JP2005213226A - Compound, liquid crystal composition containing said compound and liquid crystal display element produced by using said liquid crystal composition - Google Patents

Compound, liquid crystal composition containing said compound and liquid crystal display element produced by using said liquid crystal composition Download PDF

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JP2005213226A
JP2005213226A JP2004024711A JP2004024711A JP2005213226A JP 2005213226 A JP2005213226 A JP 2005213226A JP 2004024711 A JP2004024711 A JP 2004024711A JP 2004024711 A JP2004024711 A JP 2004024711A JP 2005213226 A JP2005213226 A JP 2005213226A
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JP4411989B2 (en
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Yutaka Nagashima
豊 長島
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound capable of increasing the Δn of a liquid crystal composition by adding to the liquid crystal composition, a liquid crystal composition containing the compound and a liquid crystal display element produced by using the liquid crystal composition. <P>SOLUTION: The compound is expressed by general formula (I) (R is a 4-12C alkenyl containing the double bond at ≥3 site; and X<SP>1</SP>and X<SP>2</SP>are each independently fluorine atom or hydrogen atom provided that at least one of X<SP>1</SP>and X<SP>2</SP>is a fluorine atom). The liquid crystal composition contains the compound, and the liquid crystal display element is produced by using the liquid crystal composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、有機電子材料や医農薬、特に電気光学的液晶表示用ネマチック液晶材料として有用な化合物、該化合物を含有する液晶組成物及び該液晶組成物を用いた液晶表示素子に関する。   The present invention relates to a compound useful as an organic electronic material or medical / agricultural chemical, in particular, a nematic liquid crystal material for electro-optical liquid crystal display, a liquid crystal composition containing the compound, and a liquid crystal display device using the liquid crystal composition.

液晶表示素子は、時計、電卓をはじめとして、各種測定機器、自動車用パネル、ワードプロセッサー、電子手帳、プリンター、コンピューター、テレビ、時計、広告表示板等に用いられるようになっている。液晶表示方式としては、その代表的なものにTN(ツイステッド・ネマチック)型、STN(スーパー・ツイステッド・ネマチック)型あるいはFLC(強誘電性液晶)等がある。
これらの液晶を用いた液晶表示素子は、偏光板を必要とするため表示を明るくすることに限界がある。
Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, as well as watches and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, FLC (ferroelectric liquid crystal), and the like.
Since the liquid crystal display element using these liquid crystals requires a polarizing plate, there is a limit to brightening the display.

一方、偏光板や配向処理を要さず、明るくコントラストのよい、大型で廉価な液晶素子を製造する方法として、液晶のカプセル化により、ポリマー中に液晶滴を分散させ、そのポリマーをフィルム化する方法が知られている。また、液晶材料が連続層を形成し、この連続層中に、透明性固体物質が三次元網目状に存在する構造を有する液晶素子が開示されている。
このような液晶材料及び透明性固体物質を含有する調光層を有する光散乱形液晶表示素子に要求される表示特性、特に広告板等の装飾表示板や時計、電卓等の表示装置等の直視形表示装置用途には、電圧無印加時の反射率、即ち白濁性を改善することによるコントラストの向上が重視されている。
On the other hand, as a method for producing a large, inexpensive liquid crystal device that does not require a polarizing plate or alignment treatment and has a bright and good contrast, liquid crystal droplets are dispersed in the polymer by encapsulating the liquid crystal, and the polymer is formed into a film. The method is known. In addition, a liquid crystal element having a structure in which a liquid crystal material forms a continuous layer and a transparent solid substance exists in a three-dimensional network in the continuous layer is disclosed.
Display characteristics required for a light-scattering liquid crystal display element having a light control layer containing such a liquid crystal material and a transparent solid substance, especially a decorative display board such as an advertising board, and a direct view of a display device such as a clock and a calculator For the display device application, importance is attached to the improvement of the contrast by improving the reflectance when no voltage is applied, that is, the white turbidity.

