JP4759949B2 - 2-naphthyl-1,3-dioxane derivatives - Google Patents
2-naphthyl-1,3-dioxane derivatives Download PDFInfo
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- JP4759949B2 JP4759949B2 JP2004221691A JP2004221691A JP4759949B2 JP 4759949 B2 JP4759949 B2 JP 4759949B2 JP 2004221691 A JP2004221691 A JP 2004221691A JP 2004221691 A JP2004221691 A JP 2004221691A JP 4759949 B2 JP4759949 B2 JP 4759949B2
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- CBRARZGZWVHMSX-UHFFFAOYSA-N 2-naphthalen-2-yl-1,3-dioxane Chemical class O1CCCOC1C1=CC=C(C=CC=C2)C2=C1 CBRARZGZWVHMSX-UHFFFAOYSA-N 0.000 title claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 2
- -1 3,4-difluorophenyl group Chemical group 0.000 description 28
- 0 *C1COC(c2ccc(cc(cc3)F)c3c2)OC1 Chemical compound *C1COC(c2ccc(cc(cc3)F)c3c2)OC1 0.000 description 23
- 239000000243 solution Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000004093 cyano group Chemical group *C#N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 description 9
- RYBZVFVHLHZLAY-UHFFFAOYSA-N 5-propyl-2-(5,6,7-trifluoronaphthalen-2-yl)-1,3-dioxane Chemical compound O1CC(CCC)COC1C1=CC=C(C(F)=C(F)C(F)=C2)C2=C1 RYBZVFVHLHZLAY-UHFFFAOYSA-N 0.000 description 8
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004988 Nematic liquid crystal Substances 0.000 description 4
- 125000003302 alkenyloxy group Chemical group 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical group C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 3
- MQJLHQUBJOXLKP-UHFFFAOYSA-N 5,6,7-trifluoronaphthalene-2-carbaldehyde Chemical compound O=CC1=CC=C2C(F)=C(F)C(F)=CC2=C1 MQJLHQUBJOXLKP-UHFFFAOYSA-N 0.000 description 3
- XYIHEFLVUNNGHS-UHFFFAOYSA-N 5,6,7-trifluoronaphthalene-2-carbonitrile Chemical compound N#CC1=CC=C2C(F)=C(F)C(F)=CC2=C1 XYIHEFLVUNNGHS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- 125000005451 3-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:1])C([H])=C(F)C([*:2])=C1[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 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
- 230000007704 transition Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 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 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- LNEMDIUSUQPKIP-UHFFFAOYSA-N 2-phenyl-1,3-dioxane Chemical class O1CCCOC1C1=CC=CC=C1 LNEMDIUSUQPKIP-UHFFFAOYSA-N 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N Trimethylene glycol Natural products OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- JEDZLBFUGJTJGQ-UHFFFAOYSA-N [Na].COCCO[AlH]OCCOC Chemical compound [Na].COCCO[AlH]OCCOC JEDZLBFUGJTJGQ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KZIBQYUFIVUOHY-UHFFFAOYSA-N bis(2-methylpropyl)alumane toluene Chemical compound Cc1ccccc1.[H][Al](CC(C)C)CC(C)C KZIBQYUFIVUOHY-UHFFFAOYSA-N 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- XNLBCXGRQWUJLU-UHFFFAOYSA-N naphthalene-2-carbonyl chloride Chemical compound C1=CC=CC2=CC(C(=O)Cl)=CC=C21 XNLBCXGRQWUJLU-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Liquid Crystal Substances (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Description
本発明は電気光学的液晶表示材料として有用な、2-ナフチル-1,3-ジオキサン骨格を有する新規液晶性化合物、それを含む液晶組成物およびそれを用いた液晶表示素子に関する。 The present invention relates to a novel liquid crystalline compound having a 2-naphthyl-1,3-dioxane skeleton, a liquid crystal composition containing the same, and a liquid crystal display device using the same, useful as an electro-optical liquid crystal display material.
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、ワープロ、電子手帳、プリンター、コンピューター、テレビ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(捩れネマチック)型、STN(超捩れネマチック)型、DS(動的光散乱)型、GH(ゲスト・ホスト)型あるいは高速応答が可能なFLC(強誘電性液晶)等を挙げることができる。また駆動方式としても従来のスタティック駆動からマルチプレックス駆動が一般的になり、さらに単純マトリックス方式、最近ではアクティブマトリックス方式が実用化されている。 Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, etc., including watches and calculators. Typical liquid crystal display methods include TN (twisted nematic), STN (super twisted nematic), DS (dynamic light scattering), GH (guest / host), or FLC capable of high-speed response. (Ferroelectric liquid crystal). As a drive system, a multiplex drive is generally used instead of a conventional static drive, and a simple matrix system and recently an active matrix system have been put into practical use.
これらに用いられる液晶材料としては、これまでにも非常に多種類の化合物が合成されてきており、その表示方式や駆動方式あるいはその用途に応じて使用されている。 As a liquid crystal material used for these, a great variety of compounds have been synthesized so far, and they are used according to the display method, driving method or use thereof.
液晶化合物は通常コアと呼ばれる中心骨格部分と両側の側鎖部分から構成されている。通常、側鎖部分の少なくとも一方は鎖状基であることが多いが、誘電率異方性が正のいわゆるp型液晶の場合には、他方の側鎖部分は極性基であることが多い。 Liquid crystal compounds are usually composed of a central skeleton part called a core and side chain parts on both sides. Usually, at least one of the side chain portions is often a chain group, but in the case of a so-called p-type liquid crystal having a positive dielectric anisotropy, the other side chain portion is often a polar group.
液晶化合物に用いられる極性基としては、シアノ基が代表的である。このシアノ基を有する液晶化合物は極性が強く液晶性にも優れる反面、粘性が比較的大きく、また高い電圧保持率が得られないため前述のアクティブマトリックス駆動方式には使用することができないなど問題点も多い。そのため、極性基としてフッ素原子が用いられることが多くなっている。この極性基としてフッ素原子を有する液晶化合物は上記シアノ系の液晶化合物と比較すると極性が弱く、誘電異方性(Δε)は小さいけれども、粘度が小さくまた高い電圧保持率を得ることも容易である。 A typical cyano group used in the liquid crystal compound is a cyano group. Although this liquid crystal compound having a cyano group has high polarity and excellent liquid crystallinity, it has a relatively high viscosity and cannot provide a high voltage holding ratio. There are also many. Therefore, a fluorine atom is often used as a polar group. This liquid crystal compound having a fluorine atom as a polar group is weaker in polarity than the above-mentioned cyano liquid crystal compound and has a small dielectric anisotropy (Δε), but has a small viscosity and can easily obtain a high voltage holding ratio. .
