JP2822579B2 - Fluorinated tricyclic compound having ether bond and intermediate thereof - Google Patents
Fluorinated tricyclic compound having ether bond and intermediate thereofInfo
- Publication number
- JP2822579B2 JP2822579B2 JP2097648A JP9764890A JP2822579B2 JP 2822579 B2 JP2822579 B2 JP 2822579B2 JP 2097648 A JP2097648 A JP 2097648A JP 9764890 A JP9764890 A JP 9764890A JP 2822579 B2 JP2822579 B2 JP 2822579B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- liquid crystal
- formula
- substituted
- mol
- 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
- 150000001875 compounds Chemical class 0.000 title claims description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052731 fluorine Chemical group 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 27
- 210000004027 cell Anatomy 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- -1 4-substituted benzoic acid Chemical class 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004988 Nematic liquid crystal Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007868 Raney catalyst Substances 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000005669 field effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- UWTUEMKLYAGTNQ-UHFFFAOYSA-N 1,2-dibromoethene Chemical group BrC=CBr UWTUEMKLYAGTNQ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical class C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- KTEARTXATWOYDB-UHFFFAOYSA-N 1-chloro-4-[1-(4-chlorophenyl)ethyl]benzene Chemical compound C=1C=C(Cl)C=CC=1C(C)C1=CC=C(Cl)C=C1 KTEARTXATWOYDB-UHFFFAOYSA-N 0.000 description 1
- GSDQYSSLIKJJOG-UHFFFAOYSA-N 4-chloro-2-(3-chloroanilino)benzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1NC1=CC=CC(Cl)=C1 GSDQYSSLIKJJOG-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical class C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000000007 visual effect Effects 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、電気光学的表示材料として有用なエーテル
結合を有するフッ素系３環式化合物及びその中間体に関
する。Description: TECHNICAL FIELD The present invention relates to a fluorine-based tricyclic compound having an ether bond useful as an electro-optical display material and an intermediate thereof.
液晶表示セルの代表的なものにエム・シャット（M.Sc
hadt）等〔APPLIED PHYSICS LESTTERS 18,127〜128（19
71）〕によって提案された電界効果型セル（フィールド
・エフェクト・モード・セル）又はジー・エイチ・ハイ
ルマイヤー（G.H.Heilmeier）等〔PROCEEDING OF THE
I.E.E.E.56 1162〜1171（1968）〕によって提案された
動的光散型セル（ダイミック・スキャッタリング・モー
ド・セル）又はジー・エイチ・ハイルマイヤー（G.H.He
ilmeier）等〔APPLIED PHYSICS LETTERS 13,91（196
8）〕あるいはディー・エル・ホワイト（D.L.White）等
［JOURNAL OF APPLIED PHYSICS 45,4718（1974）］によ
って提案されたゲスト・ホスト型セルなどがある。A typical liquid crystal display cell is M-Shut (M.Sc
hadt) etc. [APPLIED PHYSICS LESTTERS 18,127-128 (19
71)] [PROCEEDING OF THE], such as a field effect type cell (field effect mode cell) or GH Heilmeier
IEEE561162-1171 (1968)], a dynamic light-scattering type cell (a dimic scattering mode cell) or a GH Heilmeier (GHHe).
ilmeier) etc. [APPLIED PHYSICS LETTERS 13,91 (196
8)] or a guest-host type cell proposed by DL White et al. [JOURNAL OF APPLIED PHYSICS 45, 4718 (1974)].
これらの液晶表示セルの中で現在主流をなすものは、
電界効果型セルの一種のTN型セルである。このTN型セル
においては、G.BauerによってMol.Cryst.Liq.Cryst.63,
45（1981）に報告されているように、セル外観を損う原
因となるセル表面での干渉縞の発生を防止するために、
セルに充填される液晶材料の屈折率の異方性（Δｎ）と
セルにおける液晶層の厚さ（ｄ）μｍの積を或る特定の
値に設定する必要がある。実用的に使用される液晶表示
セルでは、Δｎ・ｄの値0.5、1.0、1.6又は2.2のいずれ
かに設定されている。The mainstream of these liquid crystal display cells at present is
This is a kind of TN type field effect cell. In this TN type cell, G. Bauer described Mol.Cryst.Liq.Cryst.63,
As reported in 45 (1981), in order to prevent the occurrence of interference fringes on the cell surface, which would impair the cell appearance,
It is necessary to set the product of the anisotropy (Δn) of the refractive index of the liquid crystal material filled in the cell and the thickness (d) μm of the liquid crystal layer in the cell to a specific value. In a practically used liquid crystal display cell, the value of Δn · d is set to any of 0.5, 1.0, 1.6 or 2.2.
