JP2001302579A - Phenylacetylene compound having cyclopropane ring or alkenyl group at molecular end, liquid crystal composition and liquid crystal device - Google Patents
Phenylacetylene compound having cyclopropane ring or alkenyl group at molecular end, liquid crystal composition and liquid crystal deviceInfo
- Publication number
- JP2001302579A JP2001302579A JP2000124957A JP2000124957A JP2001302579A JP 2001302579 A JP2001302579 A JP 2001302579A JP 2000124957 A JP2000124957 A JP 2000124957A JP 2000124957 A JP2000124957 A JP 2000124957A JP 2001302579 A JP2001302579 A JP 2001302579A
- Authority
- JP
- Japan
- Prior art keywords
- group
- liquid crystal
- substituted
- fluorine atom
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Phenylacetylene compound Chemical class 0.000 title claims abstract description 142
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 125000003342 alkenyl group Chemical group 0.000 title description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 title description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 36
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 44
- 125000001153 fluoro group Chemical group F* 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 75
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 46
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 238000010898 silica gel chromatography Methods 0.000 description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GRJHONXDTNBDTC-UHFFFAOYSA-N phenyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OC1=CC=CC=C1 GRJHONXDTNBDTC-UHFFFAOYSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- RBOGJRXPKONDGC-UHFFFAOYSA-N (2-methylphenyl) trifluoromethanesulfonate Chemical compound CC1=CC=CC=C1OS(=O)(=O)C(F)(F)F RBOGJRXPKONDGC-UHFFFAOYSA-N 0.000 description 2
- MKSWQHOPSDCVMS-UHFFFAOYSA-N 1-ethynyl-4-pentoxybenzene Chemical group CCCCCOC1=CC=C(C#C)C=C1 MKSWQHOPSDCVMS-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 description 2
- 125000005925 3-methylpentyloxy group Chemical group 0.000 description 2
- RZAMIGJLILLQGG-UHFFFAOYSA-N 4-(2-pentylcyclopropyl)phenol Chemical compound CCCCCC1CC1C1=CC=C(O)C=C1 RZAMIGJLILLQGG-UHFFFAOYSA-N 0.000 description 2
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 2
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- GVWIVEYSCFMROS-ZRDIBKRKSA-N CCCCC/C=C/C1=CC=C(C=C1)C#CC2=CC(=C(C=C2)C#CC3=CC=C(C=C3)OCCCCC)C Chemical compound CCCCC/C=C/C1=CC=C(C=C1)C#CC2=CC(=C(C=C2)C#CC3=CC=C(C=C3)OCCCCC)C GVWIVEYSCFMROS-ZRDIBKRKSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000006226 butoxyethyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000006612 decyloxy group Chemical group 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006611 nonyloxy group Chemical group 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000006233 propoxy propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RWWGGRCLMVYXPM-UHFFFAOYSA-N 1-ethynyl-4-(trifluoromethoxy)benzene Chemical group FC(F)(F)OC1=CC=C(C#C)C=C1 RWWGGRCLMVYXPM-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- MXDQGXMBJCGRCB-UHFFFAOYSA-N 2-(4-bromophenoxy)oxane Chemical compound C1=CC(Br)=CC=C1OC1OCCCC1 MXDQGXMBJCGRCB-UHFFFAOYSA-N 0.000 description 1
- RFEVWSXNZABXAP-UHFFFAOYSA-N 2-(4-iodo-2-methylphenoxy)oxane Chemical compound CC1=CC(I)=CC=C1OC1OCCCC1 RFEVWSXNZABXAP-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- VGJBWQRQIZVZDU-UHFFFAOYSA-N 2-methyl-4-[2-[4-(2-pentylcyclopropyl)phenyl]ethynyl]-1-[2-[4-(trifluoromethoxy)phenyl]ethynyl]benzene Chemical compound CCCCCC1CC1C1=CC=C(C#CC=2C=C(C)C(C#CC=3C=CC(OC(F)(F)F)=CC=3)=CC=2)C=C1 VGJBWQRQIZVZDU-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- DRAVTYHHOIJUOB-VOTSOKGWSA-N 4-[(e)-hept-1-enyl]phenol Chemical compound CCCCC\C=C\C1=CC=C(O)C=C1 DRAVTYHHOIJUOB-VOTSOKGWSA-N 0.000 description 1
- ACENPCSJKXEOEZ-UHFFFAOYSA-N 4-[2-[2-methyl-4-[2-[4-(2-pentylcyclopropyl)phenyl]ethynyl]phenyl]ethynyl]benzonitrile Chemical compound CCCCCC1CC1C1=CC=C(C#CC=2C=C(C)C(C#CC=3C=CC(=CC=3)C#N)=CC=2)C=C1 ACENPCSJKXEOEZ-UHFFFAOYSA-N 0.000 description 1
- GPSBBYNMQUHXRC-BQYQJAHWSA-N 4-[2-[4-[2-[4-[(e)-hept-1-enyl]phenyl]ethynyl]-2-methylphenyl]ethynyl]benzonitrile Chemical compound C1=CC(/C=C/CCCCC)=CC=C1C#CC(C=C1C)=CC=C1C#CC1=CC=C(C#N)C=C1 GPSBBYNMQUHXRC-BQYQJAHWSA-N 0.000 description 1
- LAGNMUUUMQJXBF-UHFFFAOYSA-N 4-ethynylbenzonitrile Chemical compound C#CC1=CC=C(C#N)C=C1 LAGNMUUUMQJXBF-UHFFFAOYSA-N 0.000 description 1
- WSBDSSKIWDFOBQ-UHFFFAOYSA-N 4-iodo-2-methylphenol Chemical compound CC1=CC(I)=CC=C1O WSBDSSKIWDFOBQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CVIYVSFUFGVTCV-BQYQJAHWSA-N CCCCC/C=C/C1=CC=C(C=C1)C#CC2=CC(=C(C=C2)C#CC3=CC=C(C=C3)OC(F)(F)F)C Chemical compound CCCCC/C=C/C1=CC=C(C=C1)C#CC2=CC(=C(C=C2)C#CC3=CC=C(C=C3)OC(F)(F)F)C CVIYVSFUFGVTCV-BQYQJAHWSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- LDTJUGVTOZBIBN-VOTSOKGWSA-N [(e)-hept-1-enyl]boronic acid Chemical compound CCCCC\C=C\B(O)O LDTJUGVTOZBIBN-VOTSOKGWSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical class C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- GKPOMITUDGXOSB-UHFFFAOYSA-N but-3-yn-2-ol Chemical compound CC(O)C#C GKPOMITUDGXOSB-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- HPUOAJPGWQQRNT-UHFFFAOYSA-N pentoxybenzene Chemical compound CCCCCOC1=CC=CC=C1 HPUOAJPGWQQRNT-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- GQHWSLKNULCZGI-UHFFFAOYSA-N trifluoromethoxybenzene Chemical class FC(F)(F)OC1=CC=CC=C1 GQHWSLKNULCZGI-UHFFFAOYSA-N 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液晶表示素子の構
成材料あるいは液晶組成物の配合成分として有用であ
り、骨格にシクロプロパン基又はアルケニル基を有する
新規なフェニルアセチレン化合物、それを含む液晶組成
物及びそれを用いた液晶素子に関する。The present invention is useful as a constituent material of a liquid crystal display device or a compounding component of a liquid crystal composition, and a novel phenylacetylene compound having a cyclopropane group or an alkenyl group in a skeleton, and a liquid crystal composition containing the same. The present invention relates to an object and a liquid crystal element using the same.
【０００２】[0002]
【従来の技術】近年、液晶表示素子の高性能化は、情報
化社会の進展に伴い不可欠となっている。液晶組成物と
しては、より高速化、あるいは高性能化等の物性を達成
するために、屈折率異方性の大きい材料の配合が必要と
されている。屈折率異方性が比較的大きい液晶としてト
ラン化合物が知られている[Mol.Cryst.Liq.Cryst.,第23
巻第233頁(1973年)]が、屈折率異方性は約０．２と満足
できるほどの大きさではなかった。また、下記式で表さ
れる化合物(２)が開発されている(特開平２−８３３４
０号公報)。2. Description of the Related Art In recent years, higher performance of liquid crystal display elements has become indispensable with the progress of the information society. As the liquid crystal composition, a material having a large refractive index anisotropy is required to achieve physical properties such as higher speed and higher performance. Tolan compounds are known as liquid crystals having relatively large refractive index anisotropy [Mol. Cryst. Liq.
Vol. 233 (1973)], the refractive index anisotropy was about 0.2, which was not a satisfactory size. Further, a compound (2) represented by the following formula has been developed (JP-A-2-8334).
No. 0).
【０００３】[0003]
【化３】 (式中、Ａｌｋｙｌは、アルキル基を表す。) この化合物(２)は屈折率異方性が０．３以上の値を有す
るが、他液晶との相溶性が悪く、実用的ではない。そこ
で、他液晶との相溶性を向上させることを目的として下
記式で表される化合物(３)が開発されている(特開平９
−２１６８４１号公報)。Embedded image (In the formula, Alkyl represents an alkyl group.) This compound (2) has a refractive index anisotropy of 0.3 or more, but is not practical because of poor compatibility with other liquid crystals. Therefore, a compound (3) represented by the following formula has been developed for the purpose of improving the compatibility with other liquid crystals (Japanese Patent Application Laid-Open No.
-216841).
【０００４】[0004]
【化４】 (式中、Ｒ5はアルキル基を示し、ＹはＲ5、フッ素原
子、塩素原子、臭素原子、ヨウ素原子又はシアノ基を示
し、Ｈ1〜Ｈ12は水素原子、フッ素原子又は塩素原子を
示す(但し、Ｈ1〜Ｈ12の少なくとも１つはフッ素原子又
は塩素原子である)。) この化合物(３)は、他液晶との相溶性の点で上記化合物
(２)より改善されているが、屈折率異方性の点で必ずし
も十分なものではなかった。Embedded image (Wherein, R 5 represents an alkyl group, Y represents R 5 , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a cyano group, and H 1 to H 12 represent a hydrogen atom, a fluorine atom or a chlorine atom. (However, at least one of H 1 to H 12 is a fluorine atom or a chlorine atom.) This compound (3) is the above compound in view of compatibility with other liquid crystals.
Although improved from (2), it was not always sufficient in terms of refractive index anisotropy.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、大き
い屈折率異方性を有し、他の液晶と混合し易く、かつ安
定性に優れた新規なフェニルアセチレン化合物、それを
用いた液晶組成物及びこれを用いた、光シャッターや表
示素子等に使用できる液晶素子を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel phenylacetylene compound which has a large refractive index anisotropy, is easily mixed with other liquid crystals, and is excellent in stability, and a liquid crystal using the same. An object of the present invention is to provide a composition and a liquid crystal element using the composition which can be used for an optical shutter, a display element, and the like.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意検討を加えた結果、ある種のフェニ
ルアセチレン化合物が十分大きな屈折率異方性を有する
ことを見出し、本発明を完成するに至った。即ち、本発
明によれば、式(１)で示されるフェニルアセチレン化合
物が提供される。The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a certain phenylacetylene compound has a sufficiently large refractive index anisotropy. Was completed. That is, according to the present invention, there is provided a phenylacetylene compound represented by the formula (1).
