣化を防止し、液晶組成物との相溶性が高く、液晶組成物の保存安定性を損なうことなく、かつ簡便に製造可能な安定剤化合物を提供することである。 The problem to be solved by the present invention is to prevent deterioration of the liquid crystal composition by adding it to the liquid crystal composition, to have high compatibility with the liquid crystal composition, without impairing the storage stability of the liquid crystal composition, and It is to provide a stabilizer compound which can be easily produced.
本願発明者は上記課題を解決するために鋭意検討した結果、本願発明の完成に至った。
すなわち、本発明は、一般式（Ｉ）
As a result of diligent studies to solve the above problems, the inventor of the present application has completed the invention of the present application.
That is, the present invention has the general formula (I).
（式中、Ｒａ０は水素原子、水酸基、炭素数１〜１２のアルキル基、又は炭素数３〜１２のアルケニル基を表し、
Ｒａ１，Ｒａ２，Ｒａ３及びＲａ４はそれぞれ独立して炭素数１〜８のアルキル基を表し、あるいはＲａ１とＲａ２，及び／又はＲａ３とＲａ４は一緒になって環構造を形成していてもよく、
Ｒａ５及びＲａ６はそれぞれ独立して水素原子又は炭素数１〜６のアルキル基を表し、
ｎは０又は１を表し、
ｔは１から４を表し、
Ｕは環構造を形成する２×ｔ価の有機基を表し、Ｒａ０、Ｒａ１、Ｒａ２、Ｒａ３、Ｒａ４、Ｒａ５、Ｒａ６及びｎが複数存在する場合、それらは同一であっても異なっていてもよい。）
で表される化合物を提供し、併せて当該化合物を含有する液晶組成物及び表示素子を提供する。
(In the formula, Ra0 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 3 to 12 carbon atoms.
R a1 , R a2 , R a3 and R a4 each independently represent an alkyl group having 1 to 8 carbon atoms, or R a1 and R a2 , and / or R a3 and R a4 together form a ring structure. May be formed,
R a5 and R a6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
n represents 0 or 1 and represents
t represents 1 to 4
U represents a 2 × t-valent organic group forming a ring structure, and when a plurality of R a0 , R a1 , R a2 , R a3 , R a4 , R a5 , R a6 and n are present, they are the same. May be different. )
The compound represented by the above is provided, and a liquid crystal composition and a display element containing the compound are also provided.
本発明に係る安定剤化合物は、液晶組成物の光による劣化を防止し、液晶組成物との相溶性が高く、液晶組成物の保存安定性を損なうことなく、かつ簡便に製造可能である。本発明に係る安定剤化合物を用いた液晶組成物を用いると高速応答液晶表示素子の提供が可能となる。 The stabilizer compound according to the present invention prevents deterioration of the liquid crystal composition due to light, has high compatibility with the liquid crystal composition, and can be easily produced without impairing the storage stability of the liquid crystal composition. By using a liquid crystal composition using the stabilizer compound according to the present invention, it is possible to provide a high-speed response liquid crystal display element.
一般式（Ｉ）において、Ｒａ０は光劣化防止能を高めるには水素原子又は水酸基であることが好ましく、水素原子であることが特に好ましい。また、液晶組成物との相溶性を高めるためには炭素数１〜１２のアルキル基又は炭素数３〜１２のアルケニル基であることが好ましい。
Ｒａ１，Ｒａ２，Ｒａ３及びＲａ４はそれぞれ独立して炭素数１〜４のアルキル基であることが好ましく、メチル基であることが特に好ましい。また、製造時に混入する極性不純物の除去を容易にするためにはＲａ１とＲａ２，及び／又はＲａ３とＲａ４は一緒になって環構造を形成することが好ましい。
Ｒａ５及びＲａ６はそれぞれ独立して水素原子又は炭素数１〜４のアルキル基であることが好ましく、製造の容易さから水素原子であることが特に好ましい。
ｎは１であることが好ましい。
ｔは液晶組成物の保存安定性を高めるためには１または２であることが好ましく、１であることが特に好ましい。また、光劣化防止能を高めるためには、単位重量あたりのヒンダードアミン構造の数が多くなることから３または４であることが好ましい。
Ｕは、一般式（Ｉ−ａ）
In the general formula (I), Ra0 is preferably a hydrogen atom or a hydroxyl group in order to enhance the photodegradation prevention ability, and particularly preferably a hydrogen atom. Further, in order to enhance the compatibility with the liquid crystal composition, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 3 to 12 carbon atoms is preferable.
R a1 , R a2 , R a3 and R a4 are each independently preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. Further, in order to facilitate the removal of polar impurities mixed in during production, it is preferable that Ra 1 and Ra 2 and / or Ra 3 and Ra 4 are combined to form a ring structure.
R a5 and R a6 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom from the viewpoint of ease of production.
n is preferably 1.
t is preferably 1 or 2 in order to enhance the storage stability of the liquid crystal composition, and particularly preferably 1. Further, in order to enhance the photodegradation prevention ability, the number of hindered amine structures per unit weight increases, so that the number is preferably 3 or 4.
U is the general formula (Ia)
（式中、破線は各々酸素原子への結合を表し、Ｒａ７及びＲａ８はそれぞれ独立して水素原子または１価の有機基を表し、あるいはＲａ７及びＲａ８は一緒になって環構造を形成していてもよく、ｍは０または１を表す。）で表される構造であることが液晶組成物の保存安定性を高めるためには好ましい。ここで、一般的な液晶化合物と同様の直線状の構造をとりやすく、結果として液晶組成物への相溶性が高まることから、Ｒａ７は水素原子又は炭素数１〜４のアルキル基であることが特に好ましく、ｍは１であることが特に好ましい。 (In the equation, the broken lines represent bonds to oxygen atoms, respectively, R a7 and R a8 each independently represent a hydrogen atom or monovalent organic group, or R a7 and R a8 together form a ring structure. It may be formed, and m is preferably a structure represented by 0 or 1) in order to enhance the storage stability of the liquid crystal composition. Here, Ra7 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms because it is easy to have a linear structure similar to that of a general liquid crystal compound, and as a result, the compatibility with the liquid crystal composition is enhanced. Is particularly preferable, and m is particularly preferably 1.
一般式（Ｉ）中のｔが１を表す場合、Ｒａ８は一般式（Ｉ−ｃ） When t in the general formula (I) represents 1, R a8 is the general formula (Ic).
で表される構造であることが液晶組成物との相溶性を高めるためには特に好ましく、Ｓｐａ１及びＳｐａ２はそれぞれ独立に単結合又は炭素原子数１から１２のアルキレン基を表すことが好ましく、単結合又は炭素原子数１から８のアルキレン基であることがより好ましく、アルキル基中に存在する１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−により置き換えられていることが好ましく、単結合であることが特に好ましい。Ａａ１及びＡａ２はそれぞれ独立に
（ａ） １，４−シクロヘキシレン基（この基中に存在する１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−に置き換えられてもよい。）
（ｂ） １，４−フェニレン基（この基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられてもよい。）及び
（ｃ） ナフタレン−２，６−ジイル基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基又はデカヒドロナフタレン−２，６−ジイル基（ナフタレン−２，６−ジイル基又は１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられても良い。）
からなる群より選ばれる基であることが液晶組成物の保存安定性を高めるためには好ましく、上記の基（ａ）、基（ｂ）及び基（ｃ）はそれぞれ独立してシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていることがより好ましい。Ｒａ９は水素原子または炭素原子数１から１２のアルキル基を表すことが好ましく、水素原子または炭素原子数１から６のアルキル基であることがより好ましく、アルキル基中に存在する１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−により置き換えられても良く、−Ｏ−または−ＣＨ＝ＣＨ−より置き換えられていることが好ましい。
The structure represented by is particularly preferable in order to enhance compatibility with the liquid crystal composition, and Spa 1 and Spa 2 each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms. , more preferably a single bond or an alkylene group having 1 to 8 carbon atoms, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O- , -COO-, -OCO-, -CH = CH- or -C≡C-, and it is particularly preferable that it is a single bond. A a1 and A a2 are independently (a) 1,4-cyclohexylene groups (one -CH 2 − present in this group or two or more non-adjacent −CH 2 − are −O− May be replaced with.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =) and (c). Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2) , 3,4-Tetrahydronaphthalene-2,6-Diyl group One -CH = or two or more non-adjacent -CH = may be replaced with -N =).
A group selected from the group consisting of is preferable in order to enhance the storage stability of the liquid crystal composition, and the above groups (a), (b) and group (c) are independently cyano groups and fluorine, respectively. It is more preferably substituted with an atom, a chlorine atom, a methyl group or a methoxy group. R a9 preferably represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having a hydrogen atom or 1 to 6 carbon atoms, and one − in the alkyl group. CH 2 − or two or more non-adjacent −CH 2 − are replaced by −O−, −S−, −COO−, −OCO−, −CO−, −CH = CH− or −C≡C−. It may be, and is preferably replaced by −O− or −CH = CH−.
また、Ｒａ９は一般式（Ｉ−ｄ） Further, R a9 is a general formula ( Id ).
（式中、Ｒｄ０、Ｒｄ１，Ｒｄ２，Ｒｄ３、Ｒｄ４、Ｒｄ５及びＲｄ６は一般式（Ｉ）におけるＲａ０、Ｒａ１，Ｒａ２，Ｒａ３、Ｒａ４、Ｒａ５及びＲａ６と同じ意味を表し、Ｒａ１０は水素原子または１価の有機基を表し、Ｓｐａ３はＳｐａ１又はＳｐａ２と同じ意味を表し、ｓ及びｖはそれぞれ独立に０又は１を表す。）
で表される構造であることが光劣化防止能を高めるためには好ましい。Ｒｄ０は光劣化防止能を高めるには水素原子又は水酸基であることが好ましく、製造の容易さから水素原子であることが特に好ましい。また、液晶組成物との相溶性を高めるためには炭素数１〜１２のアルキル基又は炭素数３〜１２のアルケニル基であることが好ましい。
Ｒｄ１，Ｒｄ２，Ｒｄ３及びＲｄ４はそれぞれ独立して炭素数１〜４のアルキル基であることが好ましく、メチル基であることが特に好ましい。また、製造時に混入する極性不純物の除去を容易にするためにはＲｄ１とＲｄ２，及び／又はＲｄ３とＲｄ４は一緒になって環構造を形成することが好ましい。
Ｒｄ５及びＲｄ６はそれぞれ独立して水素原子又は炭素数１〜４のアルキル基であることが好ましく、製造の容易さから水素原子であることが特に好ましい。
(In the formula, R d0 , R d1 , R d2 , R d3 , R d4 , R d5 and R d6 are R a0 , R a1 , R a2 , R a3 , R a4 , R a5 and R in the general formula (I). It has the same meaning as a6 , R a10 represents a hydrogen atom or a monovalent organic group, Sp a3 has the same meaning as Sp a1 or Sp a2, and s and v independently represent 0 or 1).
The structure represented by is preferable in order to enhance the photodegradation prevention ability. R d0 is preferably a hydrogen atom or a hydroxyl group in order to enhance the photodegradation prevention ability, and is particularly preferably a hydrogen atom from the viewpoint of ease of production. Further, in order to enhance the compatibility with the liquid crystal composition, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 3 to 12 carbon atoms is preferable.
It is preferable that R d1 , R d2 , R d3 and R d4 are independently alkyl groups having 1 to 4 carbon atoms, and particularly preferably methyl groups. Further, in order to facilitate the removal of polar impurities mixed in during production, it is preferable that R d1 and R d2 , and / or R d3 and R d4 are combined to form a ring structure.
It is preferable that R d5 and R d6 are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and it is particularly preferable that they are hydrogen atoms from the viewpoint of ease of production.
Ｓｐａ３はそれぞれ独立に単結合又は炭素原子数１から８のアルキレン基であることが好ましく、アルキル基中に存在する１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−により置き換えられていることが好ましく、単結合であることが特に好ましい。 Sp a3 is preferably a single bond or an alkylene group having 1 to 8 carbon atoms, respectively, and is preferably one −CH 2 − present in the alkyl group or two or more −CH 2 − not adjacent to each other. Is preferably replaced by -O-, -COO-, -OCO-, -CH = CH- or -C≡C-, and is particularly preferably a single bond.
Ｒａ１０は水素原子又は炭素数１〜４のアルキル基であることが特に好ましい。
ｓ及びｖはそれぞれ１であることが好ましい。
ｐ及びｑはそれぞれ０または１であることが好ましい。
It is particularly preferable that R a10 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
It is preferable that s and v are 1 respectively.
It is preferable that p and q are 0 or 1, respectively.
一般式（Ｉ）中のｔが２を表す場合、Ｕは、一般式（Ｉ−ｂ）または一般式（Ｉ−ｅ） When t in the general formula (I) represents 2, U is the general formula (Ib) or the general formula (I-e).
（式中、破線は各々酸素原子への結合を表し、ｌ及びｏはそれぞれ独立に０または１を表す。） (In the equation, the broken line represents the bond to the oxygen atom, and l and o independently represent 0 or 1, respectively.)
（式中、破線は各々酸素原子への結合を表し、ｌｅ及びｏｅはそれぞれ独立して０又は１を表し、Ｒｅ１及びＲｅ２はそれぞれ独立して水素原子または１価の有機基を表し、Ｖｅは２価の有機基を表す。）
で表される構造であることが光劣化防止能を高めるためには好ましい。ｌ、ｏ，ｌｅ及びｏｅは各々１であることが液晶組成物の保存安定性を高めるためには好ましい。Ｒｅ１及びＲｅ２は水素原子又は炭素原子数１〜１０のアルキル基であることが好ましく、水素原子又は炭素原子数１〜５のアルキル基であることが好ましく、水素原子又は炭素原子数１〜３のアルキル基であることが好ましく、水素原子、メチル基、エチル基であることがより好ましい。
(In the formula, the broken lines each represent a bond to an oxygen atom, le and oe independently represent 0 or 1, respectively, and R e1 and R e2 independently represent a hydrogen atom or a monovalent organic group. V e represents a divalent organic group.)
The structure represented by is preferable in order to enhance the photodegradation prevention ability. It is preferable that each of l, o, le and oe is 1 in order to enhance the storage stability of the liquid crystal composition. R e1 and R e2 are preferably hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, preferably hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and hydrogen atoms or 1 to 5 carbon atoms. It is preferably an alkyl group of 3, and more preferably a hydrogen atom, a methyl group, or an ethyl group.
一般式（Ｉ−ｅ）は、一般式（Ｉ−ｅ１）で表される構造であることが好ましい。 The general formula (I-e) preferably has a structure represented by the general formula (I-e1).
