JPH0585971A - Compound having 1,1-difluoroethane link and liquid crystal composition containing the compound - Google Patents
Compound having 1,1-difluoroethane link and liquid crystal composition containing the compoundInfo
- Publication number
- JPH0585971A JPH0585971A JP22316791A JP22316791A JPH0585971A JP H0585971 A JPH0585971 A JP H0585971A JP 22316791 A JP22316791 A JP 22316791A JP 22316791 A JP22316791 A JP 22316791A JP H0585971 A JPH0585971 A JP H0585971A
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- Prior art keywords
- liquid crystal
- compound
- formula
- octyloxyphenyl
- crystal composition
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は電気光学的液晶表示材料
として有用な1,1−ジフルオロエタン結合を有する化
合物に関する。TECHNICAL FIELD The present invention relates to a compound having a 1,1-difluoroethane bond which is useful as an electro-optical liquid crystal display material.
【0002】[0002]
【従来の技術】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、ワープロ、電子
手帳、プリンター、コンピューター、テレビ等に用いら
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(捩れネマチック)型、STN(超捩
れネマチック)型、DS(動的光散乱)型、GH(ゲス
ト・ホスト)型あるいはFLC(強誘電性液晶)等が知
られているが、このうち現在最もよく用いられているの
はTN型及びSTN型である。2. Description of the Related Art Liquid crystal display devices have come to be used in watches, calculators, various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions and the like. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, and FLC (ferroelectric liquid crystal). ) And the like are known, of which the TN type and the STN type are most widely used at present.
【0003】これらの表示方式に用いられる液晶材料と
しては、これまでに多数の化合物が合成され、知られて
いる。しかしながら、これらの表示方式や用途に応じた
種々の要求特性を、単独で満足するような化合物は知ら
れておらず、その要求特性に応じて多数の化合物を混合
し、液晶組成物として用いられているのが実状である。
そのため、ある特定の優れた性質を有する液晶化合物の
開発も、非常に重要である。A large number of compounds have been synthesized and known as liquid crystal materials used in these display systems. However, a compound that alone satisfies various required properties according to these display systems and applications is not known, and a large number of compounds are mixed according to the required properties and used as a liquid crystal composition. It is the actual situation.
Therefore, development of a liquid crystal compound having a certain excellent property is also very important.
【0004】液晶化合物は通常、その基本骨格として、
2個あるいは3個以上の環構造(1,4−フェニレン基
やその置換体、1,4−シクロヘキシレン基、あるいは
ピリジン−2,5−ジイル基、ピリミジン−2,5−ジイ
ル基、1,3−ジオキサン−2,5−ジイル基等)が、直
結あるいは連結基を介して結合した構造を有している。
連結基としては、エステル結合(−COO−)、オキシメ
チレン結合(−OCH2−)、アセチレン結合(−C≡C
−)、エタン結合(−CH2CH2−)等がよく用いられて
いる。このうち、エタン結合を有する化合物は低粘性で
あり、他にも優れた特性を示す化合物が得られるので、
特によく用いられている。A liquid crystal compound usually has, as its basic skeleton,
Two or three or more ring structures (1,4-phenylene group or its substitution product, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, etc.) has a structure in which it is bound directly or via a linking group.
The linking group, ester bond (-COO-), oxymethylene bond (-OCH 2 -), an acetylene bond (-C≡C
-), ethane bond (-CH 2 CH 2 -) and the like are often used. Of these, compounds having an ethane bond have low viscosity, and other compounds exhibiting excellent properties can be obtained.
Especially well used.
【0005】最近では、フッ素を含有する連結基とし
て、−OCF2−、−SCF2−、あるいは−COCF2
−を有する化合物(特開平2−289529号公報)、
あるいは−CF=CF−を有する化合物(特開平3−4
1037号公報)が報告され、興味ある特性を示すこと
が知られるようになった。しかしながら、上記のエタン
結合にフッ素を導入した連結基を有する化合物は、その
物性に興味がもたれるにもかかわらず、その合成が困難
であったこともあり、これまで知られていなかった。[0005] Recently, as a linking group containing fluorine, -OCF 2 -, - SCF 2 -, or -COCF 2
A compound having-(JP-A-2-289529),
Alternatively, a compound having -CF = CF- (Japanese Patent Laid-Open No. 3-4
No. 1037 gazette) has been reported, and it has become known to exhibit interesting characteristics. However, the compound having a linking group in which fluorine is introduced into the ethane bond has not been known so far because it is difficult to synthesize the compound, although its physical properties are interesting.
【0006】[0006]
【発明が解決しようとする課題】液晶材料に要求される
種々の特性のうち、複屈折異方性(Δn)は非常に重要
な特性である。ディスプレイの大容量化にともなって、
マルチプレックス駆動が必要となってきており、そのた
めには視覚範囲が広くなければならない。そのために、
Δnの小さい化合物が必要とされている。Among various characteristics required of liquid crystal materials, birefringence anisotropy (Δn) is a very important characteristic. With the increase in display capacity,
Multiplex drive is becoming necessary, which requires a wide visual range. for that reason,
There is a need for compounds with small Δn.
【0007】又、現在の液晶表示素子の大きな欠点は、
その応答が非常に遅いということである。この欠点を改
良し、μ秒台の高速応答が可能となる表示方式として、
前記の強誘電性液晶を用いる方式が報告され、開発が進
めれている。強誘電性液晶は、通常、アキラルな化合物
から成り、SC相を示す母体液晶に、光学活性化合物を
ドーパントとして添加することにより調製されている。
また、その温度範囲を高温域に拡大するためには、母体
液晶の構成材料として、3環式の化合物を用いることが
できるが、その応答性を悪化させることなく温度範囲を
拡大できるような化合物はほとんど知られていなかっ
た。本発明が解決しようとする課題は、Δnが小さく、
低粘性であり、母体液晶に添加した場合に液晶組成物の
温度範囲を拡大することができるような化合物を提供す
ることにある。Further, a major drawback of the current liquid crystal display element is that
The response is very slow. As a display method that improves this defect and enables high-speed response in the microsecond range,
A method using the above-mentioned ferroelectric liquid crystal has been reported and is being developed. Ferroelectric liquid crystals are usually composed of achiral compounds and are prepared by adding an optically active compound as a dopant to a host liquid crystal exhibiting an SC phase.
Further, in order to extend the temperature range to a high temperature range, a tricyclic compound can be used as a constituent material of the host liquid crystal, but a compound capable of extending the temperature range without deteriorating its responsiveness. Was little known. The problem to be solved by the present invention is that Δn is small,
It is an object of the present invention to provide a compound having a low viscosity and capable of expanding the temperature range of a liquid crystal composition when added to a host liquid crystal.
【0008】[0008]
【課題を解決するための手段】本発明は、上記課題を解
決するために、一般式(I)In order to solve the above-mentioned problems, the present invention has the general formula (I)
【0009】[0009]
【化2】 [Chemical 2]
【0010】(式中、R1 及びR2 はそれぞれ独立的
に、炭素原子数1〜16のアルキル基又はアルコキシル
基を表わすが、特に直鎖状の基が好ましい。特にネマチ
ック液晶用としては炭素原子数1〜8のアルキル基又は
アルコキシル基が好ましく、強誘電性液晶用としては炭
素原子数6〜16のアルキル基又はアルコキシル基が好
ましい。環Aは1,4−フェニレン基又はトランス−1,
4−シクロヘキシレン基を表わす。mは0又は1を表わ
し、nは1又は2を表わすが、特にm+nが1又は2で
あることが好ましい。)で表わされる化合物を提供す
る。(In the formula, R 1 and R 2 each independently represent an alkyl group or an alkoxyl group having 1 to 16 carbon atoms, and a linear group is particularly preferable. Particularly for nematic liquid crystal, carbon is preferable. An alkyl group or an alkoxyl group having 1 to 8 atoms is preferable, and an alkyl group or an alkoxyl group having 6 to 16 carbon atoms is preferable for a ferroelectric liquid crystal. Ring A is 1,4-phenylene group or trans-1,
Represents a 4-cyclohexylene group. m represents 0 or 1, n represents 1 or 2, and it is particularly preferable that m + n is 1 or 2. ) Is provided.
【0011】本発明の一般式(I)で表わされる化合物
は、例えば、次の製造方法に従っ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) of the present invention can be produced, for example, according to the following production method. That is, the general formula (II)
【0012】[0012]
【化3】 [Chemical 3]
【0013】(式中、R1、環A及びmは一般式(I)
におけると同じ意味を有する。)で表わされるジチアン
誘導体を、強塩基存在下に、一般式(III)(Wherein R 1 , the rings A and m are represented by the general formula (I)
Has the same meaning as in. ) In the presence of a strong base, a dithiane derivative represented by the general formula (III)
【0014】[0014]
【化4】 [Chemical 4]
【0015】(式中、R2 及びnは一般式(I)におけ
ると同じ意味を有し、Xは塩素、臭素又はヨウ素原子を
表わす。)で表わされるベンジルハライド誘導体と反応
させることにより、一般式(IV)(Wherein R 2 and n have the same meanings as in the general formula (I), and X represents a chlorine, bromine or iodine atom), and a benzyl halide derivative represented by the general formula (I) Formula (IV)
【0016】[0016]
【化5】 [Chemical 5]
【0017】(式中、R1 ,R2 ,環A,m及びnは一
般式(I)におけると同じ意味を有する。)で表わされ
る中間体を製造する。これを、N−ヨードこはく酸イミ
ド(NIS)、N−ブロモこはく酸イミド(NBS)等
の酸化剤存在下に、テトラブチルアンモニウムジヒドロ
トリフルオリド等のフッ素化剤と反応させることによ
り、一般式(I)で表わされる化合物を得ることができ
る。An intermediate represented by the formula: wherein R 1 , R 2 , rings A, m and n have the same meaning as in formula (I) is prepared. By reacting this with a fluorinating agent such as tetrabutylammonium dihydrotrifluoride in the presence of an oxidizing agent such as N-iodosuccinimide (NIS) or N-bromosuccinimide (NBS), the general formula ( A compound of formula I) can be obtained.
