JPH0794435B2 - Optically active lactam compound and liquid crystal composition using the same - Google Patents
Optically active lactam compound and liquid crystal composition using the sameInfo
- Publication number
- JPH0794435B2 JPH0794435B2 JP61031848A JP3184886A JPH0794435B2 JP H0794435 B2 JPH0794435 B2 JP H0794435B2 JP 61031848 A JP61031848 A JP 61031848A JP 3184886 A JP3184886 A JP 3184886A JP H0794435 B2 JPH0794435 B2 JP H0794435B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- compound
- optically active
- coo
- ring
- 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.)
- Expired - Lifetime
Links
- -1 lactam compound Chemical class 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 title claims description 14
- 239000004973 liquid crystal related substance Substances 0.000 title description 17
- 150000001875 compounds Chemical class 0.000 claims description 45
- 239000004990 Smectic liquid crystal Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000004956 cyclohexylene group Chemical class 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000012071 phase Substances 0.000 description 12
- 230000010287 polarization Effects 0.000 description 11
- 230000002269 spontaneous effect Effects 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 150000003951 lactams Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 230000001747 exhibiting effect Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000005621 ferroelectricity Effects 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 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
- 230000003287 optical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005911 haloform reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- XTBAPWCYTNCZTO-UHFFFAOYSA-N isoindol-1-one Chemical compound C1=CC=C2C(=O)N=CC2=C1 XTBAPWCYTNCZTO-UHFFFAOYSA-N 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
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- DAJRNFUDNDXVPL-UHFFFAOYSA-N 4-(4-hexylphenyl)phenol Chemical group C1=CC(CCCCCC)=CC=C1C1=CC=C(O)C=C1 DAJRNFUDNDXVPL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000011149 active material 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
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012043 crude product Substances 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
- 150000002148 esters Chemical class 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 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
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Indole Compounds (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
活性ラクタム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 lactam 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、かつ液晶分子にい垂
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 so as to form a helix with respect to the stacking direction of the layers, and spontaneous polarization occurs in a direction parallel to this 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て、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 response becomes faster when the spontaneous polarization is large and the viscosity is low, 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 for high density display have been actively conducted.
［発明が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、シッフ塩基
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, many compounds of 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）。 p-decyloxybenzylidene-p'-amino-2-methylbutyl-cinnamic acid ester (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。However, since such a Schiff base type compound is easily hydrolyzed, there is a problem that it is 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, etc.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.,1984,23L 175−177）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 L 175-177).
しかし、この化合物もシッ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、安定で高速応答性の強誘電性スメクチック液晶組
成物を構成するために使用される光学活性ラクタム化合
物および強誘電性スメクチック液晶組成物を提供するた
めのものであり、一般式、 （式中、Ｚは−COO−，−OCO−，−CH2CH2−，−OCH2−
又は−CH2O−を表し、Ｚ′は単結合、−COO−，−OCO
−，−CH2CH2−，−OCH2−又は−CH2O−を表し、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表し、Ｒ′は炭素数１〜12のアル
キル基を表し、環Ａおよび環Ｂは1,4−ジ置換フェニレ
ンまたは、トランス−1,4−ジ置換シクロヘキシレンを
表し、ｎは０または１を表し、＊は光学活性中心を表
す。）で示される光学活性ラクタム化合物であり、この
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-mentioned problems, and is an optical active material used for forming a stable and fast-responsive ferroelectric smectic liquid crystal composition. A lactam compound and a ferroelectric smectic liquid crystal composition for providing a general formula, (Wherein, Z is -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -
Or -CH 2 O-a represents, Z 'represents a single bond, -COO -, - OCO
Represents —, —CH 2 CH 2 —, —OCH 2 — or —CH 2 O—, R represents an alkyl group or alkoxy group having 1 to 12 carbon atoms, a cyano group or a halogen atom, and R ′ represents 1 carbon atom. To 12 alkyl groups, ring A and ring B represent 1,4-di-substituted phenylene or trans-1,4-di-substituted cyclohexylene, n represents 0 or 1, and * represents an optically active center. Represent ) Is an optically active lactam compound, and is a ferroelectric smectic liquid crystal composition containing at least one compound.
