JP4753064B2 - Liquid crystal composition, display element and compound containing trifluoronaphthalene derivative. - Google Patents
Liquid crystal composition, display element and compound containing trifluoronaphthalene derivative. Download PDFInfo
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- JP4753064B2 JP4753064B2 JP2004277073A JP2004277073A JP4753064B2 JP 4753064 B2 JP4753064 B2 JP 4753064B2 JP 2004277073 A JP2004277073 A JP 2004277073A JP 2004277073 A JP2004277073 A JP 2004277073A JP 4753064 B2 JP4753064 B2 JP 4753064B2
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 58
- 150000001875 compounds Chemical class 0.000 title claims description 55
- DSLKOTQBUFGMQY-UHFFFAOYSA-N 1,2,3-trifluoronaphthalene Chemical class C1=CC=C2C(F)=C(F)C(F)=CC2=C1 DSLKOTQBUFGMQY-UHFFFAOYSA-N 0.000 title claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 93
- 125000000217 alkyl group Chemical group 0.000 claims description 50
- 125000003545 alkoxy group Chemical group 0.000 claims description 25
- 125000003342 alkenyl group Chemical group 0.000 claims description 17
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 13
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 11
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 235000019000 fluorine Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- XKDLQKJOTBECCW-UHFFFAOYSA-N 1,7,8-trifluoronaphthalen-2-ol Chemical compound C1=CC(F)=C(F)C2=C(F)C(O)=CC=C21 XKDLQKJOTBECCW-UHFFFAOYSA-N 0.000 description 5
- -1 2,3-difluorophenylene group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000000062 cyclohexylmethoxy group Chemical group [H]C([H])(O*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 3
- 239000012769 display material Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 0 *c(ccc(c1c2F)ccc2F)c1F Chemical compound *c(ccc(c1c2F)ccc2F)c1F 0.000 description 2
- CRNZDXXICRYJLA-UHFFFAOYSA-N 1,2,8-trifluoro-7-propoxynaphthalene Chemical compound C1=CC(F)=C(F)C2=C(F)C(OCCC)=CC=C21 CRNZDXXICRYJLA-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- FSSLSEUSDZRBQS-UHFFFAOYSA-N 3,4,5-trifluoro-6-propoxynaphthalen-2-ol Chemical compound C1=C(O)C(F)=C(F)C2=C(F)C(OCCC)=CC=C21 FSSLSEUSDZRBQS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- WORORYHUROVRQR-UHFFFAOYSA-N (1,7,8-trifluoronaphthalen-2-yl) trifluoromethanesulfonate Chemical compound C1=CC(OS(=O)(=O)C(F)(F)F)=C(F)C2=C(F)C(F)=CC=C21 WORORYHUROVRQR-UHFFFAOYSA-N 0.000 description 1
- HYHOGBIYYIILIW-UHFFFAOYSA-N 1,3,4-trifluoronaphthalen-2-ol Chemical compound FC1=C(C(=C(C2=CC=CC=C12)F)O)F HYHOGBIYYIILIW-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZXFJOJRGTCYKOB-UHFFFAOYSA-N 6-butoxy-3,4,5-trifluoronaphthalen-2-ol Chemical compound C1=C(O)C(F)=C(F)C2=C(F)C(OCCCC)=CC=C21 ZXFJOJRGTCYKOB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GXHMMDRXHUIUMN-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O.CS(O)(=O)=O GXHMMDRXHUIUMN-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- CZFNISFYDPIDNM-UHFFFAOYSA-N n,n-dimethylformamide;oxolane Chemical compound CN(C)C=O.C1CCOC1 CZFNISFYDPIDNM-UHFFFAOYSA-N 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Liquid Crystal (AREA)
Description
本発明は電気光学的液晶表示材料として有用な、トリフルオロナフタレン誘導体を含有する誘電率異方性が負でその絶対値が大きい液晶組成物及びそれを用いた液晶表示素子、さらに液晶化合物に関する。 The present invention relates to a liquid crystal composition containing a trifluoronaphthalene derivative having a negative dielectric anisotropy and a large absolute value, a liquid crystal display device using the same, and a liquid crystal compound, which are useful as an electro-optical liquid crystal display material.
液晶表示素子は、低電圧作動、薄型表示等の優れた特徴から現在広く用いられている。従来の液晶表示素子の表示方式にはTN（ねじれネマチック）、STN（超ねじれネマチック）、又はTNをベースにしたアクティブマトリックス（TFT：薄膜トランジスタ）等があり、これらは誘電率異方性値が正の液晶組成物を利用するものである。しかし、これら表示方式の欠点の一つとして視野角の狭さがあり、近年高まっている液晶パネルの大型化の要求に伴い、その改善が大きな課題となっている。 Liquid crystal display elements are currently widely used because of their excellent features such as low voltage operation and thin display. Conventional liquid crystal display element display methods include TN (twisted nematic), STN (super twisted nematic), or active matrix (TFT: thin film transistor) based on TN, which has a positive dielectric anisotropy value. The liquid crystal composition is used. However, one of the disadvantages of these display methods is a narrow viewing angle, and with the increasing demand for larger liquid crystal panels in recent years, the improvement has become a major issue.
この解決策として近年、垂直配向方式、IPS（インプレインスイッチング）等の表示方式が新たに実用化されてきた。垂直配向方式は液晶分子の垂直配向を利用して視野角の改善を図った方式であり、誘電異方性値が負の液晶組成物が使用される。またIPSは、ガラス基板に対して水平方向の横電界を用いて液晶分子をスイッチングさせることで視野角の改善を図った方法であり、誘電異方性値が正又は負の液晶組成物が使用される。このように、視野角改善のために有効な表示方式である垂直配向方式及びIPSには誘電率異方性値が負である液晶化合物ならびに液晶組成物が必要であり、強く要望されるようになってきた。従来、誘電率異方性が負の液晶組成物は、2,3-ジフルオロフェニレン基を有する化合物（特許文献１参照）が主として用いられてきた。しかしながら、この化合物を用いた液晶組成物は誘電率異方性の絶対値が十分大きくない問題を有していた（特許文献２参照）。 In recent years, display methods such as vertical alignment and IPS (in-plane switching) have been newly put to practical use as a solution. The vertical alignment method is a method for improving the viewing angle by utilizing the vertical alignment of liquid crystal molecules, and a liquid crystal composition having a negative dielectric anisotropy value is used. IPS is a method of improving viewing angle by switching liquid crystal molecules using a horizontal electric field in the horizontal direction with respect to a glass substrate, and a liquid crystal composition having a positive or negative dielectric anisotropy value is used. Is done. As described above, the vertical alignment method and the IPS, which are effective display methods for improving the viewing angle, require a liquid crystal compound and a liquid crystal composition having a negative dielectric anisotropy value. It has become. Conventionally, a liquid crystal composition having a negative dielectric anisotropy has mainly been a compound having a 2,3-difluorophenylene group (see Patent Document 1). However, a liquid crystal composition using this compound has a problem that the absolute value of dielectric anisotropy is not sufficiently large (see Patent Document 2).
