JPH0430954B2 - - Google Patents
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- Publication number
- JPH0430954B2 JPH0430954B2 JP60042116A JP4211685A JPH0430954B2 JP H0430954 B2 JPH0430954 B2 JP H0430954B2 JP 60042116 A JP60042116 A JP 60042116A JP 4211685 A JP4211685 A JP 4211685A JP H0430954 B2 JPH0430954 B2 JP H0430954B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- liquid crystal
- compounds
- integer
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000004973 liquid crystal related substance Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000004990 Smectic liquid crystal Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- -1 (S)-2- Methylbutyl Chemical group 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 2
- WLAMNBDJUVNPJU-SCSAIBSYSA-N (R)-2-methylbutyric acid Chemical compound CC[C@@H](C)C(O)=O WLAMNBDJUVNPJU-SCSAIBSYSA-N 0.000 description 1
- QPRQEDXDYOZYLA-YFKPBYRVSA-N (S)-2-methylbutan-1-ol Chemical compound CC[C@H](C)CO QPRQEDXDYOZYLA-YFKPBYRVSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methyl-1-butanol Substances CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- QHQCRCZWVJEONX-UHFFFAOYSA-N 2-phenyl-5-undecoxypyrimidine Chemical compound C1(=CC=CC=C1)C1=NC=C(C=N1)OCCCCCCCCCCC QHQCRCZWVJEONX-UHFFFAOYSA-N 0.000 description 1
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical compound C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GKQLYSROISKDLL-UHFFFAOYSA-N EEDQ Chemical compound C1=CC=C2N(C(=O)OCC)C(OCC)C=CC2=C1 GKQLYSROISKDLL-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
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 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
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- SYQIIBRVOSBWME-UHFFFAOYSA-N trichloromethyl formate Chemical compound ClC(Cl)(Cl)OC=O SYQIIBRVOSBWME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、強誘電性カイラルスメクチツク液晶
化合物を提供するものであつて、該液晶化合物
は、電界への応答を利用した電気光学素子に使用
される。
（発明の概要）
本発明は次式
〔式中ｍは０〜８の整数、ｎは５〜14の整数を
示し、＊は不斉炭素原子であることを示す。〕で
示される光学活性な液晶化合物であつて、室温を
含む広い温度範囲でカイラルスメクチツク相を呈