通常、Δｎ・ｄの値を0.5に設定した場合、視覚特性
が良くなるという特徴があり、Δｎ・ｄの値を1.0、1.6
又は2.2に設定した場合、正面からのコントラストが良
くなるという特徴がある。Usually, when the value of Δn · d is set to 0.5, there is a feature that the visual characteristics are improved, and the value of Δn · d is set to 1.0, 1.6
Or when set to 2.2, there is a feature that the contrast from the front is improved.
従って、どの方向からも見やすい視角特性を重視する
液晶表示セルの場合は、Δｎ・ｄの値を0.5に設定し、
特に正面からのコントラストを重視する液晶表示セルの
場合は、Δｎ・ｄの値を1.0、1.6又は2.2に設定するの
が普通である。Therefore, in the case of a liquid crystal display cell that emphasizes viewing angle characteristics that are easy to see from any direction, the value of Δn · d is set to 0.5,
In particular, in the case of a liquid crystal display cell that emphasizes contrast from the front, the value of Δn · d is usually set to 1.0, 1.6 or 2.2.
一方、実用的に使用されている液晶表示セルにおける
液晶層の厚さは、通常、６〜10μｍの限定された範囲で
或る値に設定されるため、Δｎ・ｄの値を0.5に設定す
る場合は、Δｎの値の小さな液晶材料が必要となり、Δ
ｎ・ｄの値を1.0、1.6又は2.2に設定する場合は、逆
に、Δｎの値の大きな液晶材料が必要となる。このよう
に、液晶表示セルの表示特性に応じてΔｎの値が小さい
液晶材料とΔｎの値が大きい液晶材料が必要とされる。On the other hand, the thickness of the liquid crystal layer in a liquid crystal display cell that is practically used is usually set to a certain value within a limited range of 6 to 10 μm, so the value of Δn · d is set to 0.5. In this case, a liquid crystal material having a small value of Δn is required,
When the value of n · d is set to 1.0, 1.6 or 2.2, a liquid crystal material having a large value of Δn is required. Thus, a liquid crystal material having a small value of Δn and a liquid crystal material having a large value of Δn are required in accordance with the display characteristics of the liquid crystal display cell.
またTN型セルにおいては、混合液晶の誘電率の異方性
（Δε）が正である必要があるため、Δεの値が大き
く、しきい値電圧が低く、低電圧で駆動できるネマチッ
ク液晶化合物が必要とされている。In a TN type cell, since the anisotropy (Δε) of the dielectric constant of the mixed liquid crystal needs to be positive, a nematic liquid crystal compound having a large value of Δε, a low threshold voltage, and a low voltage can be driven. is necessary.
本発明が解決しようとする課題は、Δｎの値が小さ
く、Δεの値が大きく、しきい値電圧の低い新規なネマ
チック液晶化合物及びその中間体を提供することにあ
る。An object of the present invention is to provide a novel nematic liquid crystal compound having a small value of Δn, a large value of Δε, and a low threshold voltage, and an intermediate thereof.
