JPH0759541B2 - Optically active amide compound and smectic liquid crystal composition using the same - Google Patents
Optically active amide compound and smectic liquid crystal composition using the sameInfo
- Publication number
- JPH0759541B2 JPH0759541B2 JP61278746A JP27874686A JPH0759541B2 JP H0759541 B2 JPH0759541 B2 JP H0759541B2 JP 61278746 A JP61278746 A JP 61278746A JP 27874686 A JP27874686 A JP 27874686A JP H0759541 B2 JPH0759541 B2 JP H0759541B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- optically active
- compound
- ring
- general formula
- 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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Links
- 239000004990 Smectic liquid crystal Substances 0.000 title claims description 26
- -1 amide compound Chemical class 0.000 title claims description 18
- 239000000203 mixture Substances 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000004956 cyclohexylene group Chemical class 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 17
- 239000012071 phase Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000010287 polarization Effects 0.000 description 11
- 230000002269 spontaneous effect Effects 0.000 description 11
- 239000000758 substrate Substances 0.000 description 8
- 230000004044 response Effects 0.000 description 5
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 230000005621 ferroelectricity Effects 0.000 description 4
- SLTPTOCULAQQIN-UHFFFAOYSA-N n,3-dimethylpentan-2-amine Chemical compound CCC(C)C(C)NC SLTPTOCULAQQIN-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229930182844 L-isoleucine Natural products 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 3
- 150000004753 Schiff bases Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 229960000310 isoleucine Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- MWGKAIKWBCTKHF-UHFFFAOYSA-N C1(=O)OCC2=CC=CC=C12.[Na] Chemical compound C1(=O)OCC2=CC=CC=C12.[Na] MWGKAIKWBCTKHF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 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
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- 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、表示素子又は電気光学素子に用いられる光学
活性アミド化合物およびそれを用いた強誘電性スメクチ
ック液晶組成物に関するものである。TECHNICAL FIELD The present invention relates to an optically active amide compound used in a display device or an electro-optical device, and a ferroelectric smectic liquid crystal composition using the same.
［従来の技術］ 従来、時計電卓等の表示部に用いられているネマチック
液晶を使用した液晶表示素子は、その応答速度が、他の
表示素子たとえば、発光ダイオードよりも非常に遅いた
め、高速の応答が必要とされる分野、たとえば、光通
信、プリンターヘッドへの液晶表示素子への応用は制限
されていた。[Prior Art] A liquid crystal display element using a nematic liquid crystal conventionally used for a display unit of a watch calculator or the like has a response speed which is much slower than that of another display element, for example, a light emitting diode. Applications in areas where response is required, such as optical communication and liquid crystal display devices for printer heads, have been limited.
最近、高速の応答性を示す液晶表示素子として、強誘電
性を示すスメクチック液晶を使用した液晶表示素子が報
告され（例えば、N.A.Clark,S.T.Lagerwall,Appl.Phys.
Lett.36,899（1980））注目を集めている。Recently, a liquid crystal display device using a smectic liquid crystal exhibiting ferroelectricity has been reported as a liquid crystal display device exhibiting high-speed response (for example, NAClark, STLagerwall, Appl.Phys.
Lett. 36 , 899 (1980)) is attracting attention.
強誘電性を示すスメクチック液晶としては、カイラルス
クメチックＣ相と、カイラルスメクチックＨ相があり、
これらは層状構造を示し、液晶分子が層の積み重ね方向
に対して垂直でなく傾むいている。この傾むき方向が、
層の積み重ね方向に対して、らせんを巻くように液晶分
子は配列しており、この層と平行で、かつ液晶分子に垂
直な方向に自発分極が発生し強誘電性を示す。このらせ
ん構造が強誘電性を示す原因と考えられている。強誘電
性を示す材料は、電界に対して強誘電体としての応答性
を示し、電界の向きに応じて自発分極の向きを反転させ
て再配列する。Ferroelectric smectic liquid crystals include a chiral scmetic C phase and a chiral smectic H phase.
