JP4472676B2 - Benzene derivatives - Google Patents

Description

Industrial application fields

式Ｉにおいて、
Ｒは、１８個までの炭素原子を有するアルキル基またはアルケニル基であり、これらの基は非置換であるか、あるいはＣＮによりまたは少なくとも１個のハロゲンにより置換されており、そしてこれらの基中に存在する１個のＣＨ₂基または隣接していない２個以上のＣＨ₂基は−Ｏ−、−Ｓ−、−ＣＯ−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−および−Ｃ≡Ｃ−の群から選択される基により置き換えられていてもよく、 The present invention relates to a fluorinated benzene derivative represented by the following formula I:

In Formula I,
R is an alkyl or alkenyl group having up to 18 carbon atoms, which groups are unsubstituted or substituted by CN or at least one halogen, and in these groups One CH ₂ group present or two or more non-adjacent CH ₂ groups are —O—, —S—, —CO—, —O—CO—, —CO—O— and —C≡C—. Optionally substituted by a group selected from the group

A ¹ is
a) a 1,4-phenylene group in which one or two CH groups present may be replaced by N, or b) a 1,4-cyclohexylene group, this group One CH ₂ group present or _two non-adjacent CH ₂ groups may be replaced by —O— or —S—, or c) 1,4-cyclohexenylene, piperidine 1,4-diyl, 1,4-bicyclo [2.2.2] octylene or naphthalene-2,6-diyl group,
Said groups a) and b) may be substituted by one or more halogen atoms or cyano groups and / or methyl groups,

Z ¹ is —CH ₂ CH ₂ —, —CO—O—, —O—CO—, —CH═CH—, —OCH ₂ —, —CH ₂ O—, —C≡C—, — (CH ₂ ) ₄ −, —CH═CH—CH ₂ CH ₂ — or a single bond,

X is an alkyl or alkoxy group having 1 to 12 carbon atoms, NCS or QY (wherein Q is —O—, —S— or a single bond, and Y is CN, F or Cl. Or a halogenated alkyl group or a halogenated alkenyl group having 1 to 5 carbon atoms),
L ¹ and L ² are each independently H or F, and m is 0, 1 or 2.

  The present invention also relates to the use of these compounds as components of a liquid crystal mixture, and also to a liquid crystal display element and an electro-optical display element containing the liquid crystal mixture according to the present invention.

  The compounds of the formula I can be used as components of liquid crystal mixtures, in particular torsion cells with large twist angles, such as STN or SBE, including twisted cell principles, guest-host effects, deformation effects of aligned phases, or dynamics. It can be used as a component of a liquid crystal mixture for a display based on the effect of static scattering, in particular for a matrix liquid crystal display (MLC display).

  The object of the present invention was to find new and stable liquid crystal compounds or mesogenic compounds which are suitable as components of liquid crystal mixtures and in particular have a relatively low viscosity and a large positive dielectric anisotropy.

４,４−ジ置換２′,３−ジフルオロビフェニルフェニル化合物は、ＤＥ４００７８６３に記載されている。 The compound represented by the following formula is described in JP-A-5-310616:

4,4-disubstituted 2 ', 3-difluorobiphenylphenyl compounds are described in DE 4007863.

  According to the invention, it has been found that the compounds of the formula I are particularly suitable as components of liquid crystal mixtures. In particular, these compounds have a relatively low viscosity. By using these compounds, a stable, outstanding mesophase range and also with advantageous optical and dielectric anisotropy values, and at the same time having very favorable electrical resistance values A liquid crystal mixture can be obtained. As a result, particular benefits can be obtained especially in liquid crystal mixtures for matrix liquid crystal displays (MLC displays) or super twist displays.