【０００７】[0007]
【化５】 (式中、Ａ1〜Ａ12は、それぞれ独立に水素原子、フッ素
原子又はフッ素原子で置換されていてもよい炭素数１〜
１０の、アルキル基もしくはアルコキシ基を示し、少な
くとも１つはフッ素原子で置換されていてもよい炭素数
１〜１０の、アルキル基又はアルコキシ基である。ＢはEmbedded image (In the formula, A 1 to A 12 each independently represent a hydrogen atom, a fluorine atom or a carbon atom which may be substituted with a fluorine atom.
10 represents an alkyl group or an alkoxy group, at least one of which is an alkyl group or an alkoxy group having 1 to 10 carbon atoms which may be substituted by a fluorine atom. B is
【化６】 を示す。Ｒ1は直鎖もしくは分枝のフッ素原子で置換さ
れていてもよい炭素数１〜１２のアルキル基を示す。Ｒ
2は、それぞれ独立に水素原子、フッ素原子、シアノ
基、−ＳＦ5、−ＮＣＳ、４−Ｒ3−(シクロアルキル)
基、４−Ｒ3−(シクロアルケニル基)又はＲ4−(Ｏ)ｑ基
を示す(但し、Ｒ3は水素原子又は直鎖もしくは分枝のフ
ッ素原子で置換されていてもよい炭素数１〜１２のアル
キル基を示し、Ｒ4は直鎖もしくは分枝のフッ素原子で
置換されていてもよい炭素数１〜１２のアルキル基を示
す。ｑは０又は１を示す)。) また本発明によれば、上記式(１)で示される化合物を少
なくとも１種含有することを特徴とする液晶組成物が提
供される。更に本発明によれば、上記液晶組成物を一対
の電極基板間に挟持してなることを特徴とする液晶素子
が提供される。Embedded image Is shown. R 1 represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by a fluorine atom. R
2 each independently represent a hydrogen atom, a fluorine atom, a cyano group, -SF 5, -NCS, 4- R 3 - ( cycloalkyl)
Group, 4-R 3 - (cycloalkenyl group) or R 4 - (O) indicating the q group (wherein, R 3 is 1 the number hydrogen atom or a straight or branched carbon atoms which may be substituted with a fluorine atom And R 4 represents an alkyl group having 1 to 12 carbon atoms which may be substituted by a linear or branched fluorine atom, and q represents 0 or 1). According to the invention, there is provided a liquid crystal composition comprising at least one compound represented by the above formula (1). Further, according to the present invention, there is provided a liquid crystal device characterized in that the liquid crystal composition is sandwiched between a pair of electrode substrates.
【０００８】[0008]
【発明の実施の形態】以下本発明を更に詳細に説明す
る。本発明のフェニルアセチレン化合物は、上記式(１)
で表される化合物である。式(１)において、Ａ1〜Ａ12
はそれぞれ独立に水素原子、フッ素原子又はフッ素原子
で置換されていてもよい炭素数１〜１０の、アルキル基
もしくはアルコキシ基である。Ａ1〜Ａ12の少なくとも
１つは、フッ素原子で置換されていてもよい炭素数１〜
１０の、アルキル基又はアルコキシ基であるが、その中
ではＡ4、Ａ5、Ａ9及びＡ10からなる群より選択される
少なくとも１つが、フッ素原子で置換されていてもよい
炭素数１〜１０の、アルキル基又はアルコキシ基である
ことが望ましい。また、Ａ1〜Ａ12のいづれかがフッ素
原子である場合は、その数は４以下が好ましく、更には
２又は１つが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The phenylacetylene compound of the present invention has the formula (1)
It is a compound represented by these. In the formula (1), A 1 to A 12
Is each independently a hydrogen atom, a fluorine atom or an alkyl group or an alkoxy group having 1 to 10 carbon atoms which may be substituted by a fluorine atom. At least one of A 1 to A 12 has 1 to 1 carbon atoms which may be substituted with a fluorine atom.
10, an alkyl group or an alkoxy group, wherein at least one selected from the group consisting of A 4 , A 5 , A 9 and A 10 has 1 to 1 carbon atoms which may be substituted with a fluorine atom. Desirably, it is 10 alkyl groups or alkoxy groups. When any one of A 1 to A 12 is a fluorine atom, the number is preferably 4 or less, more preferably 2 or 1.
【０００９】式(１)において、Ｒ2は、それぞれ独立に
水素原子、フッ素原子、シアノ基、−ＳＦ5、−ＮＣ
Ｓ、４−Ｒ3−(シクロアルキル)基、４−Ｒ3−(シクロ
アルケニル基)又はＲ4−(Ｏ)ｑ基を示す(但し、Ｒ3は水
素原子又は直鎖もしくは分枝のフッ素原子で置換されて
いてもよい炭素数１〜１２のアルキル基を示し、Ｒ4は
直鎖もしくは分枝のフッ素原子で置換されていてもよい
炭素数１〜１２のアルキル基を示す。ｑは０又は１を示
す。In the formula (1), R 2 is independently a hydrogen atom, a fluorine atom, a cyano group, —SF 5 , —NC
S, 4-R 3 - (cycloalkyl) group, 4-R 3 - (cycloalkenyl group) or R 4 - (O) indicating the q group (wherein, R 3 is a hydrogen atom or a linear or branched fluorine R 4 represents an alkyl group having 1 to 12 carbon atoms which may be substituted by an atom, and R 4 represents an alkyl group having 1 to 12 carbon atoms which may be substituted by a linear or branched fluorine atom. Indicates 0 or 1.
【００１０】Ｒ1の具体例としては、例えば、メチル
基、エチル基、プロピル基、ブチル基、ペンチル基、ヘ
キシル基、ヘプチル基、オクチル基、ノニル基、デシル
基、ウンデシル基、ドデシル基等のアルキル基及びこれ
らがフッ素原子で置換されたフルオロアルキル基(例え
ば、トリフルオロメチル基)；メトキシ基、エトキシ
基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘ
キシルオキシ基、オクチルオキシ基、ノニルオキシ基、
デシルオキシ基、ウンデシルオキシ基、ドデシルオキシ
基等のアルコキシ基及びこれらがフッ素原子で置換され
たフルオロアルコキシ基(例えば、１〜３個のフッ素原
子で置換されたメトキシ基、１〜５個のフッ素原子で置
換されたエトキシ基)；メトキシメチル基、エトキシメ
チル基、プロポキシメチル基、ブトキシメチル基、ペン
チルオキシメチル基、ヘキシルオキシメチル基、ヘプチ
ルオキシメチル基、オクチルオキシメチル基、ノニルオ
キシメチル基、デシルオキシメチル基、メトキシエチル
基、エトキシエチル基、プロポキシエチル基、ブトキシ
エチル基、ペンチルオキシエチル基、ヘキシルオキシエ
チル基、ヘプチルオキシエチル基、オクチルオキシエチ
ル基、ノニルオキシエチル基、デシルオキシエチル基、
メトキシプロピル基、エトキシプロピル基、プロポキシ
プロピル基、ブトキシプロピル基、ペンチルオキシプロ
ピル基、ヘキシルオキシプロピル基、ヘプチルオキシプ
ロピル基、オクチルオキシプロピル基、ノニルオキシプ
ロピル基、メトキシブチル基、エトキシブチル基、プロ
ポキシブチル基、ブトキシブチル基、ペンチルオキシブ
チル基、ヘキシルオキシブチル基、ヘプチルオキシブチ
ル基、オクチルオキシブチル基、メトキシペンチル基、
エトキシペンチル基、プロポキシペンチル基、ブトキシ
ペンチル基、ペンチルオキシペンチル基、ヘキシルオキ
シペンチル基、ヘプチルオキシペンチル基等のアルコキ
シアルキル基及びこれらがフッ素原子で置換されたフル
オロアルコキシアルキル基；２−メチルプロピル基、２
−メチルブチル基、３−メチルブチル基、３−メチルペ
ンチル基等の分枝アルキル基及びこれらがフッ素原子で
置換されたフルオロ分枝アルキル基；２−メチルプロピ
ルオキシ基、２−メチルブチルオキシ基、３−メチルブ
チルオキシ基、３−メチルペンチルオキシ基等の分枝ア
ルキルオキシ基及びこれらがフッ素原子で置換されたフ
ルオロ分枝アルキルオキシ基等が挙げられる。Specific examples of R 1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like. An alkyl group and a fluoroalkyl group substituted with a fluorine atom (for example, a trifluoromethyl group); a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a nonyloxy group,
Alkoxy groups such as decyloxy group, undecyloxy group, dodecyloxy group and the like and fluoroalkoxy groups substituted by fluorine atoms (for example, methoxy group substituted by 1 to 3 fluorine atoms, 1 to 5 fluorine atoms) An ethoxy group substituted with an atom); a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pentyloxymethyl group, a hexyloxymethyl group, a heptyloxymethyl group, an octyloxymethyl group, a nonyloxymethyl group, Decyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group, heptyloxyethyl group, octyloxyethyl group, nonyloxyethyl group, decyloxyethyl group ,
Methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, pentyloxypropyl, hexyloxypropyl, heptyloxypropyl, octyloxypropyl, nonyloxypropyl, methoxybutyl, ethoxybutyl, propoxy Butyl group, butoxybutyl group, pentyloxybutyl group, hexyloxybutyl group, heptyloxybutyl group, octyloxybutyl group, methoxypentyl group,
An alkoxyalkyl group such as an ethoxypentyl group, a propoxypentyl group, a butoxypentyl group, a pentyloxypentyl group, a hexyloxypentyl group and a heptyloxypentyl group, and a fluoroalkoxyalkyl group in which these are substituted with a fluorine atom; a 2-methylpropyl group , 2
Branched alkyl groups such as -methylbutyl group, 3-methylbutyl group and 3-methylpentyl group and fluorobranched alkyl groups in which these are substituted by fluorine atoms; 2-methylpropyloxy group, 2-methylbutyloxy group, 3 A branched alkyloxy group such as -methylbutyloxy group and 3-methylpentyloxy group; and a fluorobranched alkyloxy group in which these are substituted with a fluorine atom.