なお、本発明の一般式（Ｉ）の化合物の一般名は（3R）
−又は（3S）−2,3−ジヒドロ−２−アルキル−３−メ
チル−1H−イソインドール−１−オンの誘導体である。The general name of the compound of the general formula (I) of the present invention is (3R)
-Or a derivative of (3S) -2,3-dihydro-2-alkyl-3-methyl-1H-isoindol-1-one.
一般式（Ｉ）において、Ｚは−COO−，−OCO−，−CH2C
H2−，−OCH2−又は−CH2O−を表し、Ｚ′は単結合、−
COO−，−OCO−，−CH2CH2−，−OCH2−又は−CH2O−を
表すが、一般にＺ′が単結合である場合には粘度が低
く、Ｚおよび／またはＺ′が−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、Ｚ
は−COO−が、Ｚ′は単結合又は−COO−が好ましい。In the general formula (I), Z is -COO -, - OCO -, - CH 2 C
H 2 −, —OCH 2 — or —CH 2 O—, Z ′ is a single bond,
COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 - or represents a -CH 2 O-, generally Z 'is when a single bond is a low viscosity, Z and / or Z' is -COO-,
Since the maximum temperature (Ts) indicating the smectic C phase is high, Z
Is preferably —COO—, and Z ′ is preferably a single bond or —COO—.
また、ｎ＝１の場合には、ＺとＺ′の両方が−COO−で
あると、粘度が高くなるので、その場合には、Ｚ′は単
結合であることが好ましい。Further, in the case of n = 1, if both Z and Z ′ are —COO—, the viscosity becomes high. In that case, therefore, Z ′ is preferably a single bond.
環Ａ及び環Ｂはトランス−1,4−ジ置換シクロヘキシレ
ン又は1,4−ジ置換フェニレンを表わすが、一般にトラ
ンス−1,4−ジ置換シクロヘキシレンのほうが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 trans-1,4-di-substituted cyclohexylene or 1,4-di-substituted phenylene, but since trans-1,4-di-substituted cyclohexylene generally has a lower Ts, n = 1 In this case, at least one of ring A and ring B is preferably 1,4-disubstituted phenylene, and n
When = 0, ring A is preferably 1,4-disubstituted phenylene.
また、Ｒは炭素数１〜12のアルキル基、炭素数１〜12の
アルコキシ基、シアノ基又はハロゲン原子を表すが、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ル基である
ことが好ましい。また、アルキル基、アルコキシル基の
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、Ｒの炭素数は１〜12
であるが、好ましくは、２〜８が良い。又、Ｒは直鎖状
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
ク液晶上限温度が高いので好ましい。R represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group or a halogen atom. In the case of a cyano group, the viscosity is high, and in the case of a halogen atom, Ts is Since it is low, it is preferably an alkyl group or an alkoxyl group. Further, in the case of an alkyl group or an alkoxyl group, when the carbon number is small, the melting point is high, and when it is too large, the viscosity is high.
However, 2 to 8 is preferable. Further, R may be linear or branched, but linear ones are generally preferable because the smectic liquid crystal upper limit temperature is higher when mixed with another compound exhibiting liquid crystallinity.
又、Ｒ′は、炭素数１〜12のアルキル基であるが、Ｒの
場合と動揺その炭素数が多すぎる場合には粘度が高いの
で１〜12、好ましくは２〜８とされる。R'is an alkyl group having 1 to 12 carbon atoms, and is 1 to 12 and preferably 2 to 8 because the viscosity is high in the case of R and when the number thereof is too large.
なお、一般式で（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 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あるいはスメクチッ
ク液晶あるいは光学活性物質と適宜混合し、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. Alternatively, it is appropriately mixed with a smectic liquid crystal or an optically active substance 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. , R * and R are not necessarily the same groups.
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 nothing to do with R of the present invention and represents a linear or branched alkyl group having 1 to 12 carbon atoms, and even if the same R is shown in one compound, They 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 devices 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、液晶相を
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 phase, and at least one transparent substrate having electrodes on the whole surface or a part thereof is surrounded by 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Ｚが−COO−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 in which Z is —COO— can be synthesized, for example, by the route shown below.