このような白濁性を向上させ、高いコントラスト比を達成した液晶材料及び透明性固体物質を含有する調光層を有する直視形液晶表示素子として、液晶材料の屈折率異方性が0.27以上であることを特徴とする直視形液晶表示素子の提案がある(例えば、特許文献1参照。)。
この提案では、屈折率異方性の大きい液晶材料として、1−置換フェニル2−置換シクロヘキシルフェニルアセチレン、2−(4−置換フェニル)−5−置換ピリジン、2−(4−置換フェニル)−5−(4’−置換フェニル)ピリジン、2−(4−置換フェニル)−5−(4’−置換フェニル)ピリミジン、4−置換4’−置換ターフェニル、4−置換ビフェニル4’−置換シクロヘキサン、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等の化合物が用いられている。
又、可変機能デバイスとして液晶媒質を利用した高周波デバイスとして、駆動電圧が無印加時と印加時により液晶層の誘電率を変化させることによって、マイクロストリップ線路を伝搬する電磁波の移相を可変させたり、遅延させたりすることが可能なマイクロ波帯可変移相器が開示されている(非特許文献1参照。)。
可変機能デバイスとして使用される液晶組成物は、位相制御の範囲を広くすることができることから、GHz帯での誘電率異方性Δεが大きい液晶組成物が必要となる。GHz帯での誘電率異方性は可視光域での複屈折率Δnと比例関係となっていることが知られており、結果としてΔnの大きい液晶組成物の開発が望まれていた。
特開平8−5996号公報 ドルフィ(D.Dolfi),「エレクトロニクスレター(Electronics Letters)」,(英国),1993年,29巻,10号,p.926−927
As a direct-view liquid crystal display element having a light control layer containing a liquid crystal material and a transparent solid substance that improve the white turbidity and achieve a high contrast ratio, the refractive index anisotropy of the liquid crystal material is 0.27 or more. There is a proposal of a direct-view type liquid crystal display element characterized by the above (see, for example, Patent Document 1).
In this proposal, as a liquid crystal material having a large refractive index anisotropy, 1-substituted phenyl 2-substituted cyclohexylphenylacetylene, 2- (4-substituted phenyl) -5-substituted pyridine, 2- (4-substituted phenyl) -5 are used. -(4'-substituted phenyl) pyridine, 2- (4-substituted phenyl) -5- (4'-substituted phenyl) pyrimidine, 4-substituted 4'-substituted terphenyl, 4-substituted biphenyl 4'-substituted cyclohexane, Compounds such as 4-substituted cyclohexanecarboxylic acid 4′-substituted biphenyl esters are used.
In addition, as a high-frequency device using a liquid crystal medium as a variable function device, the phase shift of the electromagnetic wave propagating through the microstrip line can be varied by changing the dielectric constant of the liquid crystal layer between when no drive voltage is applied and when the drive voltage is applied. A microwave band variable phase shifter that can be delayed is disclosed (see Non-Patent Document 1).
Since the liquid crystal composition used as the variable function device can widen the range of phase control, a liquid crystal composition having a large dielectric anisotropy Δε in the GHz band is required. It is known that the dielectric anisotropy in the GHz band is proportional to the birefringence Δn in the visible light region, and as a result, development of a liquid crystal composition having a large Δn has been desired.
JP-A-8-5996 D. Dolfi, “Electronics Letters” (UK), 1993, 29, 10, p. 926-927

しかし、特許文献1で用いた液晶組成物では、比較的Δnが大きく、コントラストがよいものの、さらにコントラストを高めるためなど、より高いΔnを示す液晶組成物への要望が高かった。
本発明が解決しようとする課題は、上記の目的に応じるため、液晶組成物に添加することにより、液晶組成物のΔnを高めることのできる化合物、該化合物を含有する液晶組成物及び該液晶組成物を用いた液晶表示素子を提供するものである。
However, although the liquid crystal composition used in Patent Document 1 has a relatively large Δn and good contrast, there has been a high demand for a liquid crystal composition exhibiting a higher Δn, for example, to further increase the contrast.
In order to meet the above-mentioned object, the problem to be solved by the present invention is that a compound capable of increasing Δn of a liquid crystal composition by adding to the liquid crystal composition, a liquid crystal composition containing the compound, and the liquid crystal composition The present invention provides a liquid crystal display element using the object.

本発明は、1.一般式(I)   The present invention provides: Formula (I)

Figure 2005213226
Figure 2005213226

(式中、Rは炭素数4〜12で二重結合の位置が3位以上であるアルケニル基を表し、X及びXはそれぞれ独立してフッ素原子又は水素原子を表し、但し、X及びXの少なくとも一つはフッ素原子を表す。)で表される化合物。
2.一般式(I)において、Rが3−アルケニル基を表す上記1記載の化合物。
3.一般式(I)において、X又はXが水素原子を表す上記1又は2記載の化合物。
4.上記1〜3のいずれか1項に記載の化合物を含有する液晶組成物。
5.上記項4記載の液晶組成物を用いた液晶表示素子。を前記解決手段とした。
(In the formula, R represents an alkenyl group having 4 to 12 carbon atoms and a double bond at the 3-position or more, and X 1 and X 2 each independently represent a fluorine atom or a hydrogen atom, provided that X 1 And at least one of X 2 represents a fluorine atom).
2. 2. The compound according to 1 above, wherein in general formula (I), R represents a 3-alkenyl group.
3. 3. The compound according to 1 or 2 above, wherein in formula (I), X 1 or X 2 represents a hydrogen atom.
4). 4. A liquid crystal composition comprising the compound according to any one of 1 to 3 above.
5). 5. A liquid crystal display device using the liquid crystal composition according to item 4. Was the solution.

本発明の化合物は、液晶組成物に添加することにより屈折率異方性(Δn)を0.3以上と従来にない液晶組成物とすることができ、高いコントラスト比の達成、可変機能デバイスにおける位相可変範囲の増大等の効果を有するため、液晶表示材料の構成部材として有用である。   The compound of the present invention can be made into an unprecedented liquid crystal composition having a refractive index anisotropy (Δn) of 0.3 or more by adding to the liquid crystal composition, achieving a high contrast ratio, in a variable function device Since it has effects such as an increase in the phase variable range, it is useful as a component of liquid crystal display materials.