【００１１】またＲ2の具体例としては、例えば、水素
原子；フッ素原子；メチル基、エチル基、プロピル基、
ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オク
チル基、ノニル基、デシル基、ウンデシル基、ドデシル
基等のアルキル基及びこれらがフッ素原子で置換された
フルオロアルキル基(例えば、トリフルオロメチル基)；
メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、
ペンチルオキシ基、ヘキシルオキシ基、オクチルオキシ
基、ノニルオキシ基、デシルオキシ基、ウンデシルオキ
シ基、ドデシルオキシ基等のアルコキシ基及びこれらが
フッ素原子で置換されたフルオロアルコキシ基(例え
ば、１〜３個のフッ素原子で置換されたメトキシ基、１
〜５個のフッ素原子で置換されたエトキシ基)；メトキ
シメチル基、エトキシメチル基、プロポキシメチル基、
ブトキシメチル基、ペンチルオキシメチル基、ヘキシル
オキシメチル基、ヘプチルオキシメチル基、オクチルオ
キシメチル基、ノニルオキシメチル基、デシルオキシメ
チル基、メトキシエチル基、エトキシエチル基、プロポ
キシエチル基、ブトキシエチル基、ペンチルオキシエチ
ル基、ヘキシルオキシエチル基、ヘプチルオキシエチル
基、オクチルオキシエチル基、ノニルオキシエチル基、
デシルオキシエチル基、メトキシプロピル基、エトキシ
プロピル基、プロポキシプロピル基、ブトキシプロピル
基、ペンチルオキシプロピル基、ヘキシルオキシプロピ
ル基、ヘプチルオキシプロピル基、オクチルオキシプロ
ピル基、ノニルオキシプロピル基、メトキシブチル基、
エトキシブチル基、プロポキシブチル基、ブトキシブチ
ル基、ペンチルオキシブチル基、ヘキシルオキシブチル
基、ヘプチルオキシブチル基、オクチルオキシブチル
基、メトキシペンチル基、エトキシペンチル基、プロポ
キシペンチル基、ブトキシペンチル基、ペンチルオキシ
ペンチル基、ヘキシルオキシペンチル基、ヘプチルオキ
シペンチル基等のアルコキシアルキル基及びこれらがフ
ッ素原子で置換されたフルオロアルコキシアルキル基；
２−メチルプロピル基、２−メチルブチル基、３−メチ
ルブチル基、３−メチルペンチル基等の分枝アルキル基
及びこれらがフッ素原子で置換されたフルオロ分枝アル
キル基；２−メチルプロピルオキシ基、２−メチルブチ
ルオキシ基、３−メチルブチルオキシ基、３−メチルペ
ンチルオキシ基等の分枝アルキルオキシ基及びこれらが
フッ素原子で置換されたフルオロ分枝アルキルオキシ
基；４−メチルシクロヘキシル基、４−エチルシクロヘ
キシル基、４−プロピルシクロヘキシル基、４−ブチル
シクロヘキシル基、４−ペンチルシクロヘキシル基、４
−ヘキシルシクロヘキシル基、４−ヘプチルシクロヘキ
シル基、４−オクチルシクロヘキシル基、４−ノニルシ
クロヘキシル基、４−デシルシクロヘキシル基等の４−
アルキル−シクロアルキル基及びこれらがフッ素原子で
置換された４−フルオロアルキル−シクロアルキル基；
４−プロピルシクロヘキセニル基、４−ペンチルシクロ
ヘキセニル基等の４−アルキル−シクロアルケニル基及
びこれらがフッ素原子で置換された４−フルオロアルキ
ル−シクロアルケニル基；シアノ基；−ＳＦ5；−ＮＣ
Ｓ等が挙げられる。Specific examples of R 2 include a hydrogen atom; a fluorine atom; a methyl group, an ethyl group, a propyl group,
Alkyl groups such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like, and fluoroalkyl groups in which these are substituted by fluorine atoms (for example, trifluoromethyl group) ;
Methoxy, ethoxy, propoxy, butoxy,
Pentyloxy group, hexyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, alkoxy groups such as dodecyloxy group and a fluoroalkoxy group in which these are substituted with a fluorine atom (for example, 1 to 3 A methoxy group substituted by a fluorine atom, 1
An ethoxy group substituted with up to 5 fluorine atoms); a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group,
Butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, octyloxymethyl group, nonyloxymethyl group, decyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, Pentyloxyethyl group, hexyloxyethyl group, heptyloxyethyl group, octyloxyethyl group, nonyloxyethyl group,
Decyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, pentyloxypropyl group, hexyloxypropyl group, heptyloxypropyl group, octyloxypropyl group, nonyloxypropyl group, methoxybutyl group,
Ethoxybutyl, propoxybutyl, butoxybutyl, pentyloxybutyl, hexyloxybutyl, heptyloxybutyl, octyloxybutyl, methoxypentyl, ethoxypentyl, propoxypentyl, butoxypentyl, pentyloxy Alkoxyalkyl groups such as a pentyl group, a hexyloxypentyl group, and a heptyloxypentyl group, and a fluoroalkoxyalkyl group in which these are substituted with a fluorine atom;
A branched alkyl group such as a 2-methylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 3-methylpentyl group, and a fluorobranched alkyl group in which these are substituted with a fluorine atom; a 2-methylpropyloxy group; Branched alkyloxy groups such as -methylbutyloxy group, 3-methylbutyloxy group, and 3-methylpentyloxy group; and fluorobranched alkyloxy groups in which these are substituted by fluorine atoms; 4-methylcyclohexyl group, Ethylcyclohexyl group, 4-propylcyclohexyl group, 4-butylcyclohexyl group, 4-pentylcyclohexyl group, 4
4-hexylcyclohexyl, 4-heptylcyclohexyl, 4-octylcyclohexyl, 4-nonylcyclohexyl, 4-decylcyclohexyl, etc.
An alkyl-cycloalkyl group and a 4-fluoroalkyl-cycloalkyl group substituted with a fluorine atom;
4-propyl cyclohexenyl, 4-pentyl-cyclohexenyl group such 4-alkyl - cycloalkenyl group and it has been substituted with a fluorine atom 4 fluoroalkyl - cycloalkenyl group; a cyano group; -SF 5; -NC
S and the like.
【００１２】式(１)で示されるフェニルアセチレン化合
物の具体例としては、下記構造式で示される化合物等が
挙げられる。但し、Ｒ1及びＲ2は、上記列挙した基が好
ましいが、これに限定されない。またＢは下記の基を示
す。Specific examples of the phenylacetylene compound represented by the formula (1) include a compound represented by the following structural formula. However, R 1 and R 2 are preferably, but not limited to, the groups listed above. B represents the following group.
【化７】 Embedded image
【００１３】[0013]
【化８】 Embedded image
【００１４】[0014]
【化９】 Embedded image
【００１５】[0015]
【化１０】 Embedded image
【００１６】[0016]
【化１１】 Embedded image
【００１７】[0017]
【化１２】 Embedded image
【００１８】[0018]
【化１３】 Embedded image
【００１９】本発明のフェニルアセチレン化合物は、通
常の有機合成的手段を駆使して合成することができる。
例えば、「遷移金属が拓く有機合成」(辻二郎著、化学
同人)等に記載の反応を組み合わせることにより得られ
る。具体的には、式(ＩＭ−１)で表される化合物と式
(ＩＭ−２)で表される化合物とをパラジウム触媒及びト
リエチルアミン等の塩基の存在下で反応させることによ
り製造することができる。The phenylacetylene compound of the present invention can be synthesized by utilizing ordinary organic synthetic means.
For example, it can be obtained by combining the reactions described in “Organic synthesis pioneered by transition metals” (by Jiro Tsuji, Doujin Kagaku). Specifically, a compound represented by the formula (IM-1) and a compound represented by the formula
It can be produced by reacting the compound represented by (IM-2) with a palladium catalyst and a base such as triethylamine.
【００２０】[0020]
【化１４】 (式(ＩＭ−１)及び(ＩＭ−２)において、Ａ1〜Ａ12、Ｒ
1及びＲ2は、式(１)中のものと同じ意味を示す。) 得られる式(１)で表されるフェニルアセチレン化合物に
おいて、Ｂが異なる化合物は、上記反応終了後、カラム
クロマトグラフィーにて分離することにより別々に得る
ことができる。Embedded image (In the formulas (IM-1) and (IM-2), A 1 to A 12 , R
1 and R 2 have the same meaning as in formula (1). ) In the obtained phenylacetylene compound represented by the formula (1), compounds having different B can be obtained separately by separation by column chromatography after completion of the above reaction.
【００２１】化合物(ＩＭ−１)の具体例としては、以下
の構造式で示される化合物等が挙げられる。Specific examples of compound (IM-1) include compounds represented by the following structural formula.
【００２２】[0022]
【化１５】 Embedded image
【００２３】[0023]
【化１６】 Embedded image
【００２４】[0024]
【化１７】 Embedded image
【００２５】[0025]
【化１８】 Embedded image
【００２６】[0026]
【化１９】 Embedded image
【００２７】[0027]
【化２０】 Embedded image
【００２８】式(ＩＭ−１)で表される化合物は、例えば
下記ルートにより製造できる。The compound represented by the formula (IM-1) can be produced, for example, by the following route.
【化２１】 (上記化合物において、Ａ1、Ａ3〜Ａ5、Ａ9〜Ａ12及び
Ｒ1は、式(１)中のものと同じ意味を示す。)Embedded image (In the above compound, A 1 , A 3 to A 5 , A 9 to A 12 and R 1 have the same meanings as those in the formula (1).)
【００２９】式(ＩＭ−１)で表される化合物と式(ＩＭ
−２)で表される化合物とから式(１)で表されるフェニ
ルアセチレン化合物を得る反応において、化合物(ＩＭ
−２)の使用量は、化合物(ＩＭ−１)に対して、通常
０．３〜１０倍当量、好ましくは０．５〜２倍当量であ
る。The compound represented by the formula (IM-1) and the compound represented by the formula (IM-1)
In the reaction for obtaining the phenylacetylene compound represented by the formula (1) from the compound represented by the formula (2),
The amount of -2) to be used is generally 0.3 to 10 equivalents, preferably 0.5 to 2 equivalents, relative to compound (IM-1).
【００３０】上記反応に用いるパラジウム触媒として
は、例えば、塩化パラジウム、酢酸パラジウム、パラジ
ウム／炭素、トリフェニルホスフィンパラジウム錯体
(例えば、テトラキストリフェニルホスフィンパラジウ
ム、ジクロロビストリフェニルホスフィンパラジウム)
等が挙げられる。パラジウム触媒の使用量は、化合物
(ＩＭ−２)に対して、通常０．０００１〜１倍当量、好
ましくは０．００１〜０．１倍当量の範囲である。ま
た、上記反応に用いる塩基としては、例えば、アルカリ
金属の炭酸塩、カルボン酸塩、アルコキシド、水酸化
物、あるいはトリエチルアミン、ジイソプロピルエチル
アミン、トリ−ｎ−ブチルアミン、テトラメチルエチレ
ンジアミン、１，８−ジアザビシクロ[５．４．０]ウン
デセン−７、１，５−ジアザビシクロ[４．３．０]ノネ
ン−５、ピリジン、Ｎ，Ｎ−ジメチルアミノピリジン、
ジメチルアニリン、Ｎ−メチルモルホリン、Ｎ−メチル
ピペリジン等の有機塩基が挙げられる。好ましくはトリ
エチルアミン等の３級アミンである。塩基の使用量は、
化合物(ＩＭ−２)に対して、通常１〜１００倍当量、好
ましくは１〜２０倍当量である。As the palladium catalyst used in the above reaction, for example, palladium chloride, palladium acetate, palladium / carbon, triphenylphosphine palladium complex
(E.g., tetrakistriphenylphosphine palladium, dichlorobistriphenylphosphine palladium)
And the like. The amount of palladium catalyst used depends on the compound
It is usually in the range of 0.0001 to 1 equivalent, preferably 0.001 to 0.1 equivalent, relative to (IM-2). Examples of the base used in the above reaction include, for example, alkali metal carbonate, carboxylate, alkoxide, hydroxide, or triethylamine, diisopropylethylamine, tri-n-butylamine, tetramethylethylenediamine, 1,8-diazabicyclo [ 5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, pyridine, N, N-dimethylaminopyridine,
Organic bases such as dimethylaniline, N-methylmorpholine, N-methylpiperidine and the like can be mentioned. Preferred are tertiary amines such as triethylamine. The amount of base used is
It is usually 1 to 100 equivalents, preferably 1 to 20 equivalents, relative to compound (IM-2).
【００３１】上記反応の反応温度は、通常−２０〜２０
０℃、好ましくは３０〜１５０℃である。必要により、
例えば、アセトニトリル、テトラヒドロフラン、ジメチ
ルホルムアミド、ヘキサメチルホスホリルアミド、Ｎ−
メチルピロリドン、Ｎ，Ｎ−ジメチルイミダゾリジノ
ン、ベンゼン、トルエン等を溶媒として使用することも
できる。溶媒の使用量は特に限定されず、適宜決定する
ことができる。The reaction temperature of the above reaction is usually -20 to 20.
