JP2750914B2 - Novel fluorine-containing compound, liquid crystal composition containing the same, and optical switching element - Google Patents
Novel fluorine-containing compound, liquid crystal composition containing the same, and optical switching elementInfo
- Publication number
- JP2750914B2 JP2750914B2 JP1249049A JP24904989A JP2750914B2 JP 2750914 B2 JP2750914 B2 JP 2750914B2 JP 1249049 A JP1249049 A JP 1249049A JP 24904989 A JP24904989 A JP 24904989A JP 2750914 B2 JP2750914 B2 JP 2750914B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- fluorine
- containing compound
- general formula
- crystal composition
- 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
- 150000001875 compounds Chemical class 0.000 title claims description 31
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 15
- 229910052731 fluorine Inorganic materials 0.000 title claims description 15
- 239000011737 fluorine Substances 0.000 title claims description 15
- 239000000203 mixture Substances 0.000 title claims description 12
- 230000003287 optical effect Effects 0.000 title claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- -1 monoethyl ester Chemical class 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 239000004990 Smectic liquid crystal Substances 0.000 description 11
- 230000010287 polarization Effects 0.000 description 9
- 230000002269 spontaneous effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PCJLCGHQGQSHFX-UHFFFAOYSA-N 2-fluoro-2-methylpropanedioic acid Chemical compound OC(=O)C(F)(C)C(O)=O PCJLCGHQGQSHFX-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003098 cholesteric effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- PHADLZACUXNNTQ-UHFFFAOYSA-N (4-hydroxyphenyl) 4-(4-octoxyphenyl)benzoate Chemical compound C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C(=O)OC=2C=CC(O)=CC=2)C=C1 PHADLZACUXNNTQ-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- YIBLNPVJFPNRCQ-UHFFFAOYSA-N 1-hydroxy-4-phenylcyclohexa-2,4-diene-1-carboxylic acid Chemical compound C1=CC(C(=O)O)(O)CC=C1C1=CC=CC=C1 YIBLNPVJFPNRCQ-UHFFFAOYSA-N 0.000 description 1
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical class CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 1
- SEGJDCGIQJESDC-UHFFFAOYSA-N 2-methylbutyl 3-phenylprop-2-enoate Chemical compound CCC(C)COC(=O)C=CC1=CC=CC=C1 SEGJDCGIQJESDC-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
- OWFHJVJZEQPHJK-UHFFFAOYSA-N 3-ethoxy-2-fluoro-2-methyl-3-oxopropanoic acid Chemical compound CCOC(=O)C(C)(F)C(O)=O OWFHJVJZEQPHJK-UHFFFAOYSA-N 0.000 description 1
- YNBBQLUKHHSKPW-UHFFFAOYSA-N 4-(4-octoxyphenyl)benzoic acid Chemical compound C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C(O)=O)C=C1 YNBBQLUKHHSKPW-UHFFFAOYSA-N 0.000 description 1
- MRCBGFDKDHZDCD-UHFFFAOYSA-N 4-(5-nonylpyrimidin-2-yl)phenol Chemical compound N1=CC(CCCCCCCCC)=CN=C1C1=CC=C(O)C=C1 MRCBGFDKDHZDCD-UHFFFAOYSA-N 0.000 description 1
- ILQFXQVEQFBFPM-UHFFFAOYSA-N 4-[2-(4-hexoxyphenyl)pyrimidin-5-yl]phenol Chemical compound C1=CC(OCCCCCC)=CC=C1C1=NC=C(C=2C=CC(O)=CC=2)C=N1 ILQFXQVEQFBFPM-UHFFFAOYSA-N 0.000 description 1
- DQQOONVCLQZWOY-UHFFFAOYSA-N 4-hexoxybenzoyl chloride Chemical compound CCCCCCOC1=CC=C(C(Cl)=O)C=C1 DQQOONVCLQZWOY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、安定なサーモトロピックな液晶状態をとり
得、例えば、液晶テレビ等のディスプレイ用、光プリン
ターヘッド、光フーリエ変換素子、ライトバルブ等、液
晶やエレクトロケミクロミズムを利用するオプトエレク
トロニクス関連素子の素材として有用な液晶材料として
利用できる新規含フッ素化合物、これを含む液晶組成及
び光スイッチング素子に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention can take a stable thermotropic liquid crystal state, for example, for displays such as liquid crystal televisions, optical printer heads, optical Fourier transform elements, light valves, etc. The present invention relates to a novel fluorine-containing compound which can be used as a liquid crystal material useful as a material for an optoelectronics-related device utilizing liquid crystal or electrochemiomic, a liquid crystal composition containing the same, and an optical switching device.