即ち、カルボン酸に塩化チオニル、オキシ塩化リン等の
塩素化剤を作用させて、酸塩化物とし、これにフェノー
ル性水酸基を有する光学活性ラクタム（２）を、ピリジ
ン等の塩基性物質存在下に反応させ、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に
より純粋なＺが−COO−の式（Ｉ）の化合物を合成する
ことができる。 That is, a chlorinating agent such as thionyl chloride or phosphorus oxychloride is caused to act on a carboxylic acid to form an acid chloride, and an optically active lactam (2) having a phenolic hydroxyl group is added thereto in the presence of a basic substance such as pyridine. By reacting and performing a series of purification treatments such as extraction, recrystallization and column chromatography, a compound of formula (I) in which pure Z is —COO— can be synthesized.
なお、原料となるラクタム（２）は、光学活性なＮ−ア
ルキル−Ｎ−α−フェネチルアミンブチルリチウムによ
りリチウム化したのち、二酸化炭素と反応させて得られ
るラクタムをニトロ化、還元、ジアゾ化分解することに
より合成することができる。The lactam (2) as a raw material is lithiated with an optically active N-alkyl-N-α-phenethylamine butyllithium and then reacted with carbon dioxide to nitrate, reduce, and diazotize the lactam obtained. It can be synthesized by
また、Ｚが−OCO−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。In addition, a compound in which Z is -OCO- can be synthesized, for example, by the route shown below.
（＋）−2,3−ジヒドロ−３−メチル−２−置換−1H−
イソインドール−１−オン（３）をアセチル化した後、
ハロホルム反応を行い、（＋）−2,3−ジヒドロ−３−
メチル−２−置換−1H−イソインドール−１−オン−６
−カルボン酸（４）とし、これを酸塩化物とした後、ヒ
ドロキシ化合物（５）とピリジン等の塩基性物質存在下
に反応させ、抽出、再結晶、カラムクロマトグラフィー
等一種の精製処理を施すことにより、純粋なＺが−OCO
−の式（Ｉ）の化合物を合成することができる。 (+)-2,3-Dihydro-3-methyl-2-substituted-1H-
After acetylating isoindol-1-one (3),
The haloform reaction is carried out, and (+)-2,3-dihydro-3-
Methyl-2-substituted-1H-isoindol-1-one-6
-The carboxylic acid (4) is converted to the acid chloride, and then reacted with the hydroxy compound (5) in the presence of a basic substance such as pyridine, and subjected to a kind of purification treatment such as extraction, recrystallization and column chromatography. Therefore, pure Z is -OCO
A compound of formula (I) -can be synthesized.
［実施例］ 次に、本発明を実施例を以て具体的に説明する。[Examples] Next, the present invention will be specifically described with reference to Examples.
実施例１ の化合物2.5g（0.01モル）と塩化チオニル10mlとを四塩
化炭素50ml中に仕込み還流温度において６時間撹拌し
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 の化合物2.5g（0.01モル）及びピリジン2mlを加え、室
温にて６時間撹拌した。反応混合物を水100mlにあけ、
トルエン100mlにて３時間抽出した。トルエン層を水100
ml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
て、ヘキサンより２回再結晶し、目的とする式 の化合物（４′−ｎ−オクチルオキシ安息香酸−（3S）
−2,3−ジヒドロ−２−ｎ−ヘキシル−３−メチル−1H
−イソインドール−６−イルエステル）2.8g（0.0058モ
ル）を無色の結晶として得た。収率58％。融点99.6℃。
この化合物のIRスペクトルを第１図に示す。Example 1 2.5 g (0.01 mol) of the compound (1) and 10 ml of thionyl chloride were charged in 50 ml of carbon tetrachloride and stirred at reflux temperature for 6 hours. After the solvent was distilled off with an evaporator, 30 ml of toluene was added, and 2.5 g (0.01 mol) of the compound of 1 and 2 ml of pyridine 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 with 100 ml of toluene for 3 hours. Toluene layer is water 100
After washing with ml, the extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off with an evaporator. The remaining yellow solid was applied to a column of alumina with toluene as a solvent and recrystallized twice from hexane to obtain the target compound. Compound (4'-n-octyloxybenzoic acid- (3S)
-2,3-Dihydro-2-n-hexyl-3-methyl-1H
2.8 g (0.0058 mol) of -isoindol-6-yl ester) were obtained as colorless crystals. Yield 58%. Melting point 99.6 ° C.
The IR spectrum of this compound is shown in FIG.