本発明は、上記課題を解決するために、一般式（Ｉ） （式中、Ｒは炭素原子数１〜５の直鎖状アルキル基を表
わし、Ｘは水素原子又はフッ素原子を表わし、 はトランス（エカトリアル−エカトリアル）配置のシク
ロヘキサン環を表わす。）で表わされる化合物及び一般
式（Ｉ）で表わされる化合物の中間体である一般式（I
I） （式中、Ｒは炭素原子数１〜５の直鎖状アルキル基を表
わし、 はトランス（エカトリアル−エカトリアル）配置のシク
ロヘキサン環を表わす。） で表わされる化合物を提供する。The present invention provides a compound represented by the general formula (I): (Wherein, R represents a linear alkyl group having 1 to 5 carbon atoms, X represents a hydrogen atom or a fluorine atom, Represents a cyclohexane ring in a trans (equatorial-equatorial) configuration. ) And a compound of the general formula (I) which is an intermediate of the compound represented by the general formula (I)
I) (Wherein, R represents a linear alkyl group having 1 to 5 carbon atoms, Represents a cyclohexane ring in a trans (equatorial-equatorial) configuration. ) Is provided.
本発明に係わる一般式（Ｉ）で表わされる化合物及び
一般式（II）で表わされる化合物は、次の製造方法に従
って、製造することができる。The compound represented by the general formula (I) and the compound represented by the general formula (II) according to the present invention can be produced according to the following production method.
（上記反応式中、Ｒは炭素原子数１〜５の直鎖状アルキ
ル基を表わし、Ｘは水素原子又はフッ素原子を表わし、 はトランス（エカトリアル−エカトリアル）のシクロヘ
キサン環を表わす。） 第１段階−式（IV）の化合物をテトラヒドロフラン中、
カリウム−ｔ−ブトキサイドの如き強塩基で処理しイリ
ドを形成した後、式（III）の化合物と反応させ、式
（Ｖ）の化合物を製造する。 (In the above reaction formula, R represents a linear alkyl group having 1 to 5 carbon atoms, X represents a hydrogen atom or a fluorine atom, Represents a cyclohexane ring of trans (equatorial-equatorial). Step 1-Compound of formula (IV) in tetrahydrofuran
After treatment with a strong base such as potassium-t-butoxide to form an ylide, it is reacted with a compound of formula (III) to produce a compound of formula (V).
第２段階−式（Ｖ）の化合物の酢酸エチル中、ラネーニ
ッケルを触媒として接触還元し、式（VI）の化合物を製
造する。Step 2-Catalytic reduction of the compound of formula (V) in ethyl acetate with Raney nickel as catalyst to produce the compound of formula (VI).
第３段階−式（VI）の化合物をトルエン−希硫酸中で加
水分解し、本発明に係わる式（II）の化合物を製造す
る。Third step—The compound of formula (VI) is hydrolyzed in toluene-dilute sulfuric acid to produce the compound of formula (II) according to the present invention.
第４段階−式（II）の化合物をテトラヒドロフラン中、
式（VII）のグリニャール試薬と反応させて、式（VII
I）の化合物を製造する。Fourth step—comprising the compound of formula (II) in tetrahydrofuran
Reaction with a Grignard reagent of formula (VII) yields a compound of formula (VII)
The compound of I) is produced.
第５段階−式（VIII）の化合物をトルエン中でｐ−トル
エンスルホン酸の如き酸性触媒存在下、脱水反応に付
し、式（IX）の化合物を製造する。Step 5-The compound of formula (VIII) is subjected to a dehydration reaction in toluene in the presence of an acidic catalyst such as p-toluenesulfonic acid to produce a compound of formula (IX).
第６段階−式（IX）の化合物をエタノールの如きアルコ
ール中でラネーニッケルを触媒として、接触還元を行な
い、本発明に係わる式（Ｉ）の化合物を製造する。Step 6-The compound of formula (IX) is catalytically reduced in an alcohol such as ethanol with Raney nickel as a catalyst to produce the compound of formula (I) according to the present invention.
斯くして製造された式（Ｉ）の代表的な化合物の相転
移温度を第１表に掲げる。The phase transition temperatures of representative compounds of formula (I) thus prepared are listed in Table 1.
