JP3632772B2 - 4-alkenyloxy-3,5-difluorobenzene derivatives - Google Patents
4-alkenyloxy-3,5-difluorobenzene derivatives Download PDFInfo
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- JP3632772B2 JP3632772B2 JP05177394A JP5177394A JP3632772B2 JP 3632772 B2 JP3632772 B2 JP 3632772B2 JP 05177394 A JP05177394 A JP 05177394A JP 5177394 A JP5177394 A JP 5177394A JP 3632772 B2 JP3632772 B2 JP 3632772B2
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- 150000001875 compounds Chemical class 0.000 claims description 72
- 239000004973 liquid crystal related substance Substances 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 239000012071 phase Substances 0.000 description 33
- 238000002844 melting Methods 0.000 description 19
- 230000008018 melting Effects 0.000 description 19
- -1 p-toluenesulfonyl group Chemical group 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000004988 Nematic liquid crystal Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CDOQKISJPOWBKC-UHFFFAOYSA-N 5-bromo-1,3-difluoro-2-methoxybenzene Chemical compound COC1=C(F)C=C(Br)C=C1F CDOQKISJPOWBKC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BPMHQKDPYSRNLG-OPMHRUBESA-N FC1=C(C(=CC(=C1)[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)CCC)F)OC Chemical compound FC1=C(C(=CC(=C1)[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)CCC)F)OC BPMHQKDPYSRNLG-OPMHRUBESA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 0 *C(CC1)CCC1C(CC1)CCC1=** Chemical compound *C(CC1)CCC1C(CC1)CCC1=** 0.000 description 3
- GPRPSJPFAAGLCA-UHFFFAOYSA-N 4-bromo-2,6-difluorophenol Chemical compound OC1=C(F)C=C(Br)C=C1F GPRPSJPFAAGLCA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical class C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- CKKOVFGIBXCEIJ-UHFFFAOYSA-N 2,6-difluorophenol Chemical compound OC1=C(F)C=CC=C1F CKKOVFGIBXCEIJ-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- TUPBHQDYRHYZKS-GARHLSDISA-N C(CC)[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)C1=CC(=C(C(=C1)F)O)F Chemical compound C(CC)[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)C1=CC(=C(C(=C1)F)O)F TUPBHQDYRHYZKS-GARHLSDISA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NBZANZVJRKXVBH-GYDPHNCVSA-N alpha-Cryptoxanthin Natural products O[C@H]1CC(C)(C)C(/C=C/C(=C\C=C\C(=C/C=C/C=C(\C=C\C=C(/C=C/[C@H]2C(C)=CCCC2(C)C)\C)/C)\C)/C)=C(C)C1 NBZANZVJRKXVBH-GYDPHNCVSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 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
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001934 cyclohexanes Chemical class 0.000 description 2
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JJMDTERTPNYIGZ-UHFFFAOYSA-N 2-cyclohexylacetaldehyde Chemical compound O=CCC1CCCCC1 JJMDTERTPNYIGZ-UHFFFAOYSA-N 0.000 description 1
- DILXLMRYFWFBGR-UHFFFAOYSA-N 2-formylbenzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C(C=O)=C1 DILXLMRYFWFBGR-UHFFFAOYSA-N 0.000 description 1
- AKCZQKBKWXBJOF-UHFFFAOYSA-N 4-(4-propylcyclohexyl)cyclohexan-1-one Chemical compound C1CC(CCC)CCC1C1CCC(=O)CC1 AKCZQKBKWXBJOF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- APHUPTDNDXUGNO-BDWYFLKXSA-N C(CC)[C@@H]1CC[C@H](CC1)C1CC=C(CC1)C1=CC(=C(C(=C1)F)OC)F Chemical compound C(CC)[C@@H]1CC[C@H](CC1)C1CC=C(CC1)C1=CC(=C(C(=C1)F)OC)F APHUPTDNDXUGNO-BDWYFLKXSA-N 0.000 description 1
- BPMHQKDPYSRNLG-MJYONLJCSA-N C(CC)[C@@H]1CC[C@H](CC1)C1CCC(CC1)C1=CC(=C(C(=C1)F)OC)F Chemical compound C(CC)[C@@H]1CC[C@H](CC1)C1CCC(CC1)C1=CC(=C(C(=C1)F)OC)F BPMHQKDPYSRNLG-MJYONLJCSA-N 0.000 description 1
- FFIXAFACUXWNCV-VVPTUSLJSA-N C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](C=2C=CC(O)=CC=2)CC1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](C=2C=CC(O)=CC=2)CC1 FFIXAFACUXWNCV-VVPTUSLJSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 1