【0018】斯くして製造された一般式(I)で表わさ
れる化合物の代表的なものの例を第1表に掲げる。Typical examples of the compounds represented by the general formula (I) thus produced are shown in Table 1.
【0019】[0019]
【表1】 [Table 1]
【0020】(第1表中、Crは結晶相を、SBはスメ
クチックB相を、Iは等方性液体相をそれぞれ表わ
す。)(In Table 1, Cr represents a crystalline phase, SB represents a smectic B phase, and I represents an isotropic liquid phase.)
【0021】本発明の一般式(I)で表わされる化合物
は、ネマチック相は示さないが、例えば、正又は負の誘
電率異方性を有する他のネマチック液晶化合物との組成
物の状態で、TN型あるいはSTN型といった電界効果
型表示セルの材料として、組成物のΔnを小さくする目
的に使用することができる。この場合には、一般式
(I)におけるR1 及びR2 が、炭素原子数8以下のア
ルキル基であることが好ましい。The compound represented by the general formula (I) of the present invention does not exhibit a nematic phase, but, for example, in the state of composition with another nematic liquid crystal compound having a positive or negative dielectric anisotropy, It can be used as a material of a field effect display cell such as a TN type or an STN type for the purpose of reducing Δn of the composition. In this case, R 1 and R 2 in the general formula (I) are preferably an alkyl group having 8 or less carbon atoms.
【0022】このように、一般式(I)で表わされる化
合物と混合して使用することのできるネマチック液晶化
合物の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、4,4′−置換ビフェニル、1−(4
−置換フェニル)−4−置換シクロヘキサン、4,4″
−置換ターフェニル、1−(4′−置換ビフェニリル)
−4−置換シクロヘキサン、2−(4−置換フェニル)
−5−置換ピリミジン等を挙げることができる。As described above, preferred examples of the nematic liquid crystal compound which can be used by mixing with the compound represented by the general formula (I) are, for example, 4-substituted benzoic acid 4-substituted phenyl ester and 4-substituted benzoic acid 4-substituted phenyl ester. 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, 4,4′-substituted biphenyl, 1- (4
-Substituted phenyl) -4-substituted cyclohexane, 4,4 "
-Substituted terphenyl, 1- (4'-substituted biphenylyl)
-4-Substituted cyclohexane, 2- (4-substituted phenyl)
-5-substituted pyrimidine etc. can be mentioned.
【0023】後述の実施例5にも示したように、粘性に
優れたネマチック液晶材料として現在汎用されているAs shown in Example 5 described later, it is currently widely used as a nematic liquid crystal material having excellent viscosity.
【0024】[0024]
【化6】 [Chemical 6]
【0025】(上記式中、シクロヘキサン環はトランス
配置を表わす。)から成る母体液晶(A)の20℃にお
けるΔnは0.117であった。これに対し、母体液晶
(A)90重量%及び、第1表に示した一般式(I)で
表わされるNo.3の化合物10重量%から成る混合液
晶(M)について、同様に測定したΔnは0.077と
非常に小さくなった。この結果から、一般式(I)で表
わされる化合物は、母体液晶(A)に少量添加すること
により、母体液晶のΔnを効果的に小さくしていること
が明らかである。The Δn at 20 ° C. of the host liquid crystal (A) consisting of (in the above formula, the cyclohexane ring represents the trans configuration) was 0.117. On the other hand, a mixed liquid crystal (M) comprising 90% by weight of the host liquid crystal (A) and 10% by weight of the compound of No. 3 represented by the general formula (I) shown in Table 1 was similarly measured for Δn. Was very small at 0.077. From this result, it is clear that the compound represented by the general formula (I) effectively reduces the Δn of the base liquid crystal by adding a small amount to the base liquid crystal (A).
【0026】更に、本発明の一般式(I)で表わされる
化合物は強誘電性液晶における母体液晶の構成成分とし
ても使用できる。この場合、一般式(I)において、R
1 及びR2 が炭素原子数6以上のアルキル基であること
が好ましい。後述の実施例6にも示したように、Further, the compound represented by the general formula (I) of the present invention can also be used as a constituent component of the matrix liquid crystal in the ferroelectric liquid crystal. In this case, in the general formula (I), R
It is preferable that 1 and R 2 are alkyl groups having 6 or more carbon atoms. As shown in Example 6 below,
【0027】[0027]
【化7】 [Chemical 7]
【0028】から成り、SC(スメクチックC)相を示
す母体液晶(B)84重量%及びAnd 84% by weight of a base liquid crystal (B), which is composed of an SC (smectic C) phase and is composed of
【0029】[0029]
【化8】 [Chemical 8]
【0030】からなるキラルドーパント(P)16重量
%から成る強誘電性液晶組成物(F−1)は、66.5
℃以下で強誘電性を示すSC*(キラルスメクチック
C)相を示し、その25℃における電気光学的応答速度
は46μ秒であった。A ferroelectric liquid crystal composition (F-1) containing 16% by weight of a chiral dopant (P) is 66.5%.
It showed an SC * (chiral smectic C) phase showing ferroelectricity at a temperature of not higher than 0 ° C., and its electro-optical response speed at 25 ° C. was 46 μsec.
【0031】これに対し、母体液晶(B)90重量%及
び、本発明の第1表中の、No.1の化合物10重量%
から成る母体液晶(C)を調製し、この母体液晶(C)
84重量%及び前記のキラルドーパンド(P)16重量
%から成る強誘電性液晶組成物(F−2)を得た。この
(F−2)のSC*相の上限温度は、68.5℃と2℃も
上昇したにもかかわらず、その25℃における電気光学
的応答速度は47μ秒とほとんど変化がなかった。以上
より、一般式(I)で表わされる化合物が液晶組成物の
応答速度を遅くすることなく、その駆動温度範囲を高温
域に拡大し得ることが理解できる。On the other hand, 90% by weight of the base liquid crystal (B) and 10% by weight of the compound No. 1 in Table 1 of the present invention.
A matrix liquid crystal (C) consisting of
A ferroelectric liquid crystal composition (F-2) consisting of 84% by weight and 16% by weight of the chiral dopant (P) was obtained. Although the upper limit temperature of the SC * phase of this (F-2) increased by 68.5 ° C. and 2 ° C., the electro-optical response speed at 25 ° C. was 47 μsec, which was almost unchanged. From the above, it can be understood that the compound represented by the general formula (I) can extend the driving temperature range to a high temperature range without slowing the response speed of the liquid crystal composition.
【0032】[0032]
【実施例】以下に本発明の実施例を示し、本発明を更に
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。EXAMPLES The present invention will be further described below by showing Examples of the present invention. However, the present invention is not limited to these examples.
【0033】尚、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及び示差走査熱量計(DSC)を併
用して行った。又、化合物の構造は、NMR、IR、M
S及び元素分析により確認した。IRにおける(nea
t)は液膜による測定を、(KBr)は錠剤成形による
測定を表わす。NMRにおけるCDCl3 は溶媒を表わ
し、sは1重線、dは2重線、tは3重線、quint
etは5重線、sextetは6重線、mは多重線を表
わし、また、例えば、dtは2重の3重線を表わし、b
roadは幅広い吸収を表わす。MSにおけるM+は親
ピークを表わし、( )内の数値はそのピークの相対
強度を表わすが、traceは相対強度が1以下である
ことを表わす。組成物中における「%」は全て「重量
%」を表わす。The phase transition temperature was measured by using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC). The structures of the compounds are NMR, IR, M
Confirmed by S and elemental analysis. (Nea in IR
t) represents the measurement by the liquid film, and (KBr) represents the measurement by the tablet molding. CDCl 3 in NMR represents a solvent, s is a singlet, d is a doublet, t is a triplet, and quint.
et represents a quintet, sext represents a 6t, m represents a multiplet, and, for example, dt represents a doublet triplet, and b.
road represents broad absorption. M + in MS represents a parent peak, and the numerical value in parentheses represents the relative intensity of the peak, while trace represents that the relative intensity is 1 or less. All "%" in the composition represent "% by weight".