1975年R.B.Meyerらによって合成された4−(4−n
−デシルオキシベンジリデンアミノ)ケイ皮酸−2−メ
チルブチルエステル(DOBAMBC)を代表例とする強誘電
性液晶の出現と、それを用いたN.A.Clarkらの提案した
新しい表示方式〔Appl.Phys.Leet.36,899(1980)〕に
よりμsecオーダーの高速応答性及び電場を切っても液
晶分子の配向が変わらない特性(メモリー性)を有する
液晶セルが可能となった。このため、現在まで多くの強
誘電性液晶材料が合成され、提案されてきた。この強誘
電性液晶を得るためには、液晶となる化合物に、光学活
性基を導入する必要があるが、この光学活性基の不斉源
として、もっぱら2−オクタノール、2−メチルブタノ
ール誘導体等が使用されてきた。4- (4-n) synthesized by RBMeyer et al. In 1975
-Decyloxybenzylideneamino) cinnamic acid-2-methylbutyl ester (DOBAMBC) as a typical example, and a new display method proposed by NAClark et al. [Appl. Phys. 36, 899 (1980)] by a liquid crystal cell having a characteristic orientation does not change the liquid crystal molecules be cut high-speed response and the electric field of μsec order (memory characteristic) becomes possible. For this reason, many ferroelectric liquid crystal materials have been synthesized and proposed to date. In order to obtain this ferroelectric liquid crystal, it is necessary to introduce an optically active group into a compound that becomes a liquid crystal. As an asymmetric source of the optically active group, 2-octanol, 2-methylbutanol derivatives, etc. are exclusively used. Have been used.
ところで、最近、不斉源として含フッ素化合物を用い
た強誘電性液晶が提案されている。例えば、次式の 〔Jpn.J.Appl.Phys.26 L77(1987)及び特開昭63−3078
37号公報〕で表される化合物は、スメクチックA相→キ
ラルスメクチックC相の相転移点(TAC)の5℃下で、6
0nC/cm2の自発分極を示している。また、本発明と同じ
不斉源S−(−)−2−Fluoro−2−methylmalonic ac
id monoethyl esterから誘導した次式の 〔Jpn.J.Appl.Phys.26 L77(1987)〕で表される化合物
は、TACの5℃下で、5nC/cm2以下の自発分極を示してい
る。By the way, recently, a ferroelectric liquid crystal using a fluorine-containing compound as an asymmetric source has been proposed. For example, [Jpn. J. Appl. Phys. 26 L77 (1987) and JP-A-63-3078]
No. 37] shows that the compound represented by the formula (6) at 5 ° C. below the phase transition point (T AC ) of the smectic A phase → chiral smectic C phase:
It shows a spontaneous polarization of 0 nC / cm 2 . Further, the same asymmetric source S-(−)-2-Fluoro-2-methylmalonic ac as in the present invention is used.
The following formula derived from id monoethyl ester [Jpn.J.Appl.Phys.26 L77 (1987) The compound represented by is a 5 ° C. under T AC, shows the following spontaneous polarization 5 nC / cm 2.
これらの2種類の化合物は、ともに大きな双極子モー
メントを有するフッ素を含有しているが、既に報告され
ているフッ素を含有しない化合物に比べ、特に大きな値
を示してはいない。例えば、次式の (国際公開88/07518号公報)で表される化合物は、TAC
の5℃下で、90nC/cm2の自発分極を示している。Although these two types of compounds both contain fluorine having a large dipole moment, they do not show particularly large values as compared with the previously reported compounds containing no fluorine. For example, Compounds represented by (WO 88/07518 Patent publication) is, T AC
Shows a spontaneous polarization of 90 nC / cm 2 at 5 ° C.