（式中、破線は各々酸素原子への結合を表し、ｌｅ及びｏｅはそれぞれ独立して０又は１を表し、Ｒｅ１及びＲｅ２はそれぞれ独立して水素原子または１価の有機基を表し、Ｓｐａｅは単結合又は炭素原子数１から１２のアルキレン基を表し、該アルキレン基中に存在する１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−により置き換えられていてもよい。）
Ｓｐａｅは単結合又は炭素原子数１から８のアルキレン基であることがより好ましい。
(Wherein, a broken line each represent a bond to an oxygen atom, le and oe is 0 or 1 each independently, R e1 and R e2 each independently represents a hydrogen atom or a monovalent organic group, sp ae represents a single bond or an alkylene group having a carbon number of from 12, the alkylene group in present in one -CH 2 - or nonadjacent two or more -CH 2 - is -O-, It may be replaced by −COO−, −OCO−, −CH = CH− or −C≡C−).
Sp ae is more preferably a single bond or an alkylene group having 1 to 8 carbon atoms.
また、一般式（Ｉ−ｅ）は、一般式（Ｉ−ｅ２）で表される構造であることが好ましい。 Further, the general formula (I-e) preferably has a structure represented by the general formula (I-e2).
（式中、破線は各々酸素原子への結合を表し、ｌｅ及びｏｅはそれぞれ独立して０又は１を表し、Ｒｅ１及びＲｅ２はそれぞれ独立して水素原子または１価の有機基を表し、Ｓｐａｅ１及びＳｐａｅ２はそれぞれ独立して一般式（Ｉ−ｃ）におけるＳｐａ１と同じ意味を表し、Ａａｄ１は一般式（Ｉ−ｃ）におけるＡａ１と同じ意味を表し、ｐｅは１又は２を表し、Ｓｐａｅ１、Ｓｐａｅ２及びＡａｅ１が複数存在する場合、それらは同一であっても異なっていてもよい。）
一般式（Ｉ）中のｔが３又は４を表す場合、Ｕは、一般式（Ｉ−ｆ）
(Wherein, a broken line each represent a bond to an oxygen atom, le and oe is 0 or 1 each independently, R e1 and R e2 each independently represents a hydrogen atom or a monovalent organic group, Sp ae1 and Sp ae2 independently represent the same meaning as Sp a1 in the general formula (Ic), A ad1 has the same meaning as A a1 in the general formula (Ic), and pe is 1 or 2 When there are a plurality of Sp ae1 , Sp ae 2 and A ae 1 , they may be the same or different.)
When t in the general formula (I) represents 3 or 4, U is the general formula (If).
（式中、破線は酸素原子への結合を表し、ｌｆは０又は１を表し、Ｒｆ７は水素原子または１価の有機基を表し、Ｓｐａｆ１及びＳｐａｆ２はそれぞれ独立して一般式（Ｉ−ｃ）におけるＳｐａ１と同じ意味を表し、Ａａｆ１は一般式（Ｉ−ｃ）におけるＡａ１と同じ意味を表し、ｐｆは０、１又は２を表し、ｔｆは３又は４を表し、Ｖｆは３価又は４価の基を表すが、Ｖｆの価数はｔｆが表す数と同じ数であり、Ｓｐａｆ１、Ｓｐａｆ２及びＡａｆ１が複数存在する場合、それらは同一であっても異なっていてもよい。）
で表される構造であることが光劣化防止能を高めるためには好ましい。Ｒｆ７は炭素原子数１〜１０のアルキル基であることが好ましく、水素原子又は炭素原子数１〜５のアルキル基であることが好ましく、水素原子又は炭素原子数１〜３のアルキル基であることが好ましく、水素原子、メチル基、エチル基であることがより好ましい。
(In the formula, the broken line represents the bond to the oxygen atom, lf represents 0 or 1, R f7 represents the hydrogen atom or the monovalent organic group, and Sp af1 and Sp af 2 are independent general formulas (I). -C ) represents the same meaning as Sp a1 , A af1 represents the same meaning as A a1 in the general formula (I-c), pf represents 0, 1 or 2, tf represents 3 or 4, and V f each represents a trivalent or tetravalent radical, the valence of the V f is the same number as the number represented by tf, if Sp af1, Sp af2 and a af1 there are a plurality, even they are the same It may be different.)
The structure represented by is preferable in order to enhance the photodegradation prevention ability. R f7 is preferably an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It is preferably a hydrogen atom, a methyl group, or an ethyl group.
一般式（Ｉ−ｆ）中のｔｆが３を表す場合、すなわち、Ｖｆの価数が３の場合、Ｖｆは炭素原子数１から１５の炭化水素基を表すことが好ましく、当該炭化水素基中の炭素原子中に存在する１個又は隣接していない２個以上の−ＣＨ２−はそれぞれ独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、又は−Ｃ≡Ｃ−で置換されてもよい。Ｖｆは、式（Ｖ３−１）〜式（Ｖ３−１２）で表される基から選択される基であることがより好ましい。 When tf in the general formula (If) represents 3, that is, when the valence of V f is 3, V f preferably represents a hydrocarbon group having 1 to 15 carbon atoms, and the hydrocarbon. two or more -CH 2 that is not one or adjacent present in carbon atoms in the group - is independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO- It may be replaced by CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF-, -OCF 2- , -CF 2 O-, or -C≡C-. It is more preferable that V f is a group selected from the groups represented by the formulas (V3-1) to (V3-12).
（式中の、Ｒｖ３１及びＲｖ３２は、水素原子、水酸基又は炭素原子数１〜１０のアルキル基を表し、該アルキル基中に存在する１個又は２個以上の−ＣＨ２−はそれぞれ独立して−Ｏ−、−Ｓ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−に置換されてもよい。また、環状構造中の水素原子はフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基又は炭素原子数１から１２のアルキル基で置換されていてもよく、該アルキル基中に存在する１個又は隣接していない２個以上の−ＣＨ２−はそれぞれ独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、又は−Ｃ≡Ｃ−で置換されてもよい。）
ＲＶ３１及びＲＶ３２は、水素原子、水酸基又は炭素原子数１〜８のアルキル基を表すことが好ましく、直鎖状であることが好ましい。また、式（Ｖ３−４）〜式（Ｖ３−１２）はそれぞれ独立して無置換であることが好ましく、又、式（Ｖ３−４）〜式（Ｖ３−１２）中の水素原子はシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていてもよい。
(In the formula, R v31 and R v32 represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 10 carbon atoms, one existing in the alkyl group or two or more -CH 2 - are each independently Then, it may be substituted with −O−, −S−, −CH = CH−, −C≡C−, −CO−O−, −O−CO−, and the hydrogen atom in the cyclic structure is fluorine. Atomic, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group , A trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 12 carbon atoms, and one or two or more -CH 2- that are not adjacent to each other in the alkyl group. Are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH- , -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- , -OCF 2- , -CF 2 O-, or -C≡C- may be substituted.)
R V31 and R V32 preferably represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and are preferably linear. Further, it is preferable that the formulas (V3-4) to (V3-12) are independently unsubstituted, and the hydrogen atom in the formulas (V3-4) to (V3-12) is a cyano group. , Fluorine atom, chlorine atom, methyl group or methoxy group may be substituted.
原料の入手容易さ及び製造の容易さの観点から、式（Ｖ３−１）、式（Ｖ３−２）、及び無置換の式（Ｖ３−３）〜（Ｖ３−１２）から選ばれる基を表すことが特に好ましい。 Represents a group selected from formulas (V3-1), formulas (V3-2), and unsubstituted formulas (V3-3) to (V3-12) from the viewpoint of availability of raw materials and ease of production. Is particularly preferred.
一般式（Ｉ−ｆ）中のｔｆが４を表す場合、すなわち、Ｖｆの価数が４の場合、Ｖｆは炭素原子数１から１５の炭化水素基を表すことが好ましく、当該炭化水素基中の炭素原子中に存在する１個又は隣接していない２個以上の−ＣＨ２−はそれぞれ独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、又は−Ｃ≡Ｃ−で置換されてもよい。Ｖｆは、式（Ｖ４−１）〜式（Ｖ４−２１）で表される基から選択される基であることがより好ましい。 When tf in the general formula (If) represents 4, that is, when the valence of V f is 4, V f preferably represents a hydrocarbon group having 1 to 15 carbon atoms, and the hydrocarbon. two or more -CH 2 that is not one or adjacent present in carbon atoms in the group - is independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO- It may be replaced by CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF-, -OCF 2- , -CF 2 O-, or -C≡C-. It is more preferable that V f is a group selected from the groups represented by the formulas (V4-1) to (V4-21).
環状構造中の水素原子はフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基又は炭素原子数１から１２のアルキル基で置換されていてもよく、該アルキル基中に存在する１個又は隣接していない２個以上の−ＣＨ２−はそれぞれ独立して−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−Ｓ−、−Ｓ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、又は−Ｃ≡Ｃ−で置換されてもよい。また、式（Ｖ４−３）〜式（Ｖ４−２１）はそれぞれ独立して無置換であることが好ましく、又、式（Ｖ４−３）〜式（Ｖ４−２１）中の水素原子はシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていてもよい。 The hydrogen atoms in the cyclic structure are fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group and dimethylamino. It may be substituted with a group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group or an alkyl group having 1 to 12 carbon atoms, and one or not adjacent to the alkyl group. Two or more -CH 2-s are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO- O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = It may be substituted with CH-, -CF = CF-, -OCF 2- , -CF 2 O-, or -C≡C-. Further, it is preferable that the formulas (V4-3) to (V4-21) are independently unsubstituted, and the hydrogen atom in the formulas (V4-3) to (V4-21) is a cyano group. , Fluorine atom, chlorine atom, methyl group or methoxy group may be substituted.
原料の入手容易さ及び製造の容易さの観点から、式（Ｖ４−１）、式（Ｖ４−２）、及び無置換の式（Ｖ−３）〜（Ｖ−２１）から選ばれる基を表すことが特に好ましい。 Represents a group selected from the formulas (V4-1), formula (V4-2), and unsubstituted formulas (V-3) to (V-21) from the viewpoint of availability of raw materials and ease of production. Is particularly preferred.
本発明の一般式（Ｉ）に示す化合物の好ましい化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of preferable compounds of the compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.
一般式（Ｉ）で表される化合物は、一般式（Ｉ−１）で表される化合物が好ましい。 The compound represented by the general formula (I) is preferably the compound represented by the general formula (I-1).
（式中、Ｒａ０１は水素原子または水酸基を表し、
Ｒａ７１は水素原子または一価の有機基を表し、
Ｓｐａ１１及びＳｐａ２１は一般式（Ｉ−ｃ）におけるＳｐａ１及びＳｐａ２と同じ意味を表し、
Ａａ１１及びＡａ２１は一般式（Ｉ−ｃ）におけるＡａ１及びＡａ２と同じ意味を表し、
Ｒａ９１は一般式（Ｉ−ｃ）におけるＲａ９と同じ意味を表し、
ｍ１、ｐ１及びｑ１はそれぞれ独立に０又は１を表す。）
Ｒａ０１は水素原子であることが好ましい。
Ｒａ７１は水素原子又は炭素数１〜４のアルキル基であることが好ましい。
(In the formula, R a01 represents a hydrogen atom or a hydroxyl group, and represents
Ra71 represents a hydrogen atom or a monovalent organic group.
Sp a11 and Sp a21 have the same meanings as Sp a1 and Sp a2 in the general formula (Ic).
A a11 and A a21 have the same meanings as A a1 and A a2 in the general formula (Ic).
R a91 has the same meaning as R a9 in the general formula (Ic).
m1, p1 and q1 independently represent 0 or 1, respectively. )
R a01 is preferably a hydrogen atom.
R a71 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Ｓｐａ１１及びＳｐａ２１はそれぞれ独立に単結合又は炭素原子数１から６のアルキレン基であることが好ましく、アルキル基中に存在する１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−により置き換えられていることが好ましく、単結合であることが特に好ましい。
Ａａ１１及びＡａ２１はそれぞれ独立に
（ａ） １，４−シクロヘキシレン基（この基中に存在する１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−に置き換えられてもよい。）
（ｂ） １，４−フェニレン基（この基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられてもよい。）及び
（ｃ） ナフタレン−２，６−ジイル基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基又はデカヒドロナフタレン−２，６−ジイル基（ナフタレン−２，６−ジイル基又は１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられても良い。）
からなる群より選ばれる基であることが液晶組成物の保存安定性を高めるためには好ましく、上記の基（ａ）、基（ｂ）及び基（ｃ）はそれぞれ独立してシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていることが液晶組成物との相溶性を高めるためには好ましい。Ｒａ９１は水素原子又は炭素原子数１から６のアルキル基であることが好ましく、アルキル基中に存在する１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−又は−ＣＨ＝ＣＨ−により置き換えられていることも好ましい。また、Ｒａ９１は一般式（Ｉ−ｄ１）
Sp a11 and Sp a21 are preferably single bonds or alkylene groups having 1 to 6 carbon atoms, respectively, and are present in the alkyl group with one -CH 2- or two or more non-adjacent-. CH 2 − is preferably replaced by −O−, −COO−, −OCO−, −CH = CH− or −C≡C−, and is particularly preferably a single bond.
A a11 and A a21 are independently (a) 1,4-cyclohexylene groups (one -CH 2 − present in this group or two or more non-adjacent −CH 2 − are −O− May be replaced with.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =) and (c). Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2) , 3,4-Tetrahydronaphthalene-2,6-Diyl group One -CH = or two or more non-adjacent -CH = may be replaced with -N =).
A group selected from the group consisting of is preferable in order to enhance the storage stability of the liquid crystal composition, and the above groups (a), (b) and group (c) are independently cyano groups and fluorine, respectively. Substitution with an atom, a chlorine atom, a methyl group or a methoxy group is preferable in order to enhance compatibility with the liquid crystal composition. R a91 is a hydrogen atom or preferably from 1 carbon atoms is 6 alkyl group, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O It is also preferable that it is replaced by − or −CH = CH−. Further, R a91 is a general formula ( Id1 ).
（式中、Ｒｄ０１は水素原子又は水酸基を表し、Ｓｐａ３１は一般式（Ｉ−ｄ）におけるＳｐａ３と同じ意味を表し、Ｒａ１０１は水素原子または一価の有機基を表し、ｓ１は０又は１を表す。）で表される構造であることが光劣化防止能を高めるためには特に好ましい。Ｒａ１０１は水素原子又は炭素数１〜４のアルキル基であることが好ましい。Ｒｄ０１は水素原子であることが好ましい。Ｓｐａ３１は単結合又は炭素原子数１から６のアルキレン基であることが好ましく、アルキル基中に存在する１個の−ＣＨ２−又は隣接していない２個以上の−ＣＨ２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−により置き換えられていることが好ましく、単結合であることが特に好ましい。ｓ１は１であることが好ましい。
ｍ１及びｐ１は１であることが好ましい。ｑ１は０であることが好ましい。
(In the formula, R d01 represents a hydrogen atom or a hydroxyl group, Sp a31 has the same meaning as Sp a3 in the general formula ( Id ), R a101 represents a hydrogen atom or a monovalent organic group, and s1 is 0. Alternatively, a structure represented by 1) is particularly preferable in order to enhance the ability to prevent light deterioration. Ra 101 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R d01 is preferably a hydrogen atom. Sp a31 is preferably an alkylene group of a single bond or a C 1 -C 6, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O It is preferably replaced by −, −COO−, −OCO−, −CH = CH− or −C≡C−, and particularly preferably a single bond. s1 is preferably 1.