（表中、Ｃは結晶相、Ｎはネマチック相、Ｉは等方性液
体相を夫々表わす。） 本発明に係わる式（Ｉ）の化合物は、正の誘電率の異
方性を有するネマチック液晶化合物であり、従って例え
ば、負の誘電率の異方性を有する他のネマチック液晶化
合物との混合物の状態で動的光散乱型表示セルの材料と
して使用することができ、また正又は負の誘電率の異方
性を有する他のネマチック液晶化合物との混合物の状態
で電界効果型表示セルの材料として使用することができ
る。 (In the table, C represents a crystal phase, N represents a nematic phase, and I represents an isotropic liquid phase.) The compound of the formula (I) according to the present invention is a nematic liquid crystal having a positive dielectric anisotropy. Compound, so that it can be used as a material for a dynamic light scattering display cell in a mixture with other nematic liquid crystal compounds having, for example, a negative dielectric anisotropy, and a positive or negative dielectric constant. It can be used as a material for a field-effect display cell in a state of a mixture with another nematic liquid crystal compound having anisotropy in the ratio.
このように、式（Ｉ）の化合物と混合して使用するこ
とのできる好ましい代表例としては、例えば４−置換安
息香酸４′−置換フェニルエステル、４−置換シクロヘ
キサンカルボン酸４′−置換フェニルエステル、４−置
換シクロヘキサンカルボン酸４′−置換ビフェニルエス
テル、４−（４−置換シクロヘキサンカルボニルオキ
シ）安息香酸４′−置換フェニルエステル、４−（４−
置換シクロヘキシル）安息香酸４′−置換フェニルエス
テル、４−（４−置換シクロヘキシル）安息香酸４′−
置換シクロヘキシルエステル、４−置換４′−置換ビフ
ェニル、４−置換フェニル−４′−置換シクロヘキサ
ン、４−置換４″−置換タ−フェニル、４−置換ビフェ
ニル４′−置換シクロヘキサン、２−（４−置換フェニ
ル）−５−置換ピリミジンなどを挙げることができる。Thus, preferable representative examples which can be used as a mixture with the compound of the formula (I) include, for example, 4-substituted benzoic acid 4'-substituted phenyl ester and 4-substituted cyclohexanecarboxylic acid 4'-substituted phenyl ester 4-substituted cyclohexanecarboxylic acid 4'-substituted biphenyl ester, 4- (4-substituted cyclohexanecarbonyloxy) benzoic acid 4'-substituted phenyl ester, 4- (4-
Substituted cyclohexyl) benzoic acid 4'-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4'-
Substituted cyclohexyl ester, 4-substituted 4'-substituted biphenyl, 4-substituted phenyl-4'-substituted cyclohexane, 4-substituted 4 "-substituted terphenyl, 4-substituted biphenyl 4'-substituted cyclohexane, 2- (4- (Substituted phenyl) -5-substituted pyrimidine and the like.
第２表はネマチック液晶材料として現在母体液晶とし
て汎用されている混合液晶（Ａ）の80重量％と第１表に
示した式（Ｉ）の化合物No.1、No.2とNo.1と類似化学構
造を有し、Δｎが低く正のΔεを有する式（ａ）化合物
の各々の20重量％とから成る各混合液晶について測定さ
れたΔｎ、Δε及びしきい値電圧を掲示し、比較のため
に混合液晶（Ａ）自体について測定されたΔｎ、Δε及
びしきい値電圧を掲示したものである。Table 2 shows that 80% by weight of the mixed liquid crystal (A), which is currently widely used as a base liquid crystal as a nematic liquid crystal material, and the compounds No. 1, No. 2, and No. 1 of the formula (I) shown in Table 1. The measured Δn, Δε and threshold voltage for each mixed liquid crystal comprising 20% by weight of each of the compounds of formula (a) having a similar chemical structure and a low Δn and a positive Δε are listed and compared. For this reason, Δn, Δε and the threshold voltage measured for the mixed liquid crystal (A) itself are shown.
尚、混合液晶（Ａ）は から成るものであり、式（ａ）の化合物は式 で表わされる公知化合物（特公昭63−44132号）であ
る。The mixed liquid crystal (A) Wherein the compound of formula (a) is of the formula (JP-B-63-44132).