以下に本発明の一例につき説明する。
上記一般式(I)において、Rは炭素数4〜12で二重結合の位置が3位以上であるアルケニル基を表す。アルケニルの二重結合の位置が2位以下であると得られる液晶組成物の安定性が低下する。二重結合の位置が3位以上であるアルケニル基のなかでは、二重結合の位置に偶奇性が有り、偶数位置に二重結合が存在すると液晶相上限温度が低下する傾向にあり、アルケニル基の炭素数が大きすぎると組成物の粘性が高くなる傾向にあるため、3−アルケニル基又は5−アルケニル基が好ましく、直鎖状の3−アルケニル基又は5−アルケニル基がより好ましい。3−アルケニル基としては末端のアルキル基が長すぎると粘性が高くなる傾向にあるため3−ブテニル基、3−ペンテニル基、3−ヘキセニル基、3−ヘプテニル基または3−オクテニル基等を挙げることができる。5−アルケニル基としては5−ヘキセニル基、5−ヘプテニル基又は5−オクテニル基等を挙げることができる。このアルケニル基としては、これらの基に含まれる水素原子の1個又はそれ以上がフッ素原子で置換されていてもよい。
このアルケニル基の中では、炭素数4〜8のアルケニル基が好ましく、炭素数4〜6のアルケニル基がより好ましく、ブテニル基又はペンテニル基がさらに好ましく、ブテニル基が特に好ましい。即ち、Rとしては、3−ブテニル基が最も好ましい。
上記一般式(I)において、X及びXはそれぞれ独立してフッ素原子又は水素原子を表し、X及びXの少なくとも一つはフッ素原子を表す。このように、フッ素原子の位置及びアルケニル基の位置が左右対称に存在するようにすることによって、この化合物を含有する液晶組成物のΔnを大きく、かつ、液晶組成物の液晶相下限温度をより低下させることができる。このようなX及びXの組み合わせの中では、X及びXの一方がフッ素原子で、他方が水素原子であることが好ましい。
一般式(I)で表される化合物中、最も好ましいのは、N,N’−ビス[4−(3−ブテニル)−3−フルオロベンジリデン]ヒドラジン及びN,N’−ビス[4−(3−ブテニル)−2−フルオロベンジリデン]ヒドラジンである。
An example of the present invention will be described below.
In the above general formula (I), R represents an alkenyl group having 4 to 12 carbon atoms and a double bond located at the 3rd position or more. When the position of the alkenyl double bond is 2 or less, the stability of the obtained liquid crystal composition is lowered. Among the alkenyl groups in which the position of the double bond is 3 or more, the double bond position is even-odd, and when the double bond exists in the even position, the liquid crystal phase upper limit temperature tends to decrease, Since the viscosity of the composition tends to be high when the number of carbon atoms in is too large, a 3-alkenyl group or a 5-alkenyl group is preferable, and a linear 3-alkenyl group or 5-alkenyl group is more preferable. As the 3-alkenyl group, the viscosity tends to increase if the terminal alkyl group is too long, and therefore 3-butenyl group, 3-pentenyl group, 3-hexenyl group, 3-heptenyl group, 3-octenyl group, etc. Can do. Examples of the 5-alkenyl group include a 5-hexenyl group, a 5-heptenyl group, and a 5-octenyl group. As this alkenyl group, one or more hydrogen atoms contained in these groups may be substituted with a fluorine atom.
Among these alkenyl groups, an alkenyl group having 4 to 8 carbon atoms is preferable, an alkenyl group having 4 to 6 carbon atoms is more preferable, a butenyl group or a pentenyl group is further preferable, and a butenyl group is particularly preferable. That is, as R, a 3-butenyl group is most preferable.
In the general formula (I), X 1 and X 2 each independently represent a fluorine atom or a hydrogen atom, and at least one of X 1 and X 2 represents a fluorine atom. Thus, by making the position of the fluorine atom and the position of the alkenyl group symmetrically, Δn of the liquid crystal composition containing this compound is increased, and the lower limit temperature of the liquid crystal phase of the liquid crystal composition is further increased. Can be reduced. Among combinations of such X 1 and X 2, one of X 1 and X 2 are fluorine atoms, it is preferred the other is hydrogen atom.
Of the compounds represented by the general formula (I), most preferred are N, N′-bis [4- (3-butenyl) -3-fluorobenzylidene] hydrazine and N, N′-bis [4- (3 -Butenyl) -2-fluorobenzylidene] hydrazine.

一般式(I)で表される化合物は以下のようにして製造することができる。即ち、一般式(II)   The compound represented by the general formula (I) can be produced as follows. That is, the general formula (II)

Figure 2005213226
Figure 2005213226

(式中、R、X1、X2は一般式(I)におけると同じ意味を表す。)で表されるベンズアルデヒド誘導体とヒドラジンとを反応させることにより容易に得ることができる。 (Wherein R, X1, and X2 have the same meaning as in formula (I)) and can be easily obtained by reacting the benzaldehyde derivative represented by formula (I) with hydrazine.