These show a layered structure in which the liquid crystal molecules are tilted rather than perpendicular to the stacking direction of the layers. This tilting direction is
The liquid crystal molecules are arranged in a spiral around the layer stacking direction, and spontaneous polarization occurs in a direction parallel to the layer and perpendicular to the liquid crystal molecules, and exhibits ferroelectricity. This helical structure is considered to be the cause of the ferroelectricity. A material exhibiting ferroelectricity exhibits responsiveness as a ferroelectric substance to an electric field, and reorients by inverting the direction of spontaneous polarization according to the direction of the electric field.
このとき、応答性は自発分極が大きく、粘度が低いほど
同じ電界強度に対しより高速となることが知られてい
る。また、強誘電性スメクチック液晶を用いた素子はメ
モリー性があり、このメモリー性を利用して高密度の表
示を行なう研究も活発になされている。At this time, it is known that the responsiveness has a large spontaneous polarization, and the lower the viscosity is, the faster the response is for the same electric field strength. In addition, an element using a ferroelectric smectic liquid crystal has a memory property, and researches using this memory property for high-density display are being actively conducted.
［発明の解決しようとする問題点］ 従来、強誘電性スメクチック液晶としては、シツフ塩基
型の下記に示すような化合物が多く研究されてきた。[Problems to be Solved by the Invention] As a ferroelectric smectic liquid crystal, conventionally, a lot of compounds having a Schiff base type as shown below have been studied.
ｐ−デシルオキシベンジリデン−ｐ′−アミノ−２−メ
チルブチル−桂皮酸エステル（DOBAMBC） しかし、このようなシツフ塩基型化合物は加水分解しや
すいため、水分によって分解しやすい問題点があった。 p-decyloxybenzylidene-p'-amino-2-methylbutyl-cinnamic acid ester (DOBAMBC) However, since such Schiff base type compounds are easily hydrolyzed, there is a problem that they are easily decomposed by water.
また、カイラルスメクチックＣ相を示すエステル型化合
物として、下記に一般式（II）で示すような化合物も知
られていた。Further, as an ester type compound exhibiting a chiral smectic C phase, a compound represented by the following general formula (II) has been known.
（G.W.Gray等Mol.Cryst.Liq.Cryst.,1976,37189−211） （Ｒは、炭素数５〜10の直鎖状アルキル基） しかしながら、このエステル化合物は水分には耐えるも
ののその自発分極の値が小さいという問題点を有してい
た。(GW Gray et al. Mol.Cryst.Liq.Cryst., 1976, 37 189−211) (R is a straight-chain alkyl group having 5 to 10 carbon atoms) However, this ester compound has a problem that its spontaneous polarization value is small although it withstands moisture.
さらに最近、自発分極の大きな化合物として、DOBA−１
−MBCと略称される下記の構造の化合物が吉野等（K.YOS
HINO等、J.J.A.P.,1984,23L175−177）によって報告さ
れている。More recently, as a compound with large spontaneous polarization, DOBA-1
-The compound of the following structure abbreviated as MBC is Yoshino et al. (K.YOS
HINO et al., JJAP, 1984, 23 L175-177).
しかし、この化合物もシツフ塩基型であるため水分によ
って分解しやすい欠点を有している。 However, since this compound is also a Schiff base type, it has a drawback that it is easily decomposed by water.
［問題を解決するための手段］ 本発明は前述の問題点を解決するためになされたもので
あり、一般式 （式中、Z,Z′は単結合、−COO−、−OCO−、−CH2CH2
−、−OCH2−又は−CH2O−をあらわし、Ｒは炭素数１〜
12のアルキル基もしくはアルコキシ基、シアノ基又はハ
ロゲン原子をあらわし、環Ａ及び環Ｂは1,4−ジ置換フ
ェニレンもしくはトランス−1,4−ジ置換シクロヘキシ
レンをあらわし、ｎは０又は１をあらわし、＊は光学活
性中心をあらわす）で示される光学活性アミド化合物で
あり、この一般式（Ｉ）で示される光学活性アミド化合
物を少なくとも１種含有する強誘電性スメクチック液晶
組成物である。[Means for Solving the Problem] The present invention has been made to solve the above-described problems, and has the general formula (Wherein, Z, Z 'represents a single bond, -COO -, - OCO -, - CH 2 CH 2
Represents —, —OCH 2 — or —CH 2 O—, and R represents 1 to 1 carbon atoms.