すると共に、化学的安定性にもすぐれ、高い応答
性を有し、更に他の各種液晶化合物との混合性に
もすぐれた液晶化合物である。
（従来の技術）
強誘電性を示す液晶化合物として、（Ｓ）−２−
メチルブチルＰ−（Ｐ−ｎ−デシロキシベンジリ
デンアミノ）シンナメート（DOBAMBC）が知
られている。このシツフ塩基系列の液晶化合物
が、強誘電性液晶の研究対象とされ、種々の化合
物が合成された。その１例として
〔式中ＸはＨ，Cl，CN，ＹはCl，C2H5，＊は
不斉炭素原子を示す。〕
の一般式で示される化合物が知られている。
しかし、この系列の化合物はカイラルスメクチ
ツク相を呈する温度が室温より高いため、室温で
は使えず、又シツフ塩基系化合物であるため水分
により分解を受け易いなどの欠点を有している。
これらを改良するために考え出された化合物とし
て、次のものが知られている。
（Ferroelectriics24巻、309頁（1980））
この系の化合物は、室温を含む広い温度範囲に
亘つてスメクチツクC*相を呈する化合物として
注目された。
更に、B.I.オストロフスキーによつて、式
〔式中ｎは９又は10を示す。〕
で表わされる化合物が、比較的室温に近い温度範
囲でカイラルスメクチツク相を呈すると報告され
ている。
又、Zaschke Horst，Stolle，Reinhardらによ
つて式
〔式中ｍは１〜11、ｎは５〜８を示す。〕
で示される化合物のいくつかがスメクチツク相を
呈するとして紹介されている。
（Z.Chem 1975 15（11） 441〜３）しかし、こ
れらの中に、強誘電性カイラルスメクチツク液晶
化合物は記載されていない。
（本発明が解決しようとする問題点）
本発明によつて提供される化合物は、式［］
〔式中ｍは０〜８の整数を示し、ｎは５〜14の
整数を示し、＊は不斉炭素原子であることを示
す。〕
で示される新規な強誘電性液晶化合物であつて、
室温を含む広い温度範囲でカイラルスメチツク相
を呈すると共に、化学的安定性にもすぐれ、高い
応答性を有し、更に他の各種液晶化合物との混合
性にも優れている。
本発明はかかる液晶化合物を提供する。
（問題点を解決するための手段）
本発明によつて提供される新規な強誘電性カイ
ラルスメクチツク液晶化合物は次のようにして造
られる。即ち
合成法 １
式
（ｎは５〜14の整数を示す）
で示される化合物と式、
〔式中、ｍは０〜８の整数を示し、＊は不斉炭
素原子であることを示す。）
で示される化合物とを適切な溶媒中、触媒を用い
て反応させることによつて造られる。
〔式中ｍ，ｎ，＊は前記と同じ〕
ここにおいて用いられる溶媒としては、エチル
エーテル、テトラヒドロフラン、ジオキサンなど
のエーテル系、ベンゼン、トルエン、キシレンな
どの芳香族系、酢酸エチルエステル、酢酸ブチル
エステルなどのエステル系、クロロホルム、ジク
ロロメタン、トリクロロエタンなどのハロアルカ
ン系などがあげられる。又、使用される触媒とし
てはジシクロヘキシルカルボジイミド、１，１−
カルボニルジイミダゾール、１−エトキシカルボ
ニル−２−エトキシ−１，２−ジヒドロキノリン
などがあげられ、ピリジン、ジメチルアミノピリ
ジン、トリエチルアミンなどの三級アミンを併用
する。
反応は室温乃至溶媒の還流温度で、２〜24時間
混合撹拌することによつて完了する。合成法 ２
式
〔ｎは５〜14の整数を示す。〕
で示される化合物と 式
〔ｍは０〜８の整数、Ｘはハロゲン原子、活性
エステル残基を示し、＊は不斉炭素原子であるこ
とを示す。）
で示される化合物とを溶媒の存在又は不存在で、
反応させることによつて造られる。
〔式中、ｍ，ｎ，Ｘ，＊は前記と同じ〕
ここにおいて、式(3)は示される化合物における
Ｘで示される基としては、クロル原子、ブロム原
子、Ｐ−ニトロフエノキシ基、エトキシカルボニ
ルオキシ基などである。用いられる溶媒としては
前記したもののほか、石油エーテル、ヘキサンな
ども使用される。
ピリジン、トリエチルアミン、ジメチルアニリ
ン、ジメチルアミノピリジンなど三級アミンを使
用して反応を好適に進めることができる。
反応は氷冷下乃至溶媒の還流温度で、２〜24時
間混合撹拌することによつて完了する。
又、本発明によつて提供される液晶化合物が１
ケの不斉炭素原子を有しているため、一対の光学
的対掌体が存在する。これら対掌体は本発明の目
的化合物に包含されるところ、その光学的性質
は、原料として使用される式(2)又は(3)で示される
化合物において、対掌体のいずれを使用するかに
従つて、一義的に定まる。
なお、（Ｓ）−アミルアルコール（すなわち、
（Ｓ）体の光学活性アミルアルコールを意味する。
以下同様）（〔α〕23 D−5.8°）から誘導される（Ｓ）