絶対値の大きい負の誘電率異方性を有する化合物としてトリフルオロナフタレン誘導体が有り、多くの化合物を含む一般的な開示は既にされている（特許文献３参照）。しかし、トリフルオロナフタレン骨格の製造は必ずしも容易ではなく、当該引用文献においては開示する全ての範囲で化合物が開示されているとは認められない。さらに、当該引用文献は強誘電性液晶組成物に使用することを念頭に置いており、誘電率異方性が負のネマチック液晶組成物として広い開示範囲のどの化合物を具体的に使用し、どの様な化合物を併用し又その効果がどの様なものであるかについての開示は無い。 There is a trifluoronaphthalene derivative as a compound having a large absolute value and negative dielectric anisotropy, and general disclosure including many compounds has already been made (see Patent Document 3). However, the production of the trifluoronaphthalene skeleton is not always easy, and it is not recognized that the compound is disclosed in the entire range disclosed in the cited document. Further, the cited document is intended for use in ferroelectric liquid crystal compositions, and which compounds in a wide disclosure range are specifically used as nematic liquid crystal compositions having a negative dielectric anisotropy. There is no disclosure of the use of such compounds and what their effects are.
一方、トリフルオロナフタレン系の化合物を用いた液晶組成物は既に知られているが（特許文献４参照）、ナフタレン環の6位にシクロヘキシルメトキシ基を有する化合物を用いた液晶組成物については開示がない。 On the other hand, a liquid crystal composition using a trifluoronaphthalene-based compound is already known (see Patent Document 4), but a liquid crystal composition using a compound having a cyclohexylmethoxy group at the 6-position of the naphthalene ring is disclosed. Absent.
また、ベンゼン環の2位にアルコキシ基を有し6位にシクロヘキシルメトキシ基を有する化合物が化学的に不安定で使用できないとの知見（非特許文献１参照）により、ナフタレン環の2位にアルコキシ基を有し、6位にシクロヘキシルメトキシ基を有する化合物についても、化学的に不安定で液晶材料として使用できないものと考えられていたため、当該化合物の液晶材料としての開発は進行していなかった。 In addition, due to the knowledge that a compound having an alkoxy group at the 2-position of the benzene ring and a cyclohexylmethoxy group at the 6-position is chemically unstable and cannot be used (see Non-Patent Document 1), the alkoxy at the 2-position of the naphthalene ring A compound having a group and having a cyclohexylmethoxy group at the 6-position was also considered to be chemically unstable and cannot be used as a liquid crystal material, and therefore development of the compound as a liquid crystal material was not progressing.
誘電率異方性が負であってその絶対値が大きい液晶組成物及び表示素子を提供することであり、誘電率異方性が負であってその絶対値が大きい化合物を提供することである。 It is to provide a liquid crystal composition and a display element having a negative dielectric anisotropy and a large absolute value, and to provide a compound having a negative dielectric anisotropy and a large absolute value. .
本発明者は、トリフルオロナフタレン誘導体及びこれを用いたネマチック液晶組成物、表示素子を検討した結果、本件発明を完成するに至った。
本発明は、一般式(1)
As a result of studying a trifluoronaphthalene derivative, a nematic liquid crystal composition using the trifluoronaphthalene derivative, and a display element, the present inventor has completed the present invention.
The present invention relates to general formula (1)
（式中、Raは炭素原子数1〜7の直鎖状アルキル基又は炭素原子数2〜7の直鎖状アルケニル基を表し、Rbは炭素原子数1〜7の直鎖状アルキル基、炭素原子数1〜7の直鎖状アルコキシル基、炭素原子数2〜7の直鎖状アルケニル基又は炭素原子数2〜7の直鎖状アルケニルオキシ基を表し、Ma及びMpはそれぞれ独立的に単結合、-CH2CH2-、-OCH2-、-CH2O-、-OCF2-、-CF2O-、-OCO-又は-COO-を表し、Ga及びGbはそれぞれ独立的にトランス-1,4-シクロヘキシレン基又は-1,4-フェニレン基を表し、p1及びp2はそれぞれ独立的に0又は1を表す。）で表されるトリフルオロナフタレン誘導体を1種又は2種以上含有し、一般式(2) (In the formula, R a represents a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, and R b represents a linear alkyl group having 1 to 7 carbon atoms. Represents a straight-chain alkoxyl group having 1 to 7 carbon atoms, a straight-chain alkenyl group having 2 to 7 carbon atoms, or a straight-chain alkenyloxy group having 2 to 7 carbon atoms, and M a and M p are respectively Independently represents a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —OCO— or —COO—, G a and G b Each independently represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group, and p1 and p2 each independently represent 0 or 1, and a trifluoronaphthalene derivative represented by 1 Contains two or more species, and has the general formula (2)
また、
一般式(1-1)
Also,
Formula (1-1)
（式中、Raは炭素原子数1〜7の直鎖状アルキル基又は炭素原子数2〜7の直鎖状アルケニル基を表し、Rbは炭素原子数1〜7の直鎖状アルキル基、炭素原子数1〜7の直鎖状アルコキシル基、炭素原子数2〜7の直鎖状アルケニル基又は炭素原子数2〜7の直鎖状アルケニルオキシ基を表し、Ma及びMpはそれぞれ独立的に単結合、-CH2CH2-、-OCH2-、-CH2O-、-OCF2-又は-CF2O-を表し、Ga及びGbはそれぞれ独立的にトランス-1,4-シクロヘキシレン基又は-1,4-フェニレン基を表し、p1及びp2はそれぞれ独立的に0又は1を表す。）で表されるトリフルオロナフタレン誘導体もあわせて提供する。 (In the formula, R a represents a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, and R b represents a linear alkyl group having 1 to 7 carbon atoms. Represents a straight-chain alkoxyl group having 1 to 7 carbon atoms, a straight-chain alkenyl group having 2 to 7 carbon atoms, or a straight-chain alkenyloxy group having 2 to 7 carbon atoms, and M a and M p are respectively Independently represents a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O—, wherein G a and G b are each independently trans-1 , 4-cyclohexylene group or 1,4-phenylene group, and p1 and p2 each independently represents 0 or 1).