It is preferable that m1 and p1 are 1. It is preferable that q1 is 0.
一般式（Ｉ−１）で表される化合物としては、以下の一般式（Ｉ−１ａ）〜（Ｉ−１ｖ）が特に好ましい。 As the compound represented by the general formula (I-1), the following general formulas (I-1a) to (I-1v) are particularly preferable.
（式中、Ｒａ０２及びＲａ０３は、前記一般式（Ｉ−１）におけるＲａ０１と同じ意味を表し、Ｒａ７２およびＲａ１０２は、前記一般式（Ｉ−１）におけるＲａ７１と同じ意味を表し、Ｒａ９２は前記一般式（Ｉ−１）におけるＲａ９１と同じ意味を表し、Ｓｐａ１２，Ｓｐａ１３及びＳｐａ１４は前記一般式（Ｉ−１）におけるＳｐａ１１又はＳｐａ２１と同じ意味を表し、Ａａ１２及びＡａ１３は前記一般式（Ｉ−１）におけるＡａ１１又はＡａ２１と同じ意味を表す。）
一般式（Ｉ）で表される化合物を１種又は２種以上含有する組成物は、室温において液晶相を有することが好ましい。一般式（Ｉ）で表される化合物は、組成物中に下限値として、０．０１％以上含有することが好ましく、０．０２％以上含有することが好ましく、０．０３％以上含有することが好ましく、０．０５％以上含有することが好ましく、０．０７％以上含有することが好ましく、０．１％以上含有することが好ましく、０．１５％以上含有することが好ましく、０．２％以上含有することが好ましく、０．２５％以上含有することが好ましく、０．３％以上含有することが好ましく、０．５％以上含有することが好ましく、１％以上含有することが好ましい。また、上限値として５％以下含有することが好ましく、３％以下含有することが好ましく、１％以下含有することが好ましく、０．５％以下含有することが好ましく、０．４５％以下含有することが好ましく、０．４％以下含有することが好ましく、０．３５％以下含有することが好ましく、０．３％以下含有することが好ましく、０．２５％以下含有することが好ましく、０．２％以下含有することが好ましく、０．１５％以下含有することが好ましく、０．１％以下含有することが好ましく、０．０７％以下含有することが好ましく、０．０５％以下含有することが好ましく、０．０３％以下含有することが好ましい。
(Wherein, R a02 and R a03 are the same meaning as R a01 in the general formula (I-1), R a72 and R a102 has the same meaning as R a71 in the general formula (I-1) R a92 has the same meaning as R a91 in the general formula (I-1), and Sp a12 , Sp a13 and Spa a14 have the same meaning as Sp a11 or Sp a21 in the general formula (I-1). , A a12 and A a13 have the same meaning as A a11 or A a21 in the general formula (I-1).)
The composition containing one or more compounds represented by the general formula (I) preferably has a liquid crystal phase at room temperature. The compound represented by the general formula (I) is preferably contained in the composition as a lower limit value of 0.01% or more, preferably 0.02% or more, and 0.03% or more. Is preferable, 0.05% or more is preferably contained, 0.07% or more is preferably contained, 0.1% or more is preferably contained, 0.15% or more is preferably contained, and 0.2. % Or more is preferable, 0.25% or more is preferably contained, 0.3% or more is preferably contained, 0.5% or more is preferably contained, and 1% or more is preferably contained. Further, as an upper limit value, it is preferably contained in an amount of 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, and 0.45% or less. It is preferable, 0.4% or less is preferably contained, 0.35% or less is preferably contained, 0.3% or less is preferably contained, 0.25% or less is preferably contained, and 0. It is preferably contained in an amount of 2% or less, preferably 0.15% or less, preferably 0.1% or less, preferably 0.07% or less, and preferably 0.05% or less. Is preferable, and the content is preferably 0.03% or less.
より具体的には、０．０１から５質量％含有することが好ましく、０．０１から０．３質量％であることが好ましく、０．０２から０．３質量％であることが更に好ましく、０．０５から０．２５質量％であることが特に好ましい。更に詳述すると、低温における析出の抑制を重視する場合にはその含有量は０．０１から０．１質量％が好ましい。 More specifically, it is preferably contained in an amount of 0.01 to 5% by mass, preferably 0.01 to 0.3% by mass, and even more preferably 0.02 to 0.3% by mass. It is particularly preferably 0.05 to 0.25% by mass. More specifically, when the suppression of precipitation at low temperature is emphasized, the content thereof is preferably 0.01 to 0.1% by mass.
一般式（Ｉ）で表される化合物を含有する組成物は、一般式（Ｉ）で表される化合物以外に、液晶相を有する化合物を含有してもよいし、液晶相を有さない化合物を含有してもよい。 The composition containing the compound represented by the general formula (I) may contain a compound having a liquid crystal phase in addition to the compound represented by the general formula (I), or a compound having no liquid crystal phase. May be contained.
本発明において、一般式（Ｉ）で表される化合物は、以下のようにして製造することができる。勿論本発明の趣旨及び適用範囲は、これら製造例により制限されるものではない。 In the present invention, the compound represented by the general formula (I) can be produced as follows. Of course, the gist and scope of the present invention are not limited by these production examples.
（製法１）一般式（Ｉ）で表される化合物の製造方法 (Production method 1) Method for producing a compound represented by the general formula (I)
（式中、Ｒａ０、Ｒａ１，Ｒａ２，Ｒａ３、Ｒａ４、Ｒａ５、Ｒａ６、ｎ、ｔ及びＵは前記一般式（Ｉ）におけるＲａ０、Ｒａ１，Ｒａ２，Ｒａ３、Ｒａ４、Ｒａ５、Ｒａ６、ｎ、ｔ及びＵと同じ意味を表す。）
一般式（Ｓ−１）で表される化合物を一般式（Ｓ−２）で表される化合物と反応させることにより一般式（Ｉ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ−１）で表される化合物及び一般式（Ｓ−２）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。酸触媒としては例えば塩酸、硫酸、重硫酸カリウムなどの無機酸や、三フッ化ホウ素などのルイス酸、フマル酸、フタル酸、オギザリル酸、カンファースルホン酸、ｐ−トルエンスルホン酸などの有機酸、アンバーリスト−１５などの固体酸等が挙げられる。この際、一般式（Ｓ−１）で表される化合物が塩基性化合物である場合、必要に応じて酸触媒は1当量を超える量を加えることができる。
(In the formula, R a0 , R a1 , R a2 , R a3 , R a4 , R a5 , R a6 , n, t and U are R a0 , R a1 , R a2 , R a3 , in the general formula (I). It has the same meaning as R a4 , R a5 , R a6 , n, t and U.)
By reacting the compound represented by the general formula (S-1) with the compound represented by the general formula (S-2), the compound represented by the general formula (I) can be obtained. Examples of the reaction include a method in which a compound represented by the general formula (S-1) and a compound represented by the general formula (S-2) are heated in the presence of an acid catalyst to cause a dehydration reaction. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and potassium bicarbonate, Lewis acids such as boron trifluoride, fumaric acid, phthalic acid, oxalylic acid, camphorsulfonic acid and organic acids such as p-toluenesulfonic acid. Examples thereof include solid acids such as Amberlist-15. At this time, when the compound represented by the general formula (S-1) is a basic compound, an amount exceeding 1 equivalent can be added to the acid catalyst, if necessary.
（製法２）一般式（Ｉ−１ａ）、（Ｉ−１ｂ）、（Ｉ−１ｋ）又は（Ｉ−１ｌ）で表される化合物の製造方法 (Production Method 2) A method for producing a compound represented by the general formula (I-1a), (I-1b), (I-1k) or (I-1l).
（式中、Ｒｓ１は前記一般式（Ｉ−１ａ）、（Ｉ−１ｂ）、（Ｉ−１ｋ）又は（Ｉ−１ｌ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ−１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ−１ｂ）又は（Ｉ−１ｌ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ−１ａ）及び／又は（Ｉ−１ｂ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ−１ｋ）及び／又は（Ｉ−１ｌ）におけるＳｐａ１３と同じ意味を表し、ｐｓ１は０又は１を表し、ｔｓ１は１又は２を表す。）
一般式（Ｓ−３）で表される化合物を一般式（Ｓ−４）で表される化合物と反応させることにより一般式（Ｉ−１ａ）、（Ｉ−１ｂ）、（Ｉ−１ｋ）又は（Ｉ−１ｌ）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ−３）で表される化合物及び一般式（Ｓ−４）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
(In the formula, R s1 has the same meaning as R a02 or R a03 in the general formula (I-1a), (I-1b), (I-1k) or (I-1l), and R s7 is the general formula. represents the same meaning as R a71 in formula (I-1), a s1 has the same meaning as a a12 or a a13 in the general formula (I-1b) or (I-1l), Y s1 is the formula (I-1a) and / or (I-1b) the same meaning as R a92 in, or the same meaning as S PA13 in formula (I-1k) and / or (I-1l), p s1 is 0 Or 1 and t s1 represents 1 or 2)
By reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-4), the general formulas (I-1a), (I-1b), (I-1k) or The compound represented by (I-1l) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-4) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
（製法３）一般式（Ｉ−１ｃ）、（Ｉ−１ｊ）、（Ｉ−１ｍ）又は（Ｉ−１ｔ）で表される化合物の製造方法 (Production Method 3) A method for producing a compound represented by the general formula (I-1c), (I-1j), (I-1m) or (I-1t).
（式中、Ｒｓ１は前記一般式（Ｉ−１ｃ）、（Ｉ−１ｊ）、（Ｉ−１ｍ）又は（Ｉ−１ｔ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ−１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ−１ｃ）、（Ｉ−１ｊ）、（Ｉ−１ｍ）又は（Ｉ−１ｔ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ−１ｃ）又は（Ｉ−１ｊ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ−１ｍ）又は（Ｉ−１ｔ）におけるＳｐａ１３と同じ意味を表し、Ｓｐｓ１は前記一般式（Ｉ−１ｃ）、（Ｉ−１ｊ）、（Ｉ−１ｍ）又は（Ｉ−１ｔ）におけるＳｐａ１２又はＳｐａ１４と同じ意味を表し、ｍｓ１及びｐｓ１は各々独立して０又は１を表し、ｔｓ１は１又は２を表す。）
一般式（Ｓ−３）で表される化合物を一般式（Ｓ−５）で表される化合物と反応させることにより一般式（Ｓ−６）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ−３）で表される化合物及び一般式（Ｓ−５）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
一般式（Ｓ−６）で表される化合物を一般式（Ｓ−７）で表される化合物と反応させることにより一般式（Ｉ−１ｃ）、（Ｉ−１ｊ）、（Ｉ−１ｍ）又は（Ｉ−１ｔ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ−６）の水酸基に対して塩化ｐ−トルエンスルホニル、塩化メチルスルホニルなどを反応させて脱離基とした後、塩基の存在下で（Ｓ−７）と反応させるウィリアムソン反応が挙げられる。塩基としては例えば炭酸カリウム、炭酸セシウムなどが挙げられる。また、水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、アルコールと反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。（製法４）一般式（Ｉ−１ｄ）、（Ｉ−１ｉ）、（Ｉ−１ｎ）又は（Ｉ−１ｓ）で表される化合物の製造方法
(In the formula, R s1 has the same meaning as R a02 or R a03 in the general formula (I-1c), (I-1j), (I-1m) or (I-1t), and R s7 is the general formula. represents the same meaning as R a71 in formula (I-1), a s1 is the formula (I-1c), (I -1j), (I-1m) or (I-1t) in a a12 or a a13 Y s1 has the same meaning as Ra 92 in the general formula (I-1c) or (I-1j), or the same as Sp a13 in the general formula (I-1m) or (I-1t). Sp s1 represents the same meaning as Sp a12 or Sp a14 in the general formulas (I-1c), (I-1j), (I-1m) or (I-1t), and sp s1 and p s1 Represents 0 or 1 independently, and t s1 represents 1 or 2).
By reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-5), the compound represented by the general formula (S-6) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-5) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
By reacting the compound represented by the general formula (S-6) with the compound represented by the general formula (S-7), the general formula (I-1c), (I-1j), (I-1m) or The compound represented by (I-1t) can be obtained. As an example of the reaction, for example, the hydroxyl group of the general formula (S-6) is reacted with p-toluenesulfonyl chloride, methylsulfonyl chloride, etc. to form a leaving group, and then reacted with (S-7) in the presence of a base. There is a Williamson reaction that causes it. Examples of the base include potassium carbonate and cesium carbonate. Another example is the Mitsunobu reaction in which a hydroxyl group is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with an alcohol. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate. (Production Method 4) A method for producing a compound represented by the general formula (I-1d), (I-1i), (I-1n) or (I-1s).
（式中、Ｒｓ１は前記一般式（Ｉ−１ｄ）、（Ｉ−１ｉ）、（Ｉ−１ｎ）又は（Ｉ−１ｓ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ−１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ−１ｄ）、（Ｉ−１ｉ）、（Ｉ−１ｎ）又は（Ｉ−１ｓ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ−１ｄ）又は（Ｉ−１ｉ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ−１ｎ）又は（Ｉ−１ｓ）におけるＳｐａ１３と同じ意味を表し、Ｓｐｓ１は前記一般式（Ｉ−１ｄ）、（Ｉ−１ｉ）、（Ｉ−１ｎ）又は（Ｉ−１ｓ）におけるＳｐａ１２又はＳｐａ１４と同じ意味を表し、ｍｓ１及びｐｓ１は各々独立して０又は１を表し、ｔｓ１は１又は２を表す。）
一般式（Ｓ−３）で表される化合物を一般式（Ｓ−８）で表される化合物と反応させることにより一般式（Ｓ−９）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ−３）で表される化合物及び一般式（Ｓ−８）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
一般式（Ｓ−９）で表される化合物を一般式（Ｓ−７）で表される化合物と反応させることにより一般式（Ｉ−１ｄ）、（Ｉ−１ｉ）、（Ｉ−１ｎ）又は（Ｉ−１ｓ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ−９）のカルボキシル基に対してハロゲン化剤を作用させて酸ハロゲン化物とした後、一般式（Ｓ−７）で表される化合物と反応させる方法が挙げられる。ハロゲン化剤としては例えば、塩化チオニル、塩化オキサリル、塩化ホスホリル、塩化スルフリル、三塩化リン、五塩化リン、三臭化リンなどが挙げられる。また、一般式（Ｓ−７）の水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、一般式（Ｓ−９）のカルボキシル基と反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。
(In the formula, R s1 has the same meaning as R a02 or R a03 in the general formula (I-1d), (I-1i), (I-1n) or (I-1s), and R s7 is the general formula. represents the same meaning as R a71 in formula (I-1), a s1 is the formula (I-1d), (I -1i), (I-1n) or (I-1s) in a a12 or a a13 Y s1 has the same meaning as Ra 92 in the general formula (I-1d) or (I-1i), or the same as Sp a13 in the general formula (I-1n) or (I-1s). Sp s1 represents the same meaning as Sp a12 or Sp a14 in the general formulas (I-1d), (I-1i), (I-1n) or (I-1s), and sp s1 and p s1 Represents 0 or 1 independently, and t s1 represents 1 or 2).
By reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-8), the compound represented by the general formula (S-9) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-8) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
By reacting the compound represented by the general formula (S-9) with the compound represented by the general formula (S-7), the general formulas (I-1d), (I-1i), (I-1n) or The compound represented by (I-1s) can be obtained. As an example of the reaction, for example, a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-9) to form an acid halide and then reacted with a compound represented by the general formula (S-7) can be mentioned. Be done. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like. Further, a Mitsunobu reaction in which the hydroxyl group of the general formula (S-7) is activated by an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-9) can be mentioned. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
（製法５）一般式（Ｉ−１ｅ）又は（Ｉ−１ｏ）で表される化合物の製造方法 (Production Method 5) A method for producing a compound represented by the general formula (I-1e) or (I-1o).
（式中、Ｒｓ１は前記一般式（Ｉ−１ｅ）又は（Ｉ−１ｏ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ−１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ−１ｅ）又は（Ｉ−１ｏ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ−１ｅ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ−１ｏ）におけるＳｐａ１３と同じ意味を表し、ｐｓ１は０又は１を表し、ｔｓ１は１又は２を表す。）
一般式（Ｓ−３）で表される化合物を一般式（Ｓ−１０）で表される化合物と反応させることにより一般式（Ｓ−１１）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ−３）で表される化合物及び一般式（Ｓ−１０）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
一般式（Ｓ−１１）で表される化合物を一般式（Ｓ−１２）で表される化合物と反応させることにより一般式（Ｉ−１ｅ）又は（Ｉ−１ｏ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ−１２）の水酸基に対して塩化ｐ−トルエンスルホニル、塩化メチルスルホニルなどを反応させて脱離基とした後、塩基の存在下で（Ｓ−１１）と反応させるウィリアムソン反応が挙げられる。塩基としては例えば水素化ナトリウムなどが挙げられる。また、水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、アルコールと反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。
(In the formula, R s1 has the same meaning as R a02 or R a03 in the general formula (I-1e) or (I-1o), and R s7 has the same meaning as R a71 in the general formula (I-1). the stands, a s1 has the same meaning as a a12 or a a13 in the general formula (I-1e) or (I-1o), Y s1 is the same meaning as R a92 in the general formula (I-1e), Alternatively, it has the same meaning as Sp a13 in the general formula (I-1o), p s1 represents 0 or 1, and t s1 represents 1 or 2).
By reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-10), the compound represented by the general formula (S-11) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-10) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
By reacting the compound represented by the general formula (S-11) with the compound represented by the general formula (S-12), the compound represented by the general formula (I-1e) or (I-1o) is obtained. be able to. As an example of the reaction, for example, the hydroxyl group of the general formula (S-12) is reacted with p-toluenesulfonyl chloride, methylsulfonyl chloride or the like to form a leaving group, and then reacted with (S-11) in the presence of a base. There is a Williamson reaction that causes it. Examples of the base include sodium hydride and the like. Another example is the Mitsunobu reaction in which a hydroxyl group is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with an alcohol. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
（製法６）一般式（Ｉ−１ｆ）又は（Ｉ−１ｐ）で表される化合物の製造方法 (Production Method 6) A method for producing a compound represented by the general formula (I-1f) or (I-1p).
（式中、Ｒｓ１は前記一般式（Ｉ−１ｆ）又は（Ｉ−１ｐ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ−１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ−１ｆ）又は（Ｉ−１ｐ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ−１ｆ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ−１ｐ）におけるＳｐａ１３と同じ意味を表し、ｐｓ１は０又は１を表し、ｔｓ１は１又は２を表す。）
一般式（Ｓ−１１）で表される化合物を一般式（Ｓ−１３）で表される化合物と反応させることにより一般式（Ｉ−１ｆ）又は（Ｉ−１ｐ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ−１３）のカルボキシル基に対してハロゲン化剤を作用させて酸ハロゲン化物とした後、一般式（Ｓ−１１）で表される化合物と反応させる方法が挙げられる。ハロゲン化剤としては例えば、塩化チオニル、塩化オキサリル、塩化ホスホリル、塩化スルフリル、三塩化リン、五塩化リン、三臭化リンなどが挙げられる。また、一般式（Ｓ−１１）の水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、一般式（Ｓ−１３）のカルボキシル基と反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。
(In the formula, R s1 has the same meaning as R a02 or R a03 in the general formula (I-1f) or (I-1p), and R s7 has the same meaning as R a71 in the general formula (I-1). the stands, a s1 has the same meaning as a a12 or a a13 in the general formula (I-1f) or (I-1p), Y s1 is the same meaning as R a92 in the general formula (I-1f), Alternatively, it has the same meaning as Sp a13 in the general formula (I-1p), p s1 represents 0 or 1, and t s1 represents 1 or 2).
By reacting the compound represented by the general formula (S-11) with the compound represented by the general formula (S-13), the compound represented by the general formula (I-1f) or (I-1p) is obtained. be able to. As an example of the reaction, for example, a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-13) to form an acid halide and then reacted with a compound represented by the general formula (S-11) can be mentioned. Be done. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like. Further, a Mitsunobu reaction in which the hydroxyl group of the general formula (S-11) is activated by an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-13) can be mentioned. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
（製法７）一般式（Ｉ−１ｇ）、（Ｉ−１ｑ）、（Ｉ−１ｈ）又は（Ｉ−１ｒ）で表される化合物の製造方法 (Production Method 7) A method for producing a compound represented by the general formula (I-1g), (I-1q), (I-1h) or (I-1r).
（式中、Ｒｓ１は前記一般式（Ｉ−１ｇ）、（Ｉ−１ｑ）、（Ｉ−１ｈ）又は（Ｉ−１ｒ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ２はアルキル基を表し、Ｒｓ７は前記一般式（Ｉ−１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ−１ｇ）、（Ｉ−１ｑ）、（Ｉ−１ｈ）又は（Ｉ−１ｒ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ−１ｇ）又は（Ｉ−１ｈ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ−１ｑ）又は（Ｉ−１ｒ）におけるＳｐａ１３と同じ意味を表し、Ｘは塩素、臭素又はヨウ素を表し、ｐｓ１は０又は１を表し、ｔｓ１は１又は２を表す。）
一般式（Ｓ−３）で表される化合物を一般式（Ｓ−１７）で表される化合物と反応させることにより一般式（Ｓ−１４）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ−３）で表される化合物及び一般式（Ｓ−１３）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
(In the formula, R s1 has the same meaning as R a02 or R a03 in the general formula (I-1g), (I-1q), (I-1h) or (I-1r), and R s2 is an alkyl group. the stands, R s7 represents the same meaning as R a71 in the general formula (I-1), a s1 is the formula (I-1g), (I -1q), (I-1h) or (I- It has the same meaning as A a12 or A a13 in 1r), and Y s1 has the same meaning as Ra 92 in the general formula (I-1g) or (I-1h), or the general formula (I-1q) or (I-1h). represents the same meaning as Sp a13 in -1R), X is chlorine, bromine or iodine, p s1 is 0 or 1, t s1 is 1 or 2.)
By reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-17), the compound represented by the general formula (S-14) can be obtained. As an example of the reaction, for example, in the same manner as in Production Method 1, a method of heating the compound represented by the general formula (S-3) and the compound represented by the general formula (S-13) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
一般式（Ｓ−１４）で表される化合物を還元することにより、一般式（Ｓ−１５）で表される化合物を得ることができる。還元剤としては、例えば水素化ジイソブチルアルミニウムなどが挙げられる。あるいは、一般式（Ｓ−１４）で表される化合物を還元してアルコールとし、続いて酸化してアルデヒドとすることにより、一般式（Ｓ−１５）で表される化合物を得ることも出来る。この場合、還元剤としては、例えば水素化リチウムアルミニウム、水素化ジイソブチルアルミニウム、水素化ビス(2-メトキシエトキシ)アルミニウムナトリウムなどが挙げられる。また、酸化剤としてはクロロクロム酸ピリジニウム、塩化オキサリルなどが挙げられる。 By reducing the compound represented by the general formula (S-14), the compound represented by the general formula (S-15) can be obtained. Examples of the reducing agent include diisobutylaluminum hydride and the like. Alternatively, the compound represented by the general formula (S-15) can be obtained by reducing the compound represented by the general formula (S-14) to an alcohol and then oxidizing it to an aldehyde. In this case, examples of the reducing agent include lithium aluminum hydride, diisobutylaluminum hydride, and sodium bis (2-methoxyethoxy) aluminum hydride. In addition, examples of the oxidizing agent include pyridinium chlorochromate and oxalyl chloride.
一般式（Ｓ−１５）で表される化合物を一般式（Ｓ−１６）で表される化合物と反応させることにより一般式（Ｉ−１ｇ）又は（Ｉ−１ｑ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ−１６）で表される化合物に対して塩基を反応させてリンイリドとした後、一般式（Ｓ−１５）で表される化合物と反応させるヴィティヒ反応が挙げられる。この際、塩基としては、例えばｔ−ブトキシカリウムなどが挙げられる。
一般式（Ｉ−１ｇ）又は（Ｉ−１ｑ）で表される化合物を還元することにより、一般式（Ｉ−１ｈ）又は（Ｉ−１ｒ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｉ−１ｇ）又は（Ｉ−１ｑ）で表される化合物と触媒を水素雰囲気下で共存させる方法が挙げられる。この際、触媒としては例えばパラジウム炭素などが挙げられる。
By reacting the compound represented by the general formula (S-15) with the compound represented by the general formula (S-16), the compound represented by the general formula (I-1g) or (I-1q) is obtained. be able to. Examples of the reaction include a Witich reaction in which a base is reacted with a compound represented by the general formula (S-16) to form phosphorus irid, and then the compound is reacted with a compound represented by the general formula (S-15). .. At this time, examples of the base include t-butoxypotassium and the like.
By reducing the compound represented by the general formula (I-1g) or (I-1q), the compound represented by the general formula (I-1h) or (I-1r) can be obtained. Examples of the reaction include a method in which a compound represented by the general formula (I-1g) or (I-1q) and a catalyst coexist in a hydrogen atmosphere. At this time, examples of the catalyst include palladium carbon and the like.
（製法８）一般式（Ｉ−１ｕ）又は（Ｉ−１ｖ）で表される化合物の製造方法 (Production Method 8) A method for producing a compound represented by the general formula (I-1u) or (I-1v).
（式中、Ｒｓ１は前記一般式（Ｉ−１ｕ）又は（Ｉ−１ｖ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ−１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ−１ｕ）又は（Ｉ−１ｖ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ−１ｕ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ−１ｖ）におけるＳｐａ１３と同じ意味を表し、Ｓｐｓ１は前記一般式（Ｉ−１ｕ）又は（Ｉ−１ｖ）におけるＳｐａ１２又はＳｐａ１４と同じ意味を表し、ｍｓ１及びｐｓ１は各々独立して０又は１を表し、ｔｓ１は１又は２を表す。）
一般式（Ｓ−３）で表される化合物を一般式（Ｓ−５）で表される化合物と反応させることにより一般式（Ｓ−６）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ−３）で表される化合物及び一般式（Ｓ−５）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
一般式（Ｓ−６）で表される化合物を一般式（Ｓ−１８）で表される化合物と反応させることにより一般式（Ｉ−１ｕ）又は（Ｉ−１ｖ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ−１８）のカルボキシル基に対してハロゲン化剤を作用させて酸ハロゲン化物とした後、一般式（Ｓ−６）で表される化合物と反応させる方法が挙げられる。ハロゲン化剤としては例えば、塩化チオニル、塩化オキサリル、塩化ホスホリル、塩化スルフリル、三塩化リン、五塩化リン、三臭化リンなどが挙げられる。また、一般式（Ｓ−６）の水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、一般式（Ｓ−１８）のカルボキシル基と反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。
前記各工程において記載した以外の反応条件として、例えば実験化学講座（日本化学会編、丸善株式会社発行）、Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｅｓ（Ａ Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，Ｉｎｃ．，Ｐｕｂｌｉｃａｔｉｏｎ）、Ｂｅｉｌｓｔｅｉｎ Ｈａｎｄｂｏｏｋ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ（Ｂｅｉｌｓｔｅｉｎ−Ｉｎｓｔｉｔｕｔ ｆｕｅｒ Ｌｉｔｅｒａｔｕｒ ｄｅｒ Ｏｒｇａｎｉｓｃｈｅｎ Ｃｈｅｍｉｅ、Ｓｐｒｉｎｇｅｒ−Ｖｅｒｌａｇ Ｂｅｒｌｉｎ ａｎｄ Ｈｅｉｄｅｌｂｅｒｇ ＧｍｂＨ ＆ Ｃｏ．Ｋ）、Ｆｉｅｓｅｒｓ’ Ｒｅａｇｅｎｔｓ ｆｏｒ Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｉｓ（Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，Ｉｎｃ．）等の文献に記載のもの又はＳｃｉＦｉｎｄｅｒ（Ｃｈｅｍｉｃａｌ Ａｂｓｔｒａｃｔｓ Ｓｅｒｖｉｃｅ，Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ）、Ｒｅａｘｙｓ（Ｅｌｓｅｖｉｅｒ Ｌｔｄ．）等のデータベースに収載のものが挙げられる。
(In the formula, R s1 has the same meaning as R a02 or R a03 in the general formula (I-1u) or (I-1v), and R s7 has the same meaning as R a71 in the general formula (I-1). the stands, a s1 has the same meaning as a a12 or a a13 in the general formula (I-1u) or (I-1v), Y s1 is the same meaning as R a92 in the general formula (I-1u), Alternatively, it has the same meaning as Sp a13 in the general formula (I-1v), and Sp s1 has the same meaning as Sp a12 or Sp a14 in the general formula (I-1u) or (I-1v), and has the same meaning as m s1 and sp a14. p s1 independently represents 0 or 1, and t s1 represents 1 or 2).
By reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-5), the compound represented by the general formula (S-6) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-5) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
By reacting the compound represented by the general formula (S-6) with the compound represented by the general formula (S-18), the compound represented by the general formula (I-1u) or (I-1v) is obtained. be able to. An example of the reaction is a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-18) to form an acid halide, and then the reaction is carried out with a compound represented by the general formula (S-6). Be done. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like. Further, a Mitsunobu reaction in which the hydroxyl group of the general formula (S-6) is activated by an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-18) can be mentioned. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
Reaction conditions other than those described in each of the above steps include, for example, Experimental Chemistry Course (edited by Japan Chemistry Society, published by Maruzen Co., Ltd.), Organic Syntheses (A John Wiley & Sons, Inc., Publication), Beilstein Handbook of Organic Chemistry (Beilstein Handbook of Organic Chemistry). -Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) as described in the literature, such as or SciFinder (Chemical Abstracts Service, American Chemical Society), Reaxys (Elsevier Ltd.) and other databases.
また、各工程において適宜反応溶媒を用いることができる。溶媒の具体例としてはエタノール、テトラヒドロフラン、トルエン、ジクロロメタン、水等が挙げられる。有機溶媒及び水の二相系で反応を行う場合、相間移動触媒を添加することも可能である。相間移動触媒の具体例としてはベンジルトリメチルアンモニウムブロミド、テトラブチルアンモニウムブロミド等が挙げられる。 In addition, a reaction solvent can be appropriately used in each step. Specific examples of the solvent include ethanol, tetrahydrofuran, toluene, dichloromethane, water and the like. When the reaction is carried out in a two-phase system of an organic solvent and water, it is also possible to add a phase transfer catalyst. Specific examples of the phase transfer catalyst include benzyltrimethylammonium bromide and tetrabutylammonium bromide.
また、各工程において必要に応じて精製を行うことができる。精製方法としてはクロマトグラフィー、再結晶、蒸留、昇華、再沈殿、吸着、分液処理等が挙げられる。精製剤の具体例としてはシリカゲル、ＮＨ２シリカゲル、アルミナ、活性炭等が挙げられる。 In addition, purification can be performed as needed in each step. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. Specific examples of the purifying agent include silica gel, NH 2 silica gel, alumina, activated carbon and the like.
以下、実施例を挙げて本発明を更に記述するが、本発明はこれらの実施例に限定されるものではない。以下の実施例及び比較例の組成物における「％」は『質量％』を意味する。化合物の純度はＧＣ又はＵＰＬＣによって分析した。化合物および反応溶媒の略称は以下の通りである：テトラヒドロフラン（ＴＨＦ）、２,２,６,６−テトラメチル−４−ピペリドン（ＴＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、水素化ジイソブチルアルミニウム（ＤＩＢＡＬ）
（実施例１）化合物（Ｉ−１ａ−５）の製造
Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. “%” In the compositions of the following Examples and Comparative Examples means “% by mass”. The purity of the compounds was analyzed by GC or UPLC. Abbreviations for compounds and reaction solvents are as follows: tetrahydrofuran (THF), 2,2,6,6-tetramethyl-4-piperidin (TMP), N, N-dimethylformamide (DMF), diisobutylaluminum hydride. (DIBAL)
(Example 1) Production of compound (I-1a-5)
窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ−トルエンスルホン酸一水和物（６．７９ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（５．１１ｇ）及び２−ペンチル−１、３−プロパンジオール（４．８２ｇ）を加え、３時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌを加えて攪拌し、有機層を分けとり、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌ、水１００ｍｌ、飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、カラムクロマトグラフィー（ＮＨ２シリカゲル、トルエン）を通過させた。得られた溶液を濃縮し、化合物（Ｉ−１ａ−５）（７．８７ｇ）を得た。
ＧＣ−ＭＳ：ｍ／ｚ ２６８．２２ [Ｍ−１５＋]
相転移温度：Ｏｉｌ（凝固点は−２０℃以下）
1H-NMR (400MHz, CDCl3)δ: 0.71-0.74(t,3H), 1.09-1.34(m,8H), 1.21(d, 12H), 1.59(s,2H), 1.79(s, 2H), 1.83-1.96(m,1H), 3.56-3.61(t,2H), 3.80-3.85(dd,2H)
実施例１と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例２（化合物（Ｉ−１ａ−３））〜実施例３（化合物（Ｉ−１ｋ−４））を製造した。
In a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (6.79 g) and 100 ml of toluene were added to a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube, and the mixture was heated under reflux for 30 minutes. The water was removed. After cooling the mixture to room temperature, TMP (5.11 g) and 2-pentyl-1,3-propanediol (4.82 g) were added, and the mixture was heated under reflux for 3 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 150 ml of 1.0 M aqueous sodium hydroxide solution was added and stirred, and the organic layer was separated and washed with 150 ml of 1.0 M aqueous sodium hydroxide solution, 100 ml of water and 100 ml of saturated brine. The obtained organic layer was concentrated and passed through column chromatography (NH 2 silica gel, toluene). The resulting solution was concentrated to give compound (I-1a-5) (7.87 g).
GC-MS: m / z 268.22 [M-15 + ]
Phase transition temperature: Oil (freezing point is -20 ° C or less)
1 1 H-NMR (400MHz, CDCl 3 ) δ: 0.71-0.74 (t, 3H), 1.09-1.34 (m, 8H), 1.21 (d, 12H), 1.59 (s, 2H), 1.79 (s, 2H) , 1.83-1.96 (m, 1H), 3.56-3.61 (t, 2H), 3.80-3.85 (dd, 2H)
Examples 2 (Compound (I-1a-3)) to Example 3 (Compound (I-1k-4)) using the same reaction as in Example 1 and, if necessary, a method based on a known method. ) Was manufactured.
（実施例７）化合物（Ｉ−１ｋ−８）の製造 (Example 7) Production of compound (I-1k-8)
撹拌装置、温度計を備えた反応容器に、tert−ブトキシカリウム（１３．０ｇ）を加え、テトラヒドロフラン（４００ｍＬ）に懸濁させた。マロン酸ジエチル（１８．６ｇ）を加え、続いて１，８−ジブロモオクタン（１５．８ｇ）を加えた。室温で３日間攪拌した。減圧濃縮をおこない、１０％塩酸を加えて酸性にした。ジクロロメタン（１５０ｍＬ）で２回抽出した。減圧濃縮後、カラムクロマトグラフィーにより精製し、１，１，８，８−テトラ（エトキシカルボニル）オクタンを１５．０ｇ、無色液体として得た。 To a reaction vessel equipped with a stirrer and a thermometer, tert-butoxypotassium (13.0 g) was added and suspended in tetrahydrofuran (400 mL). Diethyl malonate (18.6 g) was added, followed by 1,8-dibromooctane (15.8 g). The mixture was stirred at room temperature for 3 days. It was concentrated under reduced pressure and acidified by adding 10% hydrochloric acid. Extracted twice with dichloromethane (150 mL). After concentration under reduced pressure, the mixture was purified by column chromatography to obtain 15.0 g of 1,1,8,8-tetra (ethoxycarbonyl) octane as a colorless liquid.
撹拌装置、温度計、冷却管を備えた反応容器に、水素化リチウムアルミニウム（１０．６ｇ）を加え、テトラヒドロフラン（２７９ｍＬ）に懸濁させた。１，１，８，８−テトラ（エトキシカルボニル）オクタン（２０．０ｇ）を加え、６０℃で５時間攪拌した。氷冷し、水（５７．０ｇ）を注意深く加えた。４０℃で１時間攪拌し、濾過して固形分を除いた。テトラヒドロフラン溶液を濃縮し、１，１，８，８−テトラ（ヒドロキシメチル）オクタンを１０．１ｇ、無色個体として得た。 Lithium aluminum hydride (10.6 g) was added to a reaction vessel equipped with a stirrer, a thermometer and a condenser, and the mixture was suspended in tetrahydrofuran (279 mL). 1,1,8,8-Tetra (ethoxycarbonyl) octane (20.0 g) was added, and the mixture was stirred at 60 ° C. for 5 hours. It was ice-cooled and water (57.0 g) was carefully added. The mixture was stirred at 40 ° C. for 1 hour and filtered to remove solids. The tetrahydrofuran solution was concentrated to give 10.1 g of 1,1,8,8-tetra (hydroxymethyl) octane as a colorless solid.
撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、１，１，８，８−テトラ（ヒドロキシメチル）オクタンを１０．０ｇと２，２，６，６−テトラメチルピペリジン−４−オン（１０．６ｇ）、４−トルエンスルホン酸一水和物（１５．２ｇ）を加え、トルエン（１００ｍＬ）に懸濁させた。窒素雰囲気下、３時間加熱還流させ、途中で生成する水をディーンスターク管で除いた。室温に冷却後、炭酸カリウム水溶液を加えてアルカリ性した。テトラヒドロフラン（１３８ｍＬ）で２回抽出した。減圧濃縮後、カラムクロマトグラフィーと再結晶にて精製し、化合物（Ｉ−１ｋ−８）（１１．６ｇ）を無色結晶として得た。
ＧＣ−ＭＳ（ＥＩ）：ｍ／ｚ ５３６ [Ｍ＋]、５２１ [Ｍ−１５＋]
相転移温度：Ｃｒｙ １０１ Ｉｓｏ
実施例７と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例４（化合物（Ｉ−１ｋ−２））〜実施例６（化合物（Ｉ−１ｋ−６））を製造した。
10.0 g of 1,1,8,8-tetra (hydroxymethyl) octane and 2,2,6,6-tetramethylpiperidine-in a reaction vessel equipped with a stirrer, a thermometer, a cooling tube, and a Dean-Stark tube. 4-On (10.6 g) and 4-toluenesulfonic acid monohydrate (15.2 g) were added and suspended in toluene (100 mL). It was heated to reflux for 3 hours under a nitrogen atmosphere, and the water generated on the way was removed with a Dean-Stark tube. After cooling to room temperature, an aqueous potassium carbonate solution was added to make it alkaline. Extracted twice in tetrahydrofuran (138 mL). After concentration under reduced pressure, the mixture was purified by column chromatography and recrystallization to obtain compound (I-1k-8) (11.6 g) as colorless crystals.
GC-MS (EI): m / z 536 [M + ], 521 [M-15 + ]
Phase transition temperature: Cry 101 Iso
Examples 4 (Compound (I-1k-2)) to Example 6 (Compound (I-1k-6)) using the same reaction as in Example 7 and, if necessary, a method based on a known method. ) Was manufactured.
（実施例８）化合物（Ｉ−１ｂ−Ｃ３）の製造 (Example 8) Production of compound (I-1b-C3)
窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ−トルエンスルホン酸一水和物（５．０２ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３．８２ｇ）及び２−（トランス−４−プロピルシクロヘキシル）−１、３−プロパンジオール（４．９２ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌを加えて攪拌し、有機層を分けとり、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌ、水１００ｍｌ、飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、ヘキサン３ｍｌを加えて−２０℃で再結晶を行った。析出した固体をろ過し、トルエンに溶解させ、カラムクロマトグラフィー（ＮＨ２シリカゲル、トルエン）を通過させた。得られた溶液を濃縮し、ヘキサン３ｍｌを加えて−２０℃で再結晶を行った。析出した固体をろ過し、真空乾燥させ、化合物（Ｉ−１ｂ−３Ｃ）（１．９７ｇ）を得た。
ＧＣ−ＭＳ：ｍ／ｚ ３２２．２７ [Ｍ−１５＋]
相転移温度：Ｃｒｙ ７０ Ｉｓｏ
1H-NMR (400MHz, CDCl3)δ: 0.78-1.02(m,4H), 0.84-0.88(t,3H), 1.05-1.17(m,4H), 1.21(d,12H), 1.24-1.36(m,2H), 1.57(s,2H), 1.68-1.76(m,5H), 1.79(s,2H), 3.67-3.72(t,2H), 3.85-3.89(dd,2H)
実施例８と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例９（化合物（Ｉ−１ｂ−０Ｃ））〜実施例２４（化合物（Ｉ−１ｌ−Ｂ２Ｂ））を製造した。
Under a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene were added to a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube, and the mixture was heated under reflux for 30 minutes. The water was removed. After cooling this mixture to room temperature, TMP (3.82 g) and 2- (trans-4-propylcyclohexyl) -1,3-propanediol (4.92 g) were added, and the mixture was heated under reflux for 4 hours to produce water. Was removed. After cooling the reaction mixture to room temperature, 150 ml of 1.0 M aqueous sodium hydroxide solution was added and stirred, and the organic layer was separated and washed with 150 ml of 1.0 M aqueous sodium hydroxide solution, 100 ml of water and 100 ml of saturated brine. The obtained organic layer was concentrated, 3 ml of hexane was added, and recrystallization was performed at −20 ° C. The precipitated solid was filtered, dissolved in toluene, and passed through column chromatography (NH 2 silica gel, toluene). The obtained solution was concentrated, 3 ml of hexane was added, and recrystallization was performed at −20 ° C. The precipitated solid was filtered and vacuum dried to give compound (I-1b-3C) (1.97 g).
GC-MS: m / z 322.27 [M-15 + ]
Phase transition temperature: Cry 70 Iso
1 1 H-NMR (400MHz, CDCl 3 ) δ: 0.78-1.02 (m, 4H), 0.84-0.88 (t, 3H), 1.05-1.17 (m, 4H), 1.21 (d, 12H), 1.24-1.36 ( m, 2H), 1.57 (s, 2H), 1.68-1.76 (m, 5H), 1.79 (s, 2H), 3.67-3.72 (t, 2H), 3.85-3.89 (dd, 2H)
Examples 9 (Compound (I-1b-0C)) to Example 24 (Compound (I-1l-B2B)) using the same reaction as in Example 8 and, if necessary, a method based on a known method. ) Was manufactured.
（実施例２５）化合物（Ｉ−１ｃ−Ｂ３）の製造 (Example 25) Production of compound (I-1c-B3)
（化合物（Ｅ−２）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ−トルエンスルホン酸一水和物（５．０２ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３．８２ｇ）、ＤＭＦ３０ｍｌ及び化合物（Ｅ−１）（２．６０ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌを加えて攪拌し、有機層を分けとり、水１００ｍｌ、飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、化合物（Ｅ−２）（５．７１ｇ）を得た。 (Production of compound (E-2)) p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 30 minutes to remove the generated water. After cooling the mixture to room temperature, TMP (3.82 g), 30 ml of DMF and compound (E-1) (2.60 g) were added, and the mixture was heated under reflux for 4 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 150 ml of a 1.0 M aqueous sodium hydroxide solution was added and stirred, the organic layer was separated, and the mixture was washed with 100 ml of water and 100 ml of saturated brine. The obtained organic layer was concentrated to obtain compound (E-2) (5.71 g).