【0034】(実施例1) 1,1−ジフルオロ−2−
(4−オクチルオキシフェニル)−1−[4−(4−オ
クチルオキシフェニル)フェニル]エタン(第1表中、
No.1の化合物)の合成Example 1 1,1-difluoro-2-
(4-octyloxyphenyl) -1- [4- (4-octyloxyphenyl) phenyl] ethane (in Table 1,
No. 1 compound) synthesis
【0035】(1−a) 2−[4−(4−オクチルオ
キシフェニル)フェニル]−1,3−ジチアンの合成(1-a) Synthesis of 2- [4- (4-octyloxyphenyl) phenyl] -1,3-dithiane
【0036】[0036]
【化9】 [Chemical 9]
【0037】4−(4−オクチルオキシフェニル)ベン
ズアルデヒド2.3g(10ミリモル)、プロパンジチ
オール1g(10ミリモル)及びポリリン酸トリメチル
シリルエステル(PPSE)ジクロロメタン溶液20ml
(有機合成化学協会誌、43,1164(1985))
を室温で30分間攪拌した。反応終了後、飽和炭酸水素
ナトリウム水溶液50mlを加え、反応生成物をエーテル
100ml、酢酸エチル100ml、ジクロロメタン100
mlで順次抽出した。抽出液を濃縮した後、得られた残渣
をヘキサン/エーテル(5/1)混合溶媒から再結晶さ
せて、2−[4−(4−オクチルオキシフェニル)フェ
ニル]−1,3−ジチアン2.7g(収率91%)を得
た。2.3 g (10 mmol) of 4- (4-octyloxyphenyl) benzaldehyde, 1 g (10 mmol) of propanedithiol and 20 ml of a solution of trimethylsilyl polyphosphoric acid (PPSE) in dichloromethane.
(Journal of Synthetic Organic Chemistry, 43, 1164 (1985))
Was stirred at room temperature for 30 minutes. After completion of the reaction, 50 ml of saturated aqueous sodium hydrogen carbonate solution was added, and the reaction product was mixed with 100 ml of ether, 100 ml of ethyl acetate and 100 ml of dichloromethane.
Extracted sequentially with ml. After the extract was concentrated, the obtained residue was recrystallized from a hexane / ether (5/1) mixed solvent to give 2- [4- (4-octyloxyphenyl) phenyl] -1,3-dithiane 2. 7 g (yield 91%) was obtained.
【0038】無色板状晶 融点 141℃ IR(KBr) 2940,2870,1610,15
00,1470,1290,1280,1250,12
05,1180,830,815,770cm-1 1H N
MR(CDCl3) δ 0.89(t,J=7.0H
z,3H),1.2〜1.4(m,8H),1.4〜1.5
(m,2H),1.80(quintet,J=6.6H
z,2H),1.9〜2.0(m,1H),2.18(m
d,J=14Hz,1H),2.93(dt,J=13.
5and3.3Hz,2H),3.08(td,J=1
3.5and2.4Hz,2H),3.99(t,J=6.
6Hz,2H),5.20(s,1H),6.95(d,
J=8.8Hz,2H),7.49(d,J=8.8H
z,2H),7.51(s,4H) MS m/z 402(M+ +2,12),401(M
++1,26),400(M+ ,92),326(8
0),214(100),213(43),57(2
0),43(43),41(35),29(22) 元素分析:C24H32OS2 として 計算値:C,71.95%;H,8.05%;S,16.
01% 実測値:C,71.81%;H,8.18%;S,16.
06%Colorless plate-like crystal Melting point 141 ° C. IR (KBr) 2940,2870,1610,15
00, 1470, 1290, 1280, 1250, 12
05,1180,830,815,770cm -1 1 H N
MR (CDCl 3 ) δ 0.89 (t, J = 7.0H
z, 3H), 1.2-1.4 (m, 8H), 1.4-1.5
(M, 2H), 1.80 (quintet, J = 6.6H
z, 2H), 1.9 to 2.0 (m, 1H), 2.18 (m
d, J = 14 Hz, 1H), 2.93 (dt, J = 13.
5 and 3.3 Hz, 2 H), 3.08 (td, J = 1
3.5 and 2.4 Hz, 2H), 3.99 (t, J = 6.
6Hz, 2H), 5.20 (s, 1H), 6.95 (d,
J = 8.8Hz, 2H), 7.49 (d, J = 8.8H
z, 2H), 7.51 (s, 4H) MS m / z 402 (M + +2, 12), 401 (M
+ +1,26), 400 (M + , 92), 326 (8
0), 214 (100), 213 (43), 57 (2
0), 43 (43), 41 (35), 29 (22) Elemental analysis: C 24 H 32 OS 2 Calculated: C, 71.95%; H, 8.05%; S, 16.
01% Found: C, 71.81%; H, 8.18%; S, 16.
06%
【0039】(1−b) 2−[(4−オクチルオキシ
フェニル)メチル]−2−[4−(4−オクチルオキシ
フェニル)フェニル]−1,3−ジチアンの合成(1-b) Synthesis of 2-[(4-octyloxyphenyl) methyl] -2- [4- (4-octyloxyphenyl) phenyl] -1,3-dithiane
【0040】[0040]
【化10】 [Chemical 10]
【0041】2−[4−(4−オクチルオキシフェニ
ル)フェニル]−1,3−ジチアン402mg(1.0ミリ
モル)のテトラヒドロフラン(THF)5ml溶液に、−
78℃で1.55Mブチルリチウム−ヘキサン溶液0.8
ml(1.2ミリモル)を加え30分間攪拌した。この反
応液に塩化4−オクチルオキシベンジル261mg(1.
0ミリモル)のTHF2ml溶液を加え、2時間かけて−
30℃まで昇温した。続いて、2M塩酸で処理し、反応
生成物をエーテルで抽出した後、抽出液を濃縮した。得
られた残渣をカラムクロマトグラフィー(ワコーゲルC
−200、ヘキサン/酢酸エチル=20/1)を用いて
精製して、2−[(4−オクチルオキシフェニル)メチ
ル]−2−[4−(4−オクチルオキシフェニル)フェ
ニル]−1,3−ジチアン575mg(収率93%)を得
た。To a solution of 402 mg (1.0 mmol) of 2- [4- (4-octyloxyphenyl) phenyl] -1,3-dithiane in 5 ml of tetrahydrofuran (THF),
0.85M Butyllithium-Hexane solution 0.8 at 78 ° C
ml (1.2 mmol) was added and stirred for 30 minutes. To this reaction solution, 261 mg of 4-octyloxybenzyl chloride (1.
(0 mmol) in THF (2 ml) was added over 2 hours.
The temperature was raised to 30 ° C. Then, it was treated with 2M hydrochloric acid, the reaction product was extracted with ether, and the extract was concentrated. The obtained residue is subjected to column chromatography (Wako Gel C
-200, hexane / ethyl acetate = 20/1) and purified to give 2-[(4-octyloxyphenyl) methyl] -2- [4- (4-octyloxyphenyl) phenyl] -1,3. -Dithiane 575 mg (93% yield) was obtained.
【0042】無色粘稠性油状物質 IR(neat) 2950,2880,1610,1
510,1500,1475,1250,1180,8
25cm-1 1 H NMR(CDCl3) δ 0.9(t,J=7H
z,6H),1.0〜2.1(m,26H),2.7
(m,4H),3.3(s,2H),3.9(t,J=7
Hz,2H),4.0(t,J=7Hz,2H),6.7
(s,4H),7.0(d,J=8.5Hz,2H),
7.5(d,J=8.5Hz,2H),7.6(d,J=
8.5Hz,2H),7.7(d,J=8.5Hz,2
H) MS m/z 618(M+ ,3),401(13),
400(29),399(100)Colorless viscous oily substance IR (neat) 2950, 2880, 1610, 1
510, 1500, 1475, 1250, 1180, 8
25cm -1 1 H NMR (CDCl 3 ) δ 0.9 (t, J = 7H
z, 6H), 1.0-2.1 (m, 26H), 2.7
(M, 4H), 3.3 (s, 2H), 3.9 (t, J = 7)
Hz, 2H), 4.0 (t, J = 7Hz, 2H), 6.7
(S, 4H), 7.0 (d, J = 8.5Hz, 2H),
7.5 (d, J = 8.5 Hz, 2H), 7.6 (d, J =
8.5Hz, 2H), 7.7 (d, J = 8.5Hz, 2
H) MS m / z 618 (M + , 3), 401 (13),
400 (29), 399 (100)
【0043】(1−c) 1,1−ジフルオロ−2−
(4−オクチルオキシフェニル)−1−[4−(4−オ
クチルオキシフェニル)フェニル]エタンの合成(1-c) 1,1-difluoro-2-
Synthesis of (4-octyloxyphenyl) -1- [4- (4-octyloxyphenyl) phenyl] ethane
【0044】[0044]
【化11】 [Chemical 11]
【0045】テトラブチルアンモニウムジヒドロトリフ
ルオリド620mg(2.2ミリモル)、N−ヨードこは
く酸イミド(NIS)425mg(1.9ミリモル)のジ
クロロメタン10ml溶液に、−78℃で2−[(4−オ
クチルオキシフェニル)メチル]−2−[4−(4−オ
クチルオキシフェニル)フェニル]−1,3−ジチアン
425mg(0.69ミリモル)のジクロロメタン3ml溶
液を加え、3時間かけて−30℃まで昇温した。続い
て、この混合液を飽和食塩水で処理し、セライト濾過し
た後、反応生成物をエーテルで抽出した。抽出液を飽和
チオ硫酸ナトリウム水溶液で洗い、濃縮した後、得られ
た残渣をカラムクロマトグラフィー(ワコーゲルC−2
00、ヘキサン/酢酸エチル=20/1)を用いて精製
して、1,1−ジフルオロ−2−(4−オクチルオキシ
フェニル)−1−[4−(4−オクチルオキシフェニ
ル)フェニル]エタン232mg(収率61%)を得た。A solution of 620 mg (2.2 mmol) of tetrabutylammonium dihydrotrifluoride and 425 mg (1.9 mmol) of N-iodosuccinimide (NIS) in 10 ml of dichloromethane was added to 2-[(4-octyl) at -78 ° C. A solution of 425 mg (0.69 mmol) of oxyphenyl) methyl] -2- [4- (4-octyloxyphenyl) phenyl] -1,3-dithiane in 3 ml of dichloromethane was added, and the temperature was raised to -30 ° C over 3 hours. did. Subsequently, the mixture was treated with saturated saline and filtered through Celite, and the reaction product was extracted with ether. The extract was washed with saturated aqueous sodium thiosulfate solution and concentrated, and the obtained residue was subjected to column chromatography (Wakogel C-2
00, hexane / ethyl acetate = 20/1) and purified, 1,1-difluoro-2- (4-octyloxyphenyl) -1- [4- (4-octyloxyphenyl) phenyl] ethane 232 mg (Yield 61%) was obtained.