本発明の液晶組成物は誘電率異方性が負であってその絶対値が大きい特徴を有し、これを用いた表示素子は垂直配向方式、IPS等の液晶表示素子として有用である。また、本発明のトリフルオロナフタレン誘導体は誘電率異方性が負であって、その絶対値が大きく、垂直配向方式、IPS等向けの液晶組成物の構成部材として有用である。 The liquid crystal composition of the present invention is characterized by having a negative dielectric anisotropy and a large absolute value, and a display device using this is useful as a liquid crystal display device such as a vertical alignment type or IPS. Further, the trifluoronaphthalene derivative of the present invention has a negative dielectric anisotropy and a large absolute value, and is useful as a constituent member of a liquid crystal composition for a vertical alignment method, IPS, and the like.
一般式(1)において、Raは炭素原子数1〜7の直鎖状アルキル基が好ましく、エチル基、プロピル基、ブチル基又はペンチル基がより好ましい。Rbは炭素原子数1〜7の直鎖状アルキル基又はアルコキシル基が好ましく、エチル基、プロピル基、ブチル基、ペンチル基、-OCH3、-OCH2CH3、-O(CH2) 2CH3、-O(CH2) 3CH3又は-O(CH2) 4CH3がより好ましい。p1及びp2の合計は0又は1が好ましく、p1が0または1を表し、p2が0を表すことがより好ましい。Maは単結合、-CH2CH2-、-OCH2-又は-OCF2-が好ましく、-CH2CH2-又は-OCH2-がより好ましい。Mpは単結合または-CH2CH2-が好ましく、単結合がより好ましい。Ga及びGbはトランス-1,4-シクロヘキシレン基が好ましく、具体的には以下の一般式で表される化合物が特に好ましい。 In the general formula (1), R a is preferably a linear alkyl group having 1 to 7 carbon atoms, more preferably an ethyl group, a propyl group, a butyl group, or a pentyl group. R b is preferably a linear alkyl group having 1 to 7 carbon atoms or an alkoxyl group, and an ethyl group, a propyl group, a butyl group, a pentyl group, —OCH 3 , —OCH 2 CH 3 , —O (CH 2 ) 2 CH 3 , —O (CH 2 ) 3 CH 3 or —O (CH 2 ) 4 CH 3 is more preferred. The sum of p1 and p2 is preferably 0 or 1, more preferably p1 represents 0 or 1, and p2 represents 0. Ma is preferably a single bond, —CH 2 CH 2 —, —OCH 2 —, or —OCF 2 —, and more preferably —CH 2 CH 2 — or —OCH 2 —. M p is preferably a single bond or —CH 2 CH 2 —, and more preferably a single bond. G a and G b are preferably trans-1,4-cyclohexylene groups, and specifically, compounds represented by the following general formula are particularly preferable.
一般式(2)において、Rcは炭素原子数2〜7の直鎖状アルキル基、炭素原子数2〜5の1-アルケニル基又は炭素原子数4〜5の3-アルケニル基が好ましく、直鎖状アルキル基としてはエチル基、プロピル基、ブチル基又はペンチル基がより好ましく、1-アルケニル基としてはビニル基又はトランス-1-プロペニル基がより好ましく、3-アルケニル基としては3-ブテニル基又はトランス-3-ペンテニル基がより好ましい。Rdは炭素原子数1〜7の直鎖状アルキル基、炭素原子数2〜5の1-アルケニル基、炭素原子数4〜5の3-アルケニル基、炭素原子数1〜3の直鎖状アルコキシル基が好ましい。Mbが存在する場合には、Mb及びMcの少なくとも一方は単結合が好ましい。 In the general formula (2), R c is preferably a linear alkyl group having 2 to 7 carbon atoms, a 1-alkenyl group having 2 to 5 carbon atoms, or a 3-alkenyl group having 4 to 5 carbon atoms. The chain alkyl group is more preferably an ethyl group, propyl group, butyl group or pentyl group, the 1-alkenyl group is more preferably a vinyl group or a trans-1-propenyl group, and the 3-alkenyl group is a 3-butenyl group. Or, a trans-3-pentenyl group is more preferable. R d is a linear alkyl group having 1 to 7 carbon atoms, a 1-alkenyl group having 2 to 5 carbon atoms, a 3-alkenyl group having 4 to 5 carbon atoms, or a linear chain having 1 to 3 carbon atoms. Alkoxyl groups are preferred. If the M b is present, at least one of M b and M c is a single bond.
一般式(2)で表される化合物としては以下の一般式(2a)〜一般式(2m)で表される化合物が好ましく、一般式(2a)、一般式(2b)、一般式(2d)又は一般式(2e)で表される化合物が特に好ましい。 As the compound represented by the general formula (2), a compound represented by the following general formula (2a) to general formula (2m) is preferable, the general formula (2a), the general formula (2b), the general formula (2d) Or the compound represented by general formula (2e) is especially preferable.
上式中、R1及びR2はそれぞれ独立的に炭素原子数1〜7の直鎖状アルキル基、炭素原子数2〜3の1-アルケニル基又は炭素原子数4〜5の3-アルケニル基を表し、R3は炭素原子数1〜5の直鎖状アルキル基又は炭素原子数3〜4の直鎖状2-アルケニル基を表し、R4は炭素原子数1〜3の直鎖状アルキル基又は炭素原子数4〜5の3-アルケニル基を表し、R5は炭素原子数1〜3の直鎖状アルキル基又は炭素原子数3〜4の直鎖状2-アルケニル基を表す。 In the above formula, R 1 and R 2 are each independently a linear alkyl group having 1 to 7 carbon atoms, a 1-alkenyl group having 2 to 3 carbon atoms, or a 3-alkenyl group having 4 to 5 carbon atoms. R 3 represents a linear alkyl group having 1 to 5 carbon atoms or a linear 2-alkenyl group having 3 to 4 carbon atoms, and R 4 represents a linear alkyl group having 1 to 3 carbon atoms. R 5 represents a linear alkyl group having 1 to 3 carbon atoms or a linear 2-alkenyl group having 3 to 4 carbon atoms.