本発明者は、上記現状に鑑み、フッ素が有する電気的
特性を強誘電性液晶の物性(特に自発分極の増大)に反
映させるべく、鋭意、研究を進めた結果、不斉炭素及び
フッ素を含む隣接基の化学構造が液晶物性に重要な影響
を及ぼし、特に、次式に示す構造を有する基が、 強誘電性液晶の物性(特に自発分極の増大)に、大きく
寄与することを見出した。In view of the above situation, the present inventor has conducted intensive studies to reflect the electrical properties of fluorine in the physical properties of ferroelectric liquid crystals (particularly, an increase in spontaneous polarization). The chemical structure of the adjacent group has an important effect on the physical properties of the liquid crystal, and in particular, a group having a structure represented by the following formula, They have found that they greatly contribute to the physical properties of ferroelectric liquid crystals (especially, an increase in spontaneous polarization).
本発明は、かかる知見に基づきなされたもので、本発
明の目的は、ディスプレイ用材料等として有用で、新規
な化合物及び当該化合物を用いた液晶組成物、さらには
光スイッチング素子を提供することにある。The present invention has been made based on such knowledge, and an object of the present invention is to provide a novel compound, a liquid crystal composition using the compound, and a light switching element which are useful as a display material or the like. is there.
〔課題を解決するための手段〕 本発明は、一般式(I) 〔但し、式中R1、R2は、炭素数1〜18のアルキル基を示
し、この両アルキル基は同じであっても異なっていても
よく、Aは、−O−または単結合を示し、Xは、一般式
(II) −(X1)p−B−(X2)q− (II) (ここで、p、qは0、1または2で示され、Bは単結
合、−COO−、−OCO−、−OCH2−または−CH2O−より選
ばれる2価の鎖状基を示し、X1、X2は を含む含六員環基を示す)で表される含六員環基を示
し、かつ、該Xは、 を少なくとも一つ含む〕で示される含フッ素化合物、特
に前記一般式(I)において、Aが、−O−で、かつX
が、 で表わされる含フッ素化合物、及び前記一般式(I)で
表わされる含フッ素化合物を含有することからなる液晶
組成物或いは、前記一般式(I)で表わされる含フッ素
化合物の少なくとも1種を構成要素とすることからなる
光スイッチング素子である。[Means for Solving the Problems] The present invention provides a compound represented by the general formula (I): Wherein R 1 and R 2 each represent an alkyl group having 1 to 18 carbon atoms, and both alkyl groups may be the same or different, and A represents -O- or a single bond. , X is general formula (II) - (X 1) p-B- (X 2) q- (II) ( wherein, p, q is denoted by 0, 1, or 2, B is a single bond, - COO -, - OCO -, - OCH 2 - or a divalent chain group selected from -CH 2 O-, X 1, X 2 is And X represents a six-membered ring group represented by the formula: Wherein at least one of the above-mentioned general formula (I) is such that A is -O-
But, And a liquid crystal composition comprising the fluorine-containing compound represented by the general formula (I) or at least one of the fluorine-containing compounds represented by the general formula (I). And an optical switching element.
上記一般式(I)の化合物の中間体である不斉炭素及
びフッ素を含む隣接基部を合成するために必要な原料の
一つであるS−(−)−2−Fluoro−2−methylmaloni
c acid monoethyl esterは、既に、北爪らによって報告
されている2−Fluoro−2−methylmalonateを原料と
し、酵素であるLipase−MYで不斉加水分解する方法〔J.
Org.Chem.51,1003(1986)〕により得ることができる。
このエステルの光学純度が高い程、大きな自発分極が得
られ、80%ee以上のものが望ましいが、これより低くて
もかまわない。S-(-)-2-Fluoro-2-methylmaloni which is one of the raw materials necessary for synthesizing an adjacent group containing an asymmetric carbon and fluorine which is an intermediate of the compound of the above general formula (I)
c acid monoethyl ester has already been reported by Kitazume et al. using 2-Fluoro-2-methylmalonate as a raw material and asymmetric hydrolysis with Lipase-MY as an enzyme [J.
Org. Chem. 51, 1003 (1986)].
The higher the optical purity of the ester, the greater the spontaneous polarization is obtained. Desirably, the ester has an ee of 80% or more, but it may be lower.
次に、核構造、すなわち、上記一般式(I)の−X−
基の構造としては、 あるいは、次に示すエステル基 てなるもの等を例示しうる。Next, the core structure, that is, -X- of the above general formula (I)
As the structure of the group, Alternatively, the ester group shown below Can be exemplified.