第２表に掲示したデータから、式（Ｉ）の化合物は、
混合液晶のΔｎを低下させるか、さほど上昇させずに、
しきい値電圧を顕著に低下せしめるか、さほど変化させ
ずに、Δεを上昇させることが理解できる。本発明の効
果は、従来公知の化合物（ａ）が混合液晶のΔｎを上昇
させ、Δεを低下させ、しきい値電圧を著しく上昇させ
てしまうことからも明確である。 From the data presented in Table 2, the compound of formula (I)
Without decreasing or not significantly increasing Δn of the mixed liquid crystal,
It can be seen that Δε is increased without significantly lowering the threshold voltage or changing it so much. The effect of the present invention is clear from the fact that the conventionally known compound (a) increases Δn of the mixed liquid crystal, decreases Δε, and significantly increases the threshold voltage.
［実施例］ 実施例１ 式 CH3OCH2CH2CH2P（C6H5）3I の化合物324g（0.7モル）をテトラヒドロフラン１リッ
トルに加え、−４℃に冷却した。この溶液に、カリウム
−ｔ−ブトキシサイド90g（0.8モル）を10分間かけて加
えた後、同温度で10分間、次いで室温で１時間反応させ
た。反応溶液を−５℃に冷却した後、この溶液に、式 の化合物119g（0.5モル）をテトラヒドロフラン500mlに
溶解した溶液を15分間かけて加え、同温度で10分間、次
いで室温で２時間反応させた。反応終了後、反応混合物
に水１リットルを加え、酢酸エチル１リットルで２回抽
出し、抽出液を、水洗、乾燥した。抽出液から溶媒を減
圧留去して得た残渣をトルエン500mlに加熱溶解した
後、ｎ−ヘキサン500mlを加え、一晩放置した。析出し
た結晶を濾別し、濾液をシリカゲルカラムクロマトグラ
フィーを用いて精製して下記化合物131g（0.45モル）を
得た。EXAMPLES Example 1 324 g (0.7 mol) of a compound of the formula CH 3 OCH 2 CH 2 CH 2 P (C 6 H 5 ) 3 I was added to 1 liter of tetrahydrofuran and cooled to -4 ° C. After adding 90 g (0.8 mol) of potassium-t-butoxide to this solution over 10 minutes, the reaction was carried out at the same temperature for 10 minutes and then at room temperature for 1 hour. After cooling the reaction solution to −5 ° C., A solution prepared by dissolving 119 g (0.5 mol) of the compound in 500 ml of tetrahydrofuran was added over 15 minutes, and reacted at the same temperature for 10 minutes and then at room temperature for 2 hours. After completion of the reaction, 1 liter of water was added to the reaction mixture, and the mixture was extracted twice with 1 liter of ethyl acetate. The extract was washed with water and dried. The residue obtained by evaporating the solvent from the extract under reduced pressure was dissolved by heating in 500 ml of toluene, then 500 ml of n-hexane was added, and the mixture was left overnight. The precipitated crystals were separated by filtration, and the filtrate was purified using silica gel column chromatography to obtain the following compound 131 g (0.45 mol).
上記化合物131g（0.45モル）を酢酸エチル１リットル
に溶解し、ラネーニッケルを触媒として接触還元を行っ
た。反応終了後、反応溶液から触媒を濾別した後、濾液
から溶媒を減圧留去して、下記化合物124g（0.42モル）
を得た。 131 g (0.45 mol) of the above compound was dissolved in 1 liter of ethyl acetate, and catalytic reduction was carried out using Raney nickel as a catalyst. After completion of the reaction, the catalyst was separated by filtration from the reaction solution, and the solvent was distilled off from the filtrate under reduced pressure to obtain 124 g (0.42 mol) of the following compound.
I got
上記化合物124g（0.42モル）をトルエン800mlに溶解
し、この溶液に16％硫酸400mlを加えた後、14時間加熱
還流した。反応終了後、反応溶液を分液し、有機層を水
洗、乾燥した。有機層から溶媒を減圧留去して得た残渣
をｎ−ヘキサン300mlから再結晶させて精製して、下記
化合物80g（0.32モル）を得た。 124 g (0.42 mol) of the above compound was dissolved in 800 ml of toluene, 400 ml of 16% sulfuric acid was added to this solution, and the mixture was heated under reflux for 14 hours. After completion of the reaction, the reaction solution was separated, and the organic layer was washed with water and dried. The residue obtained by evaporating the solvent from the organic layer under reduced pressure was purified by recrystallization from 300 ml of n-hexane to obtain 80 g (0.32 mol) of the following compound.