0 ° C, preferably 30 to 150 ° C. If necessary,
For example, acetonitrile, tetrahydrofuran, dimethylformamide, hexamethylphosphorylamide, N-
Methylpyrrolidone, N, N-dimethylimidazolidinone, benzene, toluene and the like can also be used as a solvent. The amount of the solvent used is not particularly limited, and can be appropriately determined.
【００３２】本発明の液晶組成物は、上記式(１)で示さ
れるフェニルアセチレン化合物を少なくとも１種配合成
分として含有する。混合する他の成分は特に限定されな
いが、液晶相を示す化合物あるいはその組成物が好まし
い。本発明の液晶組成物において、式(１)で表されるフ
ェニルアセチレン化合物の配合割合は、液晶組成物中に
０．１〜９９．９重量％、好ましくは１〜９９重量％の
範囲が好ましい。本発明の液晶組成物には、捩れ剤とし
て、カイラル化合物を一種もしくは複数種含有させるこ
とができる。カイラル化合物は、特に限定されないが、
好ましくは以下に示す化合物を例示することができる
(但し、例示中の＊は不斉炭素を表す)。The liquid crystal composition of the present invention contains at least one phenylacetylene compound represented by the above formula (1) as a compounding component. The other components to be mixed are not particularly limited, but a compound exhibiting a liquid crystal phase or a composition thereof is preferable. In the liquid crystal composition of the present invention, the compounding ratio of the phenylacetylene compound represented by the formula (1) is in the range of 0.1 to 99.9% by weight, preferably 1 to 99% by weight in the liquid crystal composition. . The liquid crystal composition of the present invention may contain one or more chiral compounds as a twisting agent. The chiral compound is not particularly limited,
Preferably, the following compounds can be exemplified.
(However, * in the examples represents an asymmetric carbon).
【００３３】[0033]
【化２２】 Embedded image
【００３４】本発明の液晶組成物において、カイラル化
合物の配合割合は、配合組成等において適宜選択するこ
とができ、特に限定されない。In the liquid crystal composition of the present invention, the mixing ratio of the chiral compound can be appropriately selected depending on the mixing composition and the like, and is not particularly limited.
【００３５】本発明の液晶表示素子は、上記液晶組成物
を一対の電極基板に挟持した素子であれば、特に限定さ
れず、公知の液晶表示素子と同様な構成ものが挙げられ
る。電極の種類及び形態も特に限定されず、公知の電極
等が使用できる。また、本発明の液晶表示素子の作製
は、通常の液晶表示素子の作製にしたがって同様に行う
ことができ、他の要素を適宜付加させることも可能であ
る。The liquid crystal display device of the present invention is not particularly limited as long as the liquid crystal composition is sandwiched between a pair of electrode substrates, and may have the same configuration as a known liquid crystal display device. The type and form of the electrode are not particularly limited, and a known electrode or the like can be used. Further, the production of the liquid crystal display element of the present invention can be performed in the same manner as the production of a normal liquid crystal display element, and other elements can be appropriately added.
【００３６】[0036]
【実施例】以下実施例により、本発明に関してより詳細
に述べるが、本発明はこれらに限定されるものではな
い。実施例１ (工程１−１)攪拌装置及び温度計を装着したフラスコ内
に、窒素雰囲気下で４−ブロモフェノール２５．９５
ｇ、パラトルエンスルホン酸０．０１ｇ及びクロロホル
ム１０３．８ｇの溶液を仕込み、氷冷・攪拌した。次い
で、３，４−ジヒドロ−２Ｈ−ピラン１５．１４ｇ及び
クロロホルム１５．１ｇの溶液を、５℃以下で攪拌しな
がら滴下した。滴下終了後、同温度で２時間攪拌した
後、トリエチルアミン２ｇを加えて中和し、６０℃／２
０Ｔｏｒｒで濃縮した。得られた残渣を、ヘキサン／酢
酸エチル＝２０／１(容積比)にトリエチルアミン０．１
質量％を添加したものを移動相とするシリカゲルクロマ
トグラフィーにて精製し、１−ブロモ−４−ペルヒドロ
−２Ｈ−ピラン−２−イルオキシベンゼン３８．０７ｇ
を得た(収率９９％)。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 (Step 1-1) 4-bromophenol 25.95 in a flask equipped with a stirrer and a thermometer under a nitrogen atmosphere.
g, a solution of 0.01 g of paratoluenesulfonic acid and 103.8 g of chloroform were charged, followed by ice cooling and stirring. Next, a solution of 15.14 g of 3,4-dihydro-2H-pyran and 15.1 g of chloroform was added dropwise while stirring at 5 ° C. or lower. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and neutralized by adding 2 g of triethylamine.
Concentrated at 0 Torr. The obtained residue was dissolved in hexane / ethyl acetate = 20/1 (volume ratio) with triethylamine 0.1%.
Purified by silica gel chromatography using a mobile phase to which 1% by mass was added, and 38.07 g of 1-bromo-4-perhydro-2H-pyran-2-yloxybenzene.
Was obtained (99% yield).
【００３７】(工程１−２)攪拌装置及び温度計を装着し
たフラスコ内において、窒素雰囲気下で、工程１−１で
調製した、１−ブロモ−４−ペルヒドロ−２Ｈ−ピラン
−２−イルオキシベンゼン２５．０１ｇ、テトラキス
(トリフェニルホスフィン)パラジウム０．４６ｇ、(１
Ｅ)ヘプト−１−エニルボロン酸１５．３０ｇを、トル
エン７５ｇ及びエタノール３０ｇの混合溶液に溶解し、
７８℃に昇温・攪拌した。続いて、７．５質量％炭酸ナ
トリウム水溶液１４４．４ｇを７８〜７９℃で２時間か
けて滴下した。更に、７９℃で１時間加熱還流した後、
室温まで冷却し、トルエン及び水を加えて有機層を抽出
し、得られた有機層を３回水洗し、６０℃／２０Ｔｏｒ
ｒで濃縮た。次いで、得られた残渣を、ヘキサン／酢酸
エチル＝２０／１(容積比)にトリエチルアミン０．１質
量％を添加したものを移動相とするシリカゲルクロマト
グラフィーにて精製し、２−(４−((１Ｅ)ヘプト−１−
エニル)フェノキシ)ペルヒドロ−２Ｈ−ピラン２４．５
０ｇを得た(収率９２％)。(Step 1-2) In a flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, the 1-bromo-4-perhydro-2H-pyran-2-yloxy prepared in Step 1-1 was prepared. Benzene 25.01 g, tetrakis
0.46 g of (triphenylphosphine) palladium, (1
E) 15.30 g of hept-1-enylboronic acid is dissolved in a mixed solution of 75 g of toluene and 30 g of ethanol,
The mixture was heated to 78 ° C. and stirred. Subsequently, 144.4 g of a 7.5 mass% aqueous sodium carbonate solution was added dropwise at 78 to 79 ° C over 2 hours. Furthermore, after heating and refluxing at 79 ° C. for 1 hour,
After cooling to room temperature, toluene and water were added to extract an organic layer. The obtained organic layer was washed with water three times, and the temperature was 60 ° C./20 Torr.
Concentrated with r. Next, the obtained residue was purified by silica gel chromatography using hexane / ethyl acetate = 20/1 (volume ratio) to which 0.1% by mass of triethylamine was added as a mobile phase to obtain 2- (4- ( (1E) hept-1-
Enenyl) phenoxy) perhydro-2H-pyran 24.5
0 g was obtained (92% yield).
【００３８】(工程１−３)攪拌装置及び温度計を装着し
たフラスコ内において、窒素雰囲気下で、工程１−２で
調製した、２−(４−((１Ｅ)ヘプト−１−エニル)フェ
ノキシ)ペルヒドロ−２Ｈ−ピラン１８．５０ｇ、ジヨ
ードメタン１９．８６ｇ、銅−亜鉛(１：１)(質量比)合
金２６．０７ｇ及びヨウ素０．０１ｇを、トルエン３７
ｇ及びジエチルエーテル１５ｇの混合溶液に懸濁し、４
０℃に昇温・攪拌した。同温度で１９時間攪拌した後、
６０℃／２０Ｔｏｒｒで濃縮した。次いで、得られた残
渣を、ヘキサン／酢酸エチル＝２０／１(容積比)にトリ
エチルアミン０．１％を添加したものを移動相とするシ
リカゲルクロマトグラフィーにて精製し、２−(４−(２
−ペンチルシクロプロピル)フェノキシ)ペルヒドロ−２
Ｈ−ピランと、未反応の２−(４−((１Ｅ)ヘプト−１−
エニル)フェノキシ)ペルヒドロ−２Ｈ−ピランとの混合
物を得た。これを室温でメタノール３０ｇに溶解し、ｐ
−トルエンスルホン酸０．１ｇを加えて終夜攪拌した
後、トリエチルアミン２ｇを加えて中和し、６０℃／２
０Ｔｏｒｒで濃縮した。得られた残渣を、ヘキサン／酢
酸エチル＝２０／１(容積比)にトリエチルアミン０．１
質量％を添加したものを移動相とするシリカゲルクロマ
トグラフィーにて精製し、４−(２−ペンチルシクロプ
ロピル)フェノールと、４−((１Ｅ)ヘプト−１−エニ
ル)フェノールとの混合物７．３９ｇを得た。(Step 1-3) In a flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, the 2- (4-((1E) hept-1-enyl) phenoxy) prepared in Step 1-2 was prepared. ) 18.50 g of perhydro-2H-pyran, 19.86 g of diiodomethane, 26.07 g of a copper-zinc (1: 1) (mass ratio) alloy and 0.01 g of iodine were added to toluene 37
g and 15 g of diethyl ether.
The temperature was raised to 0 ° C. and stirred. After stirring at the same temperature for 19 hours,
Concentrated at 60 ° C./20 Torr. Next, the obtained residue was purified by silica gel chromatography using a mobile phase obtained by adding 0.1% of triethylamine to hexane / ethyl acetate = 20/1 (volume ratio) to obtain 2- (4- (2
-Pentylcyclopropyl) phenoxy) perhydro-2
H-pyran and unreacted 2- (4-((1E) hept-1-)
A mixture with enyl) phenoxy) perhydro-2H-pyran was obtained. This was dissolved in 30 g of methanol at room temperature, and p
0.1 g of toluenesulfonic acid was added and the mixture was stirred overnight, and then neutralized by adding 2 g of triethylamine.
Concentrated at 0 Torr. The obtained residue was dissolved in hexane / ethyl acetate = 20/1 (volume ratio) with triethylamine 0.1%.