体のアルキル酸は、次の反応例に従つて合成され
る。
得られた（Ｓ）体のアルキル酸を還元（例えば
LiA1H4にて）し、アルコールに変えたのち上記
反応式に従つて誘導し、各種（Ｓ）体のアルキル
酸を合成する。
実施例 １
（ｍ＝０，ｎ＝11，＊不斉炭素）
(s)５−ｎ−ウンデシルオキシ−２−〔４−（２−
メチルブチリルオキシ）フエニル〕ピリミジンの
合成、
25mlのフラスコに、(s)アミルアルコール（〔α〕
23 D−5.80（neat）より合成した２−メチル酪酸
0.328ｇ、４−（５−ｎ−ウンデシルオキシ−２−
ピリミジニル）フエノール1.1ｇ、無水クロロホ
ルム８ml、４−ジメチルアミノピリジン、Ｎ，
N′−ジシクロヘキシルカルボジイミド0.662ｇを
入れ、室温で一昼夜反応した。反応終了後、不溶
物を別し、反応生成物をクロロホルム抽出し
た。有機層は、水、2N塩酸、水で洗浄し乾燥後、
有機溶媒を留去した。得られた反応生成物をシリ
カゲルクロマドグラフイー（溶離液：クロロホル
ム）、再結晶（溶媒：エタノール）により精製し、
光学活性な５−ｎ−ウンデシルオキシ−２−〔４
−（２−メチルブチリルオキシ）フエニル〕ピリ
ミジンを収率70％で得た。
IR.νnujol nax（cm-1）：1762，1602，1550，1440，127
81
Ｈ−NMR（60MHz，CDCl3）
δ（ppm）：8.42（ｓ，2H）
8.40（ｄ，2H）
7.17（ｄ，2H）
4.40（ｔ，2H）
2.3〜2.8（ｍ，1H）
0.6〜2.2（ｍ，29H）
実施例 ２〜６
以下、(s)アミルアルコール〔［α］23 D−5.80
（neat）〕より合成した(s)体の下記アルキル酸とア
ルキルオキシピリミジニルフエノールを用いて、
実施例１と同様に操作を行ない目的化合物を得
た。
【表】
【表】
実施例 ７
（ｍ＝０，ｎ＝11）
（Ｒ）−２−〔４−（２−メチルブチリルオキシ）
フエニル〕−５−（ｎ−ウンデシルオキシ）ピリミ
ジンの合成（尚、上記化学構造式において、右端
の「−ｎ」は当該アルキル基−CnH2n＋１が直
鎖であることを表す。）
25mlフラスコに４−（５−ｎ−ウンデシルオキ
シ−２−ピリミジニル）フエノール1.71ｇ、（Ｒ）
−２−メチル酪酸（この化合物は、O.Schiitz，
W.Marckward，Ber.32，1092（1899）及びibid，
29，53（1896）の光学分割の方法により得られ
た。）0.51ｇ、乾燥酢酸エチルを入れ、溶解した
後、Ｎ，N′−ジシクロヘキシルカルボジイミド
1.03ｇ、４−ジメチルアミノピリジン25mgを入
れ、室温で一昼夜反応した。反応終了後、希塩酸
で酸性とし、ハイフロスーパーセルを用いて、不
溶物を別し、液を酢酸エチルで抽出した。酢
酸エチル層は、10％NaOH、水でよく洗浄し、
乾燥後、酢酸エチルを留去した。
得られた粗生成物をシリカゲルクロマトグラフ
イー（溶離液：クロロホルム）、再結晶（溶媒：
エタノール）により、精製し1.2ｇの（Ｒ）−２−
〔４−（２−メチルブチリルオキシ）フエニル〕−
５−（ｎ−ウンデシルオキシ）ピリミジンを得た。
この化合物の旋光度は旋光度は［α］25 D−12.83°
（Ｃ＝1.8CHCl3）であつた。
I.R νnujol nax（cm-1）：1760，1605，1552，1440，
1280，1205，1170，1125
1H−NMR （60MHZ，CDCl3）
δ（ppm）：0.7〜2.23 （ｍ，29H）
2.26〜2.97 （ｍ，1H）
4.13 （ｔ，2H）
7.19 （ｄ，2H）
8.39 （ｄ，2H）
8.43 （ｓ，2H）
実施例 ８
（Ｒ）−２−〔４−（２−メチルブチリルオキシ）
フエニル〕−５−（ｎ−オクチルオキシ）ピリミジ
ンの合成
４−（５−ｎ−オクチルオキシ−２−ピリミジ
ニル）フエノールを用いる他は、実施例７と同様
に操作を行ない（Ｒ）−２−〔４−（２−メチルブ
チリルオキシ）フエニル〕−５−（ｎ−オクチルオ
キシ）ピリミジンを得た。
このものの旋光度は〔ｄ〕25 D−14.07（Ｃ＝0.78，
CHCl3）であつた。
．Rυnujol nax（cm-1）：1760，1560，1445，1290，
1205，1160，1125
1H−NMR （60MHZ，CDCl3）
δ（ppm）：0.65〜2.15 （ｍ，23H）
2.30〜2.90 （ｍ，1H）
4.07 （ｔ，2H）
7.13 （ｄ，2H）
8.33 （ｄ，2H）
8.40 （ｓ，1H）
本発明で使用されるアルキルオキシピリミジニ
ルフエノールは次のようにして合成された。
（式中ｎは５〜14の整数を示す）
ここにおいて用いられるアルカリ金属はナトリ
ウム、カリウムであり、アルコラートはナトリウ