ここで原料として用いる一般式(II)のベンズアルデヒド誘導体は、一部については市販されており容易に入手可能であるが、市販されていない誘導体も必要とあれば一般式 (III)   The benzaldehyde derivative of the general formula (II) used as a raw material here is partly commercially available and easily available, but if a non-commercial derivative is necessary, the general formula (III)

Figure 2005213226
Figure 2005213226

(式中、R、X、Xは一般式(I)におけると同じ意味を表し、Halは塩素、臭素又はヨウ素原子を表す。)で表されるハロゲン化ベンゼン誘導体をグリニヤール反応剤又は有機リチウム反応剤のような有機金属反応剤へ導き、次いでN,N−ジメチルホルムアミド(DMF)等のホルミル化剤と反応させることにより容易に得ることができる。 (Wherein R, X 1 and X 2 represent the same meaning as in general formula (I), Hal represents a chlorine, bromine or iodine atom) and a halogenated benzene derivative represented by Grignard reagent or organic It can be easily obtained by leading to an organometallic reactant such as a lithium reactant and then reacting with a formylating agent such as N, N-dimethylformamide (DMF).

本発明の化合物が配合される液晶組成物としては、比較的屈折率異方性(Δn)が高い化合物として、末端にフッ素原子やシアノ基で置換された芳香環を有する1−置換フェニル2−置換シクロヘキシルフェニルアセチレン、2−(4−置換フェニル)−5−置換ピリジン、2−(4−置換フェニル)−5−(4’−置換フェニル)ピリジン、2−(4−置換フェニル)−5−(4’−置換フェニル)ピリミジン、4−置換4’−置換テルフェニル、4−置換ビフェニル4’−置換シクロヘキサン、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等の化合物等を含有する従来の液晶組成物を挙げることができる。また、Δnは比較的低いが、本発明で使用する液晶材料の他の特性、すなわち、等方性液体と液晶の相転移温度、融点、粘度、Δε(誘電率異方性)および透明性固体物質等との溶解性等を改善することを目的として、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−(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等を添加することができる。   The liquid crystal composition containing the compound of the present invention is a compound having a relatively high refractive index anisotropy (Δn), and a 1-substituted phenyl 2- having an aromatic ring substituted with a fluorine atom or a cyano group at the terminal. Substituted cyclohexylphenylacetylene, 2- (4-substituted phenyl) -5-substituted pyridine, 2- (4-substituted phenyl) -5- (4′-substituted phenyl) pyridine, 2- (4-substituted phenyl) -5 Conventional compounds containing compounds such as (4′-substituted phenyl) pyrimidine, 4-substituted 4′-substituted terphenyl, 4-substituted biphenyl 4′-substituted cyclohexane, 4-substituted cyclohexanecarboxylic acid 4′-substituted biphenyl ester, etc. A liquid crystal composition can be mentioned. In addition, although Δn is relatively low, other characteristics of the liquid crystal material used in the present invention, that is, phase transition temperature, melting point, viscosity, Δε (dielectric anisotropy) and transparent solid of isotropic liquid and liquid crystal For the purpose of improving solubility with substances, etc., for example, 4-substituted benzoic acid 4′-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4′-substituted phenyl ester, 4- (4-substituted cyclohexanecarbonyl) Oxy) 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 and the like can be added.

本発明の液晶組成物は、Δnが大きいので、これを用いて高いコントラスト比等を有する液晶表示素子、可変範囲の大きい可変機能デバイスを作成することができ、例えば、直視型液晶表示素子用、可変機能高周波伝送路用として有用である。   Since the liquid crystal composition of the present invention has a large Δn, it can be used to create a liquid crystal display element having a high contrast ratio and the like, and a variable function device having a large variable range. For example, for a direct-view liquid crystal display element, It is useful for variable function high frequency transmission lines.

本発明の液晶表示素子は、例えば、液晶材料と高分子形成性モノマーもしくはオリゴマーと光重合開始剤との均一溶液を、電極層を有する2枚の基板間に狭持させるか、あるいは一方の基板上にスピンコーター等のコーターを使用して塗布し、次いで他方の基板を重ねてもよく、これに紫外線を照射するか、あるいは、熱的に重合硬化させることによって製造することができる。
このようにして製造された本発明の液晶表示素子は、電圧無印加時の白濁性が非常に高く、例えば、従来の光散乱形液晶表示素子と比較して、高散乱性及び高コントラスト比の課題を達成し、直視形表示装置に有用なものである。
The liquid crystal display element of the present invention can be obtained by, for example, sandwiching a uniform solution of a liquid crystal material, a polymer-forming monomer or oligomer, and a photopolymerization initiator between two substrates having an electrode layer, or one substrate. It may be coated by using a coater such as a spin coater and then the other substrate may be overlaid, which can be produced by irradiating it with ultraviolet light or thermally polymerizing and curing.
The liquid crystal display element of the present invention thus produced has very high white turbidity when no voltage is applied. For example, the liquid crystal display element has a high scattering property and a high contrast ratio as compared with a conventional light scattering type liquid crystal display element. The present invention achieves the object and is useful for a direct-view display device.

以下に実施例を用いて本発明をさらに説明する。しかし、本発明はこれらの実施例に限定されるものではない。   The present invention will be further described below using examples. However, the present invention is not limited to these examples.

化合物の構造は、核磁気共鳴スペクトル(NMR)、質量スペクトル(MS)及び赤外吸収スペクトル(IR)により確認し、相転移温度の測定は温度調節ステージを備えた偏光顕微鏡と示差走査熱量計(DSC)を併用して行った。また、組成物における「%」は「質量%」を表す。   The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and infrared absorption spectrum (IR), and the phase transition temperature was measured with a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter ( DSC). Further, “%” in the composition represents “% by mass”.