12 represents an alkyl group or an alkoxy group, a cyano group or a halogen atom, ring A and ring B represent 1,4-di-substituted phenylene or trans-1,4-di-substituted cyclohexylene, and n represents 0 or 1. , * Represents an optically active center), and is a ferroelectric smectic liquid crystal composition containing at least one optically active amide compound represented by the general formula (I).
一般式（Ｉ）の化合物において、Ｚ及びＺ′は単結合、
−COO−、−OCO−、−CH2CH2−、−OCH2−又は−CH2O−
をあらわすが、一般に単結合である場合には粘度が低
く、−COO−である場合にはスメクチックＣ相を示す上
限温度（Ts）が高いので、単結合又は−COO−が好まし
い。In the compound of general formula (I), Z and Z ′ are single bonds,
-COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 - or -CH 2 O-
In general, when the bond is a single bond, the viscosity is low, and when it is —COO—, the maximum temperature (Ts) indicating the smectic C phase is high, and thus a single bond or —COO— is preferable.
また、ｎ＝１の場合には、Ｚ、Ｚ′の両方がが−COO−
であると粘度が高くなるので、その場合には少なくとも
一方は単結合であることが好ましい。When n = 1, both Z and Z'are -COO-
Since the viscosity becomes high, it is preferable that at least one of them is a single bond.
環Ａ及び環Ｂは1,4−ジ置換フェニレンもしくはトラン
ス−1,4−ジ置換シクロヘキシレンをあらわすが、一般
にトランス−1,4−ジ置換シクロヘキシレンの方が1,4−
ジ置換フェニレンよりもTsが低いので、ｎ＝１の場合に
は、環Ａ、環Ｂの少なくとも一方は1,4−ジ置換フェニ
レンであることが好ましく、ｎ＝０の場合には環Ａは1,
4−ジ置換フェニレンであることが好ましい。Ring A and ring B represent 1,4-di-substituted phenylene or trans-1,4-di-substituted cyclohexylene, but trans-1,4-di-substituted cyclohexylene is generally 1,4-di-substituted.
Since Ts is lower than that of di-substituted phenylene, it is preferable that at least one of ring A and ring B is 1,4-di-substituted phenylene when n = 1 and ring A when n = 0. 1,
It is preferably 4-disubstituted phenylene.
又、Ｒは炭素数は１〜12のアルキル基、炭素数は１〜12
のアルコキシ基、シアノ基又はハロゲン原子をあらわす
が、シアノ基の場合には粘度が高く、またハロゲン原子
の場合にはTsが低いのでアルキル基又はアルコキシ基で
あることが好ましい。また、アルキル基、アルコキシ基
の場合、その炭素数が少ない場合には融点が高く、多す
ぎる場合にはその粘度が高いので１〜12であるが、好ま
しくは２〜８が良い。又、直鎖状でも分岐状でも良い
が、一般に直鎖状のものの方が、他の液晶性を示す化合
物と混合した場合にそのスメクチックＣ相を示す液晶上
限温度が高いので好ましい。又、環Ａがトランス−1,4
−ジ置換シクロヘキシレンの場合には、Ｒは炭素数１〜
12のアルキル基とされる。Further, R is an alkyl group having 1 to 12 carbon atoms, and has 1 to 12 carbon atoms.
The above represents an alkoxy group, a cyano group or a halogen atom, and a cyano group is preferred because it has a high viscosity and a halogen atom has a low Ts. In the case of an alkyl group or an alkoxy group, the melting point is high when the carbon number is small, and the viscosity is high when the carbon number is too large, and therefore it is 1 to 12, but preferably 2 to 8. In addition, it may be linear or branched, but in general, a linear one is preferable because it has a higher liquid crystal upper limit temperature showing a smectic C phase when mixed with another compound having liquid crystallinity. Ring A is trans-1,4
In the case of di-substituted cyclohexylene, R is 1 to
There are 12 alkyl groups.