ムメチラート、カリウムエチラート、ナトリウム
エチラート、カリウムメチラートである。また、
ビルスマイヤー試薬はジメチルホルムアミドと塩
化チオニル、トリクロロメチルホルメート、オキ
シ塩化リンなどから常法（化学の領域19巻900ペ
ージ（1965年）参照）に従い造られる。例えば、
更に、実施例１〜６の目的化合物の相転移温度
及び、一軸配向処理を施した2.5μmのセルに実施
例１〜６の目的化合物を封入し、±20Vの電圧印
加で、直交ニコル下で測定した応答速度のデータ
を以下にまとめる。
【表】
ここで、＊印は過冷却を示す。
Cryは結晶相、Sc＊はカイラルスメクチツクＣ
相、SAはスメクチツクＡ相、Isoは等方性液体
相、S1はスメチツク１相、S2はスメクチツク２相
を意味する。
また、実施例７，８はそれぞれ実施例１，２と
光学対称体であり、ら旋の向きが逆であるだけで
ほぼ同じ特性を示したので、データは省略した。
（本発明の効果）
上記の如く、本発明による新規液晶化合物は、
室温より少し高い温度範囲でSc*相を有し、かつ
速い応答性を有する。そのため、多分割の動画表
示パネルや高速光学シヤツター等の高速応答性が
要求される分野での強誘電性液晶表示素子用の液
晶材料として有効であり、強誘電性スメクチツク
液晶素子の実用化に大きく寄与するものである。 DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a ferroelectric chiral smectic liquid crystal compound, which can be used for electro-optical devices utilizing response to an electric field. used for. (Summary of the invention) The present invention is based on the following formula [In the formula, m is an integer of 0 to 8, n is an integer of 5 to 14, and * indicates an asymmetric carbon atom. ] is an optically active liquid crystal compound that exhibits a chiral smectic phase in a wide temperature range including room temperature, has excellent chemical stability, and has high responsiveness, and is also compatible with various other liquid crystal compounds. It is a liquid crystal compound that has excellent miscibility with. (Prior art) As a liquid crystal compound exhibiting ferroelectricity, (S)-2-
Methylbutyl P-(Pn-decyloxybenzylideneamino)cinnamate (DOBAMBC) is known. This Schiff base series liquid crystal compound has been the subject of research into ferroelectric liquid crystals, and various compounds have been synthesized. As an example [In the formula, X is H, Cl, CN, Y is Cl, C 2 H 5 , * represents an asymmetric carbon atom. ] Compounds represented by the general formula are known. However, this series of compounds exhibits a chiral smectic phase at a temperature higher than room temperature, so they cannot be used at room temperature, and because they are Schiff base compounds, they have drawbacks such as being easily decomposed by moisture.