この核構造部の中間体うち、例えば、 H.Zaschkeらの方法〔Z.Chem.,15 441(1975)或いはJ.
f.Prakt.Chem.323 199(1981)〕に従い、次のスキーム
で合成することができる。Among the intermediates of this core structure, for example, H. Zaschke et al. [Z. Chem., 15 441 (1975) or J.
f. Prakt. Chem. 323 199 (1981)] and can be synthesized by the following scheme.
また についても、上記方法と同様の手段により、合成するこ
とができる。 Also Can also be synthesized by the same means as in the above method.
一方、核構造部の中間体うち、エステル系化合物は、 の合成に用いられる次の反応スキームに従い合成するこ
とができる。On the other hand, among the intermediates in the core structure, the ester compound is Can be synthesized according to the following reaction scheme used for the synthesis of
このようにして入手した核構造部の中間体とと先に示
した不斉炭素及びフッ素を含む隣接基部の中間体とを通
常のエステル化反応を行うことによって、本発明の上記
一般式(I)の化合物を合成することができる。 The intermediate of the core structure thus obtained and the intermediate of the adjacent base containing asymmetric carbon and fluorine shown above are subjected to a usual esterification reaction, whereby the above-mentioned general formula (I) of the present invention is obtained. ) Can be synthesized.
本発明の具体的な化合物を、次に例示する。 Specific compounds of the present invention are illustrated below.
〔実施例〕 実施例1 4−(2−(4−ヘキシルオキシフェニル)ピリミジニ
ル)フェニル エチル−2−フルオロ−2−メチルマロ
ン酸エステル (合成法) H.Zaschkeらの方法によって合成した2−(4−ヘキ
シルオキシフェニル)−5−(4−ヒドロキシフェニ
ル)ピリミジン870mg(2.5mmol)及び北爪らの方法によ
って得たS−(−)−2−フルオロ−2−メチルマロン
酸モノエチルエステル410mg(2.5mmol)に、N,N′−ジ
シクロヘキシルカルボジイミド(DCC)510mg及びジメチ
ルアミノピリジン10mgを加え、塩化メチレン中で、室温
下に2時間撹拌した。更に、塩化メチレン還流下で、2
時間撹拌した後、不溶物をろ別し、このろ液を濃縮し
た。得られた濃縮物をシリカゲルのカラムクロマトグラ
フィーで、展開液としてトルエン/酢酸エチル=10/1を
用いて、分離、精製したところ、530mg(1.1mmol)の次
に記載した理化学的性質を有する4−(2−(4−ヘキ
シルオキシフェニル)ピリミジニル)フェニル エチル
−2−フルオロ−2−メチルマロン酸エステルを得た。 Examples Example 1 4- (2- (4-hexyloxyphenyl) pyrimidinyl) phenyl ethyl-2-fluoro-2-methylmalonate (Synthesis method) 870 mg (2.5 mmol) of 2- (4-hexyloxyphenyl) -5- (4-hydroxyphenyl) pyrimidine synthesized by the method of H. Zaschke et al. And S-(−) obtained by the method of Kitazume et al. To 410 mg (2.5 mmol) of 2-fluoro-2-methylmalonic acid monoethyl ester, 510 mg of N, N'-dicyclohexylcarbodiimide (DCC) and 10 mg of dimethylaminopyridine were added, and the mixture was stirred in methylene chloride at room temperature for 2 hours. did. Further, under reflux of methylene chloride,
After stirring for an hour, insolubles were removed by filtration, and the filtrate was concentrated. The obtained concentrate was separated and purified by silica gel column chromatography using toluene / ethyl acetate = 10/1 as a developing solution to give 530 mg (1.1 mmol) of a compound having the following physicochemical properties. -(2- (4-Hexyloxyphenyl) pyrimidinyl) phenyl ethyl-2-fluoro-2-methylmalonate was obtained.