ところで極性基として用いられるこれらのフッ素原子は、通常分子末端のフェニル基に直結する構造で導入されている。従って、化合物としては分子の片方の末端に4-フルオロフェニル基、3,4-ジフルオロフェニル基または3,4,5-ジフルオロフェニル基を有する化合物にほぼ限定されており、その化学構造の変化の幅が非常に小さい。そのため、これらのフッ素系の液晶化合物のみでは年々高度化する液晶組成物に対する要求特性には充分応えきれなくなってきているのが実情である。 By the way, these fluorine atoms used as polar groups are usually introduced in a structure directly connected to the phenyl group at the molecular end. Therefore, the compounds are almost limited to compounds having a 4-fluorophenyl group, a 3,4-difluorophenyl group or a 3,4,5-difluorophenyl group at one end of the molecule. The width is very small. Therefore, the fact is that these fluorine-based liquid crystal compounds alone cannot sufficiently meet the required characteristics for liquid crystal compositions that are becoming more sophisticated year by year.
そこで、フルオロナフチル基(特許文献1及び2参照)、あるいは(トリフルオロメトキシ)ナフチル基(特許文献3参照)を有する化合物が報告されている。例えば、6-フルオロナフチル基を有する液晶化合物は、Δεが大きく、広い温度範囲で液晶相を示し、また高速応答が可能である液晶組成物の成分として適していることが報告されている(特許文献2)。 Therefore, a compound having a fluoronaphthyl group (see Patent Documents 1 and 2) or a (trifluoromethoxy) naphthyl group (see Patent Document 3) has been reported. For example, it has been reported that a liquid crystal compound having a 6-fluoronaphthyl group has a large Δε, exhibits a liquid crystal phase in a wide temperature range, and is suitable as a component of a liquid crystal composition capable of high-speed response (patent) Reference 2).
また、コア部位としては、上記に挙げたフェニル基、シクロヘキシル基、ナフチル基の他に、1,3-ジオキサン骨格を有する液晶化合物も知られている(特許文献4及び5参照)。例えば、2-フェニル-1,3-ジオキサン誘導体は、比較的小さい粘度および比較的大きいΔεを同時に有する液晶組成物の成分として適していることが報告されている(特許文献4及び5参照)。 In addition to the above-mentioned phenyl group, cyclohexyl group, and naphthyl group, liquid crystal compounds having a 1,3-dioxane skeleton are also known as core sites (see Patent Documents 4 and 5). For example, it has been reported that a 2-phenyl-1,3-dioxane derivative is suitable as a component of a liquid crystal composition having a relatively small viscosity and a relatively large Δε (see Patent Documents 4 and 5).
上記に挙げた材料を用いても、液晶組成物に対する要求特性に十分応えられているわけではなく、更なる特性改良、例えば、より小さい屈折率異方性(Δn)およびより大きいΔεを同時に有する液晶組成物の成分として適している材料の開発が望まれている。 Even if the above-mentioned materials are used, the required properties for the liquid crystal composition are not sufficiently satisfied, and further improvement in properties, for example, a smaller refractive index anisotropy (Δn) and a larger Δε are simultaneously provided. Development of a material suitable as a component of a liquid crystal composition is desired.
本発明が解決しようとする課題は、小さいΔnおよび大きいΔεを同時に有する液晶組成物の成分として適している材料を提供することにあり、またそれを用いて、実用的な液晶組成物を提供することにある。 The problem to be solved by the present invention is to provide a material suitable as a component of a liquid crystal composition having a small Δn and a large Δε at the same time, and to provide a practical liquid crystal composition using the material. There is.
本発明は、上記課題を解決するための手段として、一般式(I) The present invention provides a general formula (I) as a means for solving the above problems.
(式中Rは、炭素数1〜12のアルキル基、あるいは炭素数2〜12のアルケニル基を表し、
L1およびL2は、それぞれ独立して、水素原子、または-Fを表し、
Xは、水素原子、-F、-Cl、-CF3、-OCH2F、-OCHF2、-OCF3、-CH2CF3、-CHFCF3または-CF2CF3を表す。)で表される2-ナフチル-1,3-ジオキサン誘導体当該化合物を1種または2種以上含有する液晶組成物及び当該液晶組成物を構成要素とする液晶素子を提供する。
(Wherein R represents an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms,
L 1 and L 2 each independently represent a hydrogen atom or -F;
X represents a hydrogen atom, -F, -Cl, -CF 3 , -OCH 2 F, -OCHF 2 , -OCF 3 , -CH 2 CF 3 , -CHFCF 3 or -CF 2 CF 3 . 2) a 2-naphthyl-1,3-dioxane derivative represented by formula (1) or a liquid crystal composition containing one or more of the compounds, and a liquid crystal element comprising the liquid crystal composition as a constituent element.
本発明に係わる一般式(I)で表される化合物は、工業的に容易に製造でき、熱、光、水等に対し、化学的に安定であり、現在汎用されている液晶化合物あるいは液晶組成物との相溶性に優れているだけでなく、Δnが小さくかつΔεが大きく、広い温度範囲で液晶相を示し、高速応答が可能である実用的な液晶組成物の成分として適している。 The compound represented by the general formula (I) according to the present invention can be easily produced industrially, is chemically stable to heat, light, water, etc., and is currently used as a liquid crystal compound or liquid crystal composition. In addition to being excellent in compatibility with materials, it is suitable as a component of a practical liquid crystal composition that has a small Δn and a large Δε, exhibits a liquid crystal phase in a wide temperature range, and is capable of high-speed response.