The following compounds are known as compounds devised to improve these problems. (Ferroelectriics Vol. 24, p. 309 (1980)) Compounds of this type have attracted attention as compounds that exhibit a smectic C * phase over a wide temperature range including room temperature. Furthermore, by BI Ostrovsky, the formula [In the formula, n represents 9 or 10. ] It has been reported that the compound represented by the following exhibits a chiral smectic phase in a temperature range relatively close to room temperature. Also, Zaschke Horst, Stolle, Reinhard et al. [In the formula, m represents 1 to 11, and n represents 5 to 8. ] Some of the compounds shown are introduced as exhibiting a smectic phase. (Z.Chem 1975 15(11) 441-3) However, ferroelectric chiral smectic liquid crystal compounds are not described in these. (Problems to be Solved by the Present Invention) The compound provided by the present invention has the formula [] [In the formula, m represents an integer of 0 to 8, n represents an integer of 5 to 14, and * represents an asymmetric carbon atom. ] A novel ferroelectric liquid crystal compound represented by
It exhibits a chiral smect phase over a wide temperature range including room temperature, has excellent chemical stability, high responsiveness, and has excellent miscibility with various other liquid crystal compounds. The present invention provides such liquid crystal compounds. (Means for Solving the Problems) The novel ferroelectric chiral smectic liquid crystal compound provided by the present invention is produced as follows. That is, synthesis method 1 formula (n represents an integer of 5 to 14) A compound and formula represented by, [In the formula, m represents an integer of 0 to 8, and * represents an asymmetric carbon atom. ) in an appropriate solvent using a catalyst. [In the formula, m, n, and * are the same as above] The solvents used here include ethers such as ethyl ether, tetrahydrofuran, and dioxane, aromatic solvents such as benzene, toluene, and xylene, ethyl acetate, and butyl acetate. Examples include esters such as chloroform, dichloromethane, and haloalkanes such as trichloroethane. In addition, the catalyst used is dicyclohexylcarbodiimide, 1,1-
Examples include carbonyldiimidazole, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, and tertiary amines such as pyridine, dimethylaminopyridine, and triethylamine are used in combination. The reaction is completed by mixing and stirring for 2 to 24 hours at room temperature to the reflux temperature of the solvent. Synthesis method 2 formula [n represents an integer of 5 to 14. ] The compound shown by and the formula [m is an integer of 0 to 8, X represents a halogen atom or an active ester residue, and * represents an asymmetric carbon atom. ) in the presence or absence of a solvent,
It is made by reacting. [In the formula, m, n, X, * are the same as above] Here, in the formula (3), the group represented by etc. In addition to the solvents mentioned above, petroleum ether, hexane, and the like can also be used. The reaction can be suitably carried out using tertiary amines such as pyridine, triethylamine, dimethylaniline, and dimethylaminopyridine. The reaction is completed by mixing and stirring for 2 to 24 hours under ice cooling or at the reflux temperature of the solvent. Further, the liquid crystal compound provided by the present invention may be
Because it has 6 asymmetric carbon atoms, it has a pair of optical antipodes. These enantiomers are included in the target compound of the present invention, and their optical properties depend on which of the enantiomers is used in the compound represented by formula (2) or (3) used as a raw material. It is uniquely determined according to. Note that (S)-amyl alcohol (i.e.,
(S) means optically active amyl alcohol.
(S) induced from ([α] 23 D −5.8°)
The alkyl acid of the compound is synthesized according to the following reaction example. The obtained (S)-form alkyl acid is reduced (e.g.