なお、一般式（Ｉ）で示される化合物の旋光性は、左旋
性であるか右旋性であるかを問わない。The optical rotatory power of the compound represented by the general formula (I) may be levorotatory or dextrorotatory.
一般式（Ｉ）で示される化合物は、強誘電性スメクチッ
ク液晶表示素子又は電気光学素子に使用されるには、所
望の温度範囲でカイラルスメクチックＣ相を有するよう
に、他の強誘電性スメクチック液晶、スメクチック液晶
あるいは他の光学活性物質を適宜混合し、強誘電性スメ
クチック液晶組成物として使用する。更にらせんピッチ
を調整したり、カラー表示を行なうために、ネマチック
液晶，非液晶，二色性染料等を添加してもよい。本発明
の強誘電性を示すスメクチック液晶組成物中の一般式
（Ｉ）で示される化合物の含有量は、多過ぎる場合には
その強誘電性スメクチック上限温度を低下させる傾向に
あり、少なすぎる場合にはその自発分極を大きくする効
果が小さいので、１〜90Wt％とされ、好ましくは２〜50
Wt％が良い。The compound represented by the general formula (I) is used for a ferroelectric smectic liquid crystal display device or an electro-optical device, so that it has another chiral smectic C phase in a desired temperature range. , A smectic liquid crystal or other optically active substance is appropriately mixed and used as a ferroelectric smectic liquid crystal composition. Further, nematic liquid crystal, non-liquid crystal, dichroic dye or the like may be added for adjusting the spiral pitch or for displaying color. When the content of the compound represented by the general formula (I) in the ferroelectric smectic liquid crystal composition of the present invention is too large, the ferroelectric smectic maximum temperature tends to be lowered, and when it is too small. Has a small effect of increasing its spontaneous polarization, it is set to 1 to 90 Wt%, preferably 2 to 50 Wt.
Wt% is good.
本発明の一般式（Ｉ）の化合物と混合して、強誘電性ス
メクチック液晶組成物として使用される相手の化合物と
しては、例えば、以下のようなものがある。Examples of the counterpart compound used as a ferroelectric smectic liquid crystal composition by mixing with the compound of the general formula (I) of the present invention include the following.
以下の例でＲ＊は光学活性を示すアルキル基又はアルコ
キシ基を示し、Ｒは本発明のＲとは関係がなく、直鎖状
または分岐したアルキル基又はアルコキシ基を示し、一
つの化合物に同一のＲ＊、Ｒが示されていてもそれらは
同一の基とは限らない。In the following examples, R * represents an optically active alkyl group or alkoxy group, R has no relation to R of the present invention, and represents a linear or branched alkyl group or alkoxy group, which is identical to one compound. Even if R * and R are shown, they are not necessarily the same group.
これらの外、公知の種々の液晶又は非液晶の液晶添加物
が併用でき、例えば以下のようなものがある。 In addition to these, various known liquid crystal or non-liquid crystal liquid crystal additives can be used in combination, and examples thereof include the following.
及びこれらのベンゼン環、シクロヘキサン環等の水素原
子の一部をハロゲン、シアノ基、メチル基等に置換した
化合物。 And compounds obtained by substituting a part of hydrogen atoms of these benzene ring, cyclohexane ring and the like with halogen, cyano group, methyl group and the like.
この例としては、以下のような誘電率異方性が負の化合
物等の化合物がある。なお、以下の例においては、Ｒは
本発明のＲとは関係がなく、直鎖状または分岐した炭素
数１〜12のアルキル基を示し、一つの化合物に同一のＲ
が示されていてもそれら同一の基とは限らない。Examples of this are compounds such as the following compounds having a negative dielectric anisotropy. In the following examples, R has no relation to R of the present invention, and represents a linear or branched alkyl group having 1 to 12 carbon atoms, and one compound has the same R.
Are not necessarily the same groups.