- 230000001335 demethylating effect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は電気光学的液晶表示材料として有用な、新規な４−アルケニルオキシ−３，５−ジフルオロベンゼン誘導体である液晶性化合物、及びそれを含有する液晶組成物に関する。
【０００２】
【従来の技術】
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ＦＬＣ（強誘電性液晶）等が知られており、現在主流となっているのはＴＮ型及びＳＴＮ型である。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。これらのうち、アクティブマトリックス方式においては、非常に高画質の表示が可能であり、視野角が広く、高精細化、カラー化が容易で、動画表示も可能であるため、今後の液晶表示方式の主流になると考えられている。
【０００３】
このアクティブマトリックス表示方式に用いられる液晶材料としては、通常の液晶表示と同様に、種々の特性が要求されているが、特に、（１）比抵抗が高く、電圧の保持率に優れること、（２）しきい値電圧（Ｖｔｈ）が低いこと、（３）液晶相の温度範囲が広いこと等が重要である。
【０００４】
通常、液晶表示におけるしきい値電圧（Ｖｔｈ）は式（ａ）
【０００５】
【数１】
（式中、ｋは比例定数を、Ｋは弾性定数を、Δεは誘電率異方性をそれぞれ表わす。）で表わされるが、この式からわかるように、しきい値電圧を低くするためには液晶材料の弾性定数を小さくするか、あるいは誘電率異方性を大きくする必要がある。
【０００７】
しかしながら、誘電率異方性の大きい液晶化合物は、極性の大きいものが多く、高い比抵抗値や電圧保持率の液晶材料を得ることを困難にさせる傾向を有する。そのため、こうした目的には弾性定数が小さい液晶材料が必要である。
【０００８】
弾性定数の小さい液晶材料としては、２環性の化合物が挙げられる。しかしながら、２環性の化合物は、添加により組成物の液晶相の上限温度を大幅に低下させてしまう傾向を有するものが多い。
【０００９】
そこで、液晶組成物の温度範囲を特に高温域に拡大させるためには、３環性あるいは４環性の、液晶相の上限温度の高い化合物を添加する必要がある。しかしながら、このように上限温度の高い化合物は弾性定数が大きいものが多く、添加により組成物のしきい値電圧を大きく上昇させてしまう傾向を有する。
【００１０】
また、液晶相の温度範囲を狭くすることなく、しきい値電圧を低下させる化合物として、一般式（ＩＩ）
【００１１】
【化２】
（式中、Ｒはアルキル基を表わす。）で表わされる化合物等が知られている。（特開平２−２３３６２６号公報に記載）
しかしながら、この化合物の液晶相の上限温度はあまり高くなく、添加による組成物の液晶相の上限温度の上昇も、ほとんど期待できなかった。しかも融点が低くないうえに、添加による組成物の融点の降下も少なく、さらにネマチック相の低温域にスメクチック相を有するため、多量の添加により、低温域におけるネマチック相の安定性に問題が生じ、添加量もかなり制限されていた。
【００１３】
上記のような一般式（ＩＩ）で表わされる化合物の欠点を補うため、本発明者らは一般式（ＩＩＩ）
【００１４】
【化３】
（式中、ＲおよびＲ’はそれぞれアルキル基を表わす。）で表わされる、４−アルコキシ−３，５−ジフルオロベンセン系化合物を開発した。この一般式（ＩＩＩ）で表わされる化合物は、液晶相の温度範囲が特に高温域まで大きく改善され、温度範囲の広い液晶組成物を得ることが容易となったが、融点はあまり低くなっておらず、低温域における充分な液晶相の温度範囲が確保できなかった。
【００１６】
従って、液晶相の温度範囲が低温域から高温域まで広く、添加により組成物のしきい値電圧を低下させるような液晶化合物を得ることはかなり困難であった。
【００１７】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、以上の目的に応じ、融点が低く、広い温度範囲でネマチック相を有し、添加により組成物のしきい値電圧をほとんど上昇させることなく融点を降下させ、しかも液晶相の上限温度を上昇させるような化合物を提供し、また、その化合物を含有し、液晶相の温度範囲が広く、且つしきい値電圧の低い液晶組成物を提供することにある。
【００１８】
【課題を解決するための手段】
本発明は、上記課題を解決するために、一般式（Ｉ）
【００１９】
【化４】
（式中、Ｒ１は炭素原子数１〜１２のアルキル基または炭素原子数２〜１２のアルケニル基を表わすが、好ましくは炭素原子数１〜１０の直鎖状アルキル基を表わし、さらに好ましくは炭素原子数１〜７の直鎖状アルキル基を表わす。Ｌ及びＭはそれぞれ独立的に、単結合または−ＣＨ２ＣＨ２−を表わすが、少なくとも一方は単結合を表わし、特に好ましくは共に単結合を表わす。Ｒ２は炭素原子数３〜１２の直鎖状アルケニル基を表わすが、好ましくは炭素原子数３〜７の直鎖状２−アルケニル基を表わす。また、シクロヘキサン環はトランス配置である。）で表わされる４−アルケニルオキシ−３，５−ジフルオロベンゼン誘導体を提供する。
【００２１】
本発明の一般式（Ｉ）で表わされる化合物において、好ましくは一般式（Ｉａ）〜一般式（Ｉｄ）
【００２２】
【化５】
（式中、Ｒａは炭素原子数１〜７の直鎖状アルキル基を表わし、Ｒｂは炭素原子数２〜７の直鎖状アルケニル基を表わし、Ｒｃは水素原子または炭素原子数１〜４の直鎖状アルキル基を表わす。）で表わされる化合物であり、特に好ましくは、一般式（Ｉａ）で表わされる化合物である。
【００２４】
本発明の一般式（Ｉａ）で表わされる化合物は、例えば、以下の製造方法に従って製造することができる。
【００２５】
【化６】
まず、２，６−ジフルオロフェノールを臭素化して４−ブロモ−２，６−ジフルオロフェノールを得る。これを、塩基存在下でヨウ化メチルと反応させて、式（ＩＶ）の４−メトキシ−１−ブロモ−３，５−ジフルオロベンゼンを得る。
【００２７】
【化７】
（式中、Ｒａは、前述と同じ意味を表わす。）次に、式（ＩＶ）の化合物をマグネシウムと反応させてグリニヤール反応剤とし、これを一般式（Ｖａ）で表わされる４−（トランス−４−アルキルシクロヘキシル）シクロヘキサノンと反応させる。反応後、脱水、水素添加することにより中央のシクロヘキサン環の立体配置による異性体混合物が得られる。これらを分割、または塩基により異性化させて、一般式（ＶＩａ）で表わされる１−［トランス−４−（トランス−４−アルキルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−メトキシベンゼンを得ることができる。
【００２９】
【化８】
（式中、Ｒａ及びＲｃは前述と同じ意味を表わし、Ｘは塩素原子、臭素原子、ヨウ素原子またはｐ−トルエンスルホニル基等の脱離基を表わす。）
さらに、一般式（ＶＩａ）の化合物を、臭化水素酸あるいはヨウ化トリメチルシリル等により脱メチル化して、一般式（ＶＩＩａ）で表わされる４−［トランス−４−（トランス−４−アルキルシクロヘキシル）シクロヘキシル］−２，６−ジフルオロフェノールとする。ここに塩基存在下で、一般式（ＶＩＩＩ）で表わされる化合物と反応させることにより、一般式（Ｉａ）の化合物を得ることができる。
【００３１】
ここで、Ｒ２が１−アルケニル基の化合物は、一般式（Ｉａ）の化合物を強塩基で異性化させること等により得ることができる。
また、Ｒ２が１あるいは２−アルケニル基以外の化合物は、一般式（ＶＩＩＩ）の化合物に代えて、
【００３２】
【化９】
Ｘ−Ｒ２
（式中、Ｒ２及びＸは前述と同じ意味を表わす。）を用いることにより、同様にして製造することができる。
【００３３】
本発明の一般式（Ｉｂ）で表わされる化合物は、例えば、以下の製造方法に従って製造することができる。
上記の一般式（Ｉａ）で表わされる化合物の製造方法において、一般式（Ｖａ）で表わされる化合物に代えて、一般式（Ｖｂ）
【００３４】
【化１０】
（式中、Ｒａは前述と同じ意味を表わす。）で表わされる４−（トランス−４−アルキルシクロヘキシル）シクロヘキサンエタナールを用いることにより、一般式（Ｉｂ）の化合物を得ることができる。ここで一般式（Ｖｂ）の化合物は、例えば、以下の製造方法に従って製造することができる。
【００３６】
【化１１】
（式中、Ｒａは前述と同じ意味を表わす。）
即ち、一般式（Ｖａ）の化合物に、式（ＩＸａ）のウィッティヒ反応剤を反応させ、酸処理を行う工程を２回繰り返すことにより容易に得ることができる。