LiA1H 4 ), converted to alcohol, and then induced according to the above reaction formula to synthesize various (S)-form alkyl acids. Example 1 (m=0, n=11, *asymmetric carbon) (s)5-n-undecyloxy-2-[4-(2-
Synthesis of methylbutyryloxy)phenylpyrimidine, (s)amyl alcohol ([α]
2-Methylbutyric acid synthesized from 23 D −5.8 0 (neat)
0.328g, 4-(5-n-undecyloxy-2-
(pyrimidinyl) phenol 1.1 g, anhydrous chloroform 8 ml, 4-dimethylaminopyridine, N,
0.662 g of N'-dicyclohexylcarbodiimide was added and reacted at room temperature overnight. After the reaction was completed, insoluble materials were separated and the reaction product was extracted with chloroform. After washing the organic layer with water, 2N hydrochloric acid, and water and drying,
The organic solvent was distilled off. The obtained reaction product was purified by silica gel chromatography (eluent: chloroform) and recrystallization (solvent: ethanol),
Optically active 5-n-undecyloxy-2-[4
-(2-methylbutyryloxy)phenyl]pyrimidine was obtained in a yield of 70%. IR.ν nujol nax (cm -1 ): 1762, 1602, 1550, 1440, 127
8 1 H-NMR (60MHz, CDCl 3 ) δ (ppm): 8.42 (s, 2H) 8.40 (d, 2H) 7.17 (d, 2H) 4.40 (t, 2H) 2.3 ~ 2.8 (m, 1H) 0.6 ~ 2.2 (m, 29H) Examples 2 to 6 Below, (s) amyl alcohol [[α] 23 D −5.8 0
(neat)] using the following alkyl acid of the (s) form and alkyloxypyrimidinylphenol,
The same operation as in Example 1 was carried out to obtain the target compound. [Table] [Table] Example 7 (m=0, n=11) (R)-2-[4-(2-methylbutyryloxy)
Synthesis of [phenyl]-5-(n-undecyloxy)pyrimidine (In the above chemical structural formula, "-n" at the right end represents that the alkyl group -CnH2n+1 is linear.) 4 in a 25 ml flask -(5-n-undecyloxy-2-pyrimidinyl)phenol 1.71g, (R)
-2-Methylbutyric acid (this compound was developed by O.Schitz,
W.Marckward, Ber. 32 , 1092 (1899) and ibid,
29, 53 (1896). ), add 0.51 g of dry ethyl acetate and dissolve, then add N,N'-dicyclohexylcarbodiimide.
1.03 g of 4-dimethylaminopyridine and 25 mg of 4-dimethylaminopyridine were added, and the mixture was reacted at room temperature all day and night. After the reaction was completed, the mixture was made acidic with dilute hydrochloric acid, insoluble matter was separated using Hyflo Super Cell, and the liquid was extracted with ethyl acetate. The ethyl acetate layer was washed well with 10% NaOH and water.
After drying, ethyl acetate was distilled off. The obtained crude product was subjected to silica gel chromatography (eluent: chloroform) and recrystallization (solvent:
1.2 g of (R)-2-
[4-(2-methylbutyryloxy)phenyl]-
5-(n-undecyloxy)pyrimidine was obtained. The optical rotation of this compound is [α] 25 D −12.83°
(C=1.8CHCl 3 ). IR nujol nax (cm -1 ): 1760, 1605, 1552, 1440,
1280, 1205, 1170, 1125 1H-NMR (60MHZ, CDCl 3 ) δ (ppm): 0.7-2.23 (m, 29H) 2.26-2.97 (m, 1H) 4.13 (t, 2H) 7.19 (d, 2H) 8.39 (d, 2H) 8.43 (s, 2H) Example 8 (R)-2-[4-(2-methylbutyryloxy)
Synthesis of (R)-2- 4-(2-methylbutyryloxy)phenyl]-5-(n-octyloxy)pyrimidine was obtained. The optical rotation of this object is [d] 25 D −14.07 (C=0.78,
CHCl 3 ). ．． Rυ nujol nax (cm -1 ): 1760, 1560, 1445, 1290,
1205, 1160, 1125 1H-NMR (60MHZ, CDCl 3 ) δ (ppm): 0.65-2.15 (m, 23H) 2.30-2.90 (m, 1H) 4.07 (t, 2H) 7.13 (d, 2H) 8.33 (d , 2H) 8.40 (s, 1H) The alkyloxypyrimidinylphenol used in the present invention was synthesized as follows. (In the formula, n represents an integer of 5 to 14.) The alkali metals used here are sodium and potassium, and the alcoholates are sodium methylate, potassium ethylate, sodium ethylate, and potassium methylate. Also,
Vilsmeier's reagent is prepared from dimethylformamide, thionyl chloride, trichloromethylformate, phosphorus oxychloride, etc. according to a conventional method (see Chemistry, Vol. 19, p. 900 (1965)). for example, Furthermore, the target compounds of Examples 1 to 6 were sealed in a 2.5 μm cell that had been subjected to phase transition temperature and uniaxial alignment treatment, and a voltage of ±20 V was applied under crossed Nicols. The measured response speed data is summarized below. [Table] Here, the * mark indicates supercooling.