(実施例1)N,N’−ビス[4−(3−ブテニル)−3−フルオロベンジリデン]ヒドラジン(I−1) Example 1 N, N′-bis [4- (3-butenyl) -3-fluorobenzylidene] hydrazine (I-1)

Figure 2005213226
Figure 2005213226

[4−(3−ブテニル)−1−ブロモ−3−フルオロベンゼンの合成]
窒素雰囲気下で、4−ブロモ−2−フルオロベンジルブロミド50.0g(0.187mol)をテトラヒドロフラン(THF)100mlに加え、10℃以下に冷却しながら激しく攪拌している中に、2.0MアリルマグネシウムクロリドTHF溶液112ml(0.224mol)を、その温度を保ちながら滴下した。滴下終了後さらに1時間攪拌し続けた後、濃塩酸と氷の混合物中に滴下して反応を停止させた。
反応液の有機液層を分離し、水層から2回ヘキサンで抽出し、得られた有機液層を集めて、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗滌し、無水硫酸カルシウムで乾燥した。溶媒を留去し、得られた残渣をカラム(シリカゲル、ヘキサン)を用いて精製して、微黄色液状の4−(3−ブテニル)−1−ブロモ−3−フルオロベンゼン40.3g(0.160mol)を得た。
[Synthesis of 4- (3-butenyl) -1-bromo-3-fluorobenzene]
Under nitrogen atmosphere, 50.0 g (0.187 mol) of 4-bromo-2-fluorobenzyl bromide was added to 100 ml of tetrahydrofuran (THF), and while stirring vigorously while cooling to 10 ° C. or lower, 2.0 M allyl 112 ml (0.224 mol) of magnesium chloride in THF was added dropwise while maintaining the temperature. After completion of the dropwise addition, the mixture was further stirred for 1 hour, and then dropped into a mixture of concentrated hydrochloric acid and ice to stop the reaction.
The organic liquid layer of the reaction solution is separated and extracted twice from the aqueous layer with hexane. The obtained organic liquid layer is collected, washed with a saturated aqueous sodium hydrogen carbonate solution and then with saturated brine, and dried over anhydrous calcium sulfate. did. The solvent was distilled off, and the resulting residue was purified using a column (silica gel, hexane) to give 40.3 g (0. 0.3) of 4- (3-butenyl) -1-bromo-3-fluorobenzene as a slightly yellow liquid. 160 mol) was obtained.

[4−(3−ブテニル)−3−フルオロベンズアルデヒドの合成]
窒素雰囲気下で、マグネシウム4.1g(0.169mol)をTHF20ml中、室温で激しく攪拌している中に、上記で得た4−(3−ブテニル)−1−ブロモ−3−フルオロベンゼン40.3g(0.160mol)のTHF100ml溶液を、溶媒が自発的に還流する速度で滴下した。滴下終了後、さらに2時間加熱還流し続けた後、10℃以下まで冷却し、その温度を保ちながらN,N−ジメチルホルムアミド(DMF)23.4g(0.110mol)を滴下した。滴下終了後2時間加熱還流し続けた後、室温まで冷却し、濃塩酸と氷の混合物中に滴下して反応を停止させた。
反応液の有機液層を分離し、水層から2回ヘキサンで抽出し、得られた有機液層を集めて、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗滌し、無水硫酸カルシウムで乾燥した。溶媒を留去し、得られた残渣をカラム(シリカゲル、ヘキサン)を用いて精製して、微黄色液状の4−(3−ブテニル)−3−フルオロベンズアルデヒド26.0g(0.110mol)を得た。
[Synthesis of 4- (3-butenyl) -3-fluorobenzaldehyde]
In a nitrogen atmosphere, 4.1 g (0.169 mol) of magnesium was stirred vigorously in 20 ml of THF at room temperature, and 4- (3-butenyl) -1-bromo-3-fluorobenzene obtained above was obtained. A solution of 3 g (0.160 mol) of THF in 100 ml was added dropwise at a rate at which the solvent spontaneously refluxed. After completion of the dropwise addition, the mixture was further heated and refluxed for 2 hours, then cooled to 10 ° C. or lower, and 23.4 g (0.110 mol) of N, N-dimethylformamide (DMF) was added dropwise while maintaining the temperature. After completion of the dropwise addition, the mixture was continuously heated to reflux for 2 hours, cooled to room temperature, and dropped into a mixture of concentrated hydrochloric acid and ice to stop the reaction.
The organic liquid layer of the reaction solution is separated and extracted twice from the aqueous layer with hexane. The obtained organic liquid layer is collected, washed with a saturated aqueous sodium hydrogen carbonate solution and then with saturated brine, and dried over anhydrous calcium sulfate. did. The solvent was distilled off, and the resulting residue was purified using a column (silica gel, hexane) to obtain 26.0 g (0.110 mol) of 4- (3-butenyl) -3-fluorobenzaldehyde as a slightly yellow liquid. It was.