Furthermore, by providing the compounds of the formula I, the range of liquid crystal substances suitable for the preparation of liquid crystal mixtures is very generally considerably expanded from the viewpoint of various applications.
The compounds of formula I have a wide range of uses. By selecting substituents, these compounds can be used as substrates that primarily comprise liquid crystal mixtures; however, these compounds can also be added to liquid crystal substrates from other groups of compounds, For example, the dielectric anisotropy and / or optical anisotropy of such a dielectric can be varied and / or its threshold voltage and / or its viscosity and / or its electrical resistance value can be optimized. it can.

The compounds of formula I are pure and colorless and form liquid crystal mesophases in a temperature range that is favorably located for electro-optic applications. These compounds are stable to chemicals, heat and light.
The invention therefore relates to compounds of the formula I, in particular compounds in which L ¹ and / or L ² are fluorine.

The invention furthermore relates to the use of these compounds as components of liquid crystal mixtures.
The invention also relates to a liquid crystal phase containing at least one compound of the formula I, and also to a liquid crystal display element containing this type of phase, in particular an electro-optic display element, more particularly a matrix liquid crystal display.

を表わし、そしてＣｙｃは１,４−シクロヘキシレンまたは１,４−シクロヘキセニレン基を表わし、Ｄｉｏは１,３−ジオキサン−２,５−ジイル基を表わし、Ｄｉｔは１,３−ジチアン−２,５−ジイル基を表わし、Ｐｈｅは１,４−フェニレン基を表わし、Ｐｙｄはピリジン−２,５−ジイル基を表わし、Ｐｙｒはピリミジン−２,５−ジイル基を表わしそしてＢｉはビシクロ〔２.２.２〕オクチレン基を表わすものとする。これらのＣｙｃおよび／またはＰｈｅは非置換であることができ、あるいは置換基として、１個または２個のＦまたはＣＮを有することができる。 For simplicity, in the following description, A ² is

And Cyc represents a 1,4-cyclohexylene or 1,4-cyclohexenylene group, Dio represents a 1,3-dioxane-2,5-diyl group, and Dit represents 1,3-dithian-2. , 5-diyl group, Phe represents a 1,4-phenylene group, Pyd represents a pyridine-2,5-diyl group, Pyr represents a pyrimidine-2,5-diyl group, and Bi represents a bicyclo [2 2.2.2] represents an octylene group. These Cyc and / or Phe can be unsubstituted or can have 1 or 2 F or CN as substituents.

Accordingly, the compound of formula I is a bicyclic or tricyclic compound of the following appendices Ia-In:
R-Cyc-A ² -Phe-X Ia
R-Phe-A ² -Phe-X Ib
R-Dio-A ² -Phe-X Ic
R-Dit-A ² -Phe-X Id
R-Pyd-A ² -Phe-X Ie
R-Pyr-A ² -Phe-X If
^{R-Bi-A 2 -Phe-} X Ig
R-Phe-Z ¹ -A ² -Phe-X Ih
R-Cyc-Z ¹ -A ² -Phe-X Ii
R-Dio-Z ¹ -A ² -Phe-X Ij
R-Dit-Z ¹ -A ² -Phe-X Ik
R-Pyd-Z ¹ -A ² -Phe-X Il
R-Pyr-Z ¹ -A ² -Phe-X Im
^{R-Bi-Z 1 -A 2} -Phe-X In

And tetracyclic compounds represented by the following formulas Io to Iq:
^{R-A 1 -A 1 -A 2} -Phe-X Io
^{R-A 1 -Z 1 -A 1} -A 2 -Phe-X Ip
^{R-A 1 -Z 1 -A 1} -Z 1 -A 2 -Phe-X Iq
Is included.

In the compounds of the attached formulas Ia to Iq containing one or more bridging groups Z ¹ , this bridging member is preferably —CH ₂ CH ₂ —, —CO—O—, —O—CO—. , —CH ₂ O—, —OCH ₂ — or —C≡C—, in particular —CH ₂ CH ₂ —.
R is preferably linear alkyl, and also alkoxy or alkenyl.
The compounds of the formula I preferably contain no more than one group Bi, Pyd, Pyr, Dio and Dit.