本発明の液晶組成物においては一般式(1)で表される化合物を組成物中に1質量％（以下組成物中の％は質量％を表す）以上50％以下含有することが好ましく、2％〜40％含有することがより好ましく、4〜30％含有することがさらに好ましい。一般式(2)で表される化合物を1％〜50％含有することが好ましく、2％〜40％含有することがより好ましい。
本発明の液晶組成物において一般式(3)
In the liquid crystal composition of the present invention, the compound represented by the general formula (1) is preferably contained in the composition in an amount of 1% by mass (hereinafter,% in the composition represents% by mass) and 50% or less. It is more preferable that the content is from 40% to 40%, and it is more preferable that the content is from 4 to 30%. The compound represented by the general formula (2) is preferably contained in an amount of 1% to 50%, more preferably 2% to 40%.
In the liquid crystal composition of the present invention, the general formula (3)
（式中、Reは炭素原子数1〜7のアルキル基を表し、Rfは炭素原子数1〜7の直鎖状アルキル基、アルコキシル基又はアルケニルオキシ基を表し、p4は0又は1を表し、Md及びMeはそれぞれ独立的に単結合、-CH2CH2-、-OCH2-、-CH2O-、-OCF2-、-CF2O-又は-COO-を表し、Gdはトランス-1,4-シクロヘキシレン基あるいは1〜2個のフッ素により置換されていてもよい-1,4-フェニレン基を表す。）で表される2,3-ジフルオロ-1,4-フェニレン誘導体の1種又は2種以上を含有していても良い。 Wherein R e represents an alkyl group having 1 to 7 carbon atoms, R f represents a linear alkyl group having 1 to 7 carbon atoms, an alkoxyl group or an alkenyloxy group, and p4 represents 0 or 1 M d and Me each independently represent a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— or —COO—, G d represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group which may be substituted with 1 to 2 fluorines. One or more of -phenylene derivatives may be contained.
一般式(3)において、Reは炭素原子数2〜7の直鎖状アルキル基が好ましい。Rfは炭素原子数1〜5の直鎖状アルキル基、直鎖状アルコキシル基が好ましく、炭素原子数1〜3の直鎖状アルキル基又は炭素原子数1〜3の直鎖状アルコキシル基が特に好ましい。Md及びMeのうち一方は単結合であることが好ましく、他方は単結合、-CH2CH2-又は-COO-であることが好ましい。 In the general formula (3), R e is preferably a linear alkyl group having 2 to 7 carbon atoms. R f is preferably a linear alkyl group having 1 to 5 carbon atoms and a linear alkoxyl group, and a linear alkyl group having 1 to 3 carbon atoms or a linear alkoxyl group having 1 to 3 carbon atoms. Particularly preferred. Preferably one of the M d and M e is a single bond and the other is a single bond, -CH 2 CH 2 - is preferred or -COO- in which.
一般式(3)には非常に多くの化合物が含まれるが、以下の一般式(3a)〜一般式(3g)で表される化合物が好ましい。 The general formula (3) includes a large number of compounds, but compounds represented by the following general formulas (3a) to (3g) are preferable.
上式中、R6は炭素原子数1〜7の直鎖状アルキル基を表し、R7は炭素原子数1〜5の直鎖状アルキル基又は炭素原子数1〜3の直鎖状アルコキシル基を表す。
また、本発明の液晶組成物において、一般式(4)〜一般式(8)
In the above formula, R 6 represents a linear alkyl group having 1 to 7 carbon atoms, and R 7 is a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxyl group having 1 to 3 carbon atoms. Represents.
In the liquid crystal composition of the present invention, the general formula (4) ~ general formula (8)
（式中、Rg、Ri、Rk及びRmは炭素原子数1〜7の直鎖状アルキル基を表し、Rh、Rj、及びRnは炭素原子数1〜7の直鎖状アルキル基、アルコキシル基又はアルケニルオキシ基を表し、Rlは炭素原子数1〜7の直鎖状アルキル基を表し、Roは炭素原子数1〜7の直鎖状アルキル基、アルコキシル基又は炭素原子数2〜7の直鎖状アルケニル基、アルケニルオキシ基を表し、Rpは炭素原子数1〜7の直鎖状アルキル基又は炭素原子数2〜7の直鎖状アルケニル基を表し、Xa及びXbは水素原子又はフッ素原子を表し、p5、p6、p7及びp8はそれぞれ独立的に0又は1を表し、p9及びp10はそれぞれ独立的に0、1又は2を表し、p9及びp10の合計は1又は2であり、Mf及びMg、Mh及びMi、Mj及びMk、Ml及びMm、Mnはそれぞれ独立的に単結合、-CH2CH2-、-OCH2-、-CH2O-、-OCF2-、-CF2O-又は-COO-を表し、Moは単結合又は-CH2CH2-を表し、Ge、Gf、Gg、Gh、Gi及びGjはそれぞれ独立的にトランス-1,4-シクロヘキシレン基あるいは1〜2個のフッ素により置換されていてもよい-1,4-フェニレン基を表し、Gi、Gj、Mn及びMoが複数存在する場合、それらは同一であっても異なっていてもよい。）で表される化合物の1種又は2種以上を含有していても良い。 (Wherein R g , R i , R k and R m represent a linear alkyl group having 1 to 7 carbon atoms, and R h , R j and R n are linear chains having 1 to 7 carbon atoms. Represents a linear alkyl group, an alkoxyl group or an alkenyloxy group, R 1 represents a linear alkyl group having 1 to 7 carbon atoms, and R o represents a linear alkyl group having 1 to 7 carbon atoms, an alkoxyl group or A linear alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group, R p represents a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, X a and X b represent a hydrogen atom or a fluorine atom, p5, p6, p7 and p8 each independently represent 0 or 1, p9 and p10 each independently represent 0, 1 or 2, p9 and The sum of p10 is 1 or 2, and M f and M g , M h and M i , M j and M k , M l and M m , and M n are each independently a single bond, —CH 2 CH 2 — , -OCH 2- , -CH 2 O-, -OCF 2- , -CF 2 O- Represents —COO—, M o represents a single bond or —CH 2 CH 2 —, and G e , G f , G g , G h , G i and G j are each independently trans-1,4- Represents a cyclohexylene group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms, and when there are a plurality of G i , G j , M n and Mo , they are the same And may contain one or more of the compounds represented by formula (1).