{N,N’−ビス[4−(3−ブテニル)−3−フルオロベンジリデン]ヒドラジンの合成}
ドラフト中で、上記で得た4−(3−ブテニル)−3−フルオロベンズアルデヒド26.0g(0.110mol)のジクロロメタン100ml溶液に、抱水ヒドラジン27.5g(0.549mol)を加えた後、室温で1時間攪拌した。次いで、これに3M塩酸(100ml)を滴下した後、40℃で2時間加熱攪拌した。次いで反応液を室温まで冷却し、水を滴下して反応を停止させた。
反応液の有機液層を分離し、水層から3回ジクロロメタンで抽出し、得られた有機液層を集めた後、3M塩酸、水、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗滌し、無水硫酸カルシウムで乾燥した。溶媒を留去し、薄黄色の固体を得た。得られた固体をカラム(シリカゲル、トルエン)を用いて精製し、メタノール/エタノールで再結晶して黄色の結晶9.8g(0.054mol)を得た。得られた黄色結晶がN,N’−ビス[4−(3−ブテニル)−3−フルオロベンジリデン]ヒドラジンであることは下記のNMRの化学シフトで確認した。
1H−NMR(400MHz、CDCl3)δ(ppm):2.39(q、2H),2.79(t,2H),4.99−5.07(m,2H),5.80−5.90(m、1H),7.48−7.57(m、3H),8.58(s,1H)
GCで確認した純度は96.7%、相転移温度(℃)は Cry 41 N 50 Iso であった。
{Synthesis of N, N'-bis [4- (3-butenyl) -3-fluorobenzylidene] hydrazine}
In a draft, 27.5 g (0.549 mol) of hydrazine hydrate was added to a solution of 26.0 g (0.110 mol) of 4- (3-butenyl) -3-fluorobenzaldehyde obtained above in 100 ml of dichloromethane, Stir at room temperature for 1 hour. Next, 3M hydrochloric acid (100 ml) was added dropwise thereto, followed by stirring with heating at 40 ° C. for 2 hours. Next, the reaction solution was cooled to room temperature, and water was added dropwise to stop the reaction.
The organic liquid layer of the reaction solution was separated, extracted from the aqueous layer with dichloromethane three times, and the resulting organic liquid layer was collected, and then washed with 3M hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order. And dried over anhydrous calcium sulfate. The solvent was distilled off to obtain a pale yellow solid. The obtained solid was purified using a column (silica gel, toluene) and recrystallized from methanol / ethanol to obtain 9.8 g (0.054 mol) of yellow crystals. It was confirmed by the following NMR chemical shift that the obtained yellow crystals were N, N′-bis [4- (3-butenyl) -3-fluorobenzylidene] hydrazine.
1H-NMR (400 MHz, CDCl3) δ (ppm): 2.39 (q, 2H), 2.79 (t, 2H), 4.99-5.07 (m, 2H), 5.80-5. 90 (m, 1H), 7.48-7.57 (m, 3H), 8.58 (s, 1H)
The purity confirmed by GC was 96.7%, and the phase transition temperature (° C.) was Cry 41 N 50 Iso.

(実施例2)N,N’−ビス[4−(3−ブテニル)−2−フルオロベンジリデン]ヒドラジン(I−2) Example 2 N, N'-bis [4- (3-butenyl) -2-fluorobenzylidene] hydrazine (I-2)

Figure 2005213226
Figure 2005213226

[3−(3−ブテニル)−1−フルオロベンゼンの合成]
窒素雰囲気下において、3−フルオロベンジルブロミド50.0g(0.265mol)をTHF100mlに加え、10℃以下に冷却しながら激しく攪拌している中に2.0MアリルマグネシウムクロリドTHF溶液160ml(0.320mol)を、その温度を保ちながら滴下した。滴下終了後さらに1時間攪拌し続けた後、濃塩酸と氷の混合物中に滴下して反応を停止させた。
反応液の有機液層を分離し、水層から2回ヘキサンで抽出し、得られた有機液層を集めて、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗滌し、無水硫酸カルシウムで乾燥した。溶媒を留去し、減圧蒸留(96〜106℃、5.0kPa)することにより、微黄色液状の3−(3−ブテニル)−1−フルオロベンゼン36.2g(0.222mol)を得た。
[Synthesis of 3- (3-butenyl) -1-fluorobenzene]
Under a nitrogen atmosphere, 50.0 g (0.265 mol) of 3-fluorobenzyl bromide was added to 100 ml of THF, and 160 ml (0.320 mol) of a 2.0 M allylmagnesium chloride THF solution was vigorously stirred while cooling to 10 ° C. or lower. ) Was added dropwise while maintaining the temperature. After completion of the dropwise addition, the mixture was further stirred for 1 hour, and then dropped into a mixture of concentrated hydrochloric acid and ice to stop the reaction.
The organic liquid layer of the reaction solution is separated and extracted twice from the aqueous layer with hexane. The obtained organic liquid layer is collected, washed with a saturated aqueous sodium hydrogen carbonate solution and then with saturated brine, and dried over anhydrous calcium sulfate. did. The solvent was distilled off and vacuum distillation (96 to 106 ° C., 5.0 kPa) was performed to obtain 36.2 g (0.222 mol) of 3- (3-butenyl) -1-fluorobenzene as a slightly yellow liquid.