Cry is a crystalline phase, Sc* is chiral smectic C
SA means smectic A phase, Iso means isotropic liquid phase, S 1 means smectic 1 phase, and S 2 means smectic 2 phase. In addition, Examples 7 and 8 were optically symmetrical to Examples 1 and 2, respectively, and exhibited almost the same characteristics except that the helical directions were opposite, so data were omitted. (Effects of the present invention) As described above, the novel liquid crystal compound according to the present invention is
It has an Sc * phase in a temperature range slightly higher than room temperature and has fast response. Therefore, it is effective as a liquid crystal material for ferroelectric liquid crystal display elements in fields that require high-speed response, such as multi-segment video display panels and high-speed optical shutters, and will greatly contribute to the practical application of ferroelectric smectic liquid crystal elements. It is something that contributes.
Claims (1)
し、＊は不斉炭素原子であることを示す。〕[Claims] 1 formula An optically active liquid crystal compound represented by [In the formula, m is an integer of 0 to 8, n is an integer of 5 to 14, and * indicates an asymmetric carbon atom. ]
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60042116A JPS61200972A (en) | 1985-03-04 | 1985-03-04 | Liquid crystal compound |
| DE8585902658T DE3577211D1 (en) | 1984-06-07 | 1985-05-30 | LIQUID CRYSTAL CONNECTION. |
| US06/830,530 US4725688A (en) | 1984-06-07 | 1985-05-30 | Liquid crystal compound |
| PCT/JP1985/000302 WO1986000087A1 (en) | 1984-06-07 | 1985-05-30 | Liquid crystal compound |
| EP85902658A EP0191860B1 (en) | 1984-06-07 | 1985-05-30 | Liquid crystal compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60042116A JPS61200972A (en) | 1985-03-04 | 1985-03-04 | Liquid crystal compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61200972A JPS61200972A (en) | 1986-09-05 |
| JPH0430954B2 true JPH0430954B2 (en) | 1992-05-25 |
Family
ID=12626975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60042116A Granted JPS61200972A (en) | 1984-06-07 | 1985-03-04 | Liquid crystal compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61200972A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3518734A1 (en) * | 1985-05-24 | 1986-11-27 | Merck Patent Gmbh, 6100 Darmstadt | Smectic liquid crystal phases |
| CA1341038C (en) * | 1986-03-10 | 2000-06-27 | Masanao Kamei | Fluoroalkaned derivative |
| JPS63165345A (en) * | 1986-12-26 | 1988-07-08 | Chisso Corp | Optically active-2-methyl-alkanoates and utilized substance thereof |
| US4904410A (en) * | 1987-03-31 | 1990-02-27 | Canon Kabushiki Kaisha | Mesomorphic compound and liquid crystal composition containing same |
| JP2581567B2 (en) * | 1987-10-05 | 1997-02-12 | 帝国化学産業株式会社 | β-methylacyloxyphenylpyrimidine derivative |
| JP2691405B2 (en) * | 1987-11-06 | 1997-12-17 | チッソ株式会社 | Ferroelectric liquid crystal composition |
| JP3039651B2 (en) * | 1988-07-13 | 2000-05-08 | キヤノン株式会社 | Ferroelectric chiral smectic liquid crystal composition and liquid crystal device having the same |
| JP4767066B2 (en) * | 2006-03-31 | 2011-09-07 | 中国電力株式会社 | Buried object marking device |
-
1985
- 1985-03-04 JP JP60042116A patent/JPS61200972A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61200972A (en) | 1986-09-05 |
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