【００３８】
また、本発明の一般式（Ｉｃ）で表わされる化合物は、例えば、以下の方法に従って製造することができる。
前記の一般式（Ｉａ）で表わされる化合物の製造方法において、一般式（Ｖａ）で表わされる化合物に代えて、一般式（Ｖｃ）
【００３９】
【化１２】
（式中、Ｒａは前述と同じ意味を表わす。）で表わされる４−［２−（トランス−４−アルキルシクロヘキシル）エチル］シクロヘキサノンを用いることにより、一般式（Ｉｃ）の化合物を得ることができる。ここで一般式（Ｖｃ）で表わされる化合物は、例えば、以下の製造方法に従って製造することができる。
【００４１】
【化１３】
（式中、Ｒａは前述と同じ意味を表わす。）
即ち、トランス−４−アルキル−１−（２−ブロモエチル）シクロヘキサンをグリニヤール反応剤とし、これをシクロヘキサン−１，４−ジオンのモノエチレンアセタールと反応させ、脱水、水素添加の後アセタールをはずすことにより、一般式（Ｖｃ）の化合物を容易に得ることができる。
【００４３】
【化１４】
（式中、Ｒａは前述と同じ意味を表わす。）
あるいは、４−［２−［トランス−４−アルキルシクロヘキシル］エチル］フェノールをルテニウム触媒等の存在下に水素添加し、次いで水酸基を酸化しても得ることができる。
【００４５】
さらに、本発明の一般式（Ｉｄ）で表わされる化合物は、例えば、以下の製造方法に従って製造することができる。
【００４６】
【化１５】
前記の一般式（Ｉａ）で表わされる化合物の製造方法において、一般式（Ｖａ）の化合物に代えて、一般式（Ｖｄ）で表わされるビシクロヘキサン−４，４’−ジオンのモノエチレンアセタールと反応させ、脱水、水素添加の後アセタールをはずすことにより、式（Ｘ）の４−［トランス−４−（４−メトキシ−３，５−ジフルオロフェニル）シクロヘキシル］シクロヘキサノンを得る。
【００４８】
【化１６】
（式中、ｎ、ｍはそれぞれ１以上の整数を表わすが、ｎ＋ｍ≦１０である。）次いで、式（Ｘ）の化合物に、式（ＩＸａ）のウィッティヒ反応剤をｎ回反応させ、さらに式（ＩＸｂ）のウィッティヒ反応剤を反応させることにより、側鎖の任意の位置に二重結合を有する一般式（ＶＩｄ）で表わされる化合物を得る。ここで、ｍ≧２の場合、シス体が主として得られるが、これらはｐ−トルエンスルフィン酸等の触媒あるいは増感剤の存在下に光照射するなど通常の方法により、トランス体に異性化することが可能である。
【００５０】
この一般式（ＶＩｄ）の化合物を脱メチル化、アルケニル化することによって、本発明の一般式（Ｉｄ）で表わされる化合物を容易に得ることができる。
斯くして製造された一般式（Ｉ）で表わされる化合物の代表例を第１表に掲げる。
【００５１】
【表１】
（表中、Ｃｒは結晶相を、Ｎはネマチック相を、Ｉは等方性液体相をそれぞれ表わす。）
第１表から、本発明の一般式（Ｉ）で表わされる化合物は融点が低く、しかも高い温度までネマチック液晶相を示すことが明らかである。これに対し、第１表中の（Ｎｏ．１）の化合物の類似構造を有する一般式（ＩＩＩ−１）
【００５３】
【化１７】
の化合物と比較すると、ネマチック相上限温度（ＴＮ−Ｉ）はほとんど変わらないにもかかわらず、融点においては、一般式（ＩＩＩ−１）の化合物が５５．５℃であるのに対し、（Ｎｏ．１）の化合物は２３．２℃であり、本願発明の化合物が３０℃以上も低い。従って、通常の母体液晶に添加した場合に、液晶相の温度範囲を大きく拡大することが可能である。
【００５５】
本発明の一般式（Ｉ）で表わされる化合物は、他のネマチック液晶化合物との混合物の状態で、ＴＮ型あるいはＳＴＮ型といった電界効果型表示セルの材料として、組成物のしきい値電圧をほとんど上昇させることなく、液晶相の温度範囲を拡大する目的に使用することができ、アクティブマトリックス駆動用液晶材料の構成成分として特に適している。
【００５６】
この組成物中において、一般式（Ｉ）で表わ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、例えば、４−置換安息香酸４−置換フェニルエステル、４−置換シクロヘキサンカルボン酸４−置換フェニルエステル、４−置換シクロヘキサンカルボン酸４’−置換ビフェニリルエステル、４−（４−置換シクロヘキサンカルボニルオキシ）安息香酸４−置換フェニルエステル、４−（４−置換シクロヘキシル）安息香酸４−置換フェニルエステル、４−（４−置換シクロヘキシル）安息香酸４−置換シクロヘキシルエステル、４，４’−置換ビフェニル、１−（４−置換フェニル）−４−置換シクロヘキサン、４，４’−置換ビシクロヘキシル、４，４”−置換テルフェニル、１−（４’−置換ビフェニリル）−４−置換シクロヘキサン、１−（４−置換シクロヘキシル）−４−（４−置換フェニル）シクロヘキサン、４，４”−置換テルシクロヘキサン、２−（４−置換フェニル）−５−置換ピリミジン、２−（４’−置換ビフェニリル）−５−置換ピリミジンなどを挙げることができる。
【００５７】
このうち、アクティブマトリックス駆動用としては、４，４’−置換ビフェニル、１−（４−置換フェニル）−４−置換シクロヘキサン、４，４’−置換ビシクロヘキシル、４，４”−置換テルフェニル、１−（４’−置換ビフェニリル）−４−置換シクロヘキサン、１−（４−置換シクロヘキシル）−４−（４−置換フェニル）シクロヘキサン、４，４”−置換テルシクロヘキサン等が好ましく、１−（４−置換フェニル）−４−置換シクロヘキサン、１−（４’−置換ビフェニリル）−４−置換シクロヘキサン、１−（４−置換シクロヘキシル）−４−（４−置換フェニル）シクロヘキサンが適している。
【００５８】
本発明の一般式（Ｉ）の化合物の効果は、後述の実施例にも示したが、以下の例からも明らかである。
ネマチック液晶材料として、特にアクティブマトリックス用として好適な母体液晶（Ａ）
【００５９】
【化１８】
（式中、シクロヘキサン環はトランス配置を表わし、「％」は「重量％」を表わす。）は、１１６．７℃以下ネマチック相を示し、低温で放置して結晶化させた後にその融点を測定したところ、約１１℃であり、これを用いて作製したＴＮセル（セル厚８．０μｍ）のしきい値電圧（Ｖｔｈ）は２．４３Ｖであった。
【００６１】
この母体液晶（Ａ）８５重量％及び第１表中の（Ｎｏ．１）の化合物１５重量％からなる液晶組成物（Ｍ−１）を調製した。この（Ｍ−１）のネマチック相の上限温度（ＴＮ−Ｉ）は１２１．０℃と大きく上昇した。また、同様にして融点を測定したところ、−５℃と大きく低下した。さらに、これを用いて作製したＴＮセル（セル厚７．７μｍ）のしきい値電圧（Ｖｔｈ）は、２．５３Ｖとその上昇をわずかに抑えることができた。さらにこの組成物の比抵抗は１０１２Ωｃｍ以上と大きく、このセルの電圧保持率は非常に高かった。
【００６２】
以上の結果から、本発明の一般式（〓）で表わされる化合物は、ネマチック液晶相を示す母体液晶に添加することにより、しきい値電圧（Ｖｔｈ）をほとんど上昇させることなく、しかも液晶相の温度範囲を低温域にも高温域にも拡大できる効果を有することが明らかである。
【００６３】
【実施例】
以下に本発明の実施例を示し、本発明を更に説明する。しかしながら、本発明はこれらの実施例に限定されるものではない。
【００６４】
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及び示差走査熱量計（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（１Ｈ−ＮＭＲ）、質量スペクトル（ＭＳ）等により確認した。ＮＭＲにおけるＣＤＣｌ３は溶媒を表わし、ｓは１重線、ｄは２重線、ｔは３重線、ｍは多重線を表わし、Ｊはカップリング定数を表わす。ＭＳにおけるＭ＋は親ピークを表わす。
（参考例） １−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−メトキシベンゼンの合成
（１−ａ） ４−ブロモ−２，６−ジフルオロアニソールの合成
【００６５】
【化１９】
市販の２，６−ジフルオロフェノール１８．０ｇをジクロロメタン１００ｍｌ及びピリジン１１．０ｇに溶解し、５℃で冷却した。冷却後、攪拌下で臭素２７ｇを３０分間で滴下した。反応終了後、亜硫酸水素ナトリウム水溶液を加えて過剰の臭素を分解し、有機層を分離し、水層から反応生成物をジクロロメタンで抽出し、有機相を合わせた。有機相を水、飽和食塩水で洗浄し、無水硫酸ナトリウムで脱水乾燥した後、溶媒を溜去して、４−ブロモ−２，６−ジフルオロフェノールの粗結晶２８．６ｇを得た。
【００６７】