二色性染料としては、トリスアゾ系、アントラキノン系
など、いわゆるゲストホスト型液晶表示素子に使用され
る染料が挙げられる。 Examples of the dichroic dye include dyes used in so-called guest-host type liquid crystal display elements such as trisazo type and anthraquinone type.
強誘電性液晶表示素子、又は電気光学素子は、液晶層を
挟持するように配置し、少なくとも一枚が透明である複
数の全面又は一部に電極を有する基板と、前記液晶層を
囲むように前記電極基板間に形成したシール部材とから
成る。該液晶表示素子において前記基板間の厚みは、0.
5〜20μｍが好ましい。また、前記基板には、各々に平
行の配向制御処理がなされても良い。この配向制御の手
段として、配向制御膜を電極基板上に一部又は全面に塗
布してもよい。該配向制御膜としては、ポリイミド等
の、その屈折率が1.5以上の高分子材料が好ましい。更
に偏光子が少なくとも１枚、液晶素子に付設されている
ことが好ましい。該電極基板は少なくとも２枚必要であ
るが、さらに多数枚を積み重ねて使用しても良い。The ferroelectric liquid crystal display element or the electro-optical element is arranged so as to sandwich the liquid crystal layer, and at least one substrate is transparent and has a plurality of substrates having electrodes on the whole surface or a part thereof, and surrounds the liquid crystal layer. And a seal member formed between the electrode substrates. In the liquid crystal display element, the thickness between the substrates is 0.
5 to 20 μm is preferable. Further, the substrates may be subjected to alignment control processing parallel to each of them. As a means for controlling the orientation, an orientation control film may be applied partially or entirely on the electrode substrate. As the orientation control film, a polymer material such as polyimide having a refractive index of 1.5 or more is preferable. Furthermore, at least one polarizer is preferably attached to the liquid crystal element. At least two electrode substrates are required, but a larger number of electrode substrates may be stacked and used.
本発明の化合物は例えば以下に示す経路により合成する
ことができる。The compound of the present invention can be synthesized, for example, by the route shown below.
（式中Ｚ、Ｚ′、Ｒ、環Ａ、環Ｂおよびｎは前記意味を
もつ） 即ち、ｐ−置換安息香酸（III）に塩化チオニル、オキ
シ塩化リン等の塩素化剤を作用させて酸塩化物（IV）と
し、これに光学活性２−メチルアミノ−３−メチルペン
タン（Ｖ）を、炭酸カリウムやピリジン等の塩基性物質
の存在下に反応させ、抽出、再結晶、カラムクロマトグ
ラフィー等一連の精製処理を施すことより、純粋な
（Ｉ）を合成することができる。 (In the formula, Z, Z ', R, ring A, ring B and n have the above-mentioned meanings) That is, p-substituted benzoic acid (III) is reacted with a chlorinating agent such as thionyl chloride or phosphorus oxychloride to produce an acid. Chloride (IV), which is reacted with optically active 2-methylamino-3-methylpentane (V) in the presence of a basic substance such as potassium carbonate or pyridine, and extraction, recrystallization, column chromatography, etc. Pure (I) can be synthesized by performing a series of purification treatments.
なお、原料となる光学活性２−メチルアミノ−３−メチ
ルペンタン（Ｖ）は例えば次のようにして合成すること
ができる。すなわち、Ｌ−イソロイシン（VI）をエタノ
ール中で塩化水素を吹込むことによりエチルエステルと
し、水素化リチウムアルミニウムにより還元してアミノ
アルコールに変え、次いで、ｐ−トルエンスルホニルク
ロライドと反応させて、N,O−ジトシル体を得る。これ
を水素化リチウムアルミニウムにより選択的に還元して
得られる２−トシルアミノ−３−メチルペンタンを金属
ナトリウム、ついでジメチル硫酸で処理してＮ−メチル
体としたのち、ナトリウムフタライドにより脱トシル化
すると原料のＬ−イソロイシンの光学純度を保持した光
学活性２−メチルアミノ−３−メチルペンタン（Ｖ）を
合成することができる。The optically active 2-methylamino-3-methylpentane (V) as a raw material can be synthesized, for example, as follows. That is, L-isoleucine (VI) is converted into an amino alcohol by blowing hydrogen chloride in ethanol into ethyl ester, reduced with lithium aluminum hydride to an amino alcohol, and then reacted with p-toluenesulfonyl chloride to give N, An O-ditosyl form is obtained. 2-Tosylamino-3-methylpentane obtained by selectively reducing this with lithium aluminum hydride is treated with metallic sodium and then with dimethylsulfuric acid to form an N-methyl compound, and then detosylated with sodium phthalide. It is possible to synthesize optically active 2-methylamino-3-methylpentane (V) which retains the optical purity of L-isoleucine as a raw material.