Purification was performed by silica gel chromatography using a mobile phase to which the mass% had been added, and 7.39 g of a mixture of 4- (2-pentylcyclopropyl) phenol and 4-((1E) hept-1-enyl) phenol. I got
【００３９】(工程１−４)攪拌装置及び温度計を装着し
たフラスコ内において、窒素雰囲気下で、工程１−３で
調製した、４−(２−ペンチルシクロプロピル)フェノー
ルと、４−((１Ｅ)ヘプト−１−エニル)フェノールとの
混合物５．７０ｇ、４−ピロリジノピリジン０．１１ｇ
及びピリジン１１．４０ｇをトルエン２８．５ｇに溶解
し、−３℃に冷却・攪拌した。続いて、０℃以下でトリ
フルオロメタンスルホン酸無水物１１．８１ｇ及びトル
エン１７．７ｇの溶液を１時間かけて滴下した後、同温
度で終夜攪拌した。反応マスに水を加えて反応を停止し
た後、トルエンで抽出し、有機層を３回水洗した。有機
層を６０℃／２０Ｔｏｒｒで濃縮後、得られた残渣を、
ヘキサンを移動相とするシリカゲルクロマトグラフィー
にて精製し、４−(２−ペンチルシクロプロピル)フェニ
ル(トリフルオロメチル)スルホネートと、４−((１Ｅ)
ヘプト−１−エニル)フェニル(トリフルオロメチル)ス
ルホネートとの混合物６．９０ｇを得た。(Step 1-4) In a flask equipped with a stirrer and a thermometer, 4- (2-pentylcyclopropyl) phenol prepared in Step 1-3 and 4-(( 5.70 g of a mixture with 1E) hept-1-enyl) phenol, 0.11 g of 4-pyrrolidinopyridine
And 11.40 g of pyridine were dissolved in 28.5 g of toluene, cooled to −3 ° C. and stirred. Subsequently, a solution of 11.81 g of trifluoromethanesulfonic anhydride and 17.7 g of toluene was added dropwise at 0 ° C. or lower over 1 hour, and the mixture was stirred at the same temperature overnight. After stopping the reaction by adding water to the reaction mass, the mixture was extracted with toluene, and the organic layer was washed three times with water. After concentrating the organic layer at 60 ° C./20 Torr, the obtained residue was
Purification was performed by silica gel chromatography using hexane as a mobile phase, and 4- (2-pentylcyclopropyl) phenyl (trifluoromethyl) sulfonate and 4-((1E)
6.90 g of a mixture with hept-1-enyl) phenyl (trifluoromethyl) sulfonate were obtained.
【００４０】(工程２−１)４−ブロモフェノールに代え
て４−ヨード−２−メチルフェノールを使用した以外は
工程１−１と同様にして、１−ヨード−４−ペルヒドロ
−２Ｈ−ピラン−２−イルオキシ−３−メチルベンゼン
を得た。収率は９９％であった。(Step 2-1) In the same manner as in Step 1-1, except that 4-iodo-2-methylphenol was used instead of 4-bromophenol, 1-iodo-4-perhydro-2H-pyran- 2-yloxy-3-methylbenzene was obtained. The yield was 99%.
【００４１】(工程２−２)攪拌装置及び温度計を装着し
たフラスコ内において、窒素雰囲気下で、工程２−１で
調製した、１−ヨード−４−ペルヒドロ−２Ｈ−ピラン
−２−イルオキシ−３−メチルベンゼン１３．３６ｇ、
ジクロロビス(トリフェニルホスフィン)パラジウム０．
２４ｇ、トリフェニルホスフィン０．２４ｇ、ヨウ化銅
(I)０．１２ｇ及びトリエチルアミン１２．７５ｇを酢
酸エチル５０ｇに懸濁し、５８℃に昇温・攪拌した。続
いて、トリメチルシリルアセチレン６．２０ｇ及び酢酸
エチル６．２０ｇの溶液を５８〜６４℃で２時間かけて
滴下した。更に、同温度で３時間攪拌した後、室温まで
冷却・濾過し、酢酸エチルで洗浄し、得られた濾液を６
０℃／２０Ｔｏｒｒで濃縮した。得られた残渣を、ヘキ
サンにトリエチルアミン０．１質量％を添加したものを
移動相とするシリカゲルクロマトグラフィーにて精製
し、２−(４−(トリメチルシリルエチニル)−２−メチ
ルフェノキシ)ペルヒドロ−２Ｈ−ピラン１１．８７ｇ
を得た(収率９８％)。(Step 2-2) In a flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, the 1-iodo-4-perhydro-2H-pyran-2-yloxy- prepared in step 2-1 was prepared. 13.36 g of 3-methylbenzene,
Dichlorobis (triphenylphosphine) palladium
24 g, triphenylphosphine 0.24 g, copper iodide
(I) 0.12 g and 12.75 g of triethylamine were suspended in 50 g of ethyl acetate, and the temperature was raised to 58 ° C. and stirred. Subsequently, a solution of 6.20 g of trimethylsilylacetylene and 6.20 g of ethyl acetate was added dropwise at 58 to 64 ° C over 2 hours. After stirring at the same temperature for 3 hours, the mixture was cooled to room temperature, filtered, washed with ethyl acetate, and the obtained filtrate was washed with 6 mL of ethyl acetate.
Concentrated at 0 ° C./20 Torr. The obtained residue is purified by silica gel chromatography using hexane to which 0.1% by mass of triethylamine is added as a mobile phase to give 2- (4- (trimethylsilylethynyl) -2-methylphenoxy) perhydro-2H-. 11.87 g of Piran
Was obtained (98% yield).
【００４２】(工程２−３)攪拌装置及び温度計を装着し
たフラスコ内において、窒素雰囲気下で、工程２−２で
得られた２−(４−(トリメチルシリルエチニル)−２−
メチルフェノキシ)ペルヒドロ−２Ｈ−ピラン１１．８
７ｇ及び炭酸カリウム０．１３ｇをメタノール５０ｇに
懸濁し、室温で７時間攪拌して、反応マスを６０℃／２
０Ｔｏｒｒで濃縮した。得られた残渣を、ヘキサン／酢
酸エチル＝２０／１(容積比)にトリエチルアミン０．１
質量％を添加したものを移動相とするシリカゲルクロマ
トグラフィーにて精製し、２−(４−エチニル−２−メ
チルフェノキシ)ペルヒドロ−２Ｈ−ピラン８．１０ｇ
を得た。収率は９１％であった。(Step 2-3) In a flask equipped with a stirrer and a thermometer, the 2- (4- (trimethylsilylethynyl) -2-
Methylphenoxy) perhydro-2H-pyran 11.8
7 g and 0.13 g of potassium carbonate were suspended in 50 g of methanol, and the suspension was stirred at room temperature for 7 hours.
Concentrated at 0 Torr. The obtained residue was dissolved in hexane / ethyl acetate = 20/1 (volume ratio) with triethylamine 0.1%.
Purified by silica gel chromatography using a mobile phase to which the mass% was added, and 8.10 g of 2- (4-ethynyl-2-methylphenoxy) perhydro-2H-pyran.
I got The yield was 91%.
【００４３】(工程３−１)攪拌装置及び温度計を装着し
たフラスコ内において、窒素雰囲気下で、１−ブロモ−
４−ペンチルオキシベンゼン４１．０ｇ、ジクロロビス
(トリフェニルホスフィン)パラジウム０．８２ｇ、トリ
フェニルホスフィン０．８２ｇ、ヨウ化銅(Ｉ)０．４１
ｇ及びトリエチルアミン６８．３ｇを酢酸エチル１６４
ｇに懸濁し、６０℃に昇温・攪拌した。続いて、１−ブ
チン−３−オール２１．３ｇを６０〜６５℃で１時間か
けて滴下した。更に、同温度で１０時間攪拌した後、室
温まで冷却・濾過し、酢酸エチルで洗浄し、得られた濾
液を６０℃／２０Ｔｏｒｒで濃縮した。得られた残渣
を、ヘキサン／酢酸エチル＝５／１(容積比)を移動相と
するシリカゲルクロマトグラフィーにて精製し、１−ブ
チン−１−(４−ペンチルオキシフェニル)−３−オール
２１．０ｇを得た(収率５１％)。(Step 3-1) In a flask equipped with a stirrer and a thermometer, 1-bromo-
41.0 g of 4-pentyloxybenzene, dichlorobis
(Triphenylphosphine) palladium 0.82 g, triphenylphosphine 0.82 g, copper (I) iodide 0.41
g and 68.3 g of triethylamine in ethyl acetate 164.
g, and the mixture was heated to 60 ° C. and stirred. Subsequently, 21.3 g of 1-butyn-3-ol was added dropwise at 60 to 65 ° C. over 1 hour. After stirring at the same temperature for 10 hours, the mixture was cooled to room temperature, filtered, washed with ethyl acetate, and the obtained filtrate was concentrated at 60 ° C./20 Torr. The obtained residue was purified by silica gel chromatography using hexane / ethyl acetate = 5/1 (volume ratio) as a mobile phase to obtain 1-butyn-1- (4-pentyloxyphenyl) -3-ol. 0 g was obtained (yield 51%).
【００４４】(工程３−２)攪拌装置及び温度計を装着し
たフラスコ内において、窒素雰囲気下で、工程３−１で
調製した、１−ブチン−１−(４−ペンチルオキシフェ
ニル)−３−オール２１．０ｇ及び水酸化カリウム１．
０ｇをトルエン８４ｇに懸濁し、９０℃で４時間攪拌し
て、反応マスを５０℃／２０Ｔｏｒｒで濃縮した。得ら
れた残渣を、ヘキサンにトリエチルアミン０．１質量％
を添加したものを移動相とするシリカゲルクロマトグラ
フィーにて精製し、４−ペンチルオキシフェニルアセチ
レン１４．０ｇを得た(収率８８％)。(Step 3-2) In a flask equipped with a stirrer and a thermometer, 1-butyne-1- (4-pentyloxyphenyl) -3-prepared in Step 3-1 under a nitrogen atmosphere. All 21.0 g and potassium hydroxide 1.
0 g was suspended in 84 g of toluene, stirred at 90 ° C. for 4 hours, and the reaction mass was concentrated at 50 ° C./20 Torr. The obtained residue was dissolved in hexane with 0.1% by mass of triethylamine.
Was purified by silica gel chromatography using a mobile phase as a mobile phase to obtain 14.0 g of 4-pentyloxyphenylacetylene (yield: 88%).
【００４５】(工程４−１)撹拌装置及び温度計を装着し
たフラスコ内に、窒素雰囲気下で、工程１−４で調製し
た、４−(２−ペンチルシクロプロピル)フェニル(トリ
フルオロメチル)スルホネートと、４−((１Ｅ)ヘプト−
１−エニル)フェニル(トリフルオロメチル)スルホネー
トとの混合物６．９０ｇ、ジクロロビス(トリフェニル
ホスフィン)パラジウム０．２８g、トリエチルアミン
８．３０g及びＮ，Ｎ−ジメチルホルムアミド(ＤＭＦ)
３４．５ｇを仕込み、５６℃に昇温した。その後、工程
２−３で調製した、２−(４−エチニル−２−メチルフ
ェノキシ)ペルヒドロ−２Ｈ−ピラン８．１０ｇをＤＭ
Ｆ８．１０ｇに溶解した溶液を、５６〜６３℃で１時間
かけて滴下し、同温度でで６時間撹拌した。その後、水
を加えて反応を停止し、トルエンで抽出後、有機層を水
洗した。有機層を濃縮後、残渣を、ヘキサン／酢酸＝２
０／１(容積比)にトリエチルアミン０．１質量％を添加
したものを移動相とするシリカゲルクロマトグラフィー
にて精製した。得られた精製物を室温でメタノール４０
ｇに溶解し、ｐ−トルエンスルホン酸０．０１ｇを加え
て終夜攪拌した後、トリエチルアミン２ｇを加えて中和
し、６０℃／２０Ｔｏｒｒで濃縮した。得られた残渣
を、ヘキサン／酢酸エチル＝２０／１(容積比)にトリエ
チルアミン０．１質量％を添加したものを移動相とする
シリカゲルクロマトグラフィーにて精製し、４−(４−
(２−ペンチルシクロプロピル)フェニルエチニル)−２
−メチルフェノールと、４−(４−((１Ｅ)ヘプト−１−
エニル)フェニルエチニル)−２−メチルフェノールの混
合物５．１８ｇを得た。(Step 4-1) In a flask equipped with a stirrer and a thermometer, 4- (2-pentylcyclopropyl) phenyl (trifluoromethyl) sulfonate prepared in Step 1-4 under a nitrogen atmosphere. And 4-((1E) hept-
6.90 g of a mixture with 1-enyl) phenyl (trifluoromethyl) sulfonate, 0.28 g of dichlorobis (triphenylphosphine) palladium, 8.30 g of triethylamine and N, N-dimethylformamide (DMF)
34.5 g was charged, and the temperature was raised to 56 ° C. Thereafter, 8.10 g of 2- (4-ethynyl-2-methylphenoxy) perhydro-2H-pyran prepared in Step 2-3 was added to DM.