【0046】相転移温度 127℃(Cr→SB)、1
42℃(SB→I) 白色粉末 IR(KBr) 2950,2880,1610,15
15,1480,1300,1255,1210,11
80,1030,1000,830cm-1 1 H NMR(CDCl3) δ 0.9(t,J=7H
z,6H),1.1〜2.1(m,24H),3.4
(t,J=16Hz,2H),3.9(t,J=7H
z,2H),4.0(t,J=7Hz,2H),6.76
(d,J=8.7Hz,2H),6.97(d,J=8.
7Hz,2H),7.01(d,J=8.7Hz,2
H),7.33(d,J=8.7Hz,2H),7.50
(d,J=8.7Hz,2H),7.52(d,J=8.
7Hz,2H) MS m/z 551(M+ +1,21),550(M
+,57),331(41),219(52),107
(100),69(20),57(31),55(2
2),43(57),41(35),29(22) 元素分析:C36H48F2Oとして 計算値:C,78.51%;H,8.78% 実測値:C,78.21%;H,8.98%Phase transition temperature 127 ° C. (Cr → SB), 1
42 ° C. (SB → I) White powder IR (KBr) 2950,2880,1610,15
15, 1480, 1300, 1255, 1210, 11
80,1030,1000,830 cm -1 1 H NMR (CDCl 3 ) δ 0.9 (t, J = 7H
z, 6H), 1.1-2.1 (m, 24H), 3.4
(T, J = 16Hz, 2H), 3.9 (t, J = 7H
z, 2H), 4.0 (t, J = 7Hz, 2H), 6.76
(D, J = 8.7 Hz, 2H), 6.97 (d, J = 8.
7Hz, 2H), 7.01 (d, J = 8.7Hz, 2
H), 7.33 (d, J = 8.7 Hz, 2H), 7.50
(D, J = 8.7 Hz, 2H), 7.52 (d, J = 8.
7 Hz, 2H) MS m / z 551 (M + +1, 21), 550 (M
+ , 57), 331 (41), 219 (52), 107
(100), 69 (20), 57 (31), 55 (2
2), 43 (57), 41 (35), 29 (22) Elemental analysis: Calculated as C 36 H 48 F 2 O: C, 78.51%; H, 8.78% Actual value: C, 78 .21%; H, 8.98%
【0047】(実施例2) 1,1−ジフルオロ−1−
(4−ヘプチルオキシフェニル)−2−(4−オクチル
オキシフェニル)エタン(第1表中、No.2の化合
物)の合成Example 2 1,1-difluoro-1-
Synthesis of (4-heptyloxyphenyl) -2- (4-octyloxyphenyl) ethane (Compound No. 2 in Table 1)
【0048】(2−a) 2−(4−ヘプチルオキシフ
ェニル)−1,3−ジチアンの合成(2-a) Synthesis of 2- (4-heptyloxyphenyl) -1,3-dithiane
【0049】[0049]
【化12】 [Chemical 12]
【0050】4−ヘプチルオキシベンズアルデヒド1.
03g(4.7ミリモル)、プロパンジチオール0.58
g(5.4ミリモル)、PPSE−ジクロロメタン溶液
20mlを室温で13時間攪拌した。反応終了後、飽和炭
酸水素ナトリウム水溶液50mlを加え、反応生成物をエ
ーテル100mlで抽出した。抽出液を濃縮した後、得ら
れた残渣をヘキサンから再結晶させて、2−(4−ヘプ
チルオキシフェニル)−1,3−ジチアン1.39g(収
率96%)を得た。4-heptyloxybenzaldehyde 1.
03 g (4.7 mmol), propanedithiol 0.58
g (5.4 mmol) and 20 ml of PPSE-dichloromethane solution were stirred at room temperature for 13 hours. After completion of the reaction, 50 ml of saturated aqueous sodium hydrogen carbonate solution was added, and the reaction product was extracted with 100 ml of ether. After the extract was concentrated, the obtained residue was recrystallized from hexane to obtain 1.39 g of 2- (4-heptyloxyphenyl) -1,3-dithiane (yield 96%).
【0051】無色板状晶 融点 71℃ IR(KBr) 2940,1610,1510,14
75,1415,1305,1260,1175,10
30,1020,845,815,765,670cm-1 1 H NMR(CDCl3) δ 0.89(t,J=7.
0Hz,3H),1.1〜2.2(m,12H),2.8
〜3.2(m,4H),3.95(t,J=6.5Hz,
2H),5.1(s,1H),6.85(d,J=8.5
Hz,2H),7.35(d,J=8.5Hz,2H) MS m/z 310(M+,46),236(5
4),139(22),138(100),137(3
7),57(45),55(20),45(22),4
3(41),41(59),29(38) 元素分析:C17H26OS2 として 計算値:C,65.76%;H,8.44%;S,20.
65% 実測値:C,65.50%;H,8.40%;S,20.
85%Colorless plate crystal melting point 71 ° C. IR (KBr) 2940,1610,1510,14
75, 1415, 1305, 1260, 1175, 10
30,1020,845,815,765,670 cm −1 1 H NMR (CDCl 3 ) δ 0.89 (t, J = 7.
0Hz, 3H), 1.1-2.2 (m, 12H), 2.8
~ 3.2 (m, 4H), 3.95 (t, J = 6.5Hz,
2H), 5.1 (s, 1H), 6.85 (d, J = 8.5)
Hz, 2H), 7.35 (d, J = 8.5Hz, 2H) MS m / z 310 (M + , 46), 236 (5
4), 139 (22), 138 (100), 137 (3
7), 57 (45), 55 (20), 45 (22), 4
3 (41), 41 (59), 29 (38) Elemental analysis: C 17 H 26 OS 2 Calculated: C, 65.76%; H, 8.44%; S, 20.
65% Found: C, 65.50%; H, 8.40%; S, 20.
85%
【0052】(2−b) 2−(4−ヘプチルオキシフ
ェニル)−2−[(4−オクチルオキシフェニル)メチ
ル]−1,3−ジチアンの合成(2-b) Synthesis of 2- (4-heptyloxyphenyl) -2-[(4-octyloxyphenyl) methyl] -1,3-dithiane
【0053】[0053]
【化13】 [Chemical 13]
【0054】2−(4−ヘプチルオキシフェニル)−
1,3−ジチアン1g(3.2ミリモル)のTHF15ml
溶液に、−78℃で1.55Mブチルリチウム−ヘキサ
ン溶液2.3ml(3.6ミリモル)を加え、30分間攪拌
した。反応終了後、塩化4−オクチルオキシベンジル
0.95g(3.7ミリモル)のTHF5ml溶液を加え、
5時間かけて0℃まで昇温した。この混合液を2M塩酸
で処理し、反応生成物をエーテルで抽出した後、抽出液
を濃縮し、得られた残渣をカラムクロマトグラフィー
(ワコーゲルC−200,ヘキサン/酢酸エチル=20
/1)を用いて精製して、2−(4−ヘプチルオキシフ
ェニル)−2−[(4−オクチルオキシフェニル)メチ
ル]−1,3−ジチアン1.7g(収率100%)を得
た。2- (4-heptyloxyphenyl)-
1,3-dithiane 1 g (3.2 mmol) THF 15 ml
2.3 ml (3.6 mmol) of a 1.55 M butyllithium-hexane solution was added to the solution at -78 ° C, and the mixture was stirred for 30 minutes. After completion of the reaction, a solution of 4-octyloxybenzyl chloride 0.95 g (3.7 mmol) in THF 5 ml was added,
The temperature was raised to 0 ° C. over 5 hours. The mixture was treated with 2M hydrochloric acid, the reaction product was extracted with ether, the extract was concentrated, and the obtained residue was subjected to column chromatography (Wakogel C-200, hexane / ethyl acetate = 20).
/ (1) to give 2- (4-heptyloxyphenyl) -2-[(4-octyloxyphenyl) methyl] -1,3-dithiane (1.7 g, yield 100%). .
【0055】無色粘稠性油状物質 IR(neat) 2930,2870,1610,1
510,1470,1245,1175,1025,8
10,800,710cm-1 1 H NMR(CDCl3) δ 0.89(t,J=7
Hz,3H),0.90(t,J=7Hz,3H),1.
0〜2.1(m,24H),2.7(m,4H),3.2
(s,2H),3.9(t,J=7Hz,2H),4.0
(t,J=7Hz,2H),6.6(s,4H),6.8
(d,J=8.5Hz,2H),7.6(d,J=8.5
Hz,2H) MS m/z 528(M+,2),310(21),
309(100)Colorless viscous oily substance IR (neat) 2930, 2870, 1610, 1
510, 1470, 1245, 1175, 1025, 8
10,800,710 cm -1 1 H NMR (CDCl 3 ) δ 0.89 (t, J = 7)
Hz, 3H), 0.90 (t, J = 7Hz, 3H), 1.