I.R.(KBr法,cm-1):1780,1760,1755,1600,1580,1430 NMR(CDCl3中,ppm):8.95(S,2H),8.40(d,2H) 7.65(d,2H),7.25(d,2H),7.00(d,2H) 4.40(q,2H),4.05(t,2H),1.95(d,3H) 1.90〜1.30(m,11H),0.93(t,3H) (物性の評価) 上記化合物をホットステージにて温度を制御し、クロ
スニコルの顕微鏡を用いて観察することにより、相転移
挙動を測定した。昇降温速度は1分間に2℃の割合で行
った。降温過程では、101℃で等方性液体からキラルス
メクチックC相となり、94℃で結晶化した。昇温過程で
は114℃で結晶が融解し、等方性液体となった。IR (KBr method, cm -1): (in CDCl 3, ppm) 1780,1760,1755,1600,1580,1430 NMR: 8.95 (S, 2H), 8.40 (d, 2H) 7.65 (d, 2H), 7.25 (d, 2H), 7.00 (d, 2H) 4.40 (q, 2H), 4.05 (t, 2H), 1.95 (d, 3H) 1.90 to 1.30 (m, 11H), 0.93 (t, 3H) (Physical properties Evaluation) The phase transition behavior was measured by controlling the temperature of the above compound using a hot stage and observing the compound using a crossed Nicol microscope. The temperature was raised and lowered at a rate of 2 ° C. per minute. In the cooling process, the liquid changed from an isotropic liquid to a chiral smectic C phase at 101 ° C., and crystallized at 94 ° C. During the heating process, the crystals melted at 114 ° C and became an isotropic liquid.
またポリイミドを塗布し、ラビング処理を施した透明
電極付ガラスからなる厚さ3μmのセルに化合物を注入
し、三角波法により自発分極の大きさを測定したとこ
ろ、97℃で189mC/cm2と大きな値を示した。The polyimide was applied, and the compound was injected into a 3 μm-thick cell made of glass with a transparent electrode that had been subjected to a rubbing treatment. When the magnitude of spontaneous polarization was measured by a triangular wave method, it was as large as 189 mC / cm 2 at 97 ° C. The value was shown.
実施例2 4−(2−(4−ブチルオキシフェニル)ピリミジニ
ル)フェニル エチル−2−フルオロ−2−メチルマロ
ン酸エステル 実施例1に記載した方法と同様にして2−(4−ブチ
ルオキシフェニル)−5−(4−ヒドロキシフェニル)
ピリミジン及びS−(−)−2−フルオロ−2−メチル
マロン酸モノエチルエステルを縮合させることによっ
て、次の理化学的性質を有する4−(2−(4−ブチル
オキシフェニル)ピリミジニル)フェニル エチル−2
−フルオロ−2−メチルマロン酸エステルを得た。Example 2 4- (2- (4-butyloxyphenyl) pyrimidinyl) phenyl ethyl-2-fluoro-2-methylmalonic acid ester 2- (4-butyloxyphenyl) in the same manner as described in Example 1. -5- (4-hydroxyphenyl)
By condensing pyrimidine and S-(-)-2-fluoro-2-methylmalonic acid monoethyl ester, 4- (2- (4-butyloxyphenyl) pyrimidinyl) phenyl ethyl having the following physicochemical properties: 2
-Fluoro-2-methylmalonic acid ester was obtained.
I.R.(KBr法,cm-1):1780,1760,1755,1600,1580,1430 NMR(CDCl3中,ppm):8.95(S,2H),8.40(d,2H) 7.65(d,2H),7.25(d,2H),7.00(d,2H) 4.40(q,2H),4.05(t,2H),1.95(d,3H) 1.90〜1.30(m,7H),0.93(t,3H) 実施例1と同様な方法で相転移温度を測定したとこ
ろ、降温過程では125.7℃で液体から結晶化した。また
昇温過程では137℃で結晶から等方性液体となった。IR (KBr method, cm -1): (in CDCl 3, ppm) 1780,1760,1755,1600,1580,1430 NMR: 8.95 (S, 2H), 8.40 (d, 2H) 7.65 (d, 2H), 7.25 (d, 2H), 7.00 (d, 2H) 4.40 (q, 2H), 4.05 (t, 2H), 1.95 (d, 3H) 1.90 to 1.30 (m, 7H), 0.93 (t, 3H) The phase transition temperature was measured by the same method as in Example 1. As a result, the liquid crystallized from the liquid at 125.7 ° C. in the temperature decreasing process. In addition, during the temperature rise process, the crystal became an isotropic liquid at 137 ° C.