Particularly preferred compounds are benzene derivatives of the following formulas I1 to I6:

In the compounds of the formula I, X is preferably CN, NCS, OCN, F, Cl, CF ₃ , OCF ₃ , CF ₂ H, CHF ₂ , CF ₂ Cl, OCF ₂ H, OCF ₂ Cl, OCH ₂ CF ₃ , OCHFCF ₃ , OCF ₂ CF ₃ , OCH ₂ CF ₂ H, OCH = CF ₂ , OCF = CF ₂ , OCF = CCl ₂ , OCH ₂ CF ₂ Cl, CH ₂ CF ₃ , CH ₂ CF ₂ H, OCF = is a _{CH 2, CH = CF 2,} CF = CF 2, CF = CH 2, OCH 3 or C ₂ H _5.

In Formula I, X is _{F, Cl, CN, OCF 3} , OCHFCF 3, OCHF 2, OCH 2 CF 3, the compound is OCF = CF ₂ or OCH = CF ₂ may be mentioned as particularly preferred compounds.

  Furthermore, in the formula I, compounds having 1 or 2 fluorine atoms as substituents in the 1,4-phenylene ring present in the molecule can be mentioned as suitable compounds. Such substituted rings include in particular 2-fluoro-1,4-phenylene and 2,6-difluoro-1,4-phenylene.

  When R is an alkyl group or an alkoxy group, this group can be linear or branched. This group is preferably straight-chain and has 2, 3, 4, 5, 6 or 7 carbon atoms and is therefore preferably ethyl, propyl, butyl, pentyl, hexyl. , Heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, and also methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, deoxy, undecoxy, dodecoxy, tridecoxy Or it can be tetradecoxy.

  Oxaalkyl is preferably linear 2-oxapropyl (= methoxymethyl), 2-(= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

  When R is an alkenyl group, this group can be linear or branched. This group is preferably straight-chain and has 2 to 10 carbon atoms. Thus, this group is in particular vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl. Hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct -1-, -2-, -3, -4-, -5, -6, or -7-enyl, non-1-, -2-, -3-, -4-, -5,- 6-, -7- or -8-enyl, or dec-1-, -2-, -3-, -4-, -5, -6, -7-, -8- or -9-enyl It is.

Among the compounds represented by formula I and its attached formulas, preferred compounds are those in which at least one of the groups present in the molecule has one of the above preferred meanings.
In the compounds of formula I, preferred stereoisomers are those in which the ring Cyc and piperidine present in the molecule are trans-1,4-disubstituted. Each of the compounds of the above formula containing one or more groups Pyd, Pyr and / or Dio includes two 2,5-positional isomers.

The 1,4-cyclohexenylene group preferably has the following structure:

  The compounds of the formula I can be accurately obtained by methods known per se, as described in publications (for example, standard academic books such as Methoden der Organischen Chemie, Georg-Thieme by Houben-Weyl, Stuttgart). Can be produced under known reaction conditions suitable for the reaction. Variations which are known per se but are not described in detail here can also be used.

The fluorocyclohexene derivative represented by the formula I according to the present invention can be produced, for example, by the following method:

In the following, the synthesis of some particularly preferred compounds will be described in more detail:

  The liquid crystal mixture according to the invention preferably contains 2 to 40, in particular 4 to 30 components as additional components other than one or more compounds according to the invention. These mixtures very particularly preferably contain 7 to 25 components in addition to one or more compounds according to the invention. These additional components are preferably nematic or nematogenic (mono-modified or isotropic) substances, in particular azoxybenzene compounds, benzylideneaniline compounds, biphenyl compounds, terphenyl compounds, phenyl or cyclohexylbenzoate compounds, phenyl cyclohexanecarboxylic acids Or cyclohexyl ester compound, cyclohexyl benzoic acid phenyl or cyclohexyl ester compound, cyclohexyl cyclohexane carboxylic acid phenyl or cyclohexyl ester compound, benzoic acid cyclohexyl phenyl ester compound, cyclohexane carboxylic acid cyclohexyl phenyl ester compound, cyclohexyl cyclohexane carboxylic acid cyclohexyl phenyl Ester compound, phenylcyclohexa Compound, cyclohexylbiphenyl compound, phenylcyclohexylcyclohexane compound, cyclohexylcyclohexane compound, cyclohexylcyclohexene compound, cyclohexylcyclohexylcyclohexene compound, 1,4-bis-cyclohexylbenzene compound, 4,4'-bis-cyclohexylbiphenyl compound, phenyl- or cyclohexyl- Pyrimidine compound, phenyl- or cyclohexyl-pyridine compound, phenyl- or cyclohexyl-dioxane compound, phenyl- or cyclohexyl-1,3-dithiane compound, 1,2-diphenylethane compound, 1,2-dicyclohexylethane compound, 1-phenyl 2-cyclohexylethane compound, 1-cyclohexyl-2- (4-phenylcyclohexyl) Of ethane compounds, 1-cyclohexyl-2-biphenylylethane compounds, 1-phenyl-2-cyclohexylphenylethane compounds, optionally substituted halogenated stilbene compounds, benzylphenyl ether compounds, tolan compounds and substituted cinnamic acid compounds Selected from substances from the group. The 1,4-phenylene group present in these compounds may be fluorinated.

The most important compounds suitable as additional components of the mixtures according to the invention can be characterized in that they are represented by the following formulas 1, 2, 3, 4 and 5:
R'-LE-R "1
R'-L-COO-ER "2
R'-L-OOC-ER "3
_{R'-L-CH 2 CH 2} -E-R "4
R'-LC = C-E-R "5

  In the formulas 1, 2, 3, 4 and 5, L and E may be the same or different and each independently represent -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc. Divalent groups from the group formed from-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- and their mirror image groups, in these groups , Phe is unsubstituted or fluorine substituted 1,4-phenylene, Cyc is trans-1,4-cyclohexylene or 1,4-cyclohexenylene, and Pyr is pyrimidine-2,5- Diyl or pyridine-2,5-diyl, Dio is 1,3-dioxane-2,5-diyl, and G is 2- (trans-1,4-cyclohexyl) ethyl, pyrimidine-2,5- Gii , Pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.

  One of the groups L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. The mixture according to the present invention is preferably one or more components selected from the compounds selected from the group consisting of Cyc, Phe and Pyr in formulas 1, 2, 3, 4 and 5. And simultaneously, in formulas 1, 2, 3, 4 and 5, one of the groups L and E is selected from the group consisting of Cyc, Phe and Pyr and the other group is -Phe-Phe-, -Phe-Cyc One, two or more components selected from a compound selected from the group consisting of-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and also optionally formula 1, 2, 3 1 and 2 wherein the groups L and E in 4 and 5 are selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc- more than Containing component.

In the compounds of the attached formulas 1a, 2a, 3a, 4a and 5a, R 'and R "each independently of the other are alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyl having up to 8 carbon atoms In most of these compounds, R ′ and R ″ are different from each other, and one of these groups is usually alkyl or alkenyl. In the compounds represented by the attached formulas 1b, 2b, 3b, 4b and 5b, R ″ is —CN, —CF ₃ , F, Cl or —NCS. In this case, R is represented by the attached formulas 1a to 5a. The above-mentioned meanings relating to the compounds are preferred, preferably alkyl or alkenyl, but various other substituents proposed for the compounds of formulas 1, 2, 3, 4 and 5 are also conventional. Many such materials, or alternatively, mixtures thereof, are commercially available, all of which can be obtained by methods known from publications or similar methods.

The phase according to the invention is preferably in addition to the components from the group consisting of compounds 1a, 2a, 3a, 4a and 5a (group 1) and also from the group consisting of compounds 1b, 2b, 3b, 4b and 5b (group 2). ), The proportions of which are preferably as follows:
Group 1: 20-90%, especially 30-90%
Group 2: 10-80%, especially 10-50%.
The sum of the proportions of the compounds according to the invention and the proportions of the compounds from group 1 and group 2 added is up to 100%.