次に、上記で得た４−ブロモ−２，６−ジフルオロフェノール２８．６ｇをアセトン１５０ｍｌに溶解し、炭酸カリウム２８ｇを加えた。ここにヨウ化メチル２９．１ｇを滴下し、還流下で１時間加熱攪拌した後、稀塩酸を加えて酸性とし、アセトンを減圧下で溜去して、反応生成物を酢酸エチルで抽出した。有機層を水、飽和食塩水で洗浄し、無水硫酸ナトリウムで脱水乾燥した後、溶媒を溜去して、得られた粗生成物を減圧下で蒸留（９２〜９３℃／２３ｍｍＨｇ）して、４−ブロモ−２，６−ジフルオロアニソール２６．９ｇを得た。
（１−ｂ） １−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−メトキシベンゼンの合成
【００６８】
【化２０】
上記（１−ａ）で得た４−ブロモ−２，６−ジフルオロアニソール２６．９ｇを、テトラヒドロフラン（ＴＨＦ）１４０ｍｌに溶解した。この溶液を、マグネシウム３．５ｇのＴＨＦ１０ｍｌ懸濁液に、穏やかな還流が続く温度に保ちながら滴下し、さらに１時間加熱攪拌した。反応終了後、室温まで放冷し、これに４−（トランス−４−プロピルシクロヘキシル）シクロヘキサノン２６．８ｇのＴＨＦ１４０ｍｌ懸濁液を３０分間で滴下し、さらに３時間攪拌した。反応終了後、稀塩酸を加え、反応生成物を酢酸エチルで抽出した。溶媒を溜去した後、抽出物をトルエン２００ｍｌに溶解し、硫酸１ｍｌを加え、１１０℃で１時間攪拌した。反応終了後、反応生成物を室温で放冷し、飽和炭酸水素ナトリウム水溶液、水、飽和食塩水で順次洗浄し、無水硫酸ナトリウムで脱水乾燥した後、溶媒を溜去して、１−［４−（トランス−４−プロピルシクロヘキシル）シクロヘキセン−１−イル］−３，５−ジフルオロ−４−メトキシベンゼンの粗結晶３９．６ｇを得た。
【００７０】
上記で得た１−［４−（トランス−４−プロピルシクロヘキシル）シクロヘキセン−１−イル］−３，５−ジフルオロ−４−メトキシベンゼンの全量を酢酸エチル４００ｍｌに溶解し、パラジウム−炭素４．０ｇを加え、常圧の水素雰囲気下、室温で４時間接触還元した。反応終了後、触媒を濾別し、溶媒を溜去して、１−［４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−メトキシベンゼンの粘ちゅうな油状物を得た。これをエタノールから再結晶させて、白色結晶３７．４ｇを得た。
ＮＭＲ：δ＝０．８４〜０．９５（ｔ，３Ｈ），１．０〜２．３４（ｍ，１４Ｈ），３．８８（ｓ，３Ｈ），７．２６（ｄ，Ｊ＝８Ｈｚ，２Ｈ）
ＭＳ：ｍ／ｅ＝３５０（Ｍ＋）
（１−ｃ） ２，６−ジフルオロ−４−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］フェノールの合成
【００７１】
【化２１】
上記（１−ｂ）で得た、１−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−メトキシベンゼン２７．２ｇを酢酸５６０ｍｌに溶解した。溶解後、４８％臭化水素酸８００ｍｌを加え、８時間加熱還流した。反応終了後、放冷し、反応液を水にあけ、反応生成物をトルエンで抽出した。抽出後、水層が中性になるまで水で洗浄し、無水硫酸ナトリウムで脱水乾燥し、溶媒を溜去して得られた粗結晶を、ヘキサンから再結晶させて、２，６−ジフルオロ−４−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］フェノール１８．４ｇを得た。
（実施例１） １−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−アリルオキシベンゼン（第１表中のＮｏ．１の化合物）の合成
【００７３】
【化２２】
上記参考例で得た２，６−ジフルオロ−４−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］フェノール１．５ｇのＴＨＦ１５ｍｌ懸濁液を、水素化ナトリウム０．１４ｇのＴＨＦ１５ｍｌ懸濁液中に滴下し、１時間室温で攪拌した。さらに、臭化アリル０．６１ｇのＴＨＦ１０ｍｌ溶液を滴下し、さらに３時間加熱還流した。反応終了後、放冷し、反応液に水を加え、反応生成物をトルエンで抽出した。抽出液を、水及び飽和食塩水で洗浄した後、溶媒を溜去して、シリカゲルカラムクロマトグラフィー（ヘキサン／酢酸エチル）を用いて精製して、さらにエタノールから再結晶させて、１−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−アリルオキシベンゼンの白色結晶１．１ｇを得た。
相転移温度（℃）：２３．２（Ｃｒ→Ｉ）、１５４．５（Ｎ−Ｉ）
ＮＭＲ：δ＝０．８７（ｍ，５Ｈ），０．９８〜１．１６（ｍ，４Ｈ），１．７４（ｍ，４Ｈ），１．８５（ｍ，４Ｈ），２．３６（ｔｔ，Ｊ＝１２，１．５Ｈｚ，１Ｈ），４．５９（ｄ，Ｊ＝６Ｈｚ，２Ｈ），５．２４（ｄ，Ｊ＝１０Ｈｚ，１Ｈ），５．３５（ｄｄ，Ｊ＝１７，１．５Ｈｚ，１Ｈ），６．０〜６．１（ｍ，１Ｈ），６．７（ｍ，２Ｈ）
ＭＳ：３７６（Ｍ＋）
（実施例２） 液晶組成物の調製
【００７５】
【化２３】
（式中、シクロヘキサン環はトランス配置を表わし、「％」は「重量％」を表わす。）からなる母体液晶（Ａ）を調製したところ、１１６．７℃以下でネマチック（Ｎ）相を示した。また、低温で放置して結晶化させた後、融点を測定したところ、約１１℃であった。また、これを用いて作製したＴＮセルのしきい値電圧（Ｖｔｈ）は以下の通りであった。
【００７７】
Ｎ相の上限温度（ＴＮ−Ｉ） １１６．７℃
融点 約１１℃
しきい値電圧（Ｖｔｈ） ２．４３Ｖ
この母体液晶（Ａ）８５重量％及び実施例１で得られた（Ｎｏ．１）の化合物１５重量％からなる液晶組成物（Ｍ−１）を調製した。この（Ｍ−１）のＮ相の上限温度（ＴＮ−Ｉ）、融点は以下の通りであった。
【００７８】
Ｎ相の上限温度（ＴＮ−Ｉ） １２１．０℃
融点 約−５℃
しきい値電圧（Ｖｔｈ） ２．５３Ｖ
このように（Ｎｏ．１）の化合物は、組成物のＴＮ−Ｉを大きく上昇させることができ、しかもしきい値電圧をほとんど上昇させていないことが明らかである。
（比較例１）
母体液晶（Ａ）８５重量％及び（Ｎｏ．１）の化合物の類似構造を有する式（ＩＩ−１）
【００７９】
【化２４】
の化合物１５重量％からなる液晶組成物（Ｍ−２）を調製した。この（Ｍ−２）のＴＮ−Ｉ、融点及び同様にして測定したＶｔｈは以下の通りであった。
Ｎ相の上限温度（ＴＮ−Ｉ） １１２．８℃
融点 約 ６℃
しきい値電圧（Ｖｔｈ） ２．２７Ｖ
このように（Ｍ−１）と比較すると、Ｖｔｈは低下したものの、ＴＮ−Ｉも大きく低下してしまい、また融点もあまり降下しなかった。
（比較例２）
母体液晶（Ａ）８５重量％及び（Ｎｏ．１）の化合物の類似構造を有する一般式（ＩＩＩ−１）
【００８１】
【化２５】
の化合物１５重量％からなる液晶組成物（Ｍ−３）を調製した。この（Ｍ−３）のＴＮ−Ｉ、融点及び同様にして測定したＶｔｈは以下の通りであった。
Ｎ相の上限温度（ＴＮ−Ｉ） １２４．３℃
融点 約 ２℃
しきい値電圧（Ｖｔｈ） ２．５５Ｖ
このように（Ｍ−１）と比較すると、ＴＮ−Ｉはほとんど変わらなかったが、融点は大きく上昇してしまい、Ｖｔｈもやや上昇してしまった。
【００８３】
【発明の効果】
本発明に係わる一般式（Ｉ）で表わされる化合物は、実施例に示したように工業的にも容易に製造でき、熱、光、水等に対し、化学的に安定である。また、ネマチック液晶として現在汎用されている母体液晶との相溶性にも優れている。しかも、添加により、組成物のしきい値電圧（Ｖｔｈ）をあまり上昇させることなく、液晶相の温度範囲を低温域にも高温域にも拡大させることが可能である。従って、温度範囲が広く、かつ低電圧駆動が要求される各種液晶表示素子、特にアクティブマトリックス駆動用の液晶材料として非常に有用である。[0001]
[Industrial application fields]
The present invention relates to a liquid crystal compound which is a novel 4-alkenyloxy-3,5-difluorobenzene derivative useful as an electro-optical liquid crystal display material, and a liquid crystal composition containing the same.
[0002]
[Prior art]