次に、本発明を実施例を以て具体的に説明する。 Next, the present invention will be specifically described with reference to examples.
［実施例］ 実施例１ の化合物3.26g（0.01モル）を塩化チオニル10mlとを四
塩化炭素50ml中に仕込み、環流温度において６時間かく
はんした。溶媒をエバポレーターにより留去したのち、
トルエン30mlを加え、さらにＬ−イソロイシンから合成
した光学活性２−メチルアミノ−３−メチルペンタン1.
15g（0.01モル）および炭酸カリウム2gを加え、室温に
て６時間かくはんした。反応混合物を水100mlにあけ、
トルエン100mlにて３回抽出した。トルエン相を水100ml
にて洗浄したのち、無水硫酸マグネシウムにて乾燥し、
エバポーレーターにより溶媒を留去した。残った黄色固
体をトルエンを溶媒としてアルミナのカラムにかけ、ヘ
キサンより２回再結晶し、目的とする式 の化合物2.45g（0.0058モル）を無色の結晶として得
た。収率58％、融点51.7℃ ［α］D 25゜＝−3.0（Ｃ＝1.29,CHCl3） この化合物のIRスペクトルを第１図に示す。[Example] Example 1 3.26 g (0.01 mol) of the compound of 1 was charged in 10 ml of thionyl chloride in 50 ml of carbon tetrachloride and stirred at reflux temperature for 6 hours. After distilling off the solvent with an evaporator,
30 ml of toluene was added, and optically active 2-methylamino-3-methylpentane synthesized from L-isoleucine 1.
15 g (0.01 mol) and 2 g of potassium carbonate were added, and the mixture was stirred at room temperature for 6 hours. Pour the reaction mixture into 100 ml of water,
It was extracted 3 times with 100 ml of toluene. Toluene phase 100 ml of water
After washing with, dried over anhydrous magnesium sulfate,
The solvent was distilled off with an evaporator. The remaining yellow solid was applied to an alumina column using toluene as a solvent and recrystallized twice from hexane to obtain the target compound. 2.45 g (0.0058 mol) of the compound of 1. was obtained as colorless crystals. Yield 58%, melting point 51.7 ° C. [α] D 25 ° = −3.0 (C = 1.29, CHCl 3 ) The IR spectrum of this compound is shown in FIG.
この化合物のNMRスペクトルは以下のとおりであった。The NMR spectrum of this compound was as follows.
δ（ppm,CDCl3溶媒 TMS内部標準） 6.9〜7.8 Aromatic 8H complex multiplet 4.00 Ar−Ｏ−CH2 2H ｔ Ｊ＝7Hz 3.70 Ｎ−CH 1H ｑ Ｊ＝7Hz 2.90 NCH3 3H broad singlet 0.8〜2.0 Aliphatic 27H complex multiplet 実施例２〜11 の化合物に代えて対応するカルボン酸を用いるほかは、
実施例１と同様の操作を施すことにより、以下の化合物
を得ることができる。δ (ppm, CDCl 3 solvent TMS internal standard) 6.9 to 7.8 Aromatic 8H complex multiplet 4.00 Ar-O-CH 2 2H t J = 7Hz 3.70 N-CH 1H q J = 7Hz 2.90 NCH 3 3H broad singlet 0.8 to 2.0 Aliphatic 27H complex multiplet Examples 2-11 Except that the corresponding carboxylic acid is used instead of the compound of
By performing the same operation as in Example 1, the following compound can be obtained.