参考例1 4−(4−オクチルオキシビフェニル−4′−カルボニ
ルオキシ)フェニル エチル2−フルオロ−2−メチル
マロン酸エステル (合成法) 市販の4′−ヒドロキシビフェニル−4′−カルボン
酸をアルカリ条件下で、オクチルブロミドと反応させて
4−オクチルオキシビフェニル−4′−カルボン酸を
得、塩化チオニルで処理して酸クロリドとした後、ヒド
ロキノンと反応させて4−ヒドロキシフェニル4−オク
チルオキシビフェニル−4′−カルボン酸エステルを得
た。Reference Example 1 4- (4-octyloxybiphenyl-4'-carbonyloxy) phenyl ethyl 2-fluoro-2-methylmalonate (Synthesis method) A commercially available 4'-hydroxybiphenyl-4'-carboxylic acid is reacted with octyl bromide under alkaline conditions to obtain 4-octyloxybiphenyl-4'-carboxylic acid, which is treated with thionyl chloride to obtain an acid. After being converted to chloride, it was reacted with hydroquinone to obtain 4-hydroxyphenyl 4-octyloxybiphenyl-4'-carboxylate.
この化合物を、実施例1のS−(−)−2−フルオロ
−2−メチルマロン酸モノエチルエステルを得たのと同
様の方法により、エステル化して、次の理化学的性質を
有する4−(4−オクチルオキシビフェニル−4′−カ
ルボニルオキシル)フェニル エチル2−フルオロ−2
−メチルマロン酸エステルを得た。This compound was esterified by a method similar to that of obtaining monoethyl S-(-)-2-fluoro-2-methylmalonate of Example 1 to give 4- (having the following physicochemical properties: 4-octyloxybiphenyl-4'-carbonyloxyl) phenyl ethyl 2-fluoro-2
-Methylmalonic acid ester was obtained.
I.R.(KBr法,cm-1):1780,1765,1730,1600,1500 NMR(CDCl3中,ppm):8.22(d,2H),7.64(m,4H) 7.35〜6.95(m,6H),4.40(q,2H),4.01(t,2
H),1.95(d,3H),1.90〜1.30(m,15H),0.93(t,3H) (物性の評価) 実施例1と同様な方法で相転移温度をを測定したとこ
ろ、降温過程において、147.5℃で液体からスメクチッ
クA相に変化した後、96.1℃でキラルスメクチックC相
へ変化し、70.0℃で結晶化した。また、昇温過程では10
6.5℃で固体からスメクチックA相へと変化した。IR (KBr method, cm -1): (in CDCl 3, ppm) 1780,1765,1730,1600,1500 NMR: 8.22 (d, 2H), 7.64 (m, 4H) 7.35~6.95 (m, 6H), 4.40 (q, 2H), 4.01 (t, 2
H), 1.95 (d, 3H), 1.90 to 1.30 (m, 15H), 0.93 (t, 3H) (Evaluation of physical properties) The phase transition temperature was measured in the same manner as in Example 1, At 147.5.degree. C., from a liquid to a smectic A phase, at 96.1.degree. C. to a chiral smectic C phase, and crystallized at 70.0.degree. In addition, 10
At 6.5 ° C, the solid changed to a smectic A phase.
また自発分極は、91.1で20.3nC/cm、76.1℃で52.3nC/
cm2であった。The spontaneous polarization is 20.3 nC / cm at 91.1 and 52.3 nC / cm at 76.1 ° C.
It was cm 2.
実施例3 4−(5−ノニルピリミジル)フェニル エチル−2−
フルオロ−2−メチルマロン酸エステル 4−ヒドロキシベンズアミン塩酸塩とα−ノニル−β
−ジメチルアミノアクロレインを原料として、H.Zaschk
eらの方法〔Z.Chem.15 441(1975)〕に従い、5−ノニ
ル−2−(4−ヒドロキシフェニル)ピリミジンを得
た。このようにして得たピリミジン化合物をS−(−)
−2−フルオロ−2−メチルマロン酸モノエチルエステ
ルとを、実施例1に記載したのと同様の方法で合成し、
次の理化学的性質を有する4−(5−ノニルピリミジ
ル)フェニル エチル−2−フルオロ−2−メチルマロ
ン酸エステルを得た。Example 3 4- (5-nonylpyrimidyl) phenyl ethyl-2-
Fluoro-2-methylmalonate 4-hydroxybenzamine hydrochloride and α-nonyl-β
-Dimethylaminoacrolein as raw material, H. Zaschk
According to the method of e et al. [Z. Chem. 15 441 (1975)], 5-nonyl-2- (4-hydroxyphenyl) pyrimidine was obtained. The pyrimidine compound thus obtained was converted to S-(-)
-2-fluoro-2-methylmalonic acid monoethyl ester was synthesized in the same manner as described in Example 1,
4- (5-Nonylpyrimidyl) phenyl ethyl-2-fluoro-2-methylmalonic acid ester having the following physicochemical properties was obtained.