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 (ferroelectric liquid crystal). The TN type and STN type are currently mainstream. 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. Of these, the active matrix method is capable of displaying very high image quality, has a wide viewing angle, high definition, easy colorization, and video display. It is considered mainstream.
[0003]
The liquid crystal material used in this active matrix display system is required to have various characteristics as in the case of a normal liquid crystal display. In particular, (1) high specific resistance and excellent voltage holding ratio, 2) It is important that the threshold voltage (V th ) is low, and (3) the temperature range of the liquid crystal phase is wide.
[0004]
Usually, the threshold voltage (V th ) in the liquid crystal display is expressed by the formula (a)
[0005]
[Expression 1]
(Where k is a proportional constant, K is an elastic constant, and Δε is a dielectric anisotropy.) As can be seen from this equation, in order to reduce the threshold voltage, It is necessary to reduce the elastic constant of the liquid crystal material or increase the dielectric anisotropy.
[0007]
However, many liquid crystal compounds having a large dielectric anisotropy have a large polarity and tend to make it difficult to obtain a liquid crystal material having a high specific resistance value and a high voltage holding ratio. For this purpose, a liquid crystal material having a small elastic constant is required.
[0008]
Examples of the liquid crystal material having a small elastic constant include bicyclic compounds. However, many bicyclic compounds have a tendency to significantly reduce the upper limit temperature of the liquid crystal phase of the composition by addition.
[0009]
Therefore, in order to expand the temperature range of the liquid crystal composition to a particularly high temperature range, it is necessary to add a tricyclic or tetracyclic compound having a high maximum temperature of the liquid crystal phase. However, many compounds having such a high maximum temperature have a large elastic constant, and the addition tends to greatly increase the threshold voltage of the composition.
[0010]
Further, as a compound that lowers the threshold voltage without narrowing the temperature range of the liquid crystal phase, the compound represented by the general formula (II)
[0011]
[Chemical formula 2]
A compound represented by the formula (wherein R represents an alkyl group) is known. (Described in JP-A-2-233626)
However, the upper limit temperature of the liquid crystal phase of this compound is not so high, and an increase in the upper limit temperature of the liquid crystal phase of the composition due to the addition was hardly expected. In addition, the melting point is not low, the melting point of the composition is not lowered by the addition, and the nematic phase has a smectic phase in the low temperature range, so a large amount of addition causes a problem in the stability of the nematic phase in the low temperature range, The amount added was also quite limited.
[0013]
In order to compensate for the drawbacks of the compound represented by the general formula (II) as described above, the present inventors have used the general formula (III).
[0014]
[Chemical 3]
(Wherein R and R ′ each represents an alkyl group), a 4-alkoxy-3,5-difluorobencene-based compound was developed. In the compound represented by the general formula (III), the temperature range of the liquid crystal phase is greatly improved to a particularly high temperature range, and it becomes easy to obtain a liquid crystal composition having a wide temperature range, but the melting point is not so low. Therefore, a sufficient temperature range of the liquid crystal phase in the low temperature range could not be secured.