実施例 12 実施例１の化合物を４−ｎ−オクチルオキシ安息香酸−
４′−ｎ−ヘキシルオキシフェニルに5.0wt％混合しそ
の自発分極を測定した。自発分極の測定は試料を、３μ
のスペーサーをはさみ、電極面積が1cm2であるセルに封
入し、スメクチックＣ相を示す上限温度（Ts）から10℃
低い温度において20Hz、10Vの三角波を印加するMiyasat
o等の方法に従い行った。（K.Miyasato et.al.,J.J.A.
P.,22,L661（1983））この混合物の自発分極の大きさは
12.3nC/cm2であった。この大きさは従来研究されている
強誘電性液晶化合物DOBAMBCが単品で3.7nC/cm2であるの
に対し、本混合物が実施例１の化合物を5.0％に希釈し
たものであることを考えれば、きわめて大きいことがわ
かる。また、本混合物は60.9℃においてスメクチックＣ
相からスメクチックＡ相に転移し、さらに83.5℃におい
て等方性液体相に転移した。４−ｎ−オクチルオキシ安
息香酸−４′−ｎ−ヘキシルオキシフェニルのスメクチ
ックＣ相上限温度は65.0℃であるから、本発明の化合物
はスメクチックＣ相の温度範囲をあまり狭めることなく
自発分極を大きくすることができる、きわめて有用な化
合物であることがわかる。 Example 12 The compound of Example 1 was treated with 4-n-octyloxybenzoic acid-
5.0 wt% was mixed with 4'-n-hexyloxyphenyl and the spontaneous polarization was measured. The measurement of the spontaneous polarization of the sample is 3μ
10cm from the upper limit temperature (Ts) that shows smectic C phase by enclosing the spacer in between and enclosing it in a cell with an electrode area of 1cm 2.
Miyasat applying 20Hz, 10V triangular wave at low temperature
It was performed according to the method such as o. (K. Miyasato et.al., JJA
P., 22, L661 (1983)) The magnitude of spontaneous polarization of this mixture is
It was 12.3 nC / cm 2 . This size is 3.7 nC / cm 2 for the ferroelectric liquid crystal compound DOBAMBC which has been studied so far, while considering that this mixture is the compound of Example 1 diluted to 5.0%. It turns out to be extremely large. Also, this mixture had smectic C at 60.9 ° C.
The phase transitioned to the smectic A phase and then to the isotropic liquid phase at 83.5 ° C. Since the maximum temperature of the smectic C phase of 4-n-octyloxybenzoic acid-4'-n-hexyloxyphenyl is 65.0 ° C, the compound of the present invention has a large spontaneous polarization without significantly narrowing the temperature range of the smectic C phase. It turns out that it is a very useful compound that can be obtained.
さらに、本発明者らがすでに提案している の場合のTs9.3nC/cm2に比して、また、 の場合のTs8.3nC/cm2に比しても高いものであった。Furthermore, the present inventors have already proposed In comparison with Ts 9.3nC / cm 2 in the case of It was also higher than Ts 8.3 nC / cm 2 in the case of.
［発明の効果］ 本発明は自発分極が大きく、かつスメクチックＣ相の温
度範囲を狭めることのない一般式（Ｉ）で示される光学
活性ラクタム化合物、および該化合物を少なくとも１種
含有する強誘電性スメクチック液晶組成物を提供するこ
とにより、広い温度範囲にわたり高速応答が可能な表示
素子または電気光学素子を構成し得る優れた効果を有す
る。EFFECTS OF THE INVENTION The present invention provides an optically active lactam compound represented by the general formula (I) which has a large spontaneous polarization and does not narrow the temperature range of the smectic C phase, and a ferroelectric containing at least one of the compounds. By providing the smectic liquid crystal composition, it has an excellent effect that a display element or an electro-optical element capable of high-speed response over a wide temperature range can be formed.