一般式(4)〜一般式(8)において、Rg、Ri、Rk、Rm及びRpは炭素原子数2〜7の直鎖状アルキル基が好ましい。Rh、Rj、Rn及びRoは炭素原子数1〜5の直鎖状アルキル基、直鎖状アルコキシル基が好ましく、炭素原子数1〜3の直鎖状アルキル基及び直鎖状アルコキシル基が特に好ましい。Rlは炭素原子数1〜3の直鎖状アルキル基が好ましい。Mf及びMg、Mh及びMi、Mj及びMk、Ml及びMmはそれぞれ独立的に単結合、-CH2CH2-、-OCH2-、-CH2O-、-OCF2-、-CF2O-又は-COO-を表すが、一方は単結合であることが好ましく、他方は単結合、-CH2CH2-又は-COO-であることが好ましい。Mnは単結合、-CH2CH2-、-CH2O-又は-CF2O-が好ましい。 In the general formulas (4) to (8), R g , R i , R k , R m and R p are preferably linear alkyl groups having 2 to 7 carbon atoms. R h , R j , R n and R o are preferably a linear alkyl group having 1 to 5 carbon atoms and a linear alkoxyl group, and a linear alkyl group having 1 to 3 carbon atoms and a linear alkoxyl. The group is particularly preferred. R l is preferably a linear alkyl group having 1 to 3 carbon atoms. M f and M g , M h and M i , M j and M k , M l and M m are each independently a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, — OCF 2 —, —CF 2 O— or —COO— is represented, and one is preferably a single bond and the other is preferably a single bond, —CH 2 CH 2 — or —COO—. M n is preferably a single bond, —CH 2 CH 2 —, —CH 2 O— or —CF 2 O—.
かくして得られる本願発明の液晶組成物においてそのネマチック相上限温度（ＴＮ−Ｉ）が７０℃以上、より好ましくは７５℃以上であり、ネマチック相下限温度（Ｔ＞Ｎ）が−２０℃以下である。 In the liquid crystal composition of the present invention thus obtained, the nematic phase upper limit temperature (T N-I ) is 70 ° C. or higher, more preferably 75 ° C. or higher, and the nematic phase lower limit temperature (T > N ) is −20 ° C. or lower. is there.
一般式(9)において、Rqは炭素原子数2〜5の直鎖状アルキル基又は炭素原子数2〜5の直鎖状アルケニル基が好ましく、炭素原子数2〜5の直鎖状アルキル基がより好ましい。Rrは炭素原子数2〜5の直鎖状アルキル基又はアルコキシル基が好ましいが、誘電率異方性の絶対値の大きさが特に重要である場合には、アルコキシル基又はアルケニルオキシ基であることが好ましい。
本発明において、一般式(1-1)で表される化合物について、製造例を以下に挙げる。勿論本発明の主旨、及び適用範囲は、これら製造例により制限されるものではない。
In the general formula (9), R q is preferably a linear alkyl group having 2 to 5 carbon atoms or a linear alkenyl group having 2 to 5 carbon atoms, and a linear alkyl group having 2 to 5 carbon atoms. Is more preferable. R r is preferably a linear alkyl group having 2 to 5 carbon atoms or an alkoxyl group, but if the absolute value of the dielectric anisotropy is particularly important, it is an alkoxyl group or an alkenyloxy group. It is preferable.
In the present invention, production examples of the compound represented by the general formula (1-1) are given below. Of course, the gist and scope of the present invention are not limited by these production examples.
(製法1) 1,7,8-トリフルオロ-2-ナフトール(9) (Production method 1) 1,7,8-trifluoro-2-naphthol (9)
得られた一般式(10)で表される化合物を一般式(11)
The resulting compound represented by the general formula (10) is represented by the general formula (11).
得られた一般式(12)で表される化合物をリチオ化することにより一般式(13)
By lithiation of the obtained compound represented by the general formula (12), the general formula (13)
得られた一般式(13)で表される化合物をほう酸トリメチルと反応させた後、過酸化水素、過酢酸又は過蟻酸により酸化することで一般式(14)
The compound represented by the general formula (13) thus obtained is reacted with trimethyl borate, and then oxidized with hydrogen peroxide, peracetic acid or formic acid to give a general formula (14)
得られた一般式(14)で表される化合物に塩基を作用させ、一般式(15)
A base is allowed to act on the resulting compound represented by the general formula (14) to give a general formula (15)
得られた一般式(15)で表される化合物を一般式(16)
The resulting compound represented by the general formula (15) is represented by the general formula (16).
(製法2) 1,7,8-トリフルオロ-2-ナフトール(9)をトリフルオロメタンスルホニル化し、トリフルオロメタンスルホン酸 1,7,8-トリフルオロナフタレン-2-イルを得る。これを一般式(18) (Production Method 2) 1,7,8-Trifluoro-2-naphthol (9) is trifluoromethanesulfonylated to obtain 1,7,8-trifluoronaphthalen-2-yl trifluoromethanesulfonic acid. This is expressed by the general formula (18)
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。化合物の構造は、核磁気共鳴スペクトル(NMR)、質量スペクトル(MS)等により確認した。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and the like. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
化合物記載に下記の略号を使用する。
THF ：テトラヒドロフラン
DMF ：N, N-ジメチルホルムアミド
Me ：メチル基
Et ：エチル基
Pr ：プロピル基
Bu ：ブチル基
Pen ：ペンチル基
Ac ：アセチル基
（実施例１）6-(トランス-6-プロピルデカヒドロナフタレン-2-イルメトキシ) -2-プロポキシ-1,7,8-トリフルオロナフタレン(Ia)の合成
The following abbreviations are used in compound descriptions.
THF: tetrahydrofuran
DMF: N, N-dimethylformamide
Me: methyl group
Et: ethyl group
Pr: Propyl group
Bu: Butyl group
Pen: pentyl group
Ac: Acetyl group (Example 1) Synthesis of 6- (trans-6-propyldecahydronaphthalen-2-ylmethoxy) -2-propoxy-1,7,8-trifluoronaphthalene (Ia)
(1-1) 2-プロポキシ-1,7,8-トリフルオロナフタレンの合成
1,7,8-トリフルオロ-2-ナフトール440 gをアセトン2000 mLに溶解し、1-ヨードプロパン566 g及び無水炭酸カリウム460 gを加え、3時間加熱還流した。反応混合物から溶媒を減圧留去し、トルエン1000 mLを加えて30分撹拌し、不溶の塩をろ過により除いた。これをカラムクロマトグラフィー（アルミナ／トルエン）、減圧蒸留（6 - 8 mmHg, 148 162℃）、カラムクロマトグラフィー（アルミナ／トルエン）、再結晶（メタノール）で精製し、無色結晶439gを得た。
(1-1) Synthesis of 2-propoxy-1,7,8-trifluoronaphthalene
440 g of 1,7,8-trifluoro-2-naphthol was dissolved in 2000 mL of acetone, 566 g of 1-iodopropane and 460 g of anhydrous potassium carbonate were added, and the mixture was heated to reflux for 3 hours. The solvent was removed from the reaction mixture under reduced pressure, 1000 mL of toluene was added and stirred for 30 minutes, and insoluble salts were removed by filtration. This was purified by column chromatography (alumina / toluene), vacuum distillation (6-8 mmHg, 148 162 ° C.), column chromatography (alumina / toluene), and recrystallization (methanol) to obtain 439 g of colorless crystals.