[0016]
Accordingly, it has been quite difficult to obtain a liquid crystal compound in which the temperature range of the liquid crystal phase is wide from a low temperature range to a high temperature range and the threshold voltage of the composition is lowered by addition.
[0017]
[Problems to be solved by the invention]
The problem to be solved by the present invention is that the melting point is low, has a nematic phase in a wide temperature range, and lowers the melting point almost without increasing the threshold voltage of the composition by addition, Moreover, it is an object of the present invention to provide a compound that increases the upper limit temperature of the liquid crystal phase, and to provide a liquid crystal composition containing the compound, having a wide temperature range of the liquid crystal phase, and having a low threshold voltage.
[0018]
[Means for Solving the Problems]
In order to solve the above problems, the present invention provides a compound represented by the general formula (I)
[0019]
[Formula 4]
Wherein R 1 represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms, preferably a linear alkyl group having 1 to 10 carbon atoms, and more preferably Represents a straight-chain alkyl group having 1 to 7 carbon atoms, L and M each independently represent a single bond or —CH 2 CH 2 —, but at least one represents a single bond, and particularly preferably both are single bonds. R 2 represents a straight-chain alkenyl group having 3 to 12 carbon atoms, preferably a straight-chain 2-alkenyl group having 3 to 7 carbon atoms, and the cyclohexane ring has a trans configuration. A 4-alkenyloxy-3,5-difluorobenzene derivative represented by the formula:
[0021]
In the compound represented by the general formula (I) of the present invention, the general formula (Ia) to the general formula (Id) are preferable.
[0022]
[Chemical formula 5]
(In the formula, R a represents a linear alkyl group having 1 to 7 carbon atoms, R b represents a linear alkenyl group having 2 to 7 carbon atoms, and R c represents a hydrogen atom or 1 carbon atom. Represents a linear alkyl group of ˜4), and particularly preferably a compound represented by the general formula (Ia).
[0024]
The compound represented by the general formula (Ia) of the present invention can be produced, for example, according to the following production method.
[0025]
[Chemical 6]
First, 2,6-difluorophenol is brominated to give 4-bromo-2,6-difluorophenol. This is reacted with methyl iodide in the presence of a base to give 4-methoxy-1-bromo-3,5-difluorobenzene of formula (IV).
[0027]
[Chemical 7]
(Wherein, R a is. The same meanings as described above) Next, the formula is reacted with a magnesium compound of (IV) with a Grignard reagent, which represented by 4- (trans by the general formula (Va) Reaction with -4-alkylcyclohexyl) cyclohexanone. After the reaction, dehydration and hydrogenation yield an isomer mixture with the configuration of the central cyclohexane ring. These are divided or isomerized with a base to give 1- [trans-4- (trans-4-alkylcyclohexyl) cyclohexyl] -3,5-difluoro-4-methoxybenzene represented by the general formula (VIa). be able to.
[0029]
[Chemical 8]
(In the formula, R a and R c represent the same meaning as described above, and X represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, or a p-toluenesulfonyl group.)
Further, the compound of the general formula (VIa) is demethylated with hydrobromic acid or trimethylsilyl iodide and the like, and 4- [trans-4- (trans-4-alkylcyclohexyl) cyclohexyl represented by the general formula (VIIa) is obtained. ] -2,6-difluorophenol. The compound of general formula (Ia) can be obtained by reacting with the compound represented by general formula (VIII) in the presence of a base.
[0031]
Here, the compound in which R 2 is a 1-alkenyl group can be obtained by isomerizing the compound of the general formula (Ia) with a strong base.
In addition, R 2 is a compound other than 1 or 2-alkenyl group, instead of the compound of general formula (VIII),
[0032]
[Chemical 9]
X-R 2
(Wherein R 2 and X represent the same meaning as described above), and can be produced in the same manner.
[0033]
The compound represented by the general formula (Ib) of the present invention can be produced, for example, according to the following production method.
In the method for producing the compound represented by the general formula (Ia), the compound represented by the general formula (Vb) is used instead of the compound represented by the general formula (Va).
[0034]
[Chemical Formula 10]
By using 4- (trans-4-alkylcyclohexyl) cyclohexaneethanal represented by the formula (wherein Ra represents the same meaning as described above), a compound of the general formula (Ib) can be obtained. Here, the compound of the general formula (Vb) can be produced, for example, according to the following production method.
[0036]
Embedded image
(Wherein, R a has the same meaning as above.)
That is, it can be easily obtained by reacting the compound of general formula (Va) with the Wittig reactant of formula (IXa) and subjecting it to acid treatment twice.
[0038]
Moreover, the compound represented by general formula (Ic) of this invention can be manufactured according to the following method, for example.
In the method for producing the compound represented by the general formula (Ia), the compound represented by the general formula (Vc) is used instead of the compound represented by the general formula (Va).
[0039]
Embedded image
(Wherein, R a represents. The same as defined above) By using 4- [2- (trans-4-alkyl cyclohexyl) ethyl] cyclohexanone represented by, to give compounds of general formula (Ic) it can. Here, the compound represented by the general formula (Vc) can be produced, for example, according to the following production method.
[0041]
Embedded image
(Wherein, R a has the same meaning as above.)
That is, by using trans-4-alkyl-1- (2-bromoethyl) cyclohexane as a Grignard reagent, reacting it with a monoethylene acetal of cyclohexane-1,4-dione, dehydrating and hydrogenating, and then removing the acetal. The compound of the general formula (Vc) can be easily obtained.
[0043]
Embedded image
(Wherein, R a has the same meaning as above.)
Alternatively, 4- [2- [trans-4-alkylcyclohexyl] ethyl] phenol can be obtained by hydrogenation in the presence of a ruthenium catalyst or the like and then oxidizing the hydroxyl group.
[0045]
Furthermore, the compound represented by the general formula (Id) of the present invention can be produced, for example, according to the following production method.
[0046]
Embedded image
In the method for producing the compound represented by the general formula (Ia), the reaction with the monoethylene acetal of bicyclohexane-4,4′-dione represented by the general formula (Vd) instead of the compound of the general formula (Va) After dehydration and hydrogenation, the acetal is removed to obtain 4- [trans-4- (4-methoxy-3,5-difluorophenyl) cyclohexyl] cyclohexanone of the formula (X).
[0048]
Embedded image
(In the formula, n and m each represent an integer of 1 or more, but n + m ≦ 10.) Next, the compound of formula (X) is reacted n times with the Wittig reagent of formula (IXa), By reacting the Wittig reactant of (IXb), a compound represented by the general formula (VId) having a double bond at an arbitrary position of the side chain is obtained. Here, when m ≧ 2, cis isomers are mainly obtained, but these are isomerized into trans isomers by a usual method such as light irradiation in the presence of a catalyst such as p-toluenesulfinic acid or a sensitizer. It is possible.