第１図は本発明実施例１の化合物の1Rスペクトル図であ
る。FIG. 1 is a 1R spectrum diagram of the compound of Example 1 of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 255/57 255/60 Ｃ０９Ｋ 19/54 Ｂ 9279−4Ｈ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location C07C 255/57 255/60 C09K 19/54 B 9279-4H
Claims (5)
−、−OCH2−又は−CH2O−をあらわし、Ｒは炭素数１〜
12のアルキル基もしくはアルコキシ基、シアノ基又はハ
ロゲン原子をあらわし、環Ａ及び環Ｂは1,4−ジ置換フ
ェニレンもしくはトランス−1,4−ジ置換シクロヘキシ
レンをあらわし、ｎは０又は１をあらわし、＊は光学活
性中心をあらわす）で示される光学活性アミド化合物。1. A general formula (Wherein, Z, Z 'represents a single bond, -COO -, - OCO -, - CH 2 CH 2
Represents —, —OCH 2 — or —CH 2 O—, and R represents 1 to 1 carbon atoms.
12 represents an alkyl group or an alkoxy group, a cyano group or a halogen atom, ring A and ring B represent 1,4-di-substituted phenylene or trans-1,4-di-substituted cyclohexylene, and n represents 0 or 1. , * Represents an optically active center) and is an optically active amide compound.
換フェニレンをあらわし、ｎが０をあらわすところの特
許請求の範囲第１項記載の化合物。2. A compound according to claim 1, wherein in the general formula (I), ring A represents 1,4-disubstituted phenylene and n represents 0.
ある特許請求の範囲第２項記載の化合物。3. The compound according to claim 2, wherein R in the general formula (I) is an alkyl group.
である特許請求の範囲第２項記載の化合物。4. The compound according to claim 2, wherein R in the general formula (I) is an alkoxy group.
−、−OCH2−又は−CH2O−をあらわし、Ｒは炭素数１〜
12のアルキル基もしくはアルコキシ基、シアノ基又はハ
ロゲン原子をあらわし、環Ａ及び環Ｂは1,4−ジ置換フ
ェニレンもしくはトランス−1,4−ジ置換シクロヘキシ
レンをあらわし、ｎは０又は１をあらわし、＊は光学活
性中心をあらわす）で示される光学活性アミド化合物を
少なくとも１種含有する強誘電性スメクチック液晶組成
物。5. A general formula (Wherein, Z, Z 'represents a single bond, -COO -, - OCO -, - CH 2 CH 2
Represents —, —OCH 2 — or —CH 2 O—, and R represents 1 to 1 carbon atoms.
12 represents an alkyl group or an alkoxy group, a cyano group or a halogen atom, ring A and ring B represent 1,4-di-substituted phenylene or trans-1,4-di-substituted cyclohexylene, and n represents 0 or 1. , * Represents an optically active center), and is a ferroelectric smectic liquid crystal composition containing at least one optically active amide compound represented by the formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61278746A JPH0759541B2 (en) | 1986-11-25 | 1986-11-25 | Optically active amide compound and smectic liquid crystal composition using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61278746A JPH0759541B2 (en) | 1986-11-25 | 1986-11-25 | Optically active amide compound and smectic liquid crystal composition using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63132869A JPS63132869A (en) | 1988-06-04 |
| JPH0759541B2 true JPH0759541B2 (en) | 1995-06-28 |
Family
ID=17601624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61278746A Expired - Fee Related JPH0759541B2 (en) | 1986-11-25 | 1986-11-25 | Optically active amide compound and smectic liquid crystal composition using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0759541B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223539A (en) * | 1991-11-22 | 1993-06-29 | G. D. Searle & Co. | N,n-di-alkyl(phenoxy)benzamide derivatives |
| JPH06108051A (en) * | 1992-09-30 | 1994-04-19 | Showa Shell Sekiyu Kk | Antiferroelectric liquid crystal compound having new skeletal structure and liquid crystal composition containing the same |
-
1986
- 1986-11-25 JP JP61278746A patent/JPH0759541B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63132869A (en) | 1988-06-04 |
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