I.R.(KBr法,cm-1):1790,1765,1750,1585,1545,1430 NMR(CDCl3中,ppm):8.60(s,2H),8.40(d,2H),7.00
(d,2H),4.40(q,2H),2.65(t,2H),1.95(d,3H),1.
90〜1.30(m,17H),0.95(t,3H) 実施例4 4−(4−ヘキシルオキシフェニル−4′−カルボニル
オキシ)フェニル エチル−2−フルオロ−2−メチル
マロン酸エステル 市販の4−ヘキシルオキシ安息香酸クロリドとヒドロ
キノンとを反応させて得た4−ヒドロキシフェニル4−
ヘキシルオキシ安息香酸エステルとS−(−)−2−フ
ルオロ−2−メチルマロン酸モノエチルエステルとを実
施例1に記載した方法と同様の方法で合成し、次の理化
学的性質を有する4−(4−ヘキシルオキシフェニル−
4′−カルボニルオキシル)フェニル エチル−2−フ
ルオロ−2−メチルマロン酸エステルを得た。IR (KBr method, cm -1): (in CDCl 3, ppm) 1790,1765,1750,1585,1545,1430 NMR: 8.60 (s, 2H), 8.40 (d, 2H), 7.00
(D, 2H), 4.40 (q, 2H), 2.65 (t, 2H), 1.95 (d, 3H), 1.
90-1.30 (m, 17H), 0.95 (t, 3H) Example 4 4- (4-hexyloxyphenyl-4'-carbonyloxy) phenyl ethyl-2-fluoro-2-methylmalonate 4-Hydroxyphenyl 4- obtained by reacting commercially available 4-hexyloxybenzoic acid chloride with hydroquinone
Hexyloxybenzoate and S-(-)-2-fluoro-2-methylmalonic acid monoethyl ester were synthesized in the same manner as described in Example 1, and had the following physicochemical properties: (4-hexyloxyphenyl-
4'-carbonyloxyl) phenyl ethyl-2-fluoro-2-methylmalonate was obtained.
I.R.(KBr法,cm-1):1780,1763,1740,1725,1680,1610,1
500 NMR(CDCl3中,ppm):8.15(d,2H),7.40〜6.95(m,6
H),4.40(q,2H),4.01(t,2H),1.95(d,3H),1.90〜
1.30(m,10H),0.95(t,3H) 実施例5 液晶組成物及び光スイッチング素子の作製 一方、67〜62℃でコレステリック相を、62〜47℃でス
メクチックA相を、47〜7℃でスメクチックC相をとる
ノンキラルのフェニルピリミジン系化合物を混合したベ
ース液晶と実施例1で得られた4−(2−(4−ヘキシ
ルオキシフェニル)ピリミジニル)フェニル エチル−
2−フルオロ−2−メチルマロン酸エステルを重量比で
9対1で混合したところ、67.5〜65.5℃でコレステリッ
ク相を65.5〜50.6℃でスメクチックA相を50.6〜6.5℃
でキラルスメクチックC相をとる良好な強誘電性液晶組
成部が得られた。IR (KBr method, cm -1 ): 1780,1763,1740,1725,1680,1610,1
(In CDCl 3, ppm) 500 NMR: 8.15 (d, 2H), 7.40~6.95 (m, 6
H), 4.40 (q, 2H), 4.01 (t, 2H), 1.95 (d, 3H), 1.90-
1.30 (m, 10H), 0.95 (t, 3H) Example 5 Preparation of Liquid Crystal Composition and Optical Switching Element On the other hand, a cholesteric phase was formed at 67 to 62 ° C, a smectic A phase was formed at 62 to 47 ° C, and 47 to 7 ° C. The base liquid crystal mixed with a non-chiral phenylpyrimidine-based compound having a smectic C phase in the above, and the 4- (2- (4-hexyloxyphenyl) pyrimidinyl) phenyl ethyl- obtained in Example 1
When 2-fluoro-2-methylmalonate was mixed at a weight ratio of 9: 1, the cholesteric phase was changed from 67.5 to 65.5 ° C at 65.5 to 50.6 ° C, and the smectic A phase was changed from 50.6 to 6.5 ° C.