(1-2) 6-プロポキシ-3,4,5-トリフルオロナフタレン-2-ほう酸の合成
2-プロポキシ-1,7,8-トリフルオロナフタレン117 gをTHF 580 mLに溶解して窒素置換し、-60℃へ冷却した。そこへブチルリチウム（1.6 M in hexane）320 mLを30分かけて滴下し、さらに30分撹拌した。続いてほう酸トリメチル61 gを30分かけて滴下し、ゆっくり0℃まで昇温した。その後10%塩酸300 mLをゆっくり加え、2時間攪拌した。反応溶液から有機層を分取し、水層をヘキサン／THF混合溶媒で抽出し、有機層を合わせ、水、飽和食塩水で洗浄した。無水硫酸マグネシウムで乾燥後、溶媒を減圧留去して淡黄色固体を得た。これを再結晶（ヘキサン／THF）により2回精製し、ほぼ無色固体98 gを得た。
(1-2) Synthesis of 6-propoxy-3,4,5-trifluoronaphthalene-2-borate
117 g of 2-propoxy-1,7,8-trifluoronaphthalene was dissolved in 580 mL of THF and purged with nitrogen, followed by cooling to -60 ° C. Thereto, 320 mL of butyl lithium (1.6 M in hexane) was added dropwise over 30 minutes, and the mixture was further stirred for 30 minutes. Subsequently, 61 g of trimethyl borate was added dropwise over 30 minutes, and the temperature was slowly raised to 0 ° C. Thereafter, 300 mL of 10% hydrochloric acid was slowly added and stirred for 2 hours. The organic layer was separated from the reaction solution, the aqueous layer was extracted with a hexane / THF mixed solvent, the organic layers were combined, and washed with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a pale yellow solid. This was purified twice by recrystallization (hexane / THF) to obtain 98 g of an almost colorless solid.
(1-3) 6-プロポキシ-3,4,5-トリフルオロ-2-ナフトールの合成
6-プロポキシ-3,4,5-トリフルオロナフタレン-2-ほう酸98 gをTHF 500 mLに溶解し、40℃に加温した。そこへ10%過酸化水素水溶液234 mLを30分かけて滴下し、さらに2時間攪拌した。水500 mLおよびヘキサン500 mLを加え、濃塩酸を加えて中和した。有機層を分取し、水層をヘキサン／THF混合溶媒で抽出し、有機層を合わせ、水、飽和食塩水で洗浄した。無水硫酸マグネシウムで乾燥後、溶媒を減圧留去して淡黄色固体を得た。これを再結晶（ヘキサン／トルエン）により精製し、ほぼ無色固体82 gを得た。
(1-3) Synthesis of 6-propoxy-3,4,5-trifluoro-2-naphthol
98 g of 6-propoxy-3,4,5-trifluoronaphthalene-2-boric acid was dissolved in 500 mL of THF and heated to 40 ° C. Thereto, 234 mL of a 10% aqueous hydrogen peroxide solution was added dropwise over 30 minutes, and the mixture was further stirred for 2 hours. Water (500 mL) and hexane (500 mL) were added, and concentrated hydrochloric acid was added for neutralization. The organic layer was separated, the aqueous layer was extracted with a hexane / THF mixed solvent, the organic layers were combined, and washed with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a pale yellow solid. This was purified by recrystallization (hexane / toluene) to obtain 82 g of an almost colorless solid.
(1-4) 6-(トランス-6-プロピルデカリン-2-イルメトキシ) -2-プロポキシ-1,7,8-トリフルオロナフタレン(Ia)の合成
反応容器に6-プロポキシ-3,4,5-トリフルオロ-2-ナフトール7.1 g、メタンスルホン酸 トランス-6-プロピルデカリン-2-イルメチル8 g、炭酸ナトリウム4.4 g、DMF 40 mLを取り、1時間加熱還流した。反応溶液を水にあけて酢酸エチルを加え、有機層を分取した。これを水、10%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浄し、無水硫酸マグネシウムで乾燥した。溶媒を減圧留去し、残渣を再結晶（アセトン／メタノール）、カラムクロマトグラフィー（アルミナ、シリカゲル／ヘキサン）および再結晶（アセトン／メタノール）により精製し、無色結晶7.2 gを得た。
相転移温度 : Cr 114.0 N 128.4 I
MS m/z : 448 (M+), 55 (100)
1H-NMR (400 MHz, CDCl3)δ: 0.60 1.40 (m, 14 H), 0.88 (t, J = 7.3 Hz, 3 H), 1.07 (t, J = 7.3 Hz, 3 H), 1.60 2.00 (m, 8 H), 3.88 (d, J = 6.1 Hz, 2 H), 4.11 (t, J = 6.6 Hz, 2 H), 6.89 (d, J = 7.1 Hz, 1 H) , 7.21 (t, J = 8.5 Hz, 1 H), 7.37 (d, J = 9.0 Hz, 1 H)
(1-4) Synthesis of 6- (trans-6-propyldecalin-2-ylmethoxy) -2-propoxy-1,7,8-trifluoronaphthalene (Ia) 6-propoxy-3,4,5 in a reaction vessel -7.1 g of trifluoro-2-naphthol, 8 g of trans-6-propyldecalin-2-ylmethyl methanesulfonate, 4.4 g of sodium carbonate and 40 mL of DMF were taken and refluxed for 1 hour. The reaction solution was poured into water, ethyl acetate was added, and the organic layer was separated. This was washed successively with water, 10% hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by recrystallization (acetone / methanol), column chromatography (alumina, silica gel / hexane) and recrystallization (acetone / methanol) to obtain 7.2 g of colorless crystals.