[0050]
By demethylating and alkenylating the compound of the general formula (VId), the compound represented by the general formula (Id) of the present invention can be easily obtained.
Representative examples of the compounds represented by the general formula (I) thus produced are listed in Table 1.
[0051]
[Table 1]
(In the table, Cr represents a crystalline phase, N represents a nematic phase, and I represents an isotropic liquid phase.)
From Table 1, it is clear that the compound represented by the general formula (I) of the present invention has a low melting point and exhibits a nematic liquid crystal phase up to a high temperature. On the other hand, the general formula (III-1) having a similar structure to the compound of (No. 1) in Table 1
[0053]
Embedded image
Although the nematic phase upper limit temperature (T N-I ) is hardly changed compared to the compound of (5), the compound of the general formula (III-1) is 55.5 ° C. at the melting point, The compound of No. 1) is 23.2 ° C., and the compound of the present invention is as low as 30 ° C. or more. Therefore, when added to a normal base liquid crystal, the temperature range of the liquid crystal phase can be greatly expanded.
[0055]
The compound represented by the general formula (I) of the present invention has almost no threshold voltage of the composition as a material for a field effect display cell such as a TN type or STN type in a mixture with other nematic liquid crystal compounds. It can be used for the purpose of expanding the temperature range of the liquid crystal phase without being raised, and is particularly suitable as a component of the liquid crystal material for active matrix driving.
[0056]
In this composition, preferable representative examples of the nematic liquid crystal compound that can be used by mixing with the compound represented by the general formula (I) include, for example, 4-substituted benzoic acid 4-substituted phenyl ester, 4-substituted Cyclohexanecarboxylic acid 4-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4′-substituted biphenylyl ester, 4- (4-substituted cyclohexanecarbonyloxy) benzoic acid 4-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid Acid 4-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4-substituted cyclohexyl ester, 4,4′-substituted biphenyl, 1- (4-substituted phenyl) -4-substituted cyclohexane, 4,4′- Substituted bicyclohexyl, 4,4 "-substituted terphenyl, 1- (4'-substituted biphenyl) Niryl) -4-substituted cyclohexane, 1- (4-substituted cyclohexyl) -4- (4-substituted phenyl) cyclohexane, 4,4 "-substituted tercyclohexane, 2- (4-substituted phenyl) -5-substituted pyrimidine, And 2- (4′-substituted biphenylyl) -5-substituted pyrimidine.
[0057]
Among these, for active matrix driving, 4,4′-substituted biphenyl, 1- (4-substituted phenyl) -4-substituted cyclohexane, 4,4′-substituted bicyclohexyl, 4,4 ″ -substituted terphenyl, 1- (4′-substituted biphenylyl) -4-substituted cyclohexane, 1- (4-substituted cyclohexyl) -4- (4-substituted phenyl) cyclohexane, 4,4 ″ -substituted tercyclohexane and the like are preferable. -Substituted phenyl) -4-substituted cyclohexane, 1- (4'-substituted biphenylyl) -4-substituted cyclohexane, 1- (4-substituted cyclohexyl) -4- (4-substituted phenyl) cyclohexane are suitable.
[0058]
The effect of the compound of the general formula (I) of the present invention was also shown in Examples described later, but is also apparent from the following examples.
Base liquid crystal suitable for nematic liquid crystal material, especially for active matrix (A)
[0059]
Embedded image
(Wherein the cyclohexane ring represents a trans configuration and “%” represents “% by weight”) indicates a nematic phase of 116.7 ° C. or lower, and crystallized after standing at low temperature to measure its melting point. As a result, it was about 11 ° C., and the threshold voltage (V th ) of the TN cell (cell thickness 8.0 μm) produced using this was 2.43 V.
[0061]
A liquid crystal composition (M-1) comprising 85% by weight of the base liquid crystal (A) and 15% by weight of the compound (No. 1) in Table 1 was prepared. The upper limit temperature (T N-I ) of the nematic phase (M-1) was greatly increased to 121.0 ° C. Moreover, when melting | fusing point was measured similarly, it fell with -5 degreeC greatly. Furthermore, the threshold voltage (V th ) of a TN cell (cell thickness 7.7 μm) fabricated using the same was 2.53 V, and its rise could be suppressed slightly. Furthermore, the specific resistance of this composition was as large as 10 12 Ωcm or more, and the voltage holding ratio of this cell was very high.
[0062]
From the above results, the compound represented by the general formula (〓) of the present invention can be added to a base liquid crystal exhibiting a nematic liquid crystal phase, with little increase in the threshold voltage (V th ). It is apparent that this has the effect of extending the temperature range to both the low temperature range and the high temperature range.
[0063]
【Example】
The following examples further illustrate the present invention. However, the present invention is not limited to these examples.
[0064]
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 ( 1 H-NMR), mass spectrum (MS) and the like. CDCl 3 in NMR represents a solvent, s represents a single line, d represents a double line, t represents a triple line, m represents a multiple line, and J represents a coupling constant. M + in MS represents the parent peak.
Reference Example Synthesis of 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-methoxybenzene (1-a) of 4-bromo-2,6-difluoroanisole Synthesis [0065]
Embedded image
18.0 g of commercially available 2,6-difluorophenol was dissolved in 100 ml of dichloromethane and 11.0 g of pyridine, and cooled at 5 ° C. After cooling, 27 g of bromine was added dropwise over 30 minutes with stirring. After completion of the reaction, an aqueous sodium hydrogen sulfite solution was added to decompose excess bromine, the organic layer was separated, the reaction product was extracted from the aqueous layer with dichloromethane, and the organic phases were combined. The organic phase was washed with water and saturated brine, dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 28.6 g of 4-bromo-2,6-difluorophenol crude crystals.
[0067]
Next, 28.6 g of 4-bromo-2,6-difluorophenol obtained above was dissolved in 150 ml of acetone, and 28 g of potassium carbonate was added. 29.1 g of methyl iodide was added dropwise thereto, and the mixture was stirred with heating under reflux for 1 hour. The mixture was acidified with dilute hydrochloric acid, acetone was distilled off under reduced pressure, and the reaction product was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dehydrated and dried over anhydrous sodium sulfate, the solvent was distilled off, and the resulting crude product was distilled (92 to 93 ° C / 23 mmHg) under reduced pressure. 26.9 g of 4-bromo-2,6-difluoroanisole was obtained.