（化合物（Ｉ−１ｃ−Ｂ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ−２）（５．７１ｇ）、化合物（Ｅ−４）（３．００ｇ）、トリフェニルホスフィン（６．１６ｇ）及びＴＨＦ４５ｍｌを加え、５℃以下に冷却し攪拌した後、アゾジカルボン酸ジイソプロピル（４．４５ｇ）を５℃以下を保ちながら滴下し、室温で１時間撹拌した。この反応混合物に対し、水０．１ｍｌを加えて攪拌した後、溶媒を留去し、メタノール４０ｍｌ及び水２０ｍｌを加えて室温で１時間攪拌した。この反応混合物をろ過して得られた固体をヘキサン／トルエン混合溶媒に溶解させ、カラムクロマトグラフィー（ＮＨ２シリカ１０ｇ）を通した。得られた溶液を濃縮し、ヘキサン５ｍｌを加えて−２０℃で再結晶を行った。析出した固体をろ過し、真空乾燥させ、化合物（Ｉ−１ｃ−Ｂ３）（６．６６ｇ）を得た。
ＧＣ−ＭＳ：ｍ／ｚ ３６２．２６ [Ｍ−１５＋]
実施例２５と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例２６（化合物（Ｉ−１ｃ−Ｂ６））〜実施例３９（化合物（Ｉ−１ｔ−ＢＢ））を製造した。
(Production of compound (I-1c-B3)) Compound (E-2) (5.71 g) and compound (E-4) (3.00 g) were placed in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. ), Triphenylphosphine (6.16 g) and 45 ml of THF were added, cooled to 5 ° C. or lower and stirred, and then diisopropyl azodicarboxylate (4.45 g) was added dropwise while maintaining 5 ° C. or lower, and the mixture was stirred at room temperature for 1 hour. .. To this reaction mixture, 0.1 ml of water was added and stirred, then the solvent was distilled off, 40 ml of methanol and 20 ml of water were added, and the mixture was stirred at room temperature for 1 hour. The solid obtained by filtering the reaction mixture was dissolved in a hexane / toluene mixed solvent and subjected to column chromatography (10 g of NH 2 silica). The obtained solution was concentrated, 5 ml of hexane was added, and recrystallization was performed at −20 ° C. The precipitated solid was filtered and vacuum dried to obtain compound (I-1c-B3) (6.66 g).
GC-MS: m / z 362.26 [M-15 + ]
Examples 26 (Compound (I-1c-B6)) to Example 39 (Compound (I-1t-BB)) using the same reaction as in Example 25 and, if necessary, a method according to a known method. ) Was manufactured.
（実施例４０）化合物（Ｉ−１ｄ−Ｂ３）の製造 (Example 40) Production of compound (I-1d-B3)
（化合物（Ｅ−６）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ−トルエンスルホン酸一水和物（５．０２ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３．８２ｇ）、ＤＭＦ３０ｍｌ及び化合物（Ｅ−５）（３．３３ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液および水を加えてｐＨ＝７〜８程度に調整して攪拌し、有機層を分けとり、水１００ｍｌで２回及び飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、化合物（Ｅ−６）（５．３５ｇ）を得た。
（化合物（Ｉ−１ｄ−Ｂ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ−６）（５．３５ｇ）、化合物（Ｅ−７）（２．６６ｇ）、Ｎ，Ｎ−ジメチルアミノピリジン（ＤＭＡＰ）０．１２ｇ、ジクロロメタン２５ｍｌを加え、５〜１０℃で１０分間攪拌した。攪拌下、Ｎ，Ｎ−ジイソプロピルカルボジイミド（ＤＩＣ）６．２ｇを５〜１０℃を保ちながら滴下し、続いて２５度まで昇温し７時間攪拌した。この反応混合物に対して水２５ｍｌを加えた後、有機層を分離し、さらに水層をジクロロメタン２５ｍｌで抽出した。得られた有機層を混合して一つにした後、ＮＨ２シリカ１０ｇを充填したカラム上に加え、さらにヘキサン１００ｍｌを流して通過させた。得られた溶液の溶媒をおおむね留去した後、ヘキサン／トルエンを用いて−２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ−１ｄ−Ｂ３）を４．９０ｇ得た。
ＧＣ−ＭＳ：ｍ／ｚ ３７６．２４ [Ｍ−１５＋]
実施例４０と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例４１（化合物（Ｉ−１ｄ−０Ｃ））〜実施例５４（化合物（Ｉ−１ｓ−ＢＢ））を製造した。
(Production of compound (E-6)) p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 30 minutes to remove the generated water. After cooling the mixture to room temperature, TMP (3.82 g), 30 ml of DMF and compound (E-5) (3.33 g) were added, and the mixture was heated under reflux for 4 hours to remove the resulting water. After cooling this reaction mixture to room temperature, add 1.0 M aqueous sodium hydroxide solution and water to adjust the pH to about 7 to 8 and stir, separate the organic layer, and use 100 ml of water twice and saturated brine. Washed with 100 ml. The obtained organic layer was concentrated to obtain compound (E-6) (5.35 g).
(Production of compound (I-1d-B3)) Compound (E-6) (5.35 g) and compound (E-7) (2.66 g) were placed in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. ), 0.12 g of N, N-dimethylaminopyridine (DMAP) and 25 ml of nitrogen were added, and the mixture was stirred at 5 to 10 ° C. for 10 minutes. Under stirring, 6.2 g of N, N-diisopropylcarbodiimide (DIC) was added dropwise while maintaining 5 to 10 ° C., and then the temperature was raised to 25 ° C. and the mixture was stirred for 7 hours. After adding 25 ml of water to this reaction mixture, the organic layer was separated and the aqueous layer was further extracted with 25 ml of dichloromethane. After mixing the obtained organic layers into one, the mixture was added onto a column packed with 10 g of NH 2 silica, and 100 ml of hexane was further passed through the column. After the solvent of the obtained solution was generally distilled off, recrystallization was carried out at −20 ° C. using hexane / toluene. The precipitated solid was filtered and dried to obtain 4.90 g of compound (I-1d-B3).
GC-MS: m / z 376.24 [M-15 + ]
Examples 41 (Compound (I-1d-0C)) to Example 54 (Compound (I-1s-BB)) using the same reaction as in Example 40 and, if necessary, a method according to a known method. ) Was manufactured.
（実施例５５）化合物（Ｉ−１ｅ−Ｃ３）の製造 (Example 55) Production of compound (I-1e-C3)
（化合物（Ｅ−９）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ−トルエンスルホン酸一水和物（５０．２ｇ）及びトルエン１０００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３８．２ｇ）、ＤＭＦ３００ｍｌ及び化合物（Ｅ−８）（２２．５ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５００ｍｌを加えて攪拌し、有機層を分けとり、水１０００ｍｌで２回及び飽和食塩水１０００ｍｌで洗浄した。得られた有機層を濃縮し、化合物（Ｅ−９）（２２．４ｇ）を得た。
（化合物（Ｉ−１ｅ−Ｃ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ−９）（１１．２ｇ）、水素化ナトリウム１．２ｇおよびＤＭＦ１００ｍｌを加え、室温で２０分撹拌した後、化合物（Ｅ−１０）（１１．５ｇ）、を加えて９０℃で３時間撹拌した。反応混合物を室温に冷却後、トルエン１００ｍｌ、水１００ｍｌを加え有機層を分離し、さらに水層をトルエン１００ｍｌで抽出した。得られた有機層を合わせ、水１５０ｍｌ、飽和食塩水１５０ｍｌで洗浄し、得られた有機層に無水硫酸ナトリウムを加えて乾燥した。得られた溶液を濃縮し、カラムクロマトグラフィー（ＮＨ２シリカ２０ｇ）に対し、あらかじめヘキサン５０ｍｌに溶解しておいた粗体を通し、さらにヘキサン５０ｍｌで溶出させた。得られた溶液を濃縮し、ヘキサン１０ｍｌを加えて−２０℃で再結晶を行った。析出した固体をろ過し、真空乾燥させ、化合物（Ｉ−１ｅ−Ｃ３）（１２．５８ｇ）を得た。
(Production of compound (E-9)) p-toluenesulfonic acid monohydrate (50.2 g) and 1000 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 30 minutes to remove the generated water. After cooling the mixture to room temperature, TMP (38.2 g), 300 ml of DMF and compound (E-8) (22.5 g) were added, and the mixture was heated under reflux for 4 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 1500 ml of a 1.0 M aqueous sodium hydroxide solution was added and stirred, the organic layer was separated, and the mixture was washed twice with 1000 ml of water and with 1000 ml of saturated brine. The obtained organic layer was concentrated to obtain compound (E-9) (22.4 g).
(Production of compound (I-1e-C3)) Under a nitrogen atmosphere, add compound (E-9) (11.2 g), sodium hydride 1.2 g and DMF 100 ml to a reaction vessel equipped with a stirrer and a thermometer. After stirring at room temperature for 20 minutes, compound (E-10) (11.5 g) was added, and the mixture was stirred at 90 ° C. for 3 hours. After cooling the reaction mixture to room temperature, 100 ml of toluene and 100 ml of water were added to separate the organic layer, and the aqueous layer was further extracted with 100 ml of toluene. The obtained organic layers were combined, washed with 150 ml of water and 150 ml of saturated brine, and anhydrous sodium sulfate was added to the obtained organic layer and dried. The obtained solution was concentrated, passed through a crude product previously dissolved in 50 ml of hexane by column chromatography (20 g of NH 2 silica), and further eluted with 50 ml of hexane. The obtained solution was concentrated, 10 ml of hexane was added, and recrystallization was performed at −20 ° C. The precipitated solid was filtered and vacuum dried to obtain compound (I-1e-C3) (12.58 g).
実施例５５と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例５６（化合物（Ｉ−１ｅ−Ｂ６））〜実施例６４（化合物（Ｉ−１ｏ−ＢＥＢＥＢ））を製造した。 Examples 56 (Compound (I-1e-B6)) to Example 64 (Compound (I-1o-BEBEB)) using the same reaction as in Example 55 and, if necessary, a method according to a known method. ) Was manufactured.
（実施例６５）化合物（Ｉ−１ｆ−Ｃ３）の製造 (Example 65) Production of compound (I-1f-C3)
（化合物（Ｉ−１ｆ−Ｃ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ−９）（１１．２ｇ）、化合物（Ｅ−１１）（８．３２ｇ）、Ｎ，Ｎ−ジメチルアミノピリジン（ＤＭＡＰ）０．３０ｇ、ジクロロメタン８０ｍｌを加え、５〜１０℃で１０分間攪拌した。攪拌下、Ｎ，Ｎ−ジイソプロピルカルボジイミド（ＤＩＣ）８．０ｇを５〜１０℃を保ちながら滴下し、続いて２５度まで昇温し７時間攪拌した。この反応混合物に対して水２ｍｌを加えて攪拌した後、析出した固体を除去し、得られた溶液を濃縮した。得られた固体をヘキサン２０ｍｌに溶かし、ＮＨ２シリカ２０ｇを充填したカラム上に加え、さらにヘキサン１００ｍｌを流して通過させた。得られた溶液の溶媒をおおむね留去した後、ヘキサン／トルエンを用いて−２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ−１ｆ−Ｂ３）を１６．０ｇ得た。
ＧＣ−ＭＳ：ｍ／ｚ ３６６．２６ [Ｍ−１５＋]
実施例６５と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例６６（化合物（Ｉ−１ｆ−Ｂ６））〜実施例７４（化合物（Ｉ−１ｐ−ＢＥＢＥＢ））を製造した。
(Production of compound (I-1f-C3)) Compound (E-9) (11.2 g) and compound (E-11) (8.32 g) were placed in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. ), 0.30 g of N, N-dimethylaminopyridine (DMAP) and 80 ml of nitrogen were added, and the mixture was stirred at 5 to 10 ° C. for 10 minutes. Under stirring, 8.0 g of N, N-diisopropylcarbodiimide (DIC) was added dropwise while maintaining 5 to 10 ° C., and then the temperature was raised to 25 ° C. and the mixture was stirred for 7 hours. After adding 2 ml of water to the reaction mixture and stirring the mixture, the precipitated solid was removed and the obtained solution was concentrated. The obtained solid was dissolved in 20 ml of hexane, added onto a column packed with 20 g of NH 2 silica, and 100 ml of hexane was further passed through the column. After the solvent of the obtained solution was generally distilled off, recrystallization was carried out at −20 ° C. using hexane / toluene. The precipitated solid was filtered and dried to obtain 16.0 g of compound (I-1f-B3).
GC-MS: m / z 366.26 [M-15 + ]
Examples 66 (Compound (I-1f-B6)) to Example 74 (Compound (I-1p-BEBEB)) using the same reaction as in Example 65 and, if necessary, a method according to a known method. ) Was manufactured.
（実施例７５）化合物（Ｉ−１ｇ−Ｃ３）の製造 (Example 75) Production of compound (I-1g-C3)
（化合物（Ｅ−１４）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ−トルエンスルホン酸一水和物（５．０２ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３．８２ｇ）及び化合物（Ｅ−１３）（３．２８ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌ攪拌し、有機層を分けとり、水１００ｍｌで２回及び飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、化合物（Ｅ−１４）（６．３１ｇ）を得た。 (Production of compound (E-14)) p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 30 minutes to remove the generated water. After cooling the mixture to room temperature, TMP (3.82 g) and compound (E-13) (3.28 g) were added, and the mixture was heated under reflux for 4 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 150 ml of a 1.0 M aqueous sodium hydroxide solution was stirred, the organic layer was separated, and the mixture was washed twice with 100 ml of water and with 100 ml of saturated brine. The obtained organic layer was concentrated to obtain compound (E-14) (6.31 g).
（化合物（Ｅ−１５）の製造）窒素雰囲気下、撹拌装置、温度計、滴下漏斗を備えた反応容器に、化合物（Ｅ−１４）（６．３１ｇ）および乾燥トルエン５０ｍｌを加え、−７３℃に冷却した。この混合物中にＤＩＢＡＬ（１．５Ｍトルエン溶液）２７ｍｌを−６５℃以下を保ちながら滴下し、更にー７３℃で２時間攪拌した。この反応混合物に対し、−６５℃以下を保ちながら水／ＴＨＦ混合溶媒１０ｍｌを滴下した。この反応混合物を室温まで昇温させた後、１５％水酸化ナトリウム水溶液５ｍｌ、水１５ｍｌを加えて３時間攪拌した。得られた反応混合物をろ過して固体を除去し、得られた有機層から溶媒を留去し、化合物（Ｅ−１５）（５．３２ｇ）を得た。 (Production of Compound (E-15)) Under a nitrogen atmosphere, compound (E-14) (6.31 g) and 50 ml of dried toluene were added to a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, and the temperature was −73 ° C. Cooled to. 27 ml of DIBAL (1.5 M toluene solution) was added dropwise to this mixture while maintaining −65 ° C. or lower, and the mixture was further stirred at −73 ° C. for 2 hours. To this reaction mixture, 10 ml of a water / THF mixed solvent was added dropwise while maintaining −65 ° C. or lower. After raising the temperature of this reaction mixture to room temperature, 5 ml of a 15% aqueous sodium hydroxide solution and 15 ml of water were added, and the mixture was stirred for 3 hours. The obtained reaction mixture was filtered to remove the solid, and the solvent was distilled off from the obtained organic layer to obtain compound (E-15) (5.32 g).