Phase transition temperature: Cr 114.0 N 128.4 I
MS m / z: 448 (M + ), 55 (100)
1 H-NMR (400 MHz, CDCl 3 ) δ: 0.60 1.40 (m, 14 H), 0.88 (t, J = 7.3 Hz, 3 H), 1.07 (t, J = 7.3 Hz, 3 H), 1.60 2.00 (m, 8 H), 3.88 (d, J = 6.1 Hz, 2 H), 4.11 (t, J = 6.6 Hz, 2 H), 6.89 (d, J = 7.1 Hz, 1 H), 7.21 (t, J = 8.5 Hz, 1 H), 7.37 (d, J = 9.0 Hz, 1 H)
（実施例２）6-(トランス-6-エチルデカリン-2-イルメトキシ) -2-ブトキシ-1,7,8-トリフルオロナフタレンの合成
実施例１と同様な条件下、6-プロポキシ-3,4,5-トリフルオロ-2-ナフトールの代わりに6-ブトキシ-3,4,5-トリフルオロ-2-ナフトールを、メタンスルホン酸 トランス-6-プロピルデカリン-2-イルメチルの代わりにメタンスルホン酸 トランス-6-エチルデカリン-2-イルメチルを用いて6-(トランス-6-エチルデカリン-2-イルメトキシ) -2-ブトキシ-1,7,8-トリフルオロナフタレンを得た。
相転移温度 : Cr 95 N 108 I
Example 2 Synthesis of 6- (trans-6-ethyldecalin-2-ylmethoxy) -2-butoxy-1,7,8-trifluoronaphthalene Under the same conditions as in Example 1, 6-propoxy-3, 6-butoxy-3,4,5-trifluoro-2-naphthol instead of 4,5-trifluoro-2-naphthol, methanesulfonic acid methanesulfonic acid instead of trans-6-propyldecalin-2-ylmethyl 6- (Trans-6-ethyldecalin-2-ylmethoxy) -2-butoxy-1,7,8-trifluoronaphthalene was obtained using trans-6-ethyldecalin-2-ylmethyl.
Phase transition temperature: Cr 95 N 108 I
（実施例３）6-(トランス-6-(トランス-4-プロピルシクロヘキシル)デカリン-2-イルメトキシ) -2-プロポキシ-1,7,8-トリフルオロナフタレン(Ib)の合成 Example 3 Synthesis of 6- (trans-6- (trans-4-propylcyclohexyl) decalin-2-ylmethoxy) -2-propoxy-1,7,8-trifluoronaphthalene (Ib)
反応容器に6-プロポキシ-3,4,5-トリフルオロ-2-ナフトール10 g、メタンスルホン酸 トランス-6-(トランス-4-プロピルシクロヘキシル)デカリン-2-イルメチル14 g、炭酸ナトリウム6.2 g、DMF 80 mLを取り、2時間加熱還流した。トルエンおよび水を加え、有機層を分取した。これを飽和食塩水で２回洗浄し、無水硫酸マグネシウムで乾燥した。溶媒を減圧留去し、残渣を再結晶（アセトン／酢酸エチル）、カラムクロマトグラフィー（アルミナ、シリカゲル／ヘキサン）および再結晶（アセトン／酢酸エチル）により精製し、無色結晶10.5 gを得た。
相転移温度 : Cr 122.0 N 250.8 I
1H-NMR (400 MHz, CDCl3) δ: 0.70 1.20 (m, 18 H), 0.86 (t, J = 7.3 Hz, 3 H), 1.07 (t, J = 7.3 Hz, 3 H), 1.25 1.35 (m, 2H), 1.55 2.00 (m, 12 H), 3.87 (d, J = 6.3 Hz, 2 H), 4.11 (t, J = 6.6 Hz, 2 H), 6.89 (d, J = 7.3 Hz, 1 H) , 7.20 (t, J = 8.5 Hz, 1 H), 7.37 (d, J = 9.0 Hz, 1 H)
In a reaction vessel, 6 g of 6-propoxy-3,4,5-trifluoro-2-naphthol, methanesulfonic acid trans-6- (trans-4-propylcyclohexyl) decalin-2-ylmethyl 14 g, sodium carbonate 6.2 g, 80 mL of DMF was taken and heated to reflux for 2 hours. Toluene and water were added, and the organic layer was separated. This was washed twice with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by recrystallization (acetone / ethyl acetate), column chromatography (alumina, silica gel / hexane) and recrystallization (acetone / ethyl acetate) to obtain 10.5 g of colorless crystals.
Phase transition temperature: Cr 122.0 N 250.8 I
1 H-NMR (400 MHz, CDCl 3 ) δ: 0.70 1.20 (m, 18 H), 0.86 (t, J = 7.3 Hz, 3 H), 1.07 (t, J = 7.3 Hz, 3 H), 1.25 1.35 (m, 2H), 1.55 2.00 (m, 12 H), 3.87 (d, J = 6.3 Hz, 2 H), 4.11 (t, J = 6.6 Hz, 2 H), 6.89 (d, J = 7.3 Hz, 1 H), 7.20 (t, J = 8.5 Hz, 1 H), 7.37 (d, J = 9.0 Hz, 1 H)
（実施例４） 液晶組成物の調製(１)
以下の組成からなるホスト液晶組成物(H)
(Example 4) Preparation of liquid crystal composition (1)
Host liquid crystal composition comprising the following composition (H)
を調製した。ここで(H)の物性値は以下の通りである。
ネマチック相上限温度(TN-I)： 103.2℃
誘電率異方性(Δε)： 0.03
屈折率異方性(Δn)： 0.099
この母体液晶(H)90％と実施例1で得られた(Ia)10％からなる液晶組成物(M-1)を調製した。この組成物の物性値は以下の通りである。
ネマチック相上限温度(TN-I)： 105.2℃
誘電率異方性(Δε)： −0.81
屈折率異方性(Δn)： 0.102
本発明の化合物(Ia)を含有する液晶組成物(M-1)は、母体液晶(H)に比べ、誘電率異方性(Δε)は大きく減少して負の値となった。このことから、本発明の化合物は(Ia)は、誘電率異方性が負であり、その絶対値が極めて大きいことがわかる。
Was prepared. Here, the physical properties of (H) are as follows.