実施例２ マグネシウム末1.5g（0.06モル）を乾燥テトラヒドロ
フラン10mlに加え、触媒量のジブロムエチレンで活性化
した後、この溶液に、30℃以下で、式 の化合物11.6g（0.06モル）を乾燥テトラヒドロフラン2
5mlに希釈した溶液を滴下した。滴下終了後、同温度で3
0分間撹拌を続けた。反応終了後、この反応液に、実施
例１で得た化合物10.6g（0.045モル）を乾燥テトラヒド
ロフラン30mlに溶解した溶液を25℃以下で滴下した後、
室温で３時間反応させた。 Example 2 1.5 g (0.06 mol) of magnesium powder was added to 10 ml of dry tetrahydrofuran, and activated with a catalytic amount of dibromoethylene. 11.6 g (0.06 mol) of dry tetrahydrofuran 2
The solution diluted to 5 ml was added dropwise. After dropping, at the same temperature
Stirring was continued for 0 minutes. After completion of the reaction, a solution prepared by dissolving 10.6 g (0.045 mol) of the compound obtained in Example 1 in 30 ml of dry tetrahydrofuran was added dropwise to the reaction solution at 25 ° C. or lower.
The reaction was performed at room temperature for 3 hours.
反応終了後、反応液に９％塩酸50mlに加え、トルエン
100mlで３回抽出した。抽出液を水洗、乾燥した後、抽
出液から溶媒を減圧留去し、下記化合物15.2g（0.044モ
ル）を得た。After completion of the reaction, 50 ml of 9% hydrochloric acid was added to the reaction solution, and toluene was added.
Extracted three times with 100 ml. After the extract was washed with water and dried, the solvent was distilled off from the extract under reduced pressure to obtain 15.2 g (0.044 mol) of the following compound.
上記化合物をトルエン250mlに溶解し、ｐ−トルエン
スルホン酸1gを加え、除水装置で除水しながら、４時間
加熱還流した。 The above compound was dissolved in 250 ml of toluene, 1 g of p-toluenesulfonic acid was added, and the mixture was heated under reflux for 4 hours while removing water with a water removing device.
反応終了後、トルエン層を水洗、乾燥した後、トルエ
ン層から溶媒を減圧留去して得た残渣をエタノール130m
lから再結晶させて精製して、下記化合物13.0g（0.039
モル）を得た。After the completion of the reaction, the toluene layer was washed with water, dried, and the solvent was distilled off from the toluene layer under reduced pressure.
13.0 g (0.039
Mol).
上記化合物をエタノール250mlに溶解し、ラネーニッ
ケル1gを加えた後、室温下、水素圧５気圧で15時間接触
還元した。反応終了後、反応溶液から触媒を除去した
後、エタノールを減圧留去して得られた残渣をｎ−ヘキ
サン80mlから再結晶させて精製して、下記化合物8.4g
（0.025モル）を得た。 The above compound was dissolved in 250 ml of ethanol, 1 g of Raney nickel was added, and the mixture was catalytically reduced at room temperature under a hydrogen pressure of 5 atm for 15 hours. After completion of the reaction, the catalyst was removed from the reaction solution, and the residue obtained by evaporating ethanol under reduced pressure was purified by recrystallization from n-hexane (80 ml) to obtain the following compound (8.4 g).
(0.025 mol).
相転移温度 61℃（Ｃ→Ｎ） 108℃（ＮＩ） 実施例３ 実施例２と同様にして下記化合物を得た。 Phase transition temperature 61 ° C. (C → N) 108 ° C. (NI) Example 3 The following compound was obtained in the same manner as in Example 2.