一般式(I)において、Rは、炭素数1〜12のアルキル基、または炭素数2〜12のアルケニル基を表すが、炭素数1〜8のアルキル基、または炭素数2〜8のアルケニル基が好ましく、L1およびL2は、それぞれ独立して、水素原子、または-Fを表し、Xは、水素原子、-F、-Cl、-CF3、-OCH2F、-OCHF2、-OCF3、-CH2CF3、-CHFCF3または-CF2CF3を表すが、水素原子、-F、-Cl、-OCHF2または-OCF3が好ましく、-F、-OCHF2または-OCF3がより好ましい。 In the general formula (I), R represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, but an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. L 1 and L 2 each independently represent a hydrogen atom or -F, and X is a hydrogen atom, -F, -Cl, -CF 3 , -OCH 2 F, -OCHF 2 ,- Represents OCF 3 , —CH 2 CF 3 , —CHFCF 3 or —CF 2 CF 3 , preferably a hydrogen atom, —F, —Cl, —OCHF 2 or —OCF 3 , —F, —OCHF 2 or —OCF 3 is more preferable.
上述のように一般式(I)の化合物はそのR、L1、L2、およびXの選択により多種の化合物を包含しうるわけであるが、これらの中では以下の一般式(Ia)〜一般式(Il)で表される各化合物が好ましい。 As described above, the compound of the general formula (I) can include various compounds depending on the selection of R, L 1 , L 2 , and X. Among these, the following general formulas (Ia) to (Ia) to Each compound represented by the general formula (Il) is preferable.
以上の式中、R1は炭素数1〜8のアルキル基、あるいは炭素数2〜8のアルケニル基を表すが、特に炭素原子数2〜7の直鎖状アルキル基、あるいはビニル基、3-ブテニル基、トランス-1-プロペン-1-イルまたはトランス-3-ペンテン-1-イル基が好ましい。さらに、上式中では式(Ib)、式(Id)、式(If)、式(Ih)、式(Ij)、または式(Il)で表される化合物が特に好ましい。 In the above formula, R 1 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and in particular, a linear alkyl group having 2 to 7 carbon atoms, a vinyl group, 3- A butenyl group, trans-1-propen-1-yl or trans-3-penten-1-yl group is preferred. Further, in the above formula, a compound represented by formula (Ib), formula (Id), formula (If), formula (Ih), formula (Ij), or formula (Il) is particularly preferable.
本発明の(I)の化合物は、例えば、以下のようにして製造することができる。
（製法１）
一般式(II)
The compound (I) of the present invention can be produced, for example, as follows.
(Production method 1)
Formula (II)
（製法２）
一般式(V)
(Manufacturing method 2)
Formula (V)
（製法３）
一般式(VI)で表される6-シアノナフタレン化合物を加水分解することにより、一般式(VII)
(Manufacturing method 3)
By hydrolyzing the 6-cyanonaphthalene compound represented by the general formula (VI), the general formula (VII)
一般式(I)で表される化合物の多くは、他の液晶材料に対し比較的優れた相溶性を示す。また分子軸に対し2個以上のフッ素原子が同方向に導入されている場合は、極性が大きく、強いp型液晶としての特性を示す。また、高い比抵抗や電圧保持率を得ることも容易である。従って、他の液晶化合物との混合物の状態で液晶表示セル用材料として、好適に用いることができる。一般式(I)で表される化合物はその添加により誘電率異方性(Δε)を大きく増大させてその閾値電圧を低減することが可能であり、かつ高速応答と、屈折率異方性(Δn)の増大が可能であるといった特長を併せ持ち、前述の各種表示方式のいずれにおいても使用可能であるが、単純マトリックス駆動あるいはアクティブマトリックス駆動のTN型表示素子、及びSTN表示素子に用いることが適しており、特にSTN表示素子用液晶材料の極性成分として用いることが好ましい。 Many of the compounds represented by the general formula (I) exhibit relatively excellent compatibility with other liquid crystal materials. In addition, when two or more fluorine atoms are introduced in the same direction with respect to the molecular axis, the polarity is large and the characteristics as a strong p-type liquid crystal are exhibited. It is also easy to obtain a high specific resistance and voltage holding ratio. Therefore, it can be suitably used as a liquid crystal display cell material in a mixture with other liquid crystal compounds. The compound represented by the general formula (I) can greatly increase the dielectric anisotropy (Δε) and reduce the threshold voltage by the addition thereof, and has a fast response and a refractive index anisotropy ( (Δn) can be increased and can be used in any of the above-mentioned various display methods, but it is suitable for use in TN type display elements of simple matrix drive or active matrix drive, and STN display elements. In particular, it is preferably used as a polar component of the liquid crystal material for STN display elements.
このように、一般式(I)で表される化合物と混合して使用することのできるネマチック液晶化合物の好ましい代表例としては、本発明の提供する組成物においては、その第1成分として一般式(I)で表される化合物を少なくとも1種含有するが、その他の成分として特に以下の第2成分および第3成分から少なくとも1種含有することが好ましい。 Thus, as a preferred representative example of a nematic liquid crystal compound that can be used by mixing with the compound represented by the general formula (I), in the composition provided by the present invention, the first component is represented by the general formula Although at least one compound represented by (I) is contained, it is preferable to contain at least one of the following second and third components as other components.
本発明の液晶組成物の第2成分として、Δεの絶対値の小さい、一般式(A) As the second component of the liquid crystal composition of the present invention, the absolute value of Δε is small, general formula (A)
(式中、RaおよびRbはそれぞれ独立的に水素原子、炭素数1〜15のアルキル基、少なくとも一つのハロゲンにより置換された炭素数1〜15のアルキル基、炭素数2〜15のアルケニル基または少なくとも一つのハロゲンにより置換された炭素数2〜15のアルケニル基を表し、これらの基中に存在する1個または2個以上の-CH2-はそれぞれ独立して-O-が相互に直接結合しないものとして-O-、-S-、-CO-、-COO-、-OCO-または-OCO-O-により置換されていても良く、
Ba、BbおよびBcはそれぞれ独立的に
(a) トランス-1,4-シクロへキシレン基(この基中に存在する1個の-CH2-または隣接していない2個以上の-CH2-は、-O-または-S-に置換されていてもよい。)、
(b) 1,4-フェニレン基(この基中に存在する1個の-CH=または隣接していない2個以上の-CH=は、-N=に置換されていてもよい。)、および
(c) 1,4-シクロヘキセニレン基、1,4-ビシクロ[2.2.2]オクチレン基、ピペリジン-1,4-ジイル基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基および1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、
からなる群より選ばれる基を表し、上記の基(a)、基(b)または基(c)はそれぞれ-CN、-Fまたは-Clで置換されていても良く、
oは0、1または2を表し、
La、LbおよびLcはそれぞれ独立的に単結合、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-または-C≡C-を表し、LbおよびBcが複数存在する場合は、それらは同一でも異なっていても良い。)で表される化合物を含有することが好ましい。
(Wherein, R a and R b are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 15 carbon atoms substituted with at least one halogen, or an alkenyl having 2 to 15 carbon atoms) Represents an alkenyl group having 2 to 15 carbon atoms substituted by a group or at least one halogen, and one or two or more of —CH 2 — present in these groups independently represent —O— May be substituted by -O-, -S-, -CO-, -COO-, -OCO- or -OCO-O- as not directly bonded,
B a , B b and B c are each independently
(a) trans-1,4-cyclohexylene group (the one present in the group -CH 2 - or 2 nonadjacent or more -CH 2 - may, -O- or -S- in May be substituted),
(b) a 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be substituted with -N =), and
(c) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -Diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group,
The group (a), the group (b) or the group (c) may be substituted with -CN, -F or -Cl, respectively.