0-2.1 (m, 24H), 2.7 (m, 4H), 3.2
(S, 2H), 3.9 (t, J = 7Hz, 2H), 4.0
(T, J = 7 Hz, 2H), 6.6 (s, 4H), 6.8
(D, J = 8.5 Hz, 2H), 7.6 (d, J = 8.5)
Hz, 2H) MS m / z 528 (M + , 2), 310 (21),
309 (100)
【0056】(2−c) 1,1−ジフルオロ−1−
(4−ヘプチルオキシフェニル)−2−(4−オクチル
オキシフェニル)エタンの合成(2-c) 1,1-difluoro-1-
Synthesis of (4-heptyloxyphenyl) -2- (4-octyloxyphenyl) ethane
【0057】[0057]
【化14】 [Chemical 14]
【0058】テトラブチルアンモニウムジヒドロトリフ
ルオリド2g(7.0ミリモル)、NIS1.4g(6.
2ミリモル)のジクロロメタン20ml溶液に、−78℃
で2−(4−ヘプチルオキシフェニル)−2−[(4−
オクチルオキシフェニル)メチル]−1,3−ジチアン
1.4g(2.7ミリモル)のジクロロメタン15ml溶液
を加え、−30℃まで昇温した。続いて、この混合液を
飽和食塩水で処理し、更に、セライト濾過し、濾液から
反応生成物をエーテルで抽出した。抽出液を飽和チオ硫
酸ナトリウム水溶液で洗い、濃縮した後、得られた残渣
をカラムクロマトグラフィー(ワコーゲルC−200、
ヘキサン/酢酸エチル=20/1)を用いて精製して、
1,1−ジフルオロ−1−(4−ヘプチルオキシフェニ
ル)−2−(4−オクチルオキシフェニル)エタン1.
2g(収率98%)を得た。Tetrabutylammonium dihydrotrifluoride 2 g (7.0 mmol), NIS 1.4 g (6.
(2 mmol) in 20 ml of dichloromethane at -78 ° C.
2- (4-heptyloxyphenyl) -2-[(4-
A solution of 1.4 g (2.7 mmol) of octyloxyphenyl) methyl] -1,3-dithiane in 15 ml of dichloromethane was added, and the temperature was raised to -30 ° C. Subsequently, this mixed solution was treated with saturated saline and further filtered through Celite, and the reaction product was extracted with ether from the filtrate. The extract was washed with a saturated aqueous sodium thiosulfate solution and concentrated, and the obtained residue was subjected to column chromatography (Wako Gel C-200,
Purification using hexane / ethyl acetate = 20/1),
1,1-difluoro-1- (4-heptyloxyphenyl) -2- (4-octyloxyphenyl) ethane 1.
2 g (yield 98%) was obtained.
【0059】無色板状晶 融点 65℃ IR(KBr) 2940,2870,1615,15
10,1480,1305,1250,1180,11
60,1110,1030,990,885,830,
790,760cm-1 1 H NMR(CDCl3) δ 0.88(t,J=7.
0Hz,3H),0.89(t,J=6.8Hz,3
H),1.2〜2.1.5(m,18H),1.75(qu
intet,J=6.6Hz,2H),1.77(qui
ntet,J=6.6Hz,2H),3.30(t,J=
15.6Hz,2H),3.90(t,J=6.6Hz,
2H),3.94(t,J=6.6Hz,2H),6.7
4(d,J=8.7Hz,2H),6.83(d,J=
8.8Hz,2H),6.97(d,J=8.8Hz,2
H),7.21(d,J=8.7Hz,2H) MS m/z 461(M+,16),241(7
5),219(52),143(69),107(10
0),57(49),55(32),43(62),4
1(46),29(31) 元素分析:C29H42F2Oとして 計算値:C,75.62%;H,9.19% 実測値:C,75.84%;H,9.45%Colorless plate crystal melting point 65 ° C. IR (KBr) 2940,2870,1615,15
10, 1480, 1305, 1250, 1180, 11
60, 1110, 1030, 990, 885, 830,
790,760 cm -1 1 H NMR (CDCl 3 ) δ 0.88 (t, J = 7.
0Hz, 3H), 0.89 (t, J = 6.8Hz, 3
H), 1.2-2.1.5 (m, 18H), 1.75 (qu)
intet, J = 6.6Hz, 2H), 1.77 (qui)
ntet, J = 6.6 Hz, 2H), 3.30 (t, J =
15.6Hz, 2H), 3.90 (t, J = 6.6Hz,
2H), 3.94 (t, J = 6.6Hz, 2H), 6.7
4 (d, J = 8.7 Hz, 2H), 6.83 (d, J =
8.8Hz, 2H), 6.97 (d, J = 8.8Hz, 2
H), 7.21 (d, J = 8.7 Hz, 2H) MS m / z 461 (M + , 16), 241 (7
5), 219 (52), 143 (69), 107 (10
0), 57 (49), 55 (32), 43 (62), 4
1 (46), 29 (31) Elemental analysis: Calculated as C 29 H 42 F 2 O: C, 75.62%; H, 9.19% Measured value: C, 75.84%; H, 9. 45%
【0060】(実施例3) 1−(4−ブチルオキシフ
ェニル)−1,1−ジフルオロ−2−(4−プロピルフ
ェニル)エタン(第1表中、No.3の化合物)の合成Example 3 Synthesis of 1- (4-butyloxyphenyl) -1,1-difluoro-2- (4-propylphenyl) ethane (Compound No. 3 in Table 1)
【0061】(3−a) 2−(4−ブチルオキシフェ
ニル)−1,3−ジチアンの合成(3-a) Synthesis of 2- (4-butyloxyphenyl) -1,3-dithiane
【0062】[0062]
【化15】 [Chemical 15]
【0063】4−ブチルオキシベンズアルデヒド3.5
g(20ミリモル)、プロパンジチオール2.45g
(23ミリモル)、PPSE−ジクロロメタン溶液40
mlを室温で17時間攪拌した。反応終了後、飽和炭酸水
素ナトリウム水溶液50mlを加え、反応生成物をエーテ
ル100mlで抽出した。抽出液を濃縮した後、得られた
残渣をヘキサン/エーテル(10/1)混合溶媒から再
結晶させて、2−(4−ブチルオキシフェニル)−1,
3−ジチアン4.6g(収率87%)を得た。4-Butyloxybenzaldehyde 3.5
g (20 mmol), propanedithiol 2.45 g
(23 mmol), PPSE-dichloromethane solution 40
The ml was stirred at room temperature for 17 hours. After completion of the reaction, 50 ml of saturated aqueous sodium hydrogen carbonate solution was added, and the reaction product was extracted with 100 ml of ether. After concentrating the extract, the obtained residue was recrystallized from a hexane / ether (10/1) mixed solvent to give 2- (4-butyloxyphenyl) -1,
4.6 g (87% yield) of 3-dithiane was obtained.
【0064】無色板状晶 融点 81℃ IR(KBr) 2950,2900,1610,15
10,1480,1415,1310,1460,11
80,1040,1005,845,810,765,
670,585,525cm-1 1 H NMR(CDCl3) δ 0.96(t,J=7.
3Hz,3H),1.2〜2.2(m,6H),2.7〜
3.3(m,4H),3.94(t,J=6.5Hz,2
H),5.12(s,1H),6.85(d,J=8.7
Hz,2H),7.38(d,J=8.7Hz,2H), MS m/z 269(M++1,13),268
(M+,75),194(80),138(100),
137(49),57(26),45(20),41
(39),29(42) 元素分析:C14H20OS2 として 計算値:C,62.64%;H,7.51%;S,23.
89% 実測値:C,62.63%;H,7.66%;S,23.
61%Colorless plate crystal Melting point 81 ° C. IR (KBr) 2950, 2900, 1610, 15
10, 1480, 1415, 1310, 1460, 11
80,1040,1005,845,810,765,
670,585,525 cm -1 1 H NMR (CDCl 3 ) δ 0.96 (t, J = 7.
3Hz, 3H), 1.2-2.2 (m, 6H), 2.7-
3.3 (m, 4H), 3.94 (t, J = 6.5Hz, 2
H), 5.12 (s, 1H), 6.85 (d, J = 8.7)
Hz, 2H), 7.38 (d, J = 8.7Hz, 2H), MS m / z 269 (M + +1, 13), 268.
(M + , 75), 194 (80), 138 (100),
137 (49), 57 (26), 45 (20), 41
(39), 29 (42) Elemental analysis: C 14 H 20 OS 2 Calculated: C, 62.64%; H, 7.51%; S, 23.
89% Found: C, 62.63%; H, 7.66%; S, 23.