（化合物（Ｅ−１７）の製造）窒素雰囲気下、撹拌装置、温度計、滴下漏斗を備えた反応容器に、化合物（Ｅ−１６）（１２．２２ｇ）及びＴＨＦ２５ｍｌを加え、ここへｔ−ブトキシカリウム（２．８５ｇ）を１０℃以下で加えて攪拌した。この反応混合物中に、ＴＨＦ１５ｍｌに溶解させた化合物（Ｅ−１５）（５．３２ｇ）を１０℃以下を保ちながら滴下し、５℃で２時間攪拌した。この反応混合物へ水０．５ｍｌ、ヘキサン４０ｍｌを加えて室温で１時間攪拌した。得られた反応混合物をろ過して固体を除去し、得られた有機層に５％次亜塩素酸ナトリウム水溶液５ｍｌを加えて室温で１時間攪拌した。この反応混合物の有機層を分けとり、水／メタノール混合溶媒２０ｍｌ、飽和食塩水２０ｍｌで洗浄し、濃縮した。得られた混合物をカラム（ＮＨ２シリカ、ヘキサン）を通過させ、得られた溶液を濃縮し、化合物（Ｅ−１７）（７．２２ｇ）を得た。 (Production of compound (E-17)) Under a nitrogen atmosphere, add compound (E-16) (12.22 g) and 25 ml of THF to a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, and add t-butoxy to this. Potassium (2.85 g) was added at 10 ° C. or lower and stirred. Compound (E-15) (5.32 g) dissolved in 15 ml of THF was added dropwise to this reaction mixture while maintaining a temperature of 10 ° C. or lower, and the mixture was stirred at 5 ° C. for 2 hours. 0.5 ml of water and 40 ml of hexane were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The obtained reaction mixture was filtered to remove solids, 5 ml of a 5% aqueous sodium hypochlorite solution was added to the obtained organic layer, and the mixture was stirred at room temperature for 1 hour. The organic layer of this reaction mixture was separated, washed with 20 ml of a mixed water / methanol solvent and 20 ml of saturated brine, and concentrated. The resulting mixture was passed through a column (NH 2 silica, hexane) and the resulting solution was concentrated to give compound (E-17) (7.22 g).
（化合物（Ｉ−１ｇ−Ｃ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ−１７）（３．６１ｇ）、ベンゼンスルフィン酸ナトリウム・２水和物（０．５ｇ）及びトルエン２０ｍｌを加えて攪拌した。この混合物中に１０％塩酸１．１ｇを加え、３時間加熱還流した。この反応混合物を室温まで冷却し、水５ｍｌを加えた。有機層を分けとり、10%炭酸水素ナトリウム水溶液５ｍｌ、10%食塩水５ｍｌで洗浄後、硫酸ナトリウムで乾燥し、有機層を濃縮した。得られた混合物をカラム（ＮＨ２シリカ、ヘキサン）を通過させた。得られた溶液を濃縮し、ヘキサン１０ｍｌを 加えて−２０℃で再結晶を行い、化合物（Ｉ−１ｇ−Ｃ３）（２．５０ｇ）を得た。
ＧＣ−ＭＳ：ｍ／ｚ ３４８．２８ [Ｍ−１５＋]
実施例７５と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例７６（化合物（Ｉ−１ｇ−Ｂ６））〜実施例８２（化合物（Ｉ−１ｑ−ＢＥＢＥＢ））を製造した。
(Production of compound (I-1g-C3)) Compound (E-17) (3.61g) and sodium benzenesulfinate dihydrate (3.61g) in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. 0.5 g) and 20 ml of toluene were added and stirred. 1.1 g of 10% hydrochloric acid was added to this mixture, and the mixture was heated under reflux for 3 hours. The reaction mixture was cooled to room temperature and 5 ml of water was added. The organic layer was separated, washed with 5 ml of a 10% aqueous sodium hydrogen carbonate solution and 5 ml of a 10% saline solution, dried over sodium sulfate, and the organic layer was concentrated. The resulting mixture was passed through a column (NH 2 silica, hexane). The obtained solution was concentrated, 10 ml of hexane was added, and recrystallization was performed at −20 ° C. to obtain compound (I-1 g-C3) (2.50 g).
GC-MS: m / z 348.28 [M-15 + ]
Examples 76 (Compound (I-1g-B6)) to Example 82 (Compound (I-1q-BEBEB)) using the same reaction as in Example 75 and, if necessary, a method according to a known method. ) Was manufactured.
（実施例８３）化合物（Ｉ−１ｈ−Ｃ３）の製造 (Example 83) Production of compound (I-1h-C3)
（化合物（Ｉ−１ｈ−Ｃ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた耐圧反応容器に、化合物（Ｅ−１７）（３．６１ｇ）、５％パラジウム炭素（５０％含水品）（０．１８ｇ）及びＴＨＦ１５ｍｌを加え、容器内に水素（０．５ＭＰａ）を加圧充填して室温で５時間攪拌した。この反応混合物をろ過し、さらに除去された固体をＴＨＦ１００ｍｌで洗浄した。得られた溶液を濃縮し、カラム（ＮＨ２シリカ、ヘキサン）を通過させた後に濃縮し、ヘキサン１０ｍｌを 加えて−２０℃で再結晶を行い、化合物（Ｉ−１ｈ−Ｃ３）（３．４４ｇ）を得た。
ＧＣ−ＭＳ：ｍ／ｚ ３５０．３０ [Ｍ−１５＋]
実施例８３と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例８４（化合物（Ｉ−１ｈ−Ｂ６））〜実施例９０（化合物（Ｉ−１ｒ−ＢＥＢＥＢ））を製造した。
(Production of compound (I-1h-C3)) Compound (E-17) (3.61 g), 5% palladium carbon (50% hydrous product) in a pressure resistant reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. ) (0.18 g) and 15 ml of THF were added, hydrogen (0.5 MPa) was pressure-filled in the container, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was filtered and the removed solid was washed with 100 ml of THF. The obtained solution was concentrated, passed through a column (NH 2 silica, hexane), then concentrated, 10 ml of hexane was added, and recrystallization was performed at −20 ° C., compound (I-1h-C3) (3.44 g). ) Was obtained.
GC-MS: m / z 350.30 [M-15 + ]
Examples 84 (Compound (I-1h-B6)) to Example 90 (Compound (I-1r-BEBEB)) using the same reaction as in Example 83 and, if necessary, a method according to a known method. ) Was manufactured.
上記、実施例１〜９０で得られた化合物のいずれかを含有する液晶組成物について、測定した特性は以下の通りである。 The measured characteristics of the liquid crystal composition containing any of the compounds obtained in Examples 1 to 90 are as follows.
ＶＨＲ：周波数６０Ｈｚ，印加電圧１Ｖの条件下で３３３Ｋにおける電圧保持率（％）を３段階評価した。 VHR: The voltage holding ratio (%) at 333K was evaluated on a three-point scale under the conditions of a frequency of 60 Hz and an applied voltage of 1 V.
Ａ：９８〜１００％
Ｂ：９５〜９８％
Ｃ：９５％以下
耐光ＶＨＲ：液晶組成物に対して、厚さ０．５ｍｍのガラスを介して超高圧水銀ランプを用いて紫外線を１８０Ｊ／ｍ２照射する。紫外線照射後の液晶の電圧保持率を上述のＶＨＲ測定と同様の方法で測定する。但し、照射強度は３６６ｎｍで０．１Ｗ／ｍ２とした。評価は以下の３段階で行った。
A: 98-100%
B: 95-98%
C: 95% or less Light-resistant VHR: The liquid crystal composition is irradiated with ultraviolet rays at 180 J / m 2 using an ultra-high pressure mercury lamp through a glass having a thickness of 0.5 mm. The voltage retention of the liquid crystal after irradiation with ultraviolet rays is measured by the same method as the above-mentioned VHR measurement. However, the irradiation intensity was 0.1 W / m 2 at 366 nm. The evaluation was performed in the following three stages.
Ａ：９０〜１００％
Ｂ：７５〜９０％
Ｃ：７５％以下
相溶性：液晶組成物に、実施例１〜９０で得られた化合物のいずれかを５００ｐｐｍ添加した際の溶解の様子を目視で３段階評価した。
A: 90-100%
B: 75-90%
C: 75% or less Compatibility: The state of dissolution when 500 ppm of any of the compounds obtained in Examples 1 to 90 was added to the liquid crystal composition was visually evaluated in three stages.
Ａ：すべて溶解する
Ｂ：わずかに溶解せず分離している
Ｃ：一部溶解せず分離している
保存安定性：液晶組成物を−２０℃で１週間保存し、析出物の有無を目視で３段階評価した。
A: All dissolved B: Slightly dissolved and separated C: Partially dissolved and separated Storage stability: The liquid crystal composition was stored at -20 ° C for 1 week, and the presence or absence of precipitates was visually observed. Was evaluated on a three-point scale.
Ａ：析出物なし
Ｂ：わずかに白濁が見られる
Ｃ：析出物が明らかに確認できる
（実施例９１）液晶組成物の調製−１
以下の組成からなるホスト液晶組成物（Ｈ）を調製した。
A: No precipitate B: Slightly cloudy C: Precipitate can be clearly confirmed (Example 91) Preparation of liquid crystal composition-1
A host liquid crystal composition (H) having the following composition was prepared.
この母体液晶（Ｈ）に対し、実施例１で得られた化合物（Ｉ−１ａ−５）を５００ｐｐｍ添加した。
実施例中の組成例を、測定した特性は以下の通りである。
To this parent liquid crystal (H), 500 ppm of the compound (I-1a-5) obtained in Example 1 was added.
The measured characteristics of the composition examples in the examples are as follows.
ＶＨＲ：Ａ
耐光ＶＨＲ：Ａ
相溶性：Ａ
保存安定性：Ａ
以下、実施例９１と同様にして、実施例２〜実施例９０で製造した化合物を用いて、実施例９２〜実施例１８０の測定を行った結果を以下に示す。
VHR: A
Lightproof VHR: A
Compatibility: A
Storage stability: A
Hereinafter, the results of measurement of Examples 92 to 180 using the compounds produced in Examples 2 to 90 in the same manner as in Example 91 are shown below.
（実施例１８１）化合物（Ｉ−１ｕ−Ｂ３）の製造 (Example 181) Production of compound (I-1u-B3)
（化合物（Ｉ−１ｕ−Ｂ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ−２）（１１．４ｇ）、化合物（Ｅ−１８）（８．２ｇ）、Ｎ，Ｎ−ジメチルアミノピリジン（ＤＭＡＰ）０．３０ｇ、ジクロロメタン８０ｍｌを加え、５〜１０℃で１０分間攪拌した。攪拌下、Ｎ，Ｎ−ジイソプロピルカルボジイミド（ＤＩＣ）７．９ｇを５〜１０℃を保ちながら滴下し、続いて２５度まで昇温し７時間攪拌した。この反応混合物に対して水２ｍｌを加えて攪拌した後、析出した固体を除去し、得られた溶液を濃縮した。得られた固体をヘキサン２０ｍｌに溶かし、ＮＨ２シリカ２０ｇを充填したカラム上に加え、さらにヘキサン１００ｍｌを流して通過させた。得られた溶液の溶媒をおおむね留去した後、ヘキサン／トルエンを用いて−２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ−１ｕ−Ｂ３）を１３．６ｇ得た。
ＧＣ−ＭＳ：ｍ／ｚ ３８９．２６ [Ｍ−１５＋]
実施例１８１と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例１８２（化合物（Ｉ−１ｕ−Ｂ６））〜実施例１８７（化合物（Ｉ−１ｕ−Ｔ３））を製造した。
(Production of compound (I-1u-B3)) Compound (E-2) (11.4 g) and compound (E-18) (8.2 g) were placed in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. ), 0.30 g of N, N-dimethylaminopyridine (DMAP) and 80 ml of nitrogen were added, and the mixture was stirred at 5 to 10 ° C. for 10 minutes. Under stirring, 7.9 g of N, N-diisopropylcarbodiimide (DIC) was added dropwise while maintaining 5 to 10 ° C., and then the temperature was raised to 25 ° C. and the mixture was stirred for 7 hours. After adding 2 ml of water to the reaction mixture and stirring the mixture, the precipitated solid was removed and the obtained solution was concentrated. The obtained solid was dissolved in 20 ml of hexane, added onto a column packed with 20 g of NH 2 silica, and 100 ml of hexane was further passed through the column. After the solvent of the obtained solution was generally distilled off, recrystallization was carried out at −20 ° C. using hexane / toluene. The precipitated solid was filtered and dried to obtain 13.6 g of compound (I-1u-B3).
GC-MS: m / z 389.26 [M-15 + ]
Examples 182 (Compound (I-1u-B6)) to Example 187 (Compound (I-1u-T3)) using the same reaction as in Example 181 and, if necessary, a method according to a known method. ) Was manufactured.
（実施例１８８）化合物（Ｉ−１ｖ−８）の製造 (Example 188) Production of compound (I-1v-8)
（化合物（Ｉ−１ｖ−８）の製造）窒素雰囲気下、撹拌装置、滴下ろうと（モレキュラーシーブ４Ａペレット３．５ｇを中に詰めてある）、冷却管、オイルバス、温度計を備えた反応容器に、化合物（Ｅ−２）（２．２２ｇ）、化合物（Ｅ−１９）（１．０ｇ）、酸化ジブチルすず（０．１１ｇ）、キシレン１５ｍｌを加え、５時間加熱還流しながら攪拌した。この反応混合物を室温まで冷却し、ヘキサン１５ｍｌを加えた。この反応混合物を、ＮＨ２シリカ６ｇを充填したカラム上に加え、さらにヘキサン／トルエン（体積比１：１、１００ｍｌ）を流して通過させた。得られた溶液の溶媒を留去した後、ヘキサン／酢酸エチルを用いて−２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ−１ｖ−８）を１．６８ｇ得た。
ＧＣ−ＭＳ：ｍ／ｚ ６３７．４７ [Ｍ−１５＋]
相転移：Ｃｒｙ ７６ Ｉｓｏ
（実施例１８９）化合物（Ｉ−１ｖ−Ｂ）の製造
(Production of compound (I-1v-8)) A reaction vessel equipped with a stirrer, a dropping funnel (3.5 g of molecular sieve 4A pellets packed therein), a cooling tube, an oil bath, and a thermometer under a nitrogen atmosphere. Compound (E-2) (2.22 g), compound (E-19) (1.0 g), dibutyl tin oxide (0.11 g), and 15 ml of xylene were added thereto, and the mixture was stirred with heating under reflux for 5 hours. The reaction mixture was cooled to room temperature and 15 ml of hexane was added. This reaction mixture was added onto a column packed with 6 g of NH 2 silica, and hexane / toluene (volume ratio 1: 1, 100 ml) was further passed through the column. After distilling off the solvent of the obtained solution, recrystallization was carried out at −20 ° C. using hexane / ethyl acetate. The precipitated solid was filtered and dried to obtain 1.68 g of compound (I-1v-8).