o represents 0, 1 or 2,
L a , L b and L c each independently represent a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O— or —C≡C—, When a plurality of L b and B c are present, they may be the same or different. It is preferable to contain the compound represented by this.
一般式(A)において、RaおよびRbは、炭素数1〜15のアルキル基または炭素数2〜15のアルケニル基を表すことが好ましく、直鎖状炭素数1〜8のアルキル基または炭素数2〜8のアルケニル基を表すことがより好ましく、未置換の直鎖状炭素数1〜8のアルキル基または炭素数2〜6のアルケニル基を表すことが特に好ましく、アルケニル基ではビニル基、3-ブテニル基、トランス-1-プロペン-1-イルまたはトランス-3-ペンテン-1-イル基がさらに好ましく、アルケニルオキシ基では2-プロペニル基、トランス-2-ブテニル基、4-ペンテニル基またはトランス-4-ヘキセニル基がさらに好ましい。また、RaおよびRbは同一でも異なっていても良いが、同一分子中のRaおよびRbは異なっていることがより好ましい。 In the general formula (A), R a and R b preferably represent an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and a linear alkyl group having 1 to 8 carbon atoms or carbon More preferably, it represents an alkenyl group having 2 to 8 carbon atoms, particularly preferably an unsubstituted linear alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. More preferred is a 3-butenyl group, trans-1-propen-1-yl or trans-3-penten-1-yl group. In the alkenyloxy group, a 2-propenyl group, a trans-2-butenyl group, a 4-pentenyl group or A trans-4-hexenyl group is more preferred. R a and R b may be the same or different, but it is more preferable that R a and R b in the same molecule are different.
LaおよびLbは、-COO-、-OCO-、-CH2CH2-、-C≡C-、-(CH2)4-または単結合を表すことが好ましく、-CH2CH2-、-C≡C-または単結合を表すことがより好ましく、-CH2CH2-または単結合を表すことが特に好ましく、LaおよびLbが複数存在する場合、少なくとも一つは単結合を表すことが好ましい。 L a and L b preferably represent —COO—, —OCO—, —CH 2 CH 2 —, —C≡C—, — (CH 2 ) 4 — or a single bond, —CH 2 CH 2 — , —C≡C— or a single bond is more preferable, —CH 2 CH 2 — or a single bond is particularly preferable, and when a plurality of L a and L b are present, at least one of them represents a single bond. It is preferable to represent.
oは、0または1を表すことが好ましい。 o preferably represents 0 or 1.
Ba、BbおよびBcはそれぞれ独立してトランス-1,4-シクロへキシレン基、1,4-フェニレン基、3-フルオロ-1,4-フェニレン基または3,5-ジフルオロ-1,4-フェニレン基を表すことが好ましく、トランス-1,4-シクロへキシレン基または1,4-フェニレン基を表すことより好ましく、Ba、BbおよびBcのうち、少なくとも一つはトランス-1,4-シクロへキシレン基を表すことが好ましい。 B a , B b and B c are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, 3-fluoro-1,4-phenylene group or 3,5-difluoro-1, It preferably represents a 4-phenylene group, more preferably represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group, and at least one of B a , B b and B c is trans- It preferably represents a 1,4-cyclohexylene group.
一般式(A)で表される化合物は、具体的な構造として、以下の一般式(A-0)で表される構造が好ましい。 The compound represented by the general formula (A) is preferably a structure represented by the following general formula (A-0) as a specific structure.
一般式(A-0)で表される化合物は、さらに具体的な構造として、以下の一般式(A-1)〜一般式(A-3)で表される構造が好ましい。
The compound represented by the general formula (A-0) is preferably a structure represented by the following general formula (A-1) to general formula (A-3) as a more specific structure.
また、一般式(A)で表される化合物として、以下の一般式(A-4)〜一般式(A-11)で表される構造も好ましい。
Further, as the compound represented by the general formula (A), structures represented by the following general formula (A-4) to general formula (A-11) are also preferable.
(式中、RcおよびRdは、一般式(A-0)におけると同じ意味を表す。)
本発明の液晶組成物の第3成分として、Δεの比較的大きい、一般式(Ba)、一般式(Bb)、一般式(Bc)、一般式(Bd)および一般式(Be)
(Wherein R c and R d have the same meaning as in general formula (A-0).)