61%
【0065】(3−b) 2−(4−ブチルオキシフェ
ニル)−2−[(4−プロピルフェニル)メチル]−
1,3−ジチアンの合成(3-b) 2- (4-butyloxyphenyl) -2-[(4-propylphenyl) methyl]-
Synthesis of 1,3-dithiane
【0066】[0066]
【化16】 [Chemical 16]
【0067】2−(4−ブチルオキシフェニル)−1,
3−ジチアン2.7g(10ミリモル)のTHF25ml
溶液に、−78℃で1.55Mブチルリチウム−ヘキサ
ン溶液8ml(12ミリモル)を加え、30分間攪拌し
た。この反応液に4−プロピル塩化ベンジル1.8g
(11ミリモル)のTHF5ml溶液を加え、5時間かけ
て0℃まで昇温した。続いて、この混合液を2M塩酸で
処理し、反応生成物をエーテルで抽出した後、抽出液を
濃縮し、得られた残渣をカラムクロマトグラフィー(ワ
コーゲルC−200、ヘキサン/酢酸エチル=20/
1)を用いて精製して、2−(4−ブチルオキシフェニ
ル)−2−[(4−プロピルフェニル)メチル]−1,
3−ジチアン3.7g(収率92%)を得た。2- (4-butyloxyphenyl) -1,
2.7 g (10 mmol) of 3-dithiane in 25 ml of THF
To the solution was added 8 ml (12 mmol) of a 1.55 M butyllithium-hexane solution at -78 ° C, and the mixture was stirred for 30 minutes. 1.8 g of 4-propylbenzyl chloride was added to this reaction solution.
A solution of (11 mmol) in 5 ml of THF was added and the temperature was raised to 0 ° C. over 5 hours. Subsequently, the mixture was treated with 2M hydrochloric acid, the reaction product was extracted with ether, the extract was concentrated, and the obtained residue was subjected to column chromatography (Wakogel C-200, hexane / ethyl acetate = 20 /).
1) and purified with 2- (4-butyloxyphenyl) -2-[(4-propylphenyl) methyl] -1,
3.7 g (92% yield) of 3-dithiane was obtained.
【0068】無色粘稠性油状物質 IR(neat) 2970,1605,1500,1
470,1290,1245,1180,1030,8
30,580cm-1 1 H NMR(CDCl3) δ 0.89(t,J=6.
5Hz,3H),0.96(t,J=7.3Hz,3
H),1.2〜2.2(m,8H),2.4〜3.0(6
H),3.22(s,2H),3.97(t,J=6.5
Hz,2H),6.67(d,J=8.3Hz,2H),
6.80(d,J=8.7Hz,2H),6.92(d,
J=8.3Hz,2H),7.56(d,J=8.7H
z,2H) MS m/z 400(M+,trace),267
(100),137(24),133(39),91
(13)Colorless viscous oily substance IR (neat) 2970, 1605, 1500, 1
470, 1290, 1245, 1180, 1030, 8
30,580cm -1 1 H NMR (CDCl 3 ) δ 0.89 (t, J = 6.
5Hz, 3H), 0.96 (t, J = 7.3Hz, 3
H), 1.2 to 2.2 (m, 8H), 2.4 to 3.0 (6
H), 3.22 (s, 2H), 3.97 (t, J = 6.5)
Hz, 2H), 6.67 (d, J = 8.3Hz, 2H),
6.80 (d, J = 8.7 Hz, 2H), 6.92 (d,
J = 8.3Hz, 2H), 7.56 (d, J = 8.7H
z, 2H) MS m / z 400 (M + , trace), 267
(100), 137 (24), 133 (39), 91
(13)
【0069】(3−c) 1−(4−ブチルオキシフェ
ニル)−1,1−ジフルオロ−2−(4−プロピルフェ
ニル)エタンの合成(3-c) Synthesis of 1- (4-butyloxyphenyl) -1,1-difluoro-2- (4-propylphenyl) ethane
【0070】[0070]
【化17】 [Chemical 17]
【0071】テトラブチルアンモニウムジヒドロトリフ
ルオリド4.6g(16ミリモル)、NIS3.5g(1
6ミリモル)のジクロロメタン30ml溶液に、−78℃
で2−(4−ブチルオキシフェニル)−2−[(4−プ
ロピルフェニル)メチル]−1,3−ジチアン2.5g
(6.3ミリモル)のジクロロメタン20ml溶液を加
え、6時間かけて0℃まで昇温した。続いて、この混合
液を飽和食塩水で処理し、セライト濾過した後、濾液か
ら反応生成物をエーテル/酢酸エチル(1/1)混合溶
媒で抽出した後、抽出液を飽和チオ硫酸ナトリウム水溶
液で洗い、濃縮し、得られた残渣をカラムクロマトグラ
フィー(ワコーゲルC−300、ヘキサン/酢酸エチル
=30/1)を用いて精製して、1−(4−ブチルオキ
シフェニル)−1,1−ジフルオロ−2−(4−プロピ
ルフェニル)エタン1.45g(収率70%)を得た。Tetrabutylammonium dihydrotrifluoride 4.6 g (16 mmol), NIS 3.5 g (1
6 mmol) in 30 ml of dichloromethane at -78 ° C.
2.5 g of 2- (4-butyloxyphenyl) -2-[(4-propylphenyl) methyl] -1,3-dithiane
A solution of (6.3 mmol) in 20 ml of dichloromethane was added, and the temperature was raised to 0 ° C over 6 hours. Subsequently, this mixed solution was treated with saturated saline and filtered through Celite, and the reaction product was extracted from the filtrate with a mixed solvent of ether / ethyl acetate (1/1), and then the extracted solution was washed with a saturated aqueous solution of sodium thiosulfate. After washing and concentrating, the obtained residue was purified by column chromatography (Wakogel C-300, hexane / ethyl acetate = 30/1) to give 1- (4-butyloxyphenyl) -1,1-difluoro. 1.45 g (yield 70%) of 2- (4-propylphenyl) ethane was obtained.
【0072】無色板状晶 融点 62℃ IR(KBr) 2960,2880,1620,15
90,1520,1470,1420,1380,13
60,1300,1255,1185,1155,11
15,1070,1030,995,970,890,
830,770,640,580cm-1 1 H NMR(CDCl3) δ 0.91(t,J=7.
4Hz,3H),0.97(t,J=7.4Hz,3
H),1.49(sextet,J=7.4Hz,2
H),1.60(sextet,J=7.4Hz,2
H),1.76(quintet,J=7.4Hz,2
H),2.54(t,J=7.4Hz,2H),3.34
(t,J=15.8Hz,2H),3.95(t,J=
7.4Hz,2H),6.83(d,J=8.8Hz,2
H),6.99(d,J=8.1Hz,2H),7.05
(d,J=8.1Hz,2H),7.22(d,J=8.
8Hz,2H) MS m/z 332(M+,16),199(10
0),143(94),29(25) 元素分析:C21H26F2Oとして 計算値:C,75.87%;H,7.88% 実測値:C,75.94%;H,7.99%Colorless plate-like crystal Melting point 62 ° C. IR (KBr) 2960,2880,1620,15
90, 1520, 1470, 1420, 1380, 13
60, 1300, 1255, 1185, 1155, 11
15, 1070, 1030, 995, 970, 890,
830,770,640,580 cm -1 1 H NMR (CDCl 3 ) δ 0.91 (t, J = 7.
4Hz, 3H), 0.97 (t, J = 7.4Hz, 3
H), 1.49 (sextet, J = 7.4Hz, 2
H), 1.60 (sextet, J = 7.4Hz, 2
H), 1.76 (quintet, J = 7.4Hz, 2
H), 2.54 (t, J = 7.4Hz, 2H), 3.34
(T, J = 15.8 Hz, 2H), 3.95 (t, J =
7.4Hz, 2H), 6.83 (d, J = 8.8Hz, 2
H), 6.99 (d, J = 8.1 Hz, 2H), 7.05
(D, J = 8.1 Hz, 2H), 7.22 (d, J = 8.
8 Hz, 2H) MS m / z 332 (M + , 16), 199 (10
0), 143 (94), 29 (25) Elemental analysis: Calculated as C 21 H 26 F 2 O: C, 75.87%; H, 7.88% Found: C, 75.94%; H , 7.99%
【0073】(実施例4) 1,1−ジフルオロ−2−
(4−プロピルフェニル)−1−[4−(トランス−4
−プロピルシクロヘキシル)フェニル]エタン(第1表
中、No.4の化合物)の合成Example 4 1,1-difluoro-2-
(4-Propylphenyl) -1- [4- (trans-4
-Propylcyclohexyl) phenyl] ethane (Compound No. 4 in Table 1)
【0074】[0074]
【化18】 [Chemical 18]
【0075】実施例3において、4−ブチルオキシベン
ズアルデヒドに代えて、4−(トランス−4−プロピル
シクロヘキシル)ベンズアルデヒドを用いた以外は実施
例3と全く同様にして、2−[4−(4−トランス−4
−プロピルシクロヘキシル)フェニル]−1,3−ジチ
アン、次いで2−[4−(トランス−4−プロピルシク
ロヘキシル)フェニル]−2−[(4−プロピルフェニ
ル)メチル]−1,3−ジチアンを経て、1,1−ジフル
オロ−2−(4−プロピルフェニル)−1−[4−(ト
ランス−4−プロピルシクロヘキシル)フェニル]エタ
ンを得た。In the same manner as in Example 3 except that 4- (trans-4-propylcyclohexyl) benzaldehyde was used in place of 4-butyloxybenzaldehyde in Example 3, 2- [4- (4- Transformer-4
-Propylcyclohexyl) phenyl] -1,3-dithiane, then 2- [4- (trans-4-propylcyclohexyl) phenyl] -2-[(4-propylphenyl) methyl] -1,3-dithiane, There was obtained 1,1-difluoro-2- (4-propylphenyl) -1- [4- (trans-4-propylcyclohexyl) phenyl] ethane.
【0076】2−[4−(4−トランス−4−プロピル
シクロヘキシル)フェニル]−1,3−ジチアン 無色柱状晶 融点 129℃ IR(KBr) 2930,1440,1420,12
75,765cm-1 1 H NMR(CDCl3) δ 0.90(t,J=7.