GC-MS: m / z 637.47 [M-15 + ]
Phase transition: Cry 76 Iso
(Example 189) Production of compound (I-1v-B)
（化合物（Ｉ−１ｖ−Ｂ）の製造）窒素雰囲気下、撹拌装置、滴下ろうと（モレキュラーシーブ４Ａペレット１０ｇを中に詰めてある）、冷却管、オイルバス、温度計を備えた反応容器に、化合物（Ｅ−２）（８．２９ｇ）、化合物（Ｅ−２０）（３．１５ｇ）、酸化ジブチルすず（０．４０ｇ）、キシレン３５ｍｌを加え、５時間加熱還流しながら攪拌した。この反応混合物を室温まで冷却し、ヘキサン４０ｍｌを加えた。この反応混合物を、ＮＨ２シリカ６ｇを充填したカラム上に加え、さらにヘキサン／トルエン（体積比１：１、２００ｍｌ）を流して通過させた。得られた溶液の溶媒を留去した後、ＴＨＦを用いて−２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ−１ｖ−Ｂ）を６．３ｇ得た。
ＧＣ−ＭＳ：ｍ／ｚ ６０１．３７ [Ｍ−１５＋]
相転移：Ｃｒｙ １７０．４ Ｉｓｏ
（実施例１９０）化合物（Ｉ−１ｖ−ＭＢ）の製造
(Production of compound (I-1v-B)) In a reaction vessel equipped with a stirrer, a dropping funnel (10 g of molecular sieve 4A pellets are packed therein), a cooling tube, an oil bath, and a thermometer under a nitrogen atmosphere. Compound (E-2) (8.29 g), compound (E-20) (3.15 g), dibutyl tin oxide (0.40 g), and 35 ml of xylene were added, and the mixture was stirred with heating under reflux for 5 hours. The reaction mixture was cooled to room temperature and 40 ml of hexane was added. This reaction mixture was added onto a column packed with 6 g of NH 2 silica, and hexane / toluene (volume ratio 1: 1, 200 ml) was further passed through the column. After distilling off the solvent of the obtained solution, recrystallization was carried out at −20 ° C. using THF. The precipitated solid was filtered and dried to obtain 6.3 g of compound (I-1v-B).
GC-MS: m / z 601.37 [M-15 + ]
Phase transition: Cry 170.4 Iso
(Example 190) Production of compound (I-1v-MB)
（化合物（Ｅ−２２）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ−トルエンスルホン酸一水和物（６４．４ｇ）及びトルエン８００ｍｌを加え、２０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（５１．０ｇ）、ＤＭＦ３０ｍｌ及び化合物（Ｅ−２１）（３８．８ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液４００ｍｌを加えて攪拌し、有機層を分けとり、水１００ｍｌ、飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、得られた固体を再結晶（トルエン）することで、化合物（Ｅ−２２）（６０．８ｇ）を得た。 (Production of compound (E-22)) p-toluenesulfonic acid monohydrate (64.4 g) and 800 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 20 minutes to remove the generated water. After cooling the mixture to room temperature, TMP (51.0 g), 30 ml of DMF and compound (E-21) (38.8 g) were added, and the mixture was heated under reflux for 4 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 400 ml of a 1.0 M aqueous sodium hydroxide solution was added and stirred, the organic layer was separated, and the mixture was washed with 100 ml of water and 100 ml of saturated brine. The obtained organic layer was concentrated, and the obtained solid was recrystallized (toluene) to obtain compound (E-22) (60.8 g).
（化合物（Ｉ−１ｖ−ＭＢ）の製造）窒素雰囲気下、撹拌装置、滴下ろうと（モレキュラーシーブ４Ａペレット４０ｇを中に詰めてある）、冷却管、オイルバス、温度計を備えた反応容器に、化合物（Ｅ−２２）（３４．３ｇ）、化合物（Ｅ−２０）（１２．２４ｇ）、酸化ジブチルすず（１．５３ｇ）、キシレン１８０ｍｌを加え、５時間加熱還流しながら攪拌した。この反応混合物を室温まで冷却し、トルエン１５０ｍｌを加えた。この反応混合物を、ＮＨ２シリカ８０ｇを充填したカラム上に加え、さらにトルエン１５０ｍｌを流して通過させた。得られた溶液の溶媒を留去した後、ヘキサンとＴＨＦの混合溶媒（１：１、８０ｍｌ）を用いて−２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ−１ｖ−ＭＢ）を２９．５ｇ得た。
ＧＣ−ＭＳ：ｍ／ｚ ６２９．４０ [Ｍ−１５＋]
相転移：Ｃｒｙ １４８ Ｉｓｏ
1H-NMR (400MHz, CDCl3)δ: 0.96(s,6H), 1.20(s,12H), 1.23(S, 12H), 1.63(s,4H), 1.82(s,4H), 3.75(s,8H), 4.47(s,4H), 8.11(s,4H)
実施例１９０と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例１９１（化合物（Ｉ−１ｖ−ＥｔＢ））〜実施例１９７（化合物（Ｉ−１ｖ−ＥｔＢＦ））を製造した。
(Production of compound (I-1v-MB)) In a reaction vessel equipped with a stirrer, a dropping funnel (40 g of molecular sieve 4A pellets packed therein), a cooling tube, an oil bath, and a thermometer under a nitrogen atmosphere. Compound (E-22) (34.3 g), compound (E-20) (12.24 g), dibutyl tin oxide (1.53 g), and 180 ml of xylene were added, and the mixture was stirred with heating under reflux for 5 hours. The reaction mixture was cooled to room temperature and 150 ml of toluene was added. This reaction mixture was added onto a column packed with 80 g of NH 2 silica, and 150 ml of toluene was further passed through. After distilling off the solvent of the obtained solution, recrystallization was carried out at −20 ° C. using a mixed solvent of hexane and THF (1: 1, 80 ml). The precipitated solid was filtered and dried to obtain 29.5 g of compound (I-1v-MB).
GC-MS: m / z 629.40 [M-15 + ]
Phase transition: Cry 148 Iso
1 1 H-NMR (400MHz, CDCl 3 ) δ: 0.96 (s, 6H), 1.20 (s, 12H), 1.23 (S, 12H), 1.63 (s, 4H), 1.82 (s, 4H), 3.75 (s , 8H), 4.47 (s, 4H), 8.11 (s, 4H)
Examples 191 (Compound (I-1v-EtB)) to Example 197 (Compound (I-1v-EtBF)) using the same reaction as in Example 190 and, if necessary, a method according to a known method. ) Was manufactured.
上記実施例１８１〜１９７で製造した化合物を用いて、実施例９１と同様にして実施例１９８〜２１４の液晶組成物を調製し、測定を行った結果を以下に示す。 Using the compounds produced in Examples 181 to 197, the liquid crystal compositions of Examples 198 to 214 were prepared in the same manner as in Example 91, and the results of measurement are shown below.
（比較例１）
比較例として、母体液晶（Ｈ）に対し、特にさらなる化合物を添加することなく特性を測定した結果は以下の通りである。
(Comparative Example 1)
As a comparative example, the results of measuring the characteristics of the parent liquid crystal (H) without adding any further compound are as follows.
ＶＨＲ：Ａ
耐光ＶＨＲ：Ｃ
保存安定性：Ａ
この結果から、本願発明の化合物は、液晶組成物の保存安定性を損なうことなく、液晶組成物の光による劣化を防止する効果があることが分かる。
（比較例２）
母体液晶（Ｈ）に対し、化合物（Ｒ−１）を５００ｐｐｍ添加し、測定を測定した結果は以下の通りである。
VHR: A
Lightproof VHR: C
Storage stability: A
From this result, it can be seen that the compound of the present invention has an effect of preventing deterioration of the liquid crystal composition due to light without impairing the storage stability of the liquid crystal composition.
(Comparative Example 2)
The results of the measurement obtained by adding 500 ppm of the compound (R-1) to the mother liquid crystal (H) are as follows.
ＶＨＲ：Ａ
耐光ＶＨＲ：Ａ
相溶性：Ｂ
保存安定性：Ｃ
（比較例３，４）
以下、比較例２と同様にして、比較例３，４の測定を行った結果を以下に示す。
VHR: A
Lightproof VHR: A
Compatibility: B
Storage stability: C
(Comparative Examples 3 and 4)
Hereinafter, the results of the measurements of Comparative Examples 3 and 4 in the same manner as in Comparative Example 2 are shown below.
この結果から、本願発明の化合物は、液晶組成物の保存安定性を損なうことなく、液晶組成物との相溶性が高く、液晶組成物の光による劣化を防止する効果があることが分かる。 From this result, it can be seen that the compound of the present invention has high compatibility with the liquid crystal composition without impairing the storage stability of the liquid crystal composition, and has an effect of preventing deterioration of the liquid crystal composition by light.
Claims (6)
Ｒ ａ７１ は炭素数１〜４のアルキル基を表し、
Ｓｐ ａ１１ 及びＳｐ ａ２１ はそれぞれ独立に単結合又は炭素原子数１から１２のアルキレン基を表すが、アルキレン基中に存在する１個の−ＣＨ ２ −又は隣接していない２個以上の−ＣＨ ２ −は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−により置き換えられても良く、
Ａ ａ１１ 及びＡ ａ２１ はそれぞれ独立に
（ａ） １，４−シクロヘキシレン基（この基中に存在する１個の−ＣＨ ２ −又は隣接していない２個以上の−ＣＨ ２ −は−Ｏ−に置き換えられてもよい。）
（ｂ） １，４−フェニレン基又は１，３−フェニレン基（この基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられてもよい。）及び
（ｃ） ナフタレン−２，６−ジイル基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基又はデカヒドロナフタレン−２，６−ジイル基（ナフタレン−２，６−ジイル基又は１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられても良い。）
からなる群より選ばれる基を表し、上記の基（ａ）、基（ｂ）及び基（ｃ）はそれぞれ独立してシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていても良く、分子内にＳｐ ａ１ 、Ｓｐ ａ２ 、Ａ ａ１ 及びＡ ａ２ が複数存在する場合にはそれらは同一であっても異なっていても良く、
ｍ１は１を表し、
ｐ１及びｑ１はそれぞれ独立に０、１又は２を表すが、ここでｐ１＋ｑ１は１以上を表し、
Ｒ ａ９１ は水素原子または炭素原子数１から１２のアルキル基を表すが、アルキル基中に存在する１個の−ＣＨ ２ −又は隣接していない２個以上の−ＣＨ ２ −は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−により置き換えられても良く、あるいはＲ ａ９ は一般式（Ｉ−ｄ１）
を表すが、ここで存在するＳｐ ａ１１ 、Ｓｐ ａ２１ 及びＳｐ ａ３１ 中に少なくとも１つの−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−を含む。）
で表される化合物を一種又は二種以上含有する液晶組成物。 General formula (I-1)
R a71 represents an alkyl group having 1 to 4 carbon atoms.
Sp a11 and Sp a21 Although each independently represent a single bond or an alkylene group having a carbon number of 1 to 12, one -CH 2 present in the alkylene group - or nonadjacent two or more -CH 2 − May be replaced by −O−, −S−, −COO−, −OCO−, −CO−, −CH = CH− or −C≡C−.
A a11 and A a21 are independent of each other
(A) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - may be replaced by -O-.)
(B) A 1,4-phenylene group or a 1,3-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =. Good.) And
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One -CH = existing in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
Represents a group selected from the group consisting of, and the above groups (a), group (b) and group (c) are independently substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group or a methoxy group, respectively. If there are a plurality of Sp a1 , Sp a2 , A a1 and A a 2 in the molecule, they may be the same or different.
m1 represents 1
p1 and q1 independently represent 0, 1 or 2, respectively, where p1 + q1 represents 1 or more.
R a91 each represents a hydrogen atom or an alkyl group having a carbon atom number of 1 to 12, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O-, It may be replaced by −S−, −COO−, −OCO−, −CO−, −CH = CH− or −C≡C−, or R a9 is the general formula (Id1).
However, at least one -COO-, -OCO- or -CO- is contained in Sp a11 , Sp a21 and Spa 31 present here . )
A liquid crystal composition containing one or more compounds represented by .
で表される、請求項１〜３のいずれか一項に記載の液晶組成物。The liquid crystal composition according to any one of claims 1 to 3, which is represented by.
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| JP2020090441A (en) * | 2018-12-03 | 2020-06-11 | Dic株式会社 | Stabilizer compound, liquid crystal composition, and display element |
| CN112824491B (en) * | 2019-11-21 | 2022-12-30 | 江苏和成显示科技有限公司 | Liquid crystal composition and application thereof |
| JP7363414B2 (en) * | 2019-11-27 | 2023-10-18 | Dic株式会社 | Stabilizer compounds, liquid crystal compositions and display elements |
| JP7380136B2 (en) | 2019-11-27 | 2023-11-15 | Dic株式会社 | Liquid crystal composition and liquid crystal display device using the same |
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| GB1478261A (en) * | 1975-05-28 | 1977-06-29 | Ciba Geigy Ag | Derivatives of 4-oxopiperidines |
| JPS5266551A (en) * | 1975-12-01 | 1977-06-02 | Adeka Argus Chem Co Ltd | Stabilizer for plastics |
| JPS52100543A (en) * | 1976-02-18 | 1977-08-23 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin compositions |
| JPS52140555A (en) * | 1976-05-19 | 1977-11-24 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin composition |
| JPS5611932A (en) * | 1979-07-12 | 1981-02-05 | Adeka Argus Chem Co Ltd | Stabilized polymer composition |
| JPS56138189A (en) * | 1980-03-31 | 1981-10-28 | Adeka Argus Chem Co Ltd | 4-piperidone ketal derivative |
| JPS5710646A (en) * | 1980-06-23 | 1982-01-20 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin composition |
| JPS6067587A (en) * | 1983-09-22 | 1985-04-17 | Adeka Argus Chem Co Ltd | Liquid crystal composition |
| DE4219471A1 (en) * | 1992-06-13 | 1993-12-16 | Huels Chemische Werke Ag | N-oxyl derivatives of 2,2,6,6-tetramethylpiperidine and their preparation |
| WO1999052871A1 (en) * | 1998-04-10 | 1999-10-21 | Chisso Corporation | Liquid crystalline compound having piperidine ring, liquid crystal composition and liquid crystal display element |
| TWI274053B (en) * | 2000-12-14 | 2007-02-21 | Ciba Sc Holding Ag | N-alkoxy-4,4-dioxy-polyalkyl-piperidine compounds, with glycidyl or alkylcarbonyl groups as functional initiators for controlled radical polymerization |
| DE10304055A1 (en) * | 2003-02-01 | 2004-08-12 | Degussa Ag | Process for the production of ketals |
| CN102361896B (en) * | 2009-03-23 | 2015-10-07 | 巴斯夫欧洲公司 | Photo-corrosion-resisting agent composition |
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| JP6255633B2 (en) | 2018-01-10 |
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