As the third component of the liquid crystal composition of the present invention, Δε is relatively large, general formula (Ba), general formula (Bb), general formula (Bc), general formula (Bd) and general formula (Be)
(式中Reは、一般式(A)におけるRaと同じ意味を表し、Ca、CbおよびCcはそれぞれ独立して、
(d) トランス-1,4-シクロへキシレン基(この基中に存在する1個の-CH2-または隣接していない2個以上の-CH2-は、-O-または-S-に置換されていてもよい。)、
(e) 1,4-フェニレン基(この基中に存在する1個の-CH=または隣接していない2個以上の-CH=は-N=に置換されていてもよい。)および、
(f) 1,4-シクロヘキセニレン基、1,4-ビシクロ[2.2.2]オクチレン基、ピペリジン-1,4-ジイル基、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-ジイル基およびデカヒドロナフタレン-2,6-ジイル基、
からなる群より選ばれる基であり、上記の基(d)、基(e)または基(f)はそれぞれ-CN、-Fまたは-Clで置換されていても良く、
Ka、KbおよびKcはそれぞれ独立的に単結合、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-または-C≡C-を表し、
Xb、Xc、Xd、XeおよびXfはそれぞれ独立して水素原子または-Fを表し、
pおよびqはそれぞれ独立して、0、1または2を表すが、pおよびqの和は2以下であり、
Xaは、水素原子、-F、-Cl、-CN、-CF3、-OCH2F、-OCHF2、-OCF3、-CH2CF3、-CHFCF3、-CF2CF3または一般式(A)におけるRaと同じ意味を表す。)で表される化合物を含有することが好ましい。
(Wherein R e represents the same meaning as R a in formula (A), and C a , C b and C c are each independently
(d) trans-1,4-cyclohexylene group (the one present in the group -CH 2 - or 2 nonadjacent or more -CH 2 - may, -O- or -S- in May be substituted),
(e) a 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be substituted with -N =), and
(f) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, 1,2,3,4 -Tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group,
The group (d), the group (e) or the group (f) may be substituted with -CN, -F or -Cl, respectively.
K a , K b and K c each independently represent a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O— or —C≡C—,
X b , X c , X d , X e and X f each independently represent a hydrogen atom or -F;
p and q each independently represent 0, 1 or 2, but the sum of p and q is 2 or less,
X a is a hydrogen atom, -F, -Cl, -CN, -CF 3, -OCH 2 F, -OCHF 2, -OCF 3, -CH 2 CF 3, -CHFCF 3, -CF 2 CF 3 or general The same meaning as Ra in formula (A) is represented. It is preferable to contain the compound represented by this.
一般式(Ba)、一般式(Bb)、一般式(Bc)および一般式(Bd)においてReは、炭素数1〜15の直鎖状アルキル基または炭素数2〜15のアルケニル基を表すことが好ましく、炭素数1〜10の直鎖状アルキル基または炭素数2〜10のアルケニル基を表すことがより好ましく、炭素数1〜8の直鎖状アルキル基または炭素数2〜6のアルケニル基を表すことが特に好ましく、アルケニル基ではビニル基、3-ブテニル基、トランス-1-プロペン-1-イルまたはトランス-3-ペンテン-1-イル基がさらに好ましく、アルケニルオキシ基では2-プロペニル基、トランス-2-ブテニル基、4-ペンテニル基またはトランス-4-ヘキセニル基がさらに好ましい。Ka、KbおよびKcは、-COO-、-OCO-、-CH2CH2-、-C≡C-、-(CH2)4-または単結合を表すことが好ましく、-CH2CH2-、-C≡C-または単結合を表すことがより好ましく、-CH2CH2-または単結合を表すことが特に好ましく、Ka、KbまたはKcが複数存在する場合少なくとも一つは単結合であることが好ましい。pおよびqは、0または1を表すことが好ましい。Ca、CbおよびCcはそれぞれ独立してトランス-1,4-シクロへキシレン基、1,4-フェニレン基、3-フルオロ-1,4-フェニレン基または3,5-ジフルオロ-1,4-フェニレン基を表すことが好ましく、トランス-1,4-シクロへキシレン基または1,4-フェニレン基を表すことがより好ましく、トランス-1,4-シクロへキシレン基を表すことが特に好ましい。 Formula (Ba), R e in the general formula (Bb), the general formula (Bc) and the general formula (Bd), a linear alkyl group or alkenyl group having 2 to 15 carbon atoms having 1 to 15 carbon atoms It is more preferable that it represents a linear alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and a linear alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. Particularly preferably a vinyl group, a 3-butenyl group, a trans-1-propen-1-yl or trans-3-penten-1-yl group for an alkenyl group, and a 2-propenyl group for an alkenyloxy group. More preferred is a group, trans-2-butenyl group, 4-pentenyl group or trans-4-hexenyl group. K a , K b and K c preferably represent —COO—, —OCO—, —CH 2 CH 2 —, —C≡C—, — (CH 2 ) 4 — or a single bond, —CH 2 More preferably, it represents CH 2 —, —C≡C— or a single bond, particularly preferably —CH 2 CH 2 — or a single bond, and at least one when a plurality of K a , K b or K c are present. One is preferably a single bond. p and q preferably represent 0 or 1. C a , C b and C c are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, 3-fluoro-1,4-phenylene group or 3,5-difluoro-1, It preferably represents a 4-phenylene group, more preferably represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group, and particularly preferably represents a trans-1,4-cyclohexylene group. .
Xaは-F、-CN、-CF3、-OCH2F、-OCHF2、-OCF3を表すことが好ましく、-Fを表すことが特に好ましい。 X a is -F, -CN, -CF 3, -OCH 2 F, -OCHF 2, preferably represents an -OCF 3, and particularly preferably a -F.
一般式(Ba)で表される化合物は、具体的には以下の一般式(Ba-0)で表される構造を表すことが好ましい。 Specifically, the compound represented by the general formula (Ba) preferably represents a structure represented by the following general formula (Ba-0).
(式中、Rfは炭素原子数1〜8のアルキル基、炭素原子数1〜8のアルコキシル基、炭素原子数2〜8のアルケニル基または炭素原子数3〜6のアルケニルオキシ基を表し、KdおよびKeはそれぞれ独立して、-CH2CH2-、-CH=CH-、-C≡C-、-(CH2)4-または単結合を表し、Cdは1,4-フェニレン基またはトランス-1,4-シクロヘキシレン基を表し、XhおよびXiは、それぞれ独立して水素原子または-Fを表し、nは0または1を表し、Xgは-F、-Cl、-CN、-CF3、-OCH2F、-OCHF2または-OCF3を表す。)
さらに具体的には以下の一般式(Ba-1a)〜一般式(Ba-3d)
(In the formula, R f represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 3 to 6 carbon atoms, K d and Ke each independently represent —CH 2 CH 2 —, —CH═CH—, —C≡C—, — (CH 2 ) 4 — or a single bond, and C d represents 1,4- Represents a phenylene group or a trans-1,4-cyclohexylene group, X h and X i each independently represent a hydrogen atom or -F, n represents 0 or 1, and X g represents -F, -Cl , -CN, -CF 3 , -OCH 2 F, -OCHF 2 or -OCF 3 )
More specifically, the following general formula (Ba-1a) to general formula (Ba-3d)
(式中、Rf、Xg、XhおよびXiは、一般式(Ba-0)におけると同じ意味を表す。)で表される構造が好ましい。 (Wherein R f , X g , X h and X i represent the same meaning as in general formula (Ba-0)).