(1-b) Synthesis of 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-methoxybenzene
Embedded image
26.9 g of 4-bromo-2,6-difluoroanisole obtained in (1-a) above was dissolved in 140 ml of tetrahydrofuran (THF). This solution was added dropwise to a suspension of 3.5 g of magnesium in 10 ml of THF while maintaining a temperature at which gentle reflux continued, and the mixture was further heated and stirred for 1 hour. After completion of the reaction, the mixture was allowed to cool to room temperature, and a suspension of 4- (trans-4-propylcyclohexyl) cyclohexanone 26.8 g in THF 140 ml was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours. After completion of the reaction, dilute hydrochloric acid was added, and the reaction product was extracted with ethyl acetate. After the solvent was distilled off, the extract was dissolved in 200 ml of toluene, 1 ml of sulfuric acid was added, and the mixture was stirred at 110 ° C. for 1 hour. After completion of the reaction, the reaction product was allowed to cool at room temperature, washed successively with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off to give 1- [4 -39.6 g of crude crystals of-(trans-4-propylcyclohexyl) cyclohexen-1-yl] -3,5-difluoro-4-methoxybenzene were obtained.
[0070]
The total amount of 1- [4- (trans-4-propylcyclohexyl) cyclohexen-1-yl] -3,5-difluoro-4-methoxybenzene obtained above was dissolved in 400 ml of ethyl acetate, and 4.0 g of palladium-carbon was obtained. Then, catalytic reduction was performed for 4 hours at room temperature in a hydrogen atmosphere under normal pressure. After completion of the reaction, the catalyst was filtered off and the solvent was distilled off to give a viscous oily product of 1- [4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-methoxybenzene. Obtained. This was recrystallized from ethanol to obtain 37.4 g of white crystals.
NMR: δ = 0.84-0.95 (t, 3H), 1.0-2.34 (m, 14H), 3.88 (s, 3H), 7.26 (d, J = 8 Hz, 2H) )
MS: m / e = 350 (M + )
(1-c) Synthesis of 2,6-difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] phenol
Embedded image
27.2 g of 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-methoxybenzene obtained in (1-b) above was dissolved in 560 ml of acetic acid. After dissolution, 800 ml of 48% hydrobromic acid was added and heated to reflux for 8 hours. After completion of the reaction, the mixture was allowed to cool, the reaction mixture was poured into water, and the reaction product was extracted with toluene. After extraction, the aqueous layer was washed with water until neutral, dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting crude crystals were recrystallized from hexane to give 2,6-difluoro- 18.4 g of 4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] phenol was obtained.
Example 1 Synthesis of 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-allyloxybenzene (No. 1 Compound in Table 1) ]
Embedded image
A suspension of 1.5 g of 2,6-difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] phenol obtained in the above Reference Example in 15 ml of THF was suspended in 15 ml of THF in 0.14 g of sodium hydride. The solution was dropped into the liquid and stirred at room temperature for 1 hour. Further, a solution of 0.61 g of allyl bromide in 10 ml of THF was added dropwise, and the mixture was further refluxed for 3 hours. After completion of the reaction, the reaction solution was allowed to cool, water was added to the reaction solution, and the reaction product was extracted with toluene. The extract is washed with water and saturated brine, and then the solvent is distilled off. The residue is purified using silica gel column chromatography (hexane / ethyl acetate), recrystallized from ethanol, and 1- [trans 1.1 g of white crystals of -4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-allyloxybenzene were obtained.
Phase transition temperature (° C): 23.2 (Cr → I), 154.5 (N-I)
NMR: δ = 0.87 (m, 5H), 0.98 to 1.16 (m, 4H), 1.74 (m, 4H), 1.85 (m, 4H), 2.36 (tt, J = 12, 1.5 Hz, 1H), 4.59 (d, J = 6 Hz, 2H), 5.24 (d, J = 10 Hz, 1H), 5.35 (dd, J = 17, 1.5 Hz) , 1H), 6.0-6.1 (m, 1H), 6.7 (m, 2H)
MS: 376 (M <+> )
Example 2 Preparation of Liquid Crystal Composition
Embedded image
(In the formula, the cyclohexane ring represents a trans configuration, and “%” represents “% by weight”.) When the base liquid crystal (A) was prepared, it exhibited a nematic (N) phase at 116.7 ° C. or lower. . Further, after allowing to crystallize at low temperature, the melting point was measured and found to be about 11 ° C. In addition, the threshold voltage (V th ) of the TN cell fabricated using this was as follows.
[0077]
N phase upper limit temperature (T N-I ) 116.7 ° C
Melting point approx. 11 ° C
Threshold voltage (V th ) 2.43V
A liquid crystal composition (M-1) comprising 85% by weight of the base liquid crystal (A) and 15% by weight of the compound (No. 1) obtained in Example 1 was prepared. The upper limit temperature (T N-I ) and melting point of the N phase of (M-1) were as follows.
[0078]
Upper limit temperature of N phase (T N-I ) 121.0 ° C
Melting point -5 ℃
Threshold voltage (V th ) 2.53V
Thus, it is clear that the compound of (No. 1) can greatly increase the TN-I of the composition and hardly increases the threshold voltage.
(Comparative Example 1)
Formula (II-1) having a structure similar to that of the compound of the base liquid crystal (A) 85% by weight and (No. 1)
[0079]
Embedded image
A liquid crystal composition (M-2) comprising 15% by weight of the above compound was prepared. TN-I of this (M-2), melting point, and Vth measured in the same manner were as follows.
Upper limit temperature of N phase (T N-I ) 112.8 ° C
Melting point approx. 6 ° C
Threshold voltage (V th ) 2.27V
Thus, compared with (M-1), although Vth decreased, TN-I also decreased greatly, and the melting point did not decrease much.
(Comparative Example 2)
General formula (III-1) having a similar structure to the compound of the base liquid crystal (A) 85% by weight and (No. 1)
[0081]
Embedded image
A liquid crystal composition (M-3) comprising 15% by weight of the above compound was prepared. TN-I of this (M-3), melting point, and Vth measured in the same manner were as follows.
Maximum temperature of N phase (T N-I ) 124.3 ° C
Melting point approx. 2 ℃
Threshold voltage (V th ) 2.55V
Thus, when compared with (M-1), TN-I hardly changed, but the melting point greatly increased and Vth also slightly increased.
[0083]
【The invention's effect】
The compound represented by the general formula (I) according to the present invention can be easily produced industrially as shown in the Examples, and is chemically stable to heat, light, water and the like. Further, it is excellent in compatibility with a base liquid crystal that is currently widely used as a nematic liquid crystal. In addition, the temperature range of the liquid crystal phase can be expanded to a low temperature region or a high temperature region without significantly increasing the threshold voltage (V th ) of the composition. Therefore, the present invention is very useful as various liquid crystal display elements that require a wide temperature range and low voltage driving, particularly as a liquid crystal material for active matrix driving.
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05177394A JP3632772B2 (en) | 1994-03-23 | 1994-03-23 | 4-alkenyloxy-3,5-difluorobenzene derivatives |
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| CN101061202B (en) | 2004-12-10 | 2014-01-08 | 株式会社艾迪科 | Liquid crystal composition |
| US9822301B2 (en) | 2013-12-16 | 2017-11-21 | Dic Corporation | Alkenyl ether compound and a liquid crystal composition using the same |
| WO2016017615A1 (en) * | 2014-07-31 | 2016-02-04 | Dic株式会社 | Nematic liquid crystal composition |
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