この化合物の1H NMRスペクトルは次のとおりであった。The 1H NMR spectrum of this compound was as follows:
δ（ppm,CDCl3溶媒、TMS内部標準） 6.9−8.2 Aromatic 7H ｍ 4.53 Ar−CH 2H q 7Hz 3.5−4.1 OCH2,NCH 3H ｍ 2.9−3.2 NCH 1H ｍ 0.8−1.8 Aliphatic 26H ｍ 1.35 Ar−Ｃ−CH3 3H d 7Hz 実施例２〜10 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、又Ｒ′にｎ−
C8H17の化合物を用いて以下の化合物を得た。δ (ppm, CDCl 3 solvent, TMS internal standard) 6.9-8.2 Aromatic 7H m 4.53 Ar-CH 2H q 7Hz 3.5-4.1 OCH 2 , NCH 3H m 2.9-3.2 NCH 1H m 0.8-1.8 Aliphatic 26H m 1.35 Ar-C -CH 3 3H d 7Hz example 2-10 Except that the corresponding carboxylic acid is used instead of the compound of
By performing the same operation as in Example 1, R'is n-
The following compounds were obtained using the C 8 H 17 compound.
実施例11 の化合物を二硫化炭素中にて塩化アルミニウムの存在下
に塩化アセチルと反応させることにより、アセチル化
し、次いで次亜臭素酸ナトリウムを用いて、ハロホルム
反応を行い、（＋）−2,3−ジヒドロ−３−メチル−２
−ｎ−ヘキシル−1H−イソインドール−１−オン−６−
カルボン酸を得た。このカルボン酸を塩化チオニルとを
四塩化炭素中にて反応させて酸塩化物とした後、４−ｎ
−ヘキシル−４′−ヒドロキシビフェニルとトルエン中
にてピリジンの存在化反応させた。反応後、反応混合物
を水にあけ、トルエンにて抽出した。溶媒をエバポレー
ターにより留去し、残った粗生成物をヘキサンより再結
晶し、目的とする式 の化合物（（＋）−2,3−ジヒドロ−３−メチル−２−
ｎ−ヘキシル−1H−イソインドール−１−オン−６−カ
ルボン酸−４′−ｎ−ヘキシル−４″−ビフェニルエス
テルを得た。 Example 11 The compound of acetylation is reacted with acetyl chloride in the presence of aluminum chloride in carbon disulfide, followed by haloform reaction with sodium hypobromite to give (+)-2,3-dihydro. -3-methyl-2
-N-hexyl-1H-isoindol-1-one-6-
A carboxylic acid was obtained. This carboxylic acid is reacted with thionyl chloride in carbon tetrachloride to give the acid chloride, and then 4-n
-Hexyl-4'-hydroxybiphenyl was reacted with toluene in the presence of pyridine. After the reaction, the reaction mixture was poured into water and extracted with toluene. The solvent was distilled off with an evaporator, and the remaining crude product was recrystallized from hexane to obtain the desired formula. Compound ((+)-2,3-dihydro-3-methyl-2-
n-Hexyl-1H-isoindol-1-one-6-carboxylic acid-4'-n-hexyl-4 "-biphenyl ester was 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
ｍ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Miyas
ato等の方法に従い行った。（K.Miyasatoet.al.,J.J.A.
P.,22,L661（1983）） この混合物の自発分極の大きさは1.25nC/cm2であった。
この大きさは従来研究されている強誘電精液唱化合物DO
BAMBC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62.4℃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、85.8℃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、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
10m from the upper limit temperature (Ts) which shows smectic C phase by enclosing a spacer of m and enclosing in a cell with an electrode area of 1cm 2.
Miyas applying 20Hz, 10V triangular wave at low temperature ℃
It was performed according to the method of ato et al. (K.Miyasatoet.al., JJA
P., 22, L661 (1983)) The magnitude of spontaneous polarization of this mixture was 1.25 nC / cm 2 .
This size corresponds to the ferroelectric semen compound DO that has been studied in the past.
Considering that this mixture is the compound of Example 1 diluted to 5.0%, BAMBC is 3.7 nC / cm 2 as a single product, which is extremely large. In addition, the mixture was changed from smectic C phase to smectic A at 62.4 ° C.
It transformed into a phase and further into an isotropic liquid phase at 85.8 ° C. 4-n-octyloxybenzoic acid-4'-n-
The maximum temperature of the smectic C phase of hexyloxyphenyl is
Since it is 65.0 ° C, it can be seen that the compound of the present invention can increase spontaneous polarization without significantly narrowing the temperature range of the smectic C phase, and is a very useful compound.