Nematic phase upper limit temperature (TN-I): 103.2 ℃
Dielectric anisotropy (Δε): 0.03
Refractive index anisotropy (Δn): 0.099
A liquid crystal composition (M-1) comprising 90% of the base liquid crystal (H) and 10% of (Ia) obtained in Example 1 was prepared. The physical properties of this composition are as follows.
Nematic phase upper limit temperature (TN-I): 105.2 ℃
Dielectric anisotropy (Δε): −0.81
Refractive index anisotropy (Δn): 0.102
In the liquid crystal composition (M-1) containing the compound (Ia) of the present invention, the dielectric anisotropy (Δε) was greatly reduced to a negative value as compared with the base liquid crystal (H). From this, it can be seen that the compound (Ia) of the present invention has a negative dielectric anisotropy and an extremely large absolute value.
また、(M-1)の電圧保持率を80℃で測定したところ、ホスト液晶組成物(H)の電圧保持率に対して98%以上と高い値を示した。このことから本発明の化合物(Ia)は安定性の面からも液晶表示材料として十分使用可能であることがわかる。 Further, when the voltage holding ratio of (M-1) was measured at 80 ° C., it showed a high value of 98% or more with respect to the voltage holding ratio of the host liquid crystal composition (H). This shows that the compound (Ia) of the present invention can be sufficiently used as a liquid crystal display material from the viewpoint of stability.
（実施例５）液晶組成物の調製(２)
実施例４で調製した母体液晶(H)90％と実施例３で得られた(Ib)10％からなる液晶組成物(M-2)を調製した。この組成物の物性値は以下の通りである。
ネマチック相上限温度(TN-I)： 115.6℃
誘電率異方性(Δε)： −0.84
屈折率異方性(Δn)： 0.103
本発明の化合物(Ib)を含有する液晶組成物(M-2)は、母体液晶(H)に比べ、誘電率異方性(Δε)は大きく減少して負の値となった。このことから、本発明の化合物は(Ib)は、誘電率異方性が負であり、その絶対値が極めて大きいことがわかる。
(Example 5) Preparation of liquid crystal composition (2)
A liquid crystal composition (M-2) comprising 90% of the base liquid crystal (H) prepared in Example 4 and 10% of the (Ib) obtained in Example 3 was prepared. The physical properties of this composition are as follows.
Nematic phase upper limit temperature (TN-I): 115.6 ℃
Dielectric anisotropy (Δε): −0.84
Refractive index anisotropy (Δn): 0.103
In the liquid crystal composition (M-2) containing the compound (Ib) of the present invention, the dielectric anisotropy (Δε) was greatly reduced to a negative value as compared with the base liquid crystal (H). This shows that the compound (Ib) of the present invention has a negative dielectric anisotropy and an extremely large absolute value.
また、(M-2)の電圧保持率を80℃で測定したところ、ホスト液晶組成物(H)の電圧保持率に対して98%以上と高い値を示した。このことから本発明の化合物(Ib)は安定性の面からも液晶表示材料として十分使用可能であることがわかる。
（比較例１）液晶組成物の調製(３)
実施例４で調製した母体液晶(H)90％と特許文献１記載の化合物 (Ic)
When the voltage holding ratio of (M-2) was measured at 80 ° C., it showed a high value of 98% or more with respect to the voltage holding ratio of the host liquid crystal composition (H). This shows that the compound (Ib) of the present invention can be sufficiently used as a liquid crystal display material from the viewpoint of stability.
(Comparative Example 1) Preparation of liquid crystal composition (3)
90% of the base liquid crystal (H) prepared in Example 4 and the compound (Ic) described in Patent Document 1
ネマチック相上限温度(TN-I)： 87.1℃
誘電率異方性(Δε)： −0.42
屈折率異方性(Δn)： 0.095
特許文献１記載の化合物 (Ic)を含有する液晶組成物(M-3)は、実施例1記載の(M-1)及び実施例２記載の(M-2)と比べ、誘電率異方性の絶対値が小さく、またネマチック相上限温度(TN-I)も大きく低下したことがわかる。
Nematic phase upper limit temperature (TN-I): 87.1 ℃
Dielectric anisotropy (Δε): −0.42
Refractive index anisotropy (Δn): 0.095
The liquid crystal composition (M-3) containing the compound (Ic) described in Patent Document 1 is more anisotropic than (M-1) described in Example 1 and (M-2) described in Example 2. It can be seen that the absolute value of the property is small and the nematic phase upper limit temperature (TN-I) is also greatly reduced.
（実施例６）液晶組成物の調製(４)
以下の組成からなる液晶組成物(M-4)を調製した。
(Example 6) Preparation of liquid crystal composition (4)
A liquid crystal composition (M-4) having the following composition was prepared.
ネマチック相上限温度(TN-I)： 101.9℃
誘電率異方性(Δε)： −4.16
屈折率異方性(Δn)： 0.097
ここで作製した組成物を用いて、電圧保持率を測定したところ80℃で98%と高い値を示し、優れた表示特性を示す液晶表示装置を作成することができた。
Nematic phase upper limit temperature (TN-I): 101.9 ℃
Dielectric anisotropy (Δε): −4.16
Refractive index anisotropy (Δn): 0.097
When the voltage holding ratio was measured using the composition prepared here, it was as high as 98% at 80 ° C., and a liquid crystal display device having excellent display characteristics could be produced.
（実施例７）液晶組成物の調製(５)
以下の組成からなる液晶組成物(M-5)を調製した。
(Example 7) Preparation of liquid crystal composition (5)
A liquid crystal composition (M-5) having the following composition was prepared.
この(M-5)の物性値は以下の通りであった。
ネマチック相上限温度(TN-I)： 117.2℃
誘電率異方性(Δε)： -5.0
屈折率異方性(Δn)： 0.092
ここで作製した組成物を用いて、電圧保持率を測定したところ80℃で98%と高い値を示し、優れた表示特性を示す液晶表示装置を作成することができた。
The physical properties of (M-5) were as follows.
Nematic phase upper limit temperature (TN-I): 117.2 ℃
Dielectric anisotropy (Δε): -5.0
Refractive index anisotropy (Δn): 0.092
When the voltage holding ratio was measured using the composition prepared here, it was as high as 98% at 80 ° C., and a liquid crystal display device having excellent display characteristics could be produced.
本発明の液晶組成物、表示素子及び化合物は、垂直配向方式、IPS等の液晶表示素子の構成部材として有用である。
The liquid crystal composition, display element, and compound of the present invention are useful as constituent members of a liquid crystal display element such as a vertical alignment method and IPS.
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