As a result, a good ferroelectric liquid crystal composition having a chiral smectic C phase was obtained.
この様にして得られた液晶組成物をポリイミドを塗布
し、ラビング処理を施した透明電極付きガラスからなる
厚さ2.1μmのセルに注入し、等方性液体の状態が緩や
かに降温し、良い配向状態のキラルスメクチックC相を
得た後、そのセルをクロスニコルの偏光顕微鏡で観察し
ながらセルに電界を印加すると光スイッチング動作が観
測された。The liquid crystal composition thus obtained is coated with polyimide, injected into a 2.1 μm-thick cell made of rubbed glass with a transparent electrode, and the temperature of the isotropic liquid is gradually lowered, which is good. After obtaining the oriented chiral smectic C phase, an optical switching operation was observed when an electric field was applied to the cell while observing the cell with a crossed Nicol polarizing microscope.
尚、このセルの25℃における応答時間61.6μsecであ
った。The response time of this cell at 25 ° C. was 61.6 μsec.
このように、本発明の化合物の光学活性基は類似の、
従来から知られている他のフッ素系化合物に比べて大き
な自発分極を示し、また、特に、ピリミジン系混合物に
添加すると良好な液晶組成物をつくることがわかる。Thus, the optically active groups of the compounds of the invention are similar,
It shows that spontaneous polarization is larger than that of other conventionally known fluorine-based compounds, and that a good liquid crystal composition can be formed particularly when added to a pyrimidine-based mixture.
4.発明の効果 以上説明したように、本発明の新規な化合物及びそれ
を含む液晶組成物、さらにはスイッチング素子は、フッ
素原子の電子的効果を反映し、電界に対して速い応答を
し、オプトエレクトロニクス用表示材料として、極めて
有用なものである。4. Effects of the Invention As described above, the novel compound of the present invention and the liquid crystal composition containing the same, and further the switching element, reflect the electronic effect of fluorine atoms, respond quickly to an electric field, It is extremely useful as a display material for optoelectronics.
Claims (4)
し、この両アルキル基は同じであっても異なっていても
よく、Aは、単結合または−O−を示し、Xは、一般式
(II) −(X1)p−B−(X2)q− (II) (ここで、p、qは0、1または2で示され、Bは単結
合、−COO−、−OCO−、−OCH2−または−CH2O−より選
ばれる2価の鎖状基を示し、X1、X2は を含む含六員環基を示す)で表される含六員環基を示
し、かつ、該Xは、 を少なくとも一つ含む〕で表わされる新規な含フッ素化
合物。1. The compound of the general formula (I) Wherein R 1 and R 2 each represent an alkyl group having 1 to 18 carbon atoms, and both alkyl groups may be the same or different, and A represents a single bond or -O- , X is general formula (II) - (X 1) p-B- (X 2) q- (II) ( wherein, p, q is denoted by 0, 1, or 2, B is a single bond, - COO -, - OCO -, - OCH 2 - or a divalent chain group selected from -CH 2 O-, X 1, X 2 is And X represents a six-membered ring group represented by the formula: A fluorine-containing compound represented by the formula:
が、−O−で、かつXが、 で表されることを特徴とする特許請求の範囲第1項記載
の新規な含フッ素化合物。2. In the general formula (I) of claim (1),
Is -O-, and X is The novel fluorine-containing compound according to claim 1, wherein the compound is represented by the following formula:
フッ素化合物を含有することを特徴とする液晶組成物。3. A liquid crystal composition comprising the fluorine-containing compound represented by the general formula (I) according to claim 1.
フッ素化合物の少なくとも1種を構成要素とすることを
特徴とする光スイッチング素子。4. An optical switching element comprising at least one fluorine-containing compound represented by the general formula (I) according to claim 1 as a constituent element.
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Citations (2)
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JPH02178258A (en) * | 1988-12-28 | 1990-07-11 | Showa Shell Sekiyu Kk | 2-halogen-substituted carboxylic acid derivative |
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JPH01197459A (en) * | 1988-02-03 | 1989-08-09 | Nippon Telegr & Teleph Corp <Ntt> | Optically active compound and liquid crystal composition |
JPH02178258A (en) * | 1988-12-28 | 1990-07-11 | Showa Shell Sekiyu Kk | 2-halogen-substituted carboxylic acid derivative |
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