一般式(Bb)で表される化合物は、具体的には以下の一般式(Bb-1)〜一般式(Bb-2)で表される構造を表すことが好ましい。 Specifically, the compound represented by the general formula (Bb) preferably represents a structure represented by the following general formula (Bb-1) to general formula (Bb-2).
(式中、Rf、Xg、XhおよびXiは、一般式(Ba-0)におけると同じ意味を表す。)
一般式(Bc)で表される化合物は、具体的な構造として以下の一般式
(In the formula, R f , X g , X h and X i represent the same meaning as in the general formula (Ba-0).)
The compound represented by the general formula (Bc) has the following general formula as a specific structure.
(式中、Rf、Xg、XhおよびXiは、一般式(Ba-0)におけると同じ意味を表す。)で表される構造が好ましく、
一般式(Bd)で表される化合物は、具体的な構造として以下の一般式
(Wherein R f , X g , X h and X i represent the same meaning as in general formula (Ba-0)), and a structure represented by
The compound represented by the general formula (Bd) has the following general formula as a specific structure.
(式中、Rf、Xg、XhおよびXiは、一般式(Ba-0)におけると同じ意味を表す。)で表される構造が好ましい。 (Wherein R f , X g , X h and X i represent the same meaning as in general formula (Ba-0)).
一般式(Be)で表される化合物は、具体的には以下の一般式(Be-1)〜(Bb-2)で表される構造を表すことが好ましい。 Specifically, the compound represented by the general formula (Be) preferably represents a structure represented by the following general formulas (Be-1) to (Bb-2).
(式中、Rf、Xg、XhおよびXiは、一般式(Ba-0)におけると同じ意味を表す。) (In the formula, R f , X g , X h and X i represent the same meaning as in the general formula (Ba-0).)
以下に本発明の実施例を示し、本発明を更に説明する。しかし、本発明はこれらの実施例に限定されるものではない。 The following examples further illustrate the present invention. However, the present invention is not limited to these examples.
なお、相転移温度の測定は温度調節ステージを備えた偏光顕微鏡および示差走査熱量計(DSC)を併用して行った。また、化合物の構造は核磁気共鳴スペクトル(NMR)、赤外共鳴スペクトル(IR)、質量スペクトル(MS)等により確認した。
（実施例１）5-プロピル-2-(5,6,7-トリフルオロナフタレン-2-イル)-1,3-ジオキサン(I-1)の合成
The phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC). The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), infrared resonance spectrum (IR), mass spectrum (MS) and the like.
Example 1 Synthesis of 5-propyl-2- (5,6,7-trifluoronaphthalen-2-yl) -1,3-dioxane (I-1)
（実施例１−１）5,6,7-トリフルオロナフタレン-2-カルボニトリル(VI-1)
(以下、窒素雰囲気下で行う。)シアン化カリウム(11.0 g、0.168 mol)、テトラキストリフェニルホスフィンパラジウム(0)(2.1 g、0.002 mol)をテトラヒドロフラン(THF、100 ml)中、室温で激しく攪拌している中に、トリフルオロメタンスルホン酸5,6,7-トリフルオロナフタレン-2-イル(27.8 g、0.084 mol)を滴下して加えた。16時間加熱還流した後、水を加えて反応を停止させた。反応液の有機層を分離し、水層から酢酸エチルで抽出した(2回)。有機層を集めた後、3 M塩酸、水、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗條し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、再結晶(トルエン／ヘキサン)することにより、淡黄色の粉末(16.4 g)を得た。(収率 90.8%)
（実施例１−２）5,6,7-トリフルオロナフタレン-2-カルバルデヒド(III-1)
(以下、窒素雰囲気下で行う。)化合物VI-1(7.9 g、0.036 mol)のTHF溶液(50 ml)を10 ℃以下で激しく攪拌している中に、1.5 M水素化ジイソブチルアルミニウムトルエン溶液(30 ml、0.045 mol)を、その温度を保ちながら滴下して加えた。室温まで昇温した後1時間攪拌し、反応液を氷水に滴下して加えて反応を停止させた。析出した固体が溶解するまで3 M塩酸を加えた後、有機層を分離し、水層から酢酸エチルで抽出した(3回)。有機層を集めた後、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗條し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、カラム(シリカゲル、ヘキサン／酢酸エチル)により精製することにより、黄色の固体(5.6 g)を得た。(収率 73.3%)
Example 1-1 5,6,7-trifluoronaphthalene-2-carbonitrile (VI-1)
(Hereafter, performed in a nitrogen atmosphere.) Potassium cyanide (11.0 g, 0.168 mol) and tetrakistriphenylphosphine palladium (0) (2.1 g, 0.002 mol) were stirred vigorously in tetrahydrofuran (THF, 100 ml) at room temperature. Into this, trifluoromethanesulfonic acid 5,6,7-trifluoronaphthalen-2-yl (27.8 g, 0.084 mol) was added dropwise. After heating at reflux for 16 hours, water was added to stop the reaction. The organic layer of the reaction solution was separated and extracted from the aqueous layer with ethyl acetate (twice). The organic layer was collected, washed with 3M hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off, and recrystallization (toluene / hexane) gave a pale yellow powder (16.4 g). (Yield 90.8%)
Example 1-2 5,6,7-trifluoronaphthalene-2-carbaldehyde (III-1)
(The following is performed under a nitrogen atmosphere.) While a THF solution (50 ml) of compound VI-1 (7.9 g, 0.036 mol) was vigorously stirred at 10 ° C. or lower, a 1.5 M diisobutylaluminum hydride toluene solution ( 30 ml, 0.045 mol) was added dropwise while maintaining the temperature. After warming to room temperature, the mixture was stirred for 1 hour, and the reaction solution was added dropwise to ice water to stop the reaction. After adding 3 M hydrochloric acid until the precipitated solid was dissolved, the organic layer was separated and extracted from the aqueous layer with ethyl acetate (3 times). After collecting the organic layer, the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was purified by a column (silica gel, hexane / ethyl acetate) to obtain a yellow solid (5.6 g). (Yield 73.3%)