The solution dissolved in 8.10 g of F was added dropwise at 56 to 63 ° C over 1 hour, and the mixture was stirred at the same temperature for 6 hours. Thereafter, the reaction was stopped by adding water, and after extraction with toluene, the organic layer was washed with water. After concentrating the organic layer, the residue was subjected to hexane / acetic acid = 2
Purification was performed by silica gel chromatography using a mobile phase obtained by adding 0.1% by mass of triethylamine to 0/1 (volume ratio). The obtained purified product is treated with methanol 40 at room temperature.
After stirring overnight, 0.01 g of p-toluenesulfonic acid was added, neutralized by adding 2 g of triethylamine, and concentrated at 60 ° C./20 Torr. The obtained residue was purified by silica gel chromatography using a mobile phase obtained by adding 0.1% by mass of triethylamine to hexane / ethyl acetate = 20/1 (volume ratio).
(2-pentylcyclopropyl) phenylethynyl) -2
-Methylphenol and 4- (4-((1E) hept-1-)
5.18 g of a mixture of (enyl) phenylethynyl) -2-methylphenol were obtained.
【００４６】(工程４−２)工程４−１で調製した、４−
(４−(２−ペンチルシクロプロピル)フェニルエチニル)
−２−メチルフェノールと、４−(４−((１Ｅ)ヘプト−
１−エニル)フェニルエチニル)−２−メチルフェノール
との混合物５．１７ｇ、４−ピロリジノピリジン０．１
０ｇ、ピリジン１０．３４ｇ及びトルエン２５．９ｇを
窒素雰囲気下でフラスコ内に仕込み、２℃に冷却・攪拌
した。次いで、トリフルオロメタンスルホン酸無水物
６．８７ｇをトルエン１０．３ｇに溶解した溶液を、２
〜５℃で１．５時間かけて滴下し、同温度で終夜攪拌し
た。その後、水を加えて反応を停止し、トルエンで抽出
後、有機層を水洗した。有機層を濃縮後、残渣を、ヘキ
サン／酢酸＝２０／１(容積比)を移動相とするシリカゲ
ルクロマトグラフィーにて精製し、４−(４−(２−ペン
チルシクロプロピル)フェニルエチニル)−２−メチルフ
ェニル(トリフルオロメチル)スルホネートと、４−(４
−((１Ｅ)ヘプト−１−エニル)フェニルエチニル)−２
−メチルフェニル(トリフルオロメチル)スルホネートと
の混合物４．８０ｇを得た。(Step 4-2) The 4-step prepared in Step 4-1
(4- (2-pentylcyclopropyl) phenylethynyl)
-2-methylphenol and 4- (4-((1E) hept-
5.17 g of a mixture with 1-enyl) phenylethynyl) -2-methylphenol, 4-pyrrolidinopyridine 0.1
0 g, 10.34 g of pyridine and 25.9 g of toluene were charged into a flask under a nitrogen atmosphere, and cooled and stirred at 2 ° C. Next, a solution obtained by dissolving 6.87 g of trifluoromethanesulfonic anhydride in 10.3 g of toluene was added.
The mixture was added dropwise at ５5 ° C. over 1.5 hours and stirred at the same temperature overnight. Thereafter, the reaction was stopped by adding water, and after extraction with toluene, the organic layer was washed with water. After concentrating the organic layer, the residue was purified by silica gel chromatography using hexane / acetic acid = 20/1 (volume ratio) as a mobile phase to obtain 4- (4- (2-pentylcyclopropyl) phenylethynyl) -2. -Methylphenyl (trifluoromethyl) sulfonate and 4- (4
-((1E) hept-1-enyl) phenylethynyl) -2
4.80 g of a mixture with -methylphenyl (trifluoromethyl) sulfonate were obtained.
【００４７】(工程４−３)工程４−２で調製した、４−
(４−(２−ペンチルシクロプロピル)フェニルエチニル)
−２−メチルフェニル(トリフルオロメチル)スルホネー
トと、４−(４−((１Ｅ)ヘプト−１−エニル)フェニル
エチニル)−２−メチルフェニル(トリフルオロメチル)
スルホネートとの混合物１．３５ｇ、ジクロロビス(ト
リフェニルホスフィン)パラジウム０．０５ｇ、ＤＭＦ
１３．５ｇ及びトリエチルアミン０．９１ｇを窒素雰囲
気下でフラスコ内に仕込み、６０〜６５℃に昇温・攪拌
した。続いて、工程３−１で調製した、４−ペンチルオ
キシフェニルアセチレン０．８５ｇをＤＭＦ１．７０ｇ
に溶解した溶液を同温度で３０分間かけて滴下し、更
に、同温度で３時間撹拌した。その後、水を加えて反応
を停止し、トルエンで抽出後、有機層を水洗した。有機
層を濃縮後、残渣を、ヘキサンにトリエチルアミン０．
１質量％添加したものを移動相とするシリカゲルクロマ
トグラフィーにて精製した。更に、ヘキサン／クロロホ
ルム＝４０／１(容積比)にトリエチルアミン０．１質量
％添加したものを移動相とするシリカゲルクロマトグラ
フィーにて精製を繰り返し、ヘキサンで再結晶を繰り返
し、目的とする化合物１−(２−(４−(２−(４−((１
Ｅ)ヘプト−１−エニル)フェニル)エチニル)−２−メチ
ルフェニル)エチニル)−４−ペンチルオキシベンゼン
０．３６ｇ(純度９９．５％)及び１−(２−(２−メチル
−４−(２−(４−(２−ペンチルシクロプロピル)フェニ
ル)エチニル)フェニル)エチニル)−４−ペンチルオキシ
ベンゼン０．２２ｇ(純度９０．４％)を得た。(Step 4-3) The 4-form prepared in Step 4-2
(4- (2-pentylcyclopropyl) phenylethynyl)
-2-methylphenyl (trifluoromethyl) sulfonate and 4- (4-((1E) hept-1-enyl) phenylethynyl) -2-methylphenyl (trifluoromethyl)
1.35 g of a mixture with sulfonate, 0.05 g of dichlorobis (triphenylphosphine) palladium, DMF
13.5 g and 0.91 g of triethylamine were charged into a flask under a nitrogen atmosphere, and heated to 60 to 65 ° C and stirred. Subsequently, 0.85 g of 4-pentyloxyphenylacetylene prepared in Step 3-1 was added to 1.70 g of DMF.
Was added dropwise at the same temperature over 30 minutes, and further stirred at the same temperature for 3 hours. Thereafter, the reaction was stopped by adding water, and after extraction with toluene, the organic layer was washed with water. After concentrating the organic layer, the residue was dissolved in hexane with 0.1% triethylamine.
Purification was performed by silica gel chromatography using 1% by mass as a mobile phase. Further, purification was repeated by silica gel chromatography using hexane / chloroform = 40/1 (volume ratio) to which 0.1% by mass of triethylamine was added as a mobile phase, and recrystallization was repeated with hexane to obtain the desired compound 1- (2- (4- (2- (4-((1
E) Hept-1-enyl) phenyl) ethynyl) -2-methylphenyl) ethynyl) -4-pentyloxybenzene 0.36 g (purity 99.5%) and 1- (2- (2-methyl-4- ( 0.22 g (purity: 90.4%) of 2- (4- (2-pentylcyclopropyl) phenyl) ethynyl) phenyl) ethynyl) -4-pentyloxybenzene was obtained.
【００４８】１−(２−(４−(２−(４−((１Ｅ)ヘプト
−１−エニル)フェニル)エチニル)−２−メチルフェニ
ル)エチニル)−４−ペンチルオキシベンゼンの1Ｈ−Ｎ
ＭＲスペクトルデータは以下のとおりであった。1 Ｈ−ＮＭＲ(δ)：0.91(t,3H,J＝6.6Hz),0.94(t,3H,J＝
6.9Hz),1.25−1.55(m, 10H),1.78(qt,2H,J＝6.6Hz),2.2
1(dt,2H,Jd＝6.9Hz,Jt＝6.9Hz),2.49(s,3H),3.97(t,2H,
J＝6.6Hz),6.27(dt,1H,Jd＝15.8Hz,Jt＝6.9Hz),6.37(d,
1H,J＝15.8Hz),6.87(d,2H,J＝8.9Hz),7.26−7.33(m,2
H),7.39−7.48(m,5H) 1 H-N of 1- (2- (4- (2- (4-((1E) hept-1-enyl) phenyl) ethynyl) -2-methylphenyl) ethynyl) -4-pentyloxybenzene
The MR spectrum data was as follows. 1 H-NMR (δ): 0.91 (t, 3H, J = 6.6 Hz), 0.94 (t, 3H, J =
6.9Hz), 1.25-1.55 (m, 10H), 1.78 (qt, 2H, J = 6.6Hz), 2.2
1 (dt, 2H, Jd = 6.9Hz, Jt = 6.9Hz), 2.49 (s, 3H), 3.97 (t, 2H,
J = 6.6Hz), 6.27 (dt, 1H, Jd = 15.8Hz, Jt = 6.9Hz), 6.37 (d,
1H, J = 15.8Hz), 6.87 (d, 2H, J = 8.9Hz), 7.26-7.33 (m, 2
H), 7.39-7.48 (m, 5H)
【００４９】１−(２−(４−(２−(４−((１Ｅ)ヘプト
−１−エニル)フェニル)エチニル)−２−メチルフェニ
ル)エチニル)−４−ペンチルオキシベンゼンの相系列を
偏光顕微鏡観察により評価したところ、１１０℃未満で
結晶相を示し、１１０〜２３３℃の範囲でネマティック
相を示し、２３３℃を超えると等方相を示した。従っ
て、この化合物は、液晶性化合物であることがわかる。
また、該化合物を、ネマティック組成物 ＭＪ９３１３
８１(メルクジャパン社製)に１０質量％添加して測定し
た屈折率異方性Δｎから、濃度比で外挿したΔｎを求め
たところ、０．４９と極めて大きいものであった。な
お、Δｎはアッベ屈折計で測定した。測定温度は２０
℃、測定波長は５８９ｎｍで行った。The phase series of 1- (2- (4- (2- (4-((1E) hept-1-enyl) phenyl) ethynyl) -2-methylphenyl) ethynyl) -4-pentyloxybenzene was polarized. Evaluation by microscopic observation revealed a crystalline phase below 110 ° C, a nematic phase in the range of 110-233 ° C, and an isotropic phase above 233 ° C. Therefore, it is understood that this compound is a liquid crystal compound.
Further, the compound is used as a nematic composition MJ9313.
From the refractive index anisotropy Δn measured by adding 10% by mass to 81 (manufactured by Merck Japan KK), Δn extrapolated by the concentration ratio was found to be extremely large, 0.49. Note that Δn was measured with an Abbe refractometer. Measurement temperature is 20
C., the measurement wavelength was 589 nm.