相転移温度 85℃（Ｃ→Ｎ） 153℃（ＮＩ） 〔発明の効果〕 本発明に係わる式（Ｉ）の化合物は、Δｎが低く、Δ
εが大きいため、現在母体液晶として汎用されているネ
マチック混合液晶に混合することによって混合液晶のΔ
ｎを低下させるか、さほど上昇させずに、しきい値電圧
を低下させるか、さほど変化させずに、Δεを上昇させ
ることができる。 Phase transition temperature 85 ° C. (C → N) 153 ° C. (NI) [Effect of the Invention] The compound of the formula (I) according to the present invention has a low Δn
Because of the large ε, the mixed liquid crystal is mixed with a nematic mixed liquid crystal, which is currently widely used as a base liquid crystal, to obtain a Δ
It is possible to increase Δε without decreasing n or decreasing the threshold voltage without increasing it so much.
本発明に係わる式（Ｉ）の化合物は、構造類似の公知
化合物と比べ、その効果は顕著であり、視角特性に優
れ、かつ、低電圧駆動可能なTN型液晶表示セルを作製す
るための材料として極めて有用である。The compound of formula (I) according to the present invention has a remarkable effect as compared with known compounds having a similar structure, has excellent viewing angle characteristics, and is a material for producing a TN type liquid crystal display cell which can be driven at a low voltage. Is extremely useful.
また、本発明に係わる式（II）の化合物は、式（Ｉ）
の化合物の如き各種液晶化合物の合成中間体として極め
て有用である。Further, the compound of the formula (II) according to the present invention has the formula (I)
It is extremely useful as an intermediate for synthesizing various liquid crystal compounds such as the compound (1).
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 43/174 C07C 49/517 ＣＡ（ＳＴＮ) ＣＡＯＬＤ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C07C 43/174 C07C 49/517 CA (STN) CAOLD (STN) REGISTRY (STN)
Claims (2)
わし、Ｘは水素原子又はフッ素原子を表わし、 はトランス（エカトリアル−エカトリアル）配置のシク
ロヘキサン環を表わす。）で表わされる化合物。1. The compound of the general formula (I) (Wherein, R represents a linear alkyl group having 1 to 5 carbon atoms, X represents a hydrogen atom or a fluorine atom, Represents a cyclohexane ring in a trans (equatorial-equatorial) configuration. ).
わし、 はトランス（エカトリアル−エカトリアル）配置のシク
ロヘキサン環を表わす。）で表わされる請求項１記載の
一般式（Ｉ）の中間体化合物。2. A compound of the general formula (II) (Wherein, R represents a linear alkyl group having 1 to 5 carbon atoms, Represents a cyclohexane ring in a trans (equatorial-equatorial) configuration. The intermediate compound of the general formula (I) according to claim 1, which is represented by the formula:
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/557,336 US5068462A (en) | 1989-07-28 | 1990-07-26 | Fluorine-substituted compound containing ether bond and intermediate thereof |
| EP90114454A EP0415090B1 (en) | 1989-07-28 | 1990-07-27 | Fluorine-substituted compound containing ether bond and intermediate thereof |
| DE69006803T DE69006803T2 (en) | 1989-07-28 | 1990-07-27 | Fluorine-substituted compound containing ether linkage and intermediate therefor. |
| US07/709,842 US5166448A (en) | 1989-07-28 | 1991-06-04 | Intermediate for preparing fluorine-substituted compound containing ether bond |
| HK98104381A HK1005184A1 (en) | 1989-07-28 | 1998-05-21 | Fluorine-substituted compound containing ether bond and intermediate thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-196074 | 1989-07-28 | ||
| JP19607489 | 1989-07-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03130244A JPH03130244A (en) | 1991-06-04 |
| JP2822579B2 true JP2822579B2 (en) | 1998-11-11 |
Family
ID=16351770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2097648A Expired - Lifetime JP2822579B2 (en) | 1989-07-28 | 1990-04-16 | Fluorinated tricyclic compound having ether bond and intermediate thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2822579B2 (en) |
-
1990
- 1990-04-16 JP JP2097648A patent/JP2822579B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03130244A (en) | 1991-06-04 |
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