（実施例１−３）5-プロピル-2-(5,6,7-トリフルオロナフタレン-2-イル)-1,3-ジオキサン(I-1)
化合物III-1(11.6 g、0.053 mol)のトルエン溶液(100 ml)を室温で攪拌している中に、p-トルエンスルホン酸一水和物(0.6 g)を加えた。全量を加え終わった後、水分離器から留出する水がなくなるまで加熱還流した(約3時間)。反応液を放冷した後、飽和炭酸水素ナトリウム水溶液を加えた。反応液の有機層を分離し、水、飽和食塩水の順で洗條し、無水硫酸マグネシウムで乾燥した。溶媒を留去し、得られた残渣をカラム(シリカゲル、ヘキサン)により精製し、さらに再結晶(メタノール／エタノール)することにより、白色の固体(4.4 g)を得た。
1H-NMR (400MHz, CDCl3) d (ppm) 0.94 (t, 3H), 1.12 (q, 2H), 1.36 (sextet, 2H), 2.16-2.22 (m, 1H), 3.60 (t, 2H), 4.29 (dd, J1 = 11.4 Hz, , J2 = 4.6 Hz, 2H), 5.56 (s, 1H), 7.40 (dd, J1 = 8.0 Hz, J2 = 7.6 Hz, 1H), 7.66 (d, J = 8.8 Hz, 1H), 7.90 (s, 1H), 8.04 (d, J = 8.8 Hz, 1H)、相転移温度(℃) Cry 70 Iso
Example 1-3 5-Propyl-2- (5,6,7-trifluoronaphthalen-2-yl) -1,3-dioxane (I-1)
While a toluene solution (100 ml) of compound III-1 (11.6 g, 0.053 mol) was stirred at room temperature, p-toluenesulfonic acid monohydrate (0.6 g) was added. After all the amount had been added, the mixture was heated to reflux (about 3 hours) until no water distilled from the water separator. After allowing the reaction solution to cool, a saturated aqueous sodium hydrogen carbonate solution was added. The organic layer of the reaction solution was separated, washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified with a column (silica gel, hexane) and recrystallized (methanol / ethanol) to obtain a white solid (4.4 g).
1 H-NMR (400MHz, CDCl 3 ) d (ppm) 0.94 (t, 3H), 1.12 (q, 2H), 1.36 (sextet, 2H), 2.16-2.22 (m, 1H), 3.60 (t, 2H) , 4.29 (dd, J 1 = 11.4 Hz,, J 2 = 4.6 Hz, 2H), 5.56 (s, 1H), 7.40 (dd, J 1 = 8.0 Hz, J 2 = 7.6 Hz, 1H), 7.66 (d , J = 8.8 Hz, 1H), 7.90 (s, 1H), 8.04 (d, J = 8.8 Hz, 1H), phase transition temperature (° C) Cry 70 Iso
（実施例２）液晶組成物の調製(1)
低粘性で温度範囲の広いネマチック液晶として特にアクティブマトリックス駆動用に好適なホスト液晶(H)
(Example 2) Preparation of liquid crystal composition (1)
Host liquid crystal (H) especially suitable for active matrix drive as nematic liquid crystal with low viscosity and wide temperature range
ネマチック相上限温度(Tni) : 116.7℃
誘電率異方性(Δε) : 4.80
屈折率異方性(Δn) : 0.090
閾値電圧(Vth) : 1.88 V
粘度(η) : 19.7 cP
次に、このホスト液晶(H)に実施例1で得られた化合物(I-1)
Nematic phase upper limit temperature (Tni): 116.7 ℃
Dielectric Anisotropy (Δε): 4.80
Refractive index anisotropy (Δn): 0.090
Threshold voltage (Vth): 1.88 V
Viscosity (η): 19.7 cP
Next, the compound (I-1) obtained in Example 1 was added to the host liquid crystal (H).
次に、組成物(H-1)をセル厚4.5μmのTNセルに充填して液晶素子を作成し、その電気光学特性を測定したところ、以下のとおりであった。
ネマチック相上限温度(Tni) : 88.7℃
誘電率異方性(Δε) : 8.21
屈折率異方性(Δn) : 0.092
閾値電圧(Vth) : 1.49 V
組成物(H-1)のΔεは大幅に増大し、このため閾値電圧(Vth)はホスト液晶(H)と比較すると約20%減少している一方で、屈折率異方性(Δn)は、殆ど変化しなかった。
Next, the composition (H-1) was filled in a TN cell having a cell thickness of 4.5 μm to prepare a liquid crystal device, and the electro-optical characteristics thereof were measured.
Nematic phase upper limit temperature (Tni): 88.7 ℃
Dielectric Anisotropy (Δε): 8.21
Refractive index anisotropy (Δn): 0.092
Threshold voltage (Vth): 1.49 V
The Δε of the composition (H-1) is greatly increased, so that the threshold voltage (Vth) is reduced by about 20% compared to the host liquid crystal (H), while the refractive index anisotropy (Δn) is Almost no change.
以上のように一般式(I)で表される化合物は、液晶組成物のΔεを増大し、Vthを低減するため低電圧駆動可能な液晶組成物の調製するうえにおいて、非常に有用であることがわかる。 As described above, the compound represented by the general formula (I) is very useful in preparing a liquid crystal composition that can be driven at a low voltage in order to increase Δε of the liquid crystal composition and reduce Vth. I understand.
（比較例１）
ホスト液晶(H)に化合物(I-1)と比較的類似の構造を有するが、1,3-ジオキサン骨格をフェニル基に替えた化合物(A)
(Comparative Example 1)
Compound (A) having a structure relatively similar to that of compound (I-1) in host liquid crystal (H) but having a 1,3-dioxane skeleton replaced with a phenyl group
をホスト液晶(H)に同量(20%)添加して調製した液晶組成物(H-A)の物性値ならびにそれを用いて作成した液晶素子の電気光学的特性値は以下のとおりとなった。
ネマチック相上限温度(Tni) : 90.1℃
誘電率異方性(Δε) : 7.15
屈折率異方性(Δn) : 0.110
閾値電圧(Vth) : 1.63 V
従って、化合物(A)の添加により、ホスト液晶(H)と比較するとVthおよび応答は改善しているものの、屈折率異方性(Δn)は0.018も増加した。また、組成物(H-A)は、組成物(M-1)と比較してVthは0.14 Vも高いことがわかった。
The physical properties of the liquid crystal composition (HA) prepared by adding the same amount (20%) to the host liquid crystal (H) and the electro-optical characteristics of the liquid crystal device prepared using the same were as follows.