2Hz,2H),0.98〜1.08(m,2H),1.
15〜1.46(m,7H),1.81〜1.95(m,
5H),2.165(dm,J=14.1Hz,1H),
2.44(tt,J=12.2and3.2Hz,1
H),2.90(ddd,J=14.5,4.2,and
2.4Hz,2H),5.14(s,1H),7.16
(d,J=8.1Hz,2H),7.37(d,J=8.
1Hz,2H) MS m/z 321(M++1,17),320
(M+,76),247(24),246(100),
148(22),147(19),136(16),1
35(17),129(19),105(20),91
(35),83(26),69(49),55(3
1),45(32),43(25) 元素分析:C19H28S2 として 計算値:C,71.19%;H,8.80%;S,20.
01% 実測値:C,71.35%;H,8.95%;S,20.
07%2- [4- (4-trans-4-propylcyclohexyl) phenyl] -1,3-dithiane Colorless columnar crystal Melting point 129 ° C. IR (KBr) 2930,1440,1420,12
75,765cm -1 1 H NMR (CDCl 3 ) δ 0.90 (t, J = 7.
2Hz, 2H), 0.98 to 1.08 (m, 2H), 1.
15-1.46 (m, 7H), 1.81-1.95 (m,
5H), 2.165 (dm, J = 14.1Hz, 1H),
2.44 (tt, J = 12.2 and 3.2Hz, 1
H), 2.90 (ddd, J = 14.5, 4.2, and
2.4Hz, 2H), 5.14 (s, 1H), 7.16
(D, J = 8.1 Hz, 2H), 7.37 (d, J = 8.
1 Hz, 2H) MS m / z 321 (M + +1, 17), 320
(M + , 76), 247 (24), 246 (100),
148 (22), 147 (19), 136 (16), 1
35 (17), 129 (19), 105 (20), 91
(35), 83 (26), 69 (49), 55 (3
1), 45 (32), 43 (25) Elemental analysis: C 19 H 28 S 2 Calculated value: C, 71.19%; H, 8.80%; S, 20.
01% Found: C, 71.35%; H, 8.95%; S, 20.
07%
【0077】2−[4−(トランス−4−プロピルシク
ロヘキシル)フェニル]−2−[(4−プロピルフェニ
ル)メチル]−1,3−ジチアン 無色針状晶 融点 82℃ IR(KBr) 2920,1500,1440,14
15,970,835,590cm-1 1 H NMR(CDCl3) δ 0.89(t,J=7.
4Hz,3H),091(t,J=7.3Hz,3
H),1.00〜1.12(m,2H),1.18〜1.6
2(m,11H),1.84〜1.96(m,6H),
2.42〜2.52(m,3H),2.58〜2.75
(m,4H),3.20(s,2H),6.63(d,J
=8.1Hz,2H),6.89(d,J=8.1Hz,
2H),7.11(d,J=8.4Hz,2H),7.5
9(d,J=8.4Hz,2H) MS m/z 452(M+,1),319(100) 元素分析:C29H40S2 として 計算値:C,76.93%;H,9.91%;S,14.
16% 実測値:C,77.11%;H,9.14%;S,14.
39%2- [4- (trans-4-propylcyclohexyl) phenyl] -2-[(4-propylphenyl) methyl] -1,3-dithiane colorless needles melting point 82 ° C IR (KBr) 2920,1500 , 1440, 14
15,970,835,590 cm -1 1 H NMR (CDCl 3 ) δ 0.89 (t, J = 7.
4Hz, 3H), 091 (t, J = 7.3Hz, 3
H), 1.00-1.12 (m, 2H), 1.18-1.6
2 (m, 11H), 1.84 to 1.96 (m, 6H),
2.42 to 2.52 (m, 3H), 2.58 to 2.75
(M, 4H), 3.20 (s, 2H), 6.63 (d, J
= 8.1Hz, 2H), 6.89 (d, J = 8.1Hz,
2H), 7.11 (d, J = 8.4Hz, 2H), 7.5
9 (d, J = 8.4 Hz, 2H) MS m / z 452 (M + , 1), 319 (100) Elemental analysis: Calculated as C 29 H 40 S 2 : C, 76.93%; H, 9.91%; S, 14.
16% Found: C, 77.11%; H, 9.14%; S, 14.
39%
【0078】1,1−ジフルオロ−2−(4−プロピル
フェニル)−1−[4−(トランス−4−プロピルシク
ロヘキシル)フェニル]エタン 無色粉末 融点 76℃ IR(KBr) 2950,1360,1265,10
30,1000,890,830,770,590cm-1 1 H NMR(CDCl3) δ 0.90(t,J=7.
3Hz,3H),092(t,J=7.3Hz,3
H),0.98〜1.12(m,2H),1.18〜1.5
0(m,7H),1.61(sextet,J=7.3H
z,2H),1.83〜1.92(m,4H),2.47
(tt,J=12.2and3.0Hz,1H),2.5
5(t,J=7.3Hz,2H),3.34(t,J=1
6.3Hz,2H),7.03(d,J=8.4Hz,2
H),7.06(d,J=8.4Hz,2H),7.18
(d,J=8.4Hz,2H),7.26(d,J=8.
4Hz,2H) MS m/z 384(M+,5),251(10
0),133(21),127(21) 元素分析:C26H34F2 として 計算値:C,81.21%;H,8.91% 実測値:C,81.01%;H,9.03%1,1-difluoro-2- (4-propylphenyl) -1- [4- (trans-4-propylcyclohexyl) phenyl] ethane colorless powder melting point 76 ° C IR (KBr) 2950,1360,1265,10
30, 1000, 890, 830, 770, 590 cm -1 1 H NMR (CDCl 3 ) δ 0.90 (t, J = 7.
3Hz, 3H), 092 (t, J = 7.3Hz, 3
H), 0.98 to 1.12 (m, 2H), 1.18 to 1.5
0 (m, 7H), 1.61 (sextet, J = 7.3H
z, 2H), 1.83-1.92 (m, 4H), 2.47.
(Tt, J = 12.2 and 3.0 Hz, 1H), 2.5
5 (t, J = 7.3 Hz, 2H), 3.34 (t, J = 1
6.3 Hz, 2 H), 7.03 (d, J = 8.4 Hz, 2
H), 7.06 (d, J = 8.4 Hz, 2H), 7.18
(D, J = 8.4 Hz, 2H), 7.26 (d, J = 8.
4 Hz, 2H) MS m / z 384 (M + , 5), 251 (10
0), 133 (21), 127 (21) Elemental analysis: C 26 H 34 F 2 Calculated: C, 81.21%; H, 8.91% Found: C, 81.01%; H, 9.03%
【0079】(実施例5) ネマチック液晶組成物の調
製Example 5 Preparation of Nematic Liquid Crystal Composition
【0080】[0080]
【化19】 [Chemical 19]
【0081】から成るネマチック母体液晶(A)を調製
したところ、50.5℃以下でネマチック相を示した。
この母体液晶(A)の20℃における物性値を測定した
ところ、次の通りであった。 複屈折異方性(Δn) 0.117 しきい値電圧(V) 1.50 誘電率異方性 12.0 この母体液晶(A)90%及び実施例3で得られた式When a nematic matrix liquid crystal (A) consisting of was prepared, it showed a nematic phase at 50.5 ° C. or lower.
The physical properties of the host liquid crystal (A) at 20 ° C. were measured and the results were as follows. Birefringence anisotropy (Δn) 0.117 Threshold voltage (V) 1.50 Dielectric anisotropy 12.0 90% of the host liquid crystal (A) and the formula obtained in Example 3
【0082】[0082]
【化20】 [Chemical 20]
【0083】の化合物10%から成る液晶組成物(M)
を調製したところ、34.5℃以下でネマチック相を示
した。この液晶組成物(M)について、上記と同様にし
て測定した20℃における物性値は、次の通りであっ
た。 複屈折異方性(Δn) 0.077 しきい値電圧(V) 1.05 誘電率異方性 9.4Liquid crystal composition (M) comprising 10% of the compound of
Was prepared, it exhibited a nematic phase at 34.5 ° C. or lower. The physical properties of this liquid crystal composition (M) at 20 ° C. measured in the same manner as above were as follows. Birefringence anisotropy (Δn) 0.077 Threshold voltage (V) 1.05 Dielectric anisotropy 9.4
【0084】以上の結果から、本発明の一般式(I)で
表わされる化合物は、母体液晶の複屈折異方性(Δn)
を効果的に減少させていることが理解できる。From the above results, the compound represented by the general formula (I) of the present invention was found to have the birefringence anisotropy (Δn) of the host liquid crystal.
Can be understood to be effectively reduced.
【0085】(実施例6) 強誘電性液晶組成物の調製Example 6 Preparation of Ferroelectric Liquid Crystal Composition
【0086】[0086]
【化21】 [Chemical 21]
【0087】から成るSC相を示す母体液晶(B)を調
製した。この母体液晶(B)84%及びA matrix liquid crystal (B) having an SC phase consisting of was prepared. This matrix liquid crystal (B) 84% and
【0088】[0088]
【化22】 [Chemical formula 22]
【0089】から成るキラルドーパント(P)16%か
ら成る強誘電性液晶組成物(以下、SC*液晶組成物と
省略する。)(F−1)を調製した。A ferroelectric liquid crystal composition (hereinafter abbreviated as SC * liquid crystal composition) (F-1) containing 16% of a chiral dopant (P) was prepared.