[4−(3−ブテニル)−2−フルオロベンズアルデヒドの合成]
窒素雰囲気下において、t−ブトキシカリウム12.6g(0.112mol)をTHF100ml中で−60℃以下に冷却しながら激しく攪拌している中に、その温度を保ちながら上記で得た3−(3−ブテニル)−1−フルオロベンゼン36.2g(0.222mol)をTHF50mlに溶解した溶液を滴下した。滴下終了後、さらに5分間攪拌した後、その温度を保ちながら反応液に2.44Mブチルリチウムヘキサン溶液100ml(0.244mol)滴下した。滴下終了後、1時間攪拌を続けた後、その温度を保ちながら、反応液にDMF33.0g(0.451mol)を滴下した。冷却を止めて放置して液温を室温にまで戻した後、1時間攪拌し、これを濃塩酸と氷の混合物中に滴下して反応を停止させた。
反応液の有機層を分離し、水層から2回酢酸エチルで抽出した。得られた有機液層を集めて、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗滌し、無水硫酸カルシウムで乾燥した。溶媒を留去し、得られた残渣をカラム(シリカゲル、ヘキサン/酢酸エチル)を用いて精製し、さらに減圧蒸留(140〜160℃、2.5〜3.0kPa)することにより、黄色液状の4−(3−ブテニル)−2−フルオロベンズアルデヒド19.5g(0.090mol)を得た。
[Synthesis of 4- (3-butenyl) -2-fluorobenzaldehyde]
In a nitrogen atmosphere, while 12.6 g (0.112 mol) of t-butoxypotassium was vigorously stirred in 100 ml of THF while being cooled to −60 ° C. or lower, the above obtained 3- (3 -Butenyl) -1-fluorobenzene 36.2 g (0.222 mol) dissolved in 50 ml of THF was added dropwise. After completion of the dropwise addition, the mixture was further stirred for 5 minutes, and then 100 ml (0.244 mol) of a 2.44 M butyllithium hexane solution was added dropwise to the reaction solution while maintaining the temperature. After completion of the dropwise addition, stirring was continued for 1 hour, and then 33.0 g (0.451 mol) of DMF was added dropwise to the reaction solution while maintaining the temperature. The cooling was stopped and the solution was allowed to return to room temperature. After stirring for 1 hour, this was dropped into a mixture of concentrated hydrochloric acid and ice to stop the reaction.
The organic layer of the reaction solution was separated and extracted twice from the aqueous layer with ethyl acetate. The obtained organic liquid layers were collected, washed in order with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous calcium sulfate. The solvent was distilled off, and the resulting residue was purified using a column (silica gel, hexane / ethyl acetate), and further distilled under reduced pressure (140 to 160 ° C., 2.5 to 3.0 kPa). 19.5 g (0.090 mol) of 4- (3-butenyl) -2-fluorobenzaldehyde was obtained.

{N,N’−ビス[4−(3−ブテニル)−2−フルオロベンジリデン]ヒドラジンの合成}
ドラフト中で、上記で得た4−(3−ブテニル)−2−フルオロベンズアルデヒド19.5g(0.090mol)のジクロロメタン100ml溶液に、抱水ヒドラジン22.4g(0.447mol)を加えた後、室温で5分間攪拌した。次いで、これに3M塩酸(50ml)を滴下した後、40℃で3時間加熱攪拌した。次いで反応液を室温まで冷却し、水を滴下して反応を停止させた。
反応液の有機液層を分離し、水層から3回ジクロロメタンで抽出し、得られた有機液層を集めた後、3M塩酸、水、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗滌し、無水硫酸カルシウムで乾燥した。溶媒を留去し、薄黄色の固体を得た。得られた固体をカラム(シリカゲル、トルエン)を用いて精製し、メタノール/エタノールで再結晶して黄色の結晶9.9g(0.055mol)を得た。得られた黄色結晶がN,N’−ビス[4−(3−ブテニル)−2−フルオロベンジリデン]ヒドラジンであることは下記のNMRの化学シフトで確認した。
1H−NMR(400MHz、CDCl3)δ(ppm):2.40(q、2H),2.76(t,2H),5.00−5.07(m,2H),5.78−5.89(m、1H),6.96(d、1H,J=11.2Hz)7.05(d、1H,J=8.0Hz),8.02(t、1H,J=7.6Hz),8.90(s,1H)
GCで確認した純度は97.6%、相転移温度(℃)は Cry 53 N 57 Iso であった。
{Synthesis of N, N'-bis [4- (3-butenyl) -2-fluorobenzylidene] hydrazine}
In a draft, 22.4 g (0.447 mol) of hydrazine hydrate was added to a solution of 19.5 g (0.090 mol) of 4- (3-butenyl) -2-fluorobenzaldehyde obtained above in 100 ml of dichloromethane, Stir at room temperature for 5 minutes. Next, 3M hydrochloric acid (50 ml) was added dropwise thereto, followed by stirring with heating at 40 ° C. for 3 hours. Next, the reaction solution was cooled to room temperature, and water was added dropwise to stop the reaction.
The organic liquid layer of the reaction solution was separated, extracted from the aqueous layer with dichloromethane three times, and the resulting organic liquid layer was collected, and then washed with 3M hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order. And dried over anhydrous calcium sulfate. The solvent was distilled off to obtain a pale yellow solid. The obtained solid was purified using a column (silica gel, toluene) and recrystallized from methanol / ethanol to obtain 9.9 g (0.055 mol) of yellow crystals. It was confirmed by the following NMR chemical shift that the obtained yellow crystals were N, N′-bis [4- (3-butenyl) -2-fluorobenzylidene] hydrazine.
1H-NMR (400 MHz, CDCl3) δ (ppm): 2.40 (q, 2H), 2.76 (t, 2H), 5.00-5.07 (m, 2H), 5.78-5. 89 (m, 1H), 6.96 (d, 1H, J = 11.2 Hz) 7.05 (d, 1H, J = 8.0 Hz), 8.02 (t, 1H, J = 7.6 Hz) , 8.90 (s, 1H)
The purity confirmed by GC was 97.6%, and the phase transition temperature (° C.) was Cry 53 N 57 Iso.