Nematic phase upper limit temperature (Tni): 90.1 ℃
Dielectric Anisotropy (Δε): 7.15
Refractive index anisotropy (Δn): 0.110
Threshold voltage (Vth): 1.63 V
Therefore, the addition of the compound (A) improved the refractive index anisotropy (Δn) by 0.018, although the Vth and response were improved as compared with the host liquid crystal (H). The composition (HA) was found to have a Vth as high as 0.14 V compared to the composition (M-1).
(比較例２)
ホスト液晶(H)に化合物(I-1)と比較的類似の構造を有するが、1,3-ジオキサン骨格を2-フルオロフェニル基に替えた化合物(B)
(Comparative Example 2)
Compound (B) having a structure relatively similar to that of compound (I-1) in host liquid crystal (H), but replacing the 1,3-dioxane skeleton with a 2-fluorophenyl group
次に、組成物(H-B)をセル厚4.5μmのTNセルに充填して液晶素子を作成し、その電気光学特性を測定したところ、以下のとおりであった。
ネマチック相上限温度(Tni) : 85.5℃
誘電率異方性(Δε) : 8.04
屈折率異方性(Δn) : 0.104
閾値電圧(Vth) : 1.47V
化合物(B)の添加により、ホスト液晶(H)と比較するとVthおよび応答は大幅に改善した。組成物(H-B)は、組成物(H-1)と比較すると、ほぼ同程度のΔεとVthを示したが、Δnは0.012も大きかった。
（実施例３）液晶組成物の調製(2)
実施例1で得られた化合物(I-1)を用いて、低粘性で温度範囲の広い実用的な、特にアクティブマトリックス駆動用に好適な液晶組成物(M-1)および(M-2)を調製した。得られた組成物(M-1)および(M-2)をそれぞれセル厚4.5μmのTNセルに充填して液晶素子を作成し、その電気光学特性を測定した結果、以下のとおりであった。
Next, the composition (HB) was filled in a TN cell having a cell thickness of 4.5 μm to prepare a liquid crystal device, and the electro-optical characteristics thereof were measured.
Nematic phase upper limit temperature (Tni): 85.5 ℃
Dielectric Anisotropy (Δε): 8.04
Refractive index anisotropy (Δn): 0.104
Threshold voltage (Vth): 1.47V
The addition of compound (B) significantly improved Vth and response compared to host liquid crystal (H). The composition (HB) showed substantially the same Δε and Vth as compared with the composition (H-1), but Δn was as large as 0.012.
(Example 3) Preparation of liquid crystal composition (2)
Using the compound (I-1) obtained in Example 1, a practical liquid crystal composition (M-1) and (M-2) suitable for driving an active matrix having a low viscosity and a wide temperature range Was prepared. The obtained compositions (M-1) and (M-2) were each filled into a TN cell having a cell thickness of 4.5 μm to prepare a liquid crystal element, and the electro-optical characteristics thereof were measured. The results were as follows. .
表中、化合物略号は以下のとおりである。 In the table, compound abbreviations are as follows.
末端のn(数字) -CnH2n+1
F -F
-m(数字)dn(数字) -(CH2)n-1-CH=CH-CmH2m+1
Terminal n (number) -C n H 2n + 1
F -F
-m (number) dn (number)-(CH 2 ) n-1 -CH = CH-C m H 2m + 1
化合物(I-1)を用いた組成物(M-1)および(M-2)のΔεは非常に大きく、1.5V付近の低電圧で駆動することができた。また、これら組成物(M-1)および(M-2)を150℃で1時間放置した後、そのTniを測定したが、ほとんど変化がみられなかった。また、紫外線を1時間照射したが、Tniに変化はみられなかった。次にこれら組成物の電圧保持率を測定したところ、調製時、加熱後及び紫外線照射後ともに同様に充分高い値を示した。 The Δε of the compositions (M-1) and (M-2) using the compound (I-1) was very large and could be driven at a low voltage around 1.5V. Further, these compositions (M-1) and (M-2) were allowed to stand at 150 ° C. for 1 hour and then their Tni was measured, but almost no change was observed. In addition, ultraviolet rays were irradiated for 1 hour, but Tni did not change. Next, when the voltage holding ratio of these compositions was measured, it showed a sufficiently high value both during preparation, after heating and after ultraviolet irradiation.
(比較例３)
化合物(I-1)を用いていない、低粘性で温度範囲の広い実用的な、アクティブマトリックス駆動用に好適な液晶組成物(M-3)を調製した。得られた組成物(M-3)をセル厚4.5μmのTNセルに充填して液晶素子を作成し、その電気光学特性を測定した結果、以下のとおりであった。
(Comparative Example 3)
A practical liquid crystal composition (M-3) suitable for active matrix driving was prepared without using the compound (I-1) and having a low viscosity and a wide temperature range. The obtained composition (M-3) was filled in a TN cell having a cell thickness of 4.5 μm to prepare a liquid crystal element, and the electro-optical characteristics thereof were measured. The results were as follows.
組成物(M-1)および(M-2)と比較してΔεが0.67〜0.85小さく、その結果、Vthは0.07〜0.08V高くなった。
Compared with the compositions (M-1) and (M-2), Δε was 0.67 to 0.85 smaller, and as a result, Vth was 0.07 to 0.08 V higher.
Claims (4)
L1およびL2は、それぞれ独立して、水素原子または-Fを表し、
Xは、水素原子、-F、-Cl、-CF3、-OCH2F、-OCHF2、-OCF3、-CH2CF3、-CHFCF3または-CF2CF3を表す。)で表される2-ナフチル-1,3-ジオキサン誘導体。 Formula (I)
L 1 and L 2 each independently represent a hydrogen atom or -F;
X represents a hydrogen atom, -F, -Cl, -CF 3 , -OCH 2 F, -OCHF 2 , -OCF 3 , -CH 2 CF 3 , -CHFCF 3 or -CF 2 CF 3 . 2-naphthyl-1,3-dioxane derivatives represented by
4. A liquid crystal device comprising the liquid crystal composition according to claim 3 as a constituent element.
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