【0090】このSC*液晶組成物(F−1)は66.5
℃以下でSC*相を示し、69℃以下でSA(スメクチ
ックA)相を、75℃以下でN*(キラルネマチック)
相を示し、それ以上の温度でI(等方性液体)相となっ
た。The SC * liquid crystal composition (F-1) had a composition of 66.5.
Shows SC * phase below ℃, SA (smectic A) phase below 69 ℃, N * (chiral nematic) below 75 ℃
It showed a phase and became an I (isotropic liquid) phase at higher temperatures.
【0091】このSC*液晶組成物(F−1)を用い、
以下のようにして、液晶表示素子を作成した。ポリイミ
ドでコーティングし、ナイロン布でラビング処理した2
枚のガラス透明電極板を、粒径2μmのグラスファイバ
ー性ビーズを介して張り合わせ、セルを作成した。この
セルに上記SC*液晶組成物(F−1)をI相まで加熱
した状態で封入し、次いで室温まで徐冷を行って、N*
相、SA相次いでSC*を配向させ、均一に配向した厚
さ約2μmの液晶表示素子を得た。この液晶表示素子
に、電界強度10VP-P/μm、50Hzの矩形波を印
加してその電気光学的応答速度を測定したところ、25
℃で46μ秒であった。又、この時の自発分極は17.
6nC/cm2、チルト角は29.5°であり、コントラス
ト良好であった。Using this SC * liquid crystal composition (F-1),
A liquid crystal display device was prepared as follows. Coated with polyimide and rubbed with nylon cloth 2
A glass transparent electrode plate was attached to each other via glass fiber beads having a particle diameter of 2 μm to prepare a cell. The SC * liquid crystal composition (F-1) was sealed in this cell in a state of being heated to the I phase, and then gradually cooled to room temperature to obtain N *.
Phase, SA phase and then SC * were oriented to obtain a uniformly oriented liquid crystal display element having a thickness of about 2 μm. A rectangular wave of 50 Hz with an electric field strength of 10 V PP / μm was applied to this liquid crystal display element, and its electro-optical response speed was measured.
It was 46 microseconds at ° C. The spontaneous polarization at this time is 17.
The contrast was 6 nC / cm 2 , the tilt angle was 29.5 °, and the contrast was good.
【0092】次に、母体液晶(B)90%及び実施例1
で得られた式Next, 90% of the base liquid crystal (B) and Example 1
Expression obtained by
【0093】[0093]
【化23】 [Chemical formula 23]
【0094】の化合物10%から成る母体液晶(C)を
調製した。A host liquid crystal (C) consisting of 10% of the compound of was prepared.
【0095】この母体液晶(C)84%及び前述のキラ
ルドーパント(P)16%から成るSC*液晶組成物
(F−2)を調製した。このSC*液晶組成物(F−
2)のSC*相の上限温度は68.5℃であり、SC*液
晶組成物(F−1)と比較して2℃上昇した。又、69
℃以下でSA相を、75℃以下でN*相を示し、それ以
上の温度でI相となった。An SC * liquid crystal composition (F-2) comprising 84% of the base liquid crystal (C) and 16% of the above chiral dopant (P) was prepared. This SC * liquid crystal composition (F-
The maximum temperature of the SC * phase in 2) was 68.5 ° C, which was 2 ° C higher than that of the SC * liquid crystal composition (F-1). Also, 69
The SA phase was shown at a temperature of 75 ° C or lower, the N * phase was shown at a temperature of 75 ° C or lower, and the I phase was obtained at a temperature higher than that.
【0096】このSC* 液晶組成物(F−2)を用い、
同様にして液晶表示素子を作成した。同様にして測定し
た電気光学的応答速度は、25℃で47μ秒と、SC*
液晶組成物(F−1)の場合とほとんど変化がなかっ
た。又、この時の自発分極は17.2nC/cm2、チルト
角は27.7°であり、コントラストは良好であった。Using this SC * liquid crystal composition (F-2),
A liquid crystal display device was prepared in the same manner. The electro-optical response speed measured in the same manner was 47 μs at 25 ° C. and SC *
There was almost no change from the case of the liquid crystal composition (F-1). At this time, the spontaneous polarization was 17.2 nC / cm 2 , the tilt angle was 27.7 °, and the contrast was good.
【0097】以上の結果から、一般式(I)で表わされ
る化合物を添加することにより、強誘電性液晶組成物の
応答性をほとんど変化させることなく、その駆動温度範
囲を高温域に拡大できる効果を示すことが理解できる。From the above results, it is possible to extend the driving temperature range to a high temperature range by adding the compound represented by the general formula (I) without changing the response of the ferroelectric liquid crystal composition. Can be understood to show.
【0098】[0098]
【発明の効果】本発明に係わる一般式(I)で表わされ
る化合物は、ネマチック液晶として現在汎用されている
母体液晶との相溶性に優れており、少量添加することに
より、その複屈折異方性(Δn)を効果的に減少させる
ことが可能である。又、一般式(I)で表わされる化合
物は、母体液晶の構成成分として、強誘電性を示す液晶
組成物に少量添加することにより、その高速応答性を保
ちながら、その駆動温度範囲を高温域に拡大することが
可能となる。従って、本発明の一般式(I)で表わされ
る化合物は、各種液晶表示セルの材料として有用であ
る。The compound represented by the general formula (I) according to the present invention has excellent compatibility with the host liquid crystal which is currently widely used as a nematic liquid crystal, and when added in a small amount, its birefringent anisotropic It is possible to effectively reduce the sex (Δn). In addition, the compound represented by the general formula (I) is added as a constituent component of the host liquid crystal to a liquid crystal composition exhibiting ferroelectricity in a small amount, so that its driving temperature range can be kept in a high temperature range while maintaining its high-speed response. Can be expanded to. Therefore, the compound represented by the general formula (I) of the present invention is useful as a material for various liquid crystal display cells.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C09K 19/42 6742−4H 19/58 6742−4H (72)発明者 高津 晴義 東京都小平市仲町500−14 (72)発明者 竹内 清文 東京都板橋区高島平1−12−14−103 (72)発明者 檜山 為次郎 神奈川県相模原市上鶴間4−29−3−101 (72)発明者 楠本 哲生 神奈川県相模原市南台1−9−2−102 (72)発明者 佐藤 健一 神奈川県相模原市上溝35−11 (72)発明者 中山 昭子 東京都町田市山崎町1380−K−702 (72)発明者 黒星 学 神奈川県相模原市西大沼4−4−1─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical indication C09K 19/42 6742-4H 19/58 6742-4H (72) Inventor Haruyoshi Takatsu Nakamachi, Kodaira-shi, Tokyo 500-14 (72) Inventor Kiyofumi Takeuchi 1-12-14-103 Takashimadaira Itabashi-ku, Tokyo (72) Inventor Taijiro Hiyama 4-29-3-101 Kamizuruma, Sagamihara City, Kanagawa (72) Inventor Tetsuo Kusumoto 1-9-2-102 Minamidai, Sagamihara-shi, Kanagawa Prefecture (72) Inventor Kenichi Sato 35-11, Kamizomi, Sagamihara-shi, Kanagawa Prefecture (72) Akiko Nakayama 1380-K-702 (72) inventor, Yamazaki-cho, Machida-shi, Tokyo Kuroboshi Gaku 4-4-1 Nishionuma, Sagamihara City, Kanagawa Prefecture
Claims (3)
1〜16のアルキル基又はアルコキシル基を表わし、環
Aは1,4−フェニレン基又はトランス−1,4−シクロ
ヘキシレン基を表わし、mは0又は1を表わし、nは1
又は2を表わす。)で表わされる化合物。1. A compound represented by the general formula (I): (In the formula, R 1 and R 2 each independently represent an alkyl group or an alkoxyl group having 1 to 16 carbon atoms, and the ring A represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group. , M represents 0 or 1, and n represents 1
Or represents 2. ) The compound represented by.
成物。3. A liquid crystal composition containing the compound according to claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22316791A JPH0585971A (en) | 1991-09-03 | 1991-09-03 | Compound having 1,1-difluoroethane link and liquid crystal composition containing the compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22316791A JPH0585971A (en) | 1991-09-03 | 1991-09-03 | Compound having 1,1-difluoroethane link and liquid crystal composition containing the compound |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0585971A true JPH0585971A (en) | 1993-04-06 |
Family
ID=16793853
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP22316791A Withdrawn JPH0585971A (en) | 1991-09-03 | 1991-09-03 | Compound having 1,1-difluoroethane link and liquid crystal composition containing the compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0585971A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1149885A1 (en) * | 2000-04-26 | 2001-10-31 | Chisso Corporation | Cyclohexane derivatives, liquid crystal compositions comprising the same and liquid crystal display devices |
US9868276B2 (en) | 2011-11-29 | 2018-01-16 | Corning Incorporated | Method of treating joint in ceramic assembly |
-
1991
- 1991-09-03 JP JP22316791A patent/JPH0585971A/en not_active Withdrawn
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1149885A1 (en) * | 2000-04-26 | 2001-10-31 | Chisso Corporation | Cyclohexane derivatives, liquid crystal compositions comprising the same and liquid crystal display devices |
US6500503B2 (en) | 2000-04-26 | 2002-12-31 | Chisso Corporation | Cyclohexane derivatives, liquid crystal compositions comprising the same and liquid crystal display devices |
US9868276B2 (en) | 2011-11-29 | 2018-01-16 | Corning Incorporated | Method of treating joint in ceramic assembly |
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