【００５０】１−(２−(２−メチル−４−(２−(４−
(２−ペンチルシクロプロピル)フェニル)エチニル)フェ
ニル)エチニル)−４−ペンチルオキシベンゼンの1Ｈ−
ＮＭＲスペクトルデータは以下のとおりであった。1 Ｈ-ＮＭＲ(δ)：0.76−0.84(m,1H),0.86−0.97(m,7H),
0.98−1.10(m,1H),1.24−1.50(m,12H),1.56−1.64(m,1
H),1.74−1.84(m,2H),2.49(s,3H),3.97(d,2H,J＝6.6H
z),6.87(d,2H,J＝8.9Hz),7.00(d,2H,J＝8.3Hz),7.27−
7.36(m,1H),7.37−7.53(m,6H)1- (2- (2-methyl-4- (2- (4-
Of (2-pentyl-cyclopropyl) phenyl) ethynyl) phenyl) ethynyl) -4-pentyloxy benzene 1 H-
The NMR spectrum data was as follows. 1 H-NMR (δ): 0.76-0.84 (m, 1H), 0.86-0.97 (m, 7H),
0.98-1.10 (m, 1H), 1.24-1.50 (m, 12H), 1.56-1.64 (m, 1
H), 1.74-1.84 (m, 2H), 2.49 (s, 3H), 3.97 (d, 2H, J = 6.6H
z), 6.87 (d, 2H, J = 8.9Hz), 7.00 (d, 2H, J = 8.3Hz), 7.27−
7.36 (m, 1H), 7.37-7.53 (m, 6H)
【００５１】１−(２−(２−メチル−４−(２−(４−
(２−ペンチルシクロプロピル)フェニル)エチニル)フェ
ニル)エチニル)−４−ペンチルオキシベンゼンの相系列
を偏光顕微鏡観察により評価したところ、７５℃未満で
結晶相を示し、７５〜１７０℃の範囲でネマティック相
を示し、１７０℃を超えると等方相を示した。従って、
この化合物は、液晶性化合物であることがわかる。ま
た、該化合物のΔｎを測定したところ０．４０と極めて
大きいものであった。1- (2- (2-methyl-4- (2- (4-
When the phase series of (2-pentylcyclopropyl) phenyl) ethynyl) phenyl) ethynyl) -4-pentyloxybenzene was evaluated by observation with a polarizing microscope, it showed a crystalline phase below 75 ° C and a nematic in the range of 75 to 170 ° C. A phase above 170 ° C. showed an isotropic phase. Therefore,
This compound is understood to be a liquid crystal compound. The Δn of the compound measured was 0.40, which was extremely large.
【００５２】実施例２ 撹拌装置及び温度計を装着したフラスコ内に、窒素雰囲
気下で、工程４−２で調製した、４−(４−(２−ペンチ
ルシクロプロピル)フェニルエチニル)−２−メチルフェ
ニル(トリフルオロメチル)スルホネートと、４−(４−
((１Ｅ)ヘプト−１−エニル)フェニルエチニル)−２−
メチルフェニル(トリフルオロメチル)スルホネートとの
混合物１．３５ｇ、ジクロロビス(トリフェニルホスフ
ィン)パラジウム０．０５ｇ、ＤＭＦ１３．５ｇ及びト
リエチルアミン０．９１ｇを仕込み、５３〜５５℃に昇
温した。続いて、４−トリフルオロメトキシフェニルア
セチレン１．２６ｇをＤＭＦ２．７０ｇに溶解した溶液
を、同温度で２時間かけて滴下し、５時間撹拌した。そ
の後、水を加えて反応を停止し、トルエンで抽出後、有
機層を水洗した。有機層を濃縮後、残渣を、ヘキサンに
トリエチルアミン０．１質量％添加したものを移動相と
するシリカゲルクロマトグラフィーにて精製した。更
に、エタノール及びヘキサンによる再結晶を繰り返し、
目的とする化合物１−(２−(４−(２−(４−((１Ｅ)ヘ
プト−１−エニル)フェニル)エチニル)−２−メチルフ
ェニル)エチニル)−４−トリフルオロメトキシベンゼン
０．１９ｇ(純度９９．７％)及び１−(２−(２−メチル
−４−(２−(４−(２−ペンチルシクロプロピル)フェニ
ル)エチニル)フェニル)エチニル)−４−トリフルオロメ
トキシベンゼン０．１１ｇ(純度８５．３％)を得た。 Example 2 In a flask equipped with a stirrer and a thermometer, 4- (4- (2-pentylcyclopropyl) phenylethynyl) -2-methyl prepared in Step 4-2 was placed under a nitrogen atmosphere. Phenyl (trifluoromethyl) sulfonate and 4- (4-
((1E) hept-1-enyl) phenylethynyl) -2-
1.35 g of a mixture with methylphenyl (trifluoromethyl) sulfonate, 0.05 g of dichlorobis (triphenylphosphine) palladium, 13.5 g of DMF and 0.91 g of triethylamine were charged, and the temperature was raised to 53 to 55 ° C. Subsequently, a solution in which 1.26 g of 4-trifluoromethoxyphenylacetylene was dissolved in 2.70 g of DMF was added dropwise at the same temperature over 2 hours, followed by stirring for 5 hours. Thereafter, the reaction was stopped by adding water, and after extraction with toluene, the organic layer was washed with water. After concentrating the organic layer, the residue was purified by silica gel chromatography using a mobile phase obtained by adding 0.1% by mass of triethylamine to hexane. Furthermore, recrystallization with ethanol and hexane is repeated,
0.19 g of desired compound 1- (2- (4- (2- (4-((1E) hept-1-enyl) phenyl) ethynyl) -2-methylphenyl) ethynyl) -4-trifluoromethoxybenzene (Purity 99.7%) and 1- (2- (2-methyl-4- (2- (4- (2-pentylcyclopropyl) phenyl) ethynyl) phenyl) ethynyl) -4-trifluoromethoxybenzene. 11 g (85.3% purity) were obtained.
【００５３】１−(２−(４−(２−(４−((１Ｅ)ヘプト
−１−エニル)フェニル)エチニル)−２−メチルフェニ
ル)エチニル)−４−トリフルオロメトキシベンゼンの1
Ｈ−ＮＭＲスペクトルデータは以下のとおりであった。1 Ｈ−ＮＭＲ(δ)：0.91(t,3H,J＝6.6Hz),1.30−1.53(m,
6H),2.22(dt,2H,Jd＝6.9Hz,Jt＝6.9Hz),2.49(s,3H),6.2
7(dt,1H,Jd＝15.7Hz,Jt＝6.9Hz),6.37(d,1H,J＝15.7H
z),7.18-7.58(m,11H) １−(２−(４−(２−(４−((１Ｅ)ヘプト−１−エニル)
フェニル)エチニル)−２−メチルフェニル)エチニル)−
４−トリフルオロメトキシベンゼンの相系列を偏光顕微
鏡観察により評価したところ、１０８℃未満で結晶相を
示し、１０８〜１９４℃の範囲でスメクチック相を示
し、１９４〜２２４℃の範囲でネマティック相を示し、
２２４℃を超えると等方相を示した。従って、この化合
物は、液晶性化合物であることが判る。また、該化合物
のΔｎを測定したところ、０．４５と極めて大きいもの
であった。１−(２−(２−メチル−４−(２−(４−(２
−ペンチルシクロプロピル)フェニル)エチニル)フェニ
ル)エチニル)−４−トリフルオロメトキシベンゼンの1
Ｈ−ＮＭＲスペクトルデータは以下のとおりであった。1 Ｈ−ＮＭＲ(δ)：0.76−0.84(m,1H),0.86−0.94(m,4
H),1.05−1.08(m,1H),1.25−1.41(m,8H),1.56−1.64(m,
1H),2.49(s,3H),6.98−7.58(m,11H)[0053] 1- - of (2- (4- (2- (4 ((1E) hept-1-enyl) phenyl) ethynyl) -2-methylphenyl) ethynyl) -4-trifluoromethyl-methoxybenzene 1
1 H-NMR spectrum data was as follows. 1 H-NMR (δ): 0.91 (t, 3H, J = 6.6Hz), 1.30-1.53 (m,
6H), 2.22 (dt, 2H, Jd = 6.9Hz, Jt = 6.9Hz), 2.49 (s, 3H), 6.2
7 (dt, 1H, Jd = 15.7Hz, Jt = 6.9Hz), 6.37 (d, 1H, J = 15.7H
z), 7.18-7.58 (m, 11H) 1- (2- (4- (2- (4-((1E) hept-1-enyl))
(Phenyl) ethynyl) -2-methylphenyl) ethynyl)-
When the phase series of 4-trifluoromethoxybenzene was evaluated by observation with a polarizing microscope, it showed a crystalline phase below 108 ° C, showed a smectic phase in the range of 108 to 194 ° C, and showed a nematic phase in the range of 194 to 224 ° C. ,
Exceeding 224 ° C. showed an isotropic phase. Therefore, it is understood that this compound is a liquid crystal compound. In addition, when the Δn of the compound was measured, it was as extremely large as 0.45. 1- (2- (2-methyl-4- (2- (4- (2
- a pentyl cyclopropyl) phenyl) ethynyl) phenyl) ethynyl) -4-trifluoromethyl-methoxybenzene 1
1 H-NMR spectrum data was as follows. 1 H-NMR (δ): 0.76-0.84 (m, 1H), 0.86-0.94 (m, 4
H), 1.05-1.08 (m, 1H), 1.25-1.41 (m, 8H), 1.56-1.64 (m,
1H), 2.49 (s, 3H), 6.98-7.58 (m, 11H)
【００５４】実施例３ 撹拌装置及び温度計を装着したフラスコ内に、窒素雰囲
気下で、工程４−２で調製した、４−(４−(２−ペンチ
ルシクロプロピル)フェニルエチニル)−２−メチルフェ
ニル(トリフルオロメチル)スルホネートと、４−(４−
((１Ｅ)ヘプト−１−エニル)フェニルエチニル)−２−
メチルフェニル(トリフルオロメチル)スルホネートとの
混合物２．００ｇ、ジクロロビス(トリフェニルホスフ
ィン)パラジウム０．０８ｇ、ＤＭＦ２０．０ｇ及びト
リエチルアミン１．３５ｇを仕込み、５３〜５５℃に昇
温した。続いて、ｐ−エチニルベンゾニトリル２．２６
ｇを仕込み、同温度で５時間撹拌した。その後、水を加
えて反応を停止し、トルエンで抽出後、有機層を水洗し
た。有機層を濃縮後、残渣を、ヘキサン／クロロホルム
＝１０／１(容積比)にトリエチルアミン０．１質量％添
加したものを移動相とするシリカゲルクロマトグラフィ
ーにて精製した。更に、メタノール及びヘキサンによる
再結晶を繰り返し、目的とする化合物４−(２−(４−
(２−(４−((１Ｅ)ヘプト−１−エニル)フェニル)エチ
ニル)−２−メチルフェニル)エチニル)ベンゾニトリル
０．０７ｇ(純度９８．９％)及び４−(２−(２−メチル
−４−(２−(４−(２−ペンチルシクロプロピル)フェニ
ル)エチニル)フェニル)エチニル)ベンゾニトリル０．０
０１ｇ(純度８８．４％)を得た。 Example 3 In a flask equipped with a stirrer and a thermometer, 4- (4- (2-pentylcyclopropyl) phenylethynyl) -2-methyl prepared in Step 4-2 under a nitrogen atmosphere. Phenyl (trifluoromethyl) sulfonate and 4- (4-
((1E) hept-1-enyl) phenylethynyl) -2-
2.00 g of a mixture with methylphenyl (trifluoromethyl) sulfonate, 0.08 g of dichlorobis (triphenylphosphine) palladium, 20.0 g of DMF, and 1.35 g of triethylamine were charged, and the temperature was raised to 53 to 55 ° C. Subsequently, p-ethynylbenzonitrile 2.26
g and stirred at the same temperature for 5 hours. Thereafter, the reaction was stopped by adding water, and after extraction with toluene, the organic layer was washed with water. After concentrating the organic layer, the residue was purified by silica gel chromatography using a mobile phase obtained by adding 0.1% by mass of triethylamine to hexane / chloroform = 10/1 (volume ratio). Further, recrystallization with methanol and hexane was repeated to obtain the desired compound 4- (2- (4-
0.07 g (purity 98.9%) of (2- (4-((1E) hept-1-enyl) phenyl) ethynyl) -2-methylphenyl) ethynyl) benzonitrile and 4- (2- (2-methyl -4- (2- (4- (2-pentylcyclopropyl) phenyl) ethynyl) phenyl) ethynyl) benzonitrile 0.0
01 g (88.4% purity) were obtained.