［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
度範囲をあまり狭めることのない一般式（Ｉ）で示され
る光学活性ランタム化合物、および該化合物を少なくと
も１種を含有する強誘導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ような優
れた効果を有する。EFFECTS OF THE INVENTION The present invention provides an optically active lantam 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 strong compound containing at least one compound. The provision of the inductive smectic liquid crystal composition has an excellent effect such 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の化合物とIRスペクトル図であ
る。FIG. 1 is a compound and IR spectrum of Example 1 of the present invention.
Claims (3)
又は−CH2O−を表し、Ｚ′は単結合、−COO−，−OCO
−，−CH2CH2−，−OCH2−又は−CH2O−を表し、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表し、Ｒ′は炭素数１〜12のアル
キル基を表し、環Ａおよび環Ｂは1,4−ジ置換フェニレ
ンまたは、トランス−1,4−ジ置換シクロヘキシレンを
表し、ｎは０または１を表し、＊は光学活性中心を表
す。）で示される光学活性ラクタム化合物。1. A general formula (Wherein, Z is -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -
Or -CH 2 O-a represents, Z 'represents a single bond, -COO -, - OCO
Represents —, —CH 2 CH 2 —, —OCH 2 — or —CH 2 O—, R represents an alkyl group or alkoxy group having 1 to 12 carbon atoms, a cyano group or a halogen atom, and R ′ represents 1 carbon atom. To 12 alkyl groups, ring A and ring B represent 1,4-di-substituted phenylene or trans-1,4-di-substituted cyclohexylene, n represents 0 or 1, and * represents an optically active center. Represent ) An optically active lactam compound represented by
し、環Ａが1,4−ジ置換フェニレンを表し、ｎが０を表
すところの特許請求の範囲第１項記載の化合物。2. The compound according to claim 1, wherein in the general formula (I), Z represents --COO--, ring A represents 1,4-disubstituted phenylene, and n represents 0. .
又は−CH2O−を表し、Ｚ′は単結合、−COO−，−OCO
−，−CH2CH2−，−OCH2−又は−CH2O−を表し、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表し、Ｒ′は炭素数１〜12のアル
キル基を表し、環Ａおよび環Ｂは1,4−ジ置換フェニレ
ンまたは、トランス−1,4−ジ置換シクロヘキシレンを
表し、ｎは０または１を表し、＊は光学活性中心を表
す。）で示される光学活性ラクタム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。3. General formula (Wherein, Z is -COO -, - OCO -, - CH 2 CH 2 -, - OCH 2 -
Or -CH 2 O-a represents, Z 'represents a single bond, -COO -, - OCO
Represents —, —CH 2 CH 2 —, —OCH 2 — or —CH 2 O—, R represents an alkyl group or alkoxy group having 1 to 12 carbon atoms, a cyano group or a halogen atom, and R ′ represents 1 carbon atom. To 12 alkyl groups, ring A and ring B represent 1,4-di-substituted phenylene or trans-1,4-di-substituted cyclohexylene, n represents 0 or 1, and * represents an optically active center. Represent ) A ferroelectric smectic liquid crystal composition containing at least one optically active lactam compound represented by the formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61031848A JPH0794435B2 (en) | 1986-02-18 | 1986-02-18 | Optically active lactam compound and liquid crystal composition using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61031848A JPH0794435B2 (en) | 1986-02-18 | 1986-02-18 | Optically active lactam compound and liquid crystal composition using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62190162A JPS62190162A (en) | 1987-08-20 |
| JPH0794435B2 true JPH0794435B2 (en) | 1995-10-11 |
Family
ID=12342472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61031848A Expired - Lifetime JPH0794435B2 (en) | 1986-02-18 | 1986-02-18 | Optically active lactam compound and liquid crystal composition using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0794435B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2621194B2 (en) * | 1987-07-23 | 1997-06-18 | 株式会社ツムラ | New phthalide derivatives |
| EP0313379B1 (en) * | 1987-10-23 | 1992-07-22 | Mitsubishi Rayon Co., Ltd. | Optically active compound having delta-valerolactone ring and liquid crystal composition comprising same |
-
1986
- 1986-02-18 JP JP61031848A patent/JPH0794435B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62190162A (en) | 1987-08-20 |
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