(実施例3、4) 実施例1で得られたN,N’−ビス[4−(3−ブテニル)−3−フルオロベンジリデン]ヒドラジン(I−1)を用い、表1に記載の液晶化合物を混合して液晶組成物を得た。得られた液晶組成物のネマチック相上限温度(Tni)及び屈折率異方性(Δn)を表1に示す。 Examples 3 and 4 Using the N, N′-bis [4- (3-butenyl) -3-fluorobenzylidene] hydrazine (I-1) obtained in Example 1, liquid crystal compounds described in Table 1 Were mixed to obtain a liquid crystal composition. Table 1 shows the nematic phase upper limit temperature (T ni ) and refractive index anisotropy (Δn) of the obtained liquid crystal composition.

Figure 2005213226
Figure 2005213226

表1において、5−Ph−Ph−CNは下記式の化合物を示し、   In Table 1, 5-Ph-Ph-CN represents a compound of the following formula:

Figure 2005213226
Figure 2005213226

4−Ph−Ma−Ph−CNは下記式の化合物を示し、 4-Ph-Ma-Ph-CN represents a compound of the following formula:

Figure 2005213226
Figure 2005213226

3−Ph1−Ph−Ph−CNは下記式の化合物を示し、   3-Ph1-Ph-Ph-CN represents a compound of the following formula:

Figure 2005213226
Figure 2005213226

3−Ph1−Ph−T−Ph1−Fは下記式の化合物を示し、 3-Ph1-Ph-T-Ph1-F represents a compound of the following formula:

Figure 2005213226
Figure 2005213226

3−Ph1−Ph−T−Ph3−Fは下記式の化合物を示し、 3-Ph1-Ph-T-Ph3-F represents a compound of the following formula:

Figure 2005213226
Figure 2005213226

5−Cy−Ph−Ph−CNは下記式の化合物を示す。 5-Cy-Ph-Ph-CN represents a compound of the following formula.

Figure 2005213226
Figure 2005213226

表1の実施例3、4から、本発明の化合物を含有する液晶組成物は、この化合物を含有しない代わりに5−Ph−Ph−CNを増量した液晶組成物(比較例1)に比べてΔnが高くなっていることがわかる。又、ネマチック相上限温度も高くなり、液晶として使用できる温度範囲が拡大していることがわかる。   From Examples 3 and 4 of Table 1, the liquid crystal composition containing the compound of the present invention was compared with the liquid crystal composition (Comparative Example 1) in which 5-Ph-Ph-CN was increased instead of containing this compound. It can be seen that Δn is high. Moreover, it turns out that the upper limit temperature of a nematic phase also becomes high and the temperature range which can be used as a liquid crystal has expanded.

本発明の化合物は従来の液晶組成物に添加して、その屈折率異方性を高めることができ、高コントラスト比の液晶組成物とすることができ、広告板などの装飾表示板や時計、電卓の表示装置等の直視型表示装置用の液晶に有用である。

The compound of the present invention can be added to a conventional liquid crystal composition to increase its refractive index anisotropy, and can be a liquid crystal composition having a high contrast ratio. It is useful for liquid crystals for direct-view display devices such as calculator display devices.

Claims (5)

一般式(I)
Figure 2005213226
(式中、Rは炭素数4〜12で二重結合の位置が3位以上であるアルケニル基を表し、X及びXはそれぞれ独立してフッ素原子又は水素原子を表し、但し、X及びXの少なくとも一つはフッ素原子を表す。)で表される化合物。
Formula (I)
Figure 2005213226
(In the formula, R represents an alkenyl group having 4 to 12 carbon atoms and a double bond at the 3-position or more, and X 1 and X 2 each independently represent a fluorine atom or a hydrogen atom, provided that X 1 And at least one of X 2 represents a fluorine atom).
一般式(I)において、Rが3−アルケニル基を表す請求項1記載の化合物。   The compound according to claim 1, wherein in formula (I), R represents a 3-alkenyl group. 一般式(I)において、X又はXが水素原子を表す請求項1又は2記載の化合物。 The compound according to claim 1 or 2, wherein in the general formula (I), X 1 or X 2 represents a hydrogen atom. 請求項1〜3のいずれか1項に記載の化合物を含有する液晶組成物。   The liquid crystal composition containing the compound of any one of Claims 1-3. 請求項4記載の液晶組成物を用いた液晶表示素子。

A liquid crystal display device using the liquid crystal composition according to claim 4.

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