【００５５】４−(２−(４−(２−(４−((１Ｅ)ヘプト
−１−エニル)フェニル)エチニル)−２−メチルフェニ
ル)エチニル)ベンゾニトリルの1Ｈ−ＮＭＲスペクトル
データは以下のとおりであった。1 Ｈ−ＮＭＲ(δ)：0.91(t,3H,J＝6.6Hz),1.25−1.54(m,
6H),2.22(dt,2H,Jd＝6.9Hz,Jt＝6.9Hz),2.50(s,3H),6.2
7(dt,1H,Jd＝15.7Hz,Jt＝6.9Hz),6.37(d,1H,J＝15.7H
z),7.26−7.72(m,11H)４−(２−(４−(２−(４−((１
Ｅ)ヘプト−１−エニル)フェニル)エチニル)−２−メチ
ルフェニル)エチニル)ベンゾニトリルの相系列を偏光顕
微鏡観察により評価したところ、１０７℃未満で結晶相
を示し、１０７〜２７０℃の範囲でネマティック相を示
し、２７０℃を超えると等方相を示した。従って、この
化合物は、液晶性化合物であることが判る。また、該化
合物のΔｎを測定したところ、０．５８と極めて大きい
ものであった。４−(２−(２−メチル−４−(２−(４−
(２−ペンチルシクロプロピル)フェニル)エチニル)フェ
ニル)エチニル)ベンゾニトリルの1Ｈ−ＮＭＲスペクト
ルデータは以下のとおりであった。1 Ｈ-ＮＭＲ(δ)：0.76−0.92(m,5H),1.05−1.43(m,9H),
1.55−1.64(m,1H),2.50(s,3H),7.00−7.66(m,11H)The 1 H-NMR spectrum data of 4- (2- (4- (2- (4-((1E) hept-1-enyl) phenyl) ethynyl) -2-methylphenyl) ethynyl) benzonitrile is as follows. It was as follows. 1 H-NMR (δ): 0.91 (t, 3H, J = 6.6 Hz), 1.25-1.54 (m,
6H), 2.22 (dt, 2H, Jd = 6.9Hz, Jt = 6.9Hz), 2.50 (s, 3H), 6.2
7 (dt, 1H, Jd = 15.7Hz, Jt = 6.9Hz), 6.37 (d, 1H, J = 15.7H
z), 7.26-7.72 (m, 11H) 4- (2- (4- (2- (4-((1
E) When the phase series of hept-1-enyl) phenyl) ethynyl) -2-methylphenyl) ethynyl) benzonitrile was evaluated by observation with a polarizing microscope, it showed a crystalline phase at less than 107 ° C, and a crystalline phase at a temperature in the range of 107 to 270 ° C. A nematic phase was exhibited, and above 270 ° C., an isotropic phase was exhibited. Therefore, it is understood that this compound is a liquid crystal compound. The Δn of the compound was measured and found to be as extremely large as 0.58. 4- (2- (2-methyl-4- (2- (4-
The 1 H-NMR spectrum data of (2-pentylcyclopropyl) phenyl) ethynyl) phenyl) ethynyl) benzonitrile were as follows. 1 H-NMR (δ): 0.76-0.92 (m, 5H), 1.05-1.43 (m, 9H),
1.55-1.64 (m, 1H), 2.50 (s, 3H), 7.00-7.66 (m, 11H)
【００５６】[0056]
【発明の効果】本発明の骨格にシクロプロパン基又はア
ルケニル基を有するフェニルアセチレン化合物及びこの
化合物を用いた液晶組成物は、屈折率異方性が大きく、
安定で、他液晶に混合し易く、例えば、ＳＴＮ(超ねじ
れネマティック)型液晶素子やＰＤＬＣ(ポリマ−分散型
液晶)型液晶素子に代表される液晶素子を構成する材料
として特に有用である。The phenylacetylene compound having a cyclopropane group or an alkenyl group in the skeleton of the present invention and the liquid crystal composition using this compound have a large refractive index anisotropy,
It is stable and easily mixed with other liquid crystals, and is particularly useful as a material constituting a liquid crystal element represented by, for example, an STN (super twisted nematic) liquid crystal element or a PDLC (polymer-dispersed liquid crystal) liquid crystal element.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０２Ｆ 1/13 ５００ Ｇ０２Ｆ 1/13 ５００ (72)発明者 関根 千津 茨城県つくば市北原６ 住友化学工業株式 会社内 (72)発明者 藤沢 幸一 茨城県つくば市北原６ 住友化学工業株式 会社内 (72)発明者 岩倉 和憲 大阪府高槻市塚原二丁目10番１号 住友化 学工業株式会社内 (72)発明者 南井 正好 大阪府高槻市塚原二丁目10番１号 住友化 学工業株式会社内 Ｆターム(参考） 4H006 AA01 AB64 GP03 4H027 BB04 BB11 BD01 BD07 BD24 CE02 CE03 CE04 CE05 DP01 DP03 DP04 DP05 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) G02F 1/13 500 G02F 1/13 500 (72) Inventor Chizu Sekine 6 Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd. In-company (72) Inventor Koichi Fujisawa 6 Kitahara, Tsukuba, Ibaraki Prefecture Sumitomo Chemical Co., Ltd.In-company (72) Inventor Kazunori Iwakura 2-1-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Co., Ltd. (72) Invention Person Masayoshi Minami 2-10-1 Tsukahara, Takatsuki-shi, Osaka F-term in Sumitomo Chemical Co., Ltd. 4H006 AA01 AB64 GP03 4H027 BB04 BB11 BD01 BD07 BD24 CE02 CE03 CE04 CE05 DP01 DP03 DP04 DP05
Claims (3)
合物。 【化１】 (式中、Ａ1〜Ａ12は、それぞれ独立に水素原子、フッ素
原子又はフッ素原子で置換されていてもよい炭素数１〜
１０の、アルキル基もしくはアルコキシ基を示し、少な
くとも１つはフッ素原子で置換されていてもよい炭素数
１〜１０の、アルキル基又はアルコキシ基である。Ｂ
は、 【化２】 を示す。Ｒ1は直鎖もしくは分枝のフッ素原子で置換さ
れていてもよい炭素数１〜１２のアルキル基を示す。Ｒ
2は、それぞれ独立に水素原子、フッ素原子、シアノ
基、−ＳＦ5、−ＮＣＳ、４−Ｒ3−(シクロアルキル)
基、４−Ｒ3−(シクロアルケニル基)又はＲ4−(Ｏ)ｑ基
を示す(但し、Ｒ3は水素原子又は直鎖もしくは分枝のフ
ッ素原子で置換されていてもよい炭素数１〜１２のアル
キル基を示し、Ｒ4は直鎖もしくは分枝のフッ素原子で
置換されていてもよい炭素数１〜１２のアルキル基を示
す。ｑは０又は１を示す)。)1. A phenylacetylene compound represented by the formula (1). Embedded image (In the formula, A 1 to A 12 each independently represent a hydrogen atom, a fluorine atom or a carbon atom which may be substituted with a fluorine atom.
10 represents an alkyl group or an alkoxy group, at least one of which is an alkyl group or an alkoxy group having 1 to 10 carbon atoms which may be substituted by a fluorine atom. B
Is Is shown. R 1 represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by a fluorine atom. R
2 each independently represent a hydrogen atom, a fluorine atom, a cyano group, -SF 5, -NCS, 4- R 3 - ( cycloalkyl)
Group, 4-R 3 - (cycloalkenyl group) or R 4 - (O) indicating the q group (wherein, R 3 is 1 the number hydrogen atom or a straight or branched carbon atoms which may be substituted with a fluorine atom And R 4 represents an alkyl group having 1 to 12 carbon atoms which may be substituted by a linear or branched fluorine atom, and q represents 0 or 1). )
を少なくとも１種含有することを特徴とする液晶組成
物。2. A liquid crystal composition comprising at least one compound represented by the formula (1) according to claim 1.
基板間に挟持してなることを特徴とする液晶素子。3. A liquid crystal device comprising the liquid crystal composition according to claim 2 sandwiched between a pair of electrode substrates.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000124957A JP4344456B2 (en) | 2000-04-25 | 2000-04-25 | Phenylacetylene compound having cyclopropane group or alkenyl group at skeleton end, liquid crystal composition, and liquid crystal element |
| GB0110057A GB2364050B (en) | 2000-04-25 | 2001-04-24 | Phenylacetylene compound liquid crystal composition and liquid crystal element produced with the same |
| DE10120024A DE10120024A1 (en) | 2000-04-25 | 2001-04-24 | Novel phenylacetylene compounds are useful for production of liquid crystal mixtures for the fabrication of flat-screen displays |
| US09/840,983 US6623810B2 (en) | 2000-04-25 | 2001-04-25 | Phenylacetylene compound, liquid crystal composition, and liquid crystal element produced with the same |
| KR1020010022345A KR100742977B1 (en) | 2000-04-25 | 2001-04-25 | Phenylacetylene compound, liquid crystal composition, and liquid crystal element produced with the same |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2000124957A JP4344456B2 (en) | 2000-04-25 | 2000-04-25 | Phenylacetylene compound having cyclopropane group or alkenyl group at skeleton end, liquid crystal composition, and liquid crystal element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001302579A true JP2001302579A (en) | 2001-10-31 |
| JP4344456B2 JP4344456B2 (en) | 2009-10-14 |
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| JP2000124957A Expired - Lifetime JP4344456B2 (en) | 2000-04-25 | 2000-04-25 | Phenylacetylene compound having cyclopropane group or alkenyl group at skeleton end, liquid crystal composition, and liquid crystal element |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254910A (en) * | 2013-05-10 | 2013-08-21 | 石家庄诚志永华显示材料有限公司 | Large optically anisotropic liquid crystal composition |
| JP2014511399A (en) * | 2011-01-21 | 2014-05-15 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Liquid crystal media, components for high frequency technology and mesogenic compounds |
-
2000
- 2000-04-25 JP JP2000124957A patent/JP4344456B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014511399A (en) * | 2011-01-21 | 2014-05-15 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Liquid crystal media, components for high frequency technology and mesogenic compounds |
| CN103254910A (en) * | 2013-05-10 | 2013-08-21 | 石家庄诚志永华显示材料有限公司 | Large optically anisotropic liquid crystal composition |
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| Publication number | Publication date |
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| JP4344456B2 (en) | 2009-10-14 |
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