  The mixture according to the invention preferably contains 1 to 40%, particularly preferably 5 to 30% of the compound according to the invention. Further preferred mixtures contain more than 40% of the compounds according to the invention, in particular 45 to 90%. The mixtures according to the invention preferably contain 3, 4 or 5 compounds according to the invention.

The mixtures according to the invention can themselves be prepared by conventional methods. In general, the components are dissolved in each other, preferably at elevated temperatures. By using suitable additives, these liquid crystal mixtures can be modified in accordance with the present invention in such a manner that these mixtures can be used in any type of liquid crystal display device previously disclosed. . Such additives are known to the person skilled in the art and are described in detail in the publication (Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980 by H. Kelker / R. Hatz). For example, pleochroic dyes can be added to prepare a colored guest-host system, or materials can be added to alter the dielectric anisotropy, viscosity and / or orientation of the nematic phase. .
In particular, the phase according to the invention is suitable for use in MLC displays.

The following examples are illustrative of the invention and are not intended to limit the invention. In the above description and the following description, the percentage is weight percent. All temperatures are given in degrees Celsius. mp = melting point and cp = clearing point. Further, C = crystalline state, N = nematic state, S = smectic phase, and I = isotropic phase. The number between these symbols represents the transition temperature. Δn represents the optical anisotropy (589 nm, 20 ° C.), and the viscosity (mm ² / sec) was measured at 20 ° C.

The term “work-up in a conventional manner” means that water is added, the mixture is extracted with dichloromethane, methyl tert-butyl ether or diethyl ether, the organic phase is separated off, dried and then evaporated, It shall be meant that the product is purified by crystallization and / or chromatography. Use the following abbreviations:
DAST diethylaminosulfur trifluoride DCC dicyclohexylcarbodiimide DDQ dichlorodicyanobenzoquinone DIBALH diisobutylaluminum hydride DMSO dimethylsulfoxide POT potassium tert-butoxide THF tetrahydrofuran pTsOH p-toluenesulfonic acid

ＴＨＦ ２５０ml中のマグネシウム片１モルの懸濁液に、臭素数滴を添加する。引き続いて、ＴＨＦ ２５０ml中の１−ブロモ−４−フルオロベンゼン１モルの溶液を、少しずつ滴下して添加する。この混合物を１.５時間還流させ、次いでこのグリニアル試薬に、沸騰温度で、ＴＨＦ ５００ml中の４−トランス−４−プロピルシクロヘキシルシクロヘキサノン０.９モルを滴下して添加する。この混合物を１.５時間還流させ、次いで３０℃において、水１.５リットルおよび濃ＨＣｌ ２００mlを添加する。この混合物をさらに１／４時間撹拌し、この有機相を分離採取し、この水性相はメチル tert−ブチルエーテルにより抽出し、これらの有機相を集め、次いで慣用の方法で仕上げ処理する。 Example 1

A few drops of bromine are added to a suspension of 1 mole of magnesium in 250 ml of THF. Subsequently, a solution of 1 mol of 1-bromo-4-fluorobenzene in 250 ml of THF is added dropwise in small portions. The mixture is refluxed for 1.5 hours and then 0.9 mol of 4-trans-4-propylcyclohexylcyclohexanone in 500 ml of THF is added dropwise to the Grignard reagent at the boiling temperature. The mixture is refluxed for 1.5 hours, then at 30 ° C. 1.5 liters of water and 200 ml of concentrated HCl are added. The mixture is stirred for a further 1/4 hour, the organic phase is separated off, the aqueous phase is extracted with methyl tert-butyl ether, the organic phases are collected and then worked up in the conventional manner.

１ａ）からのシクロヘキセン誘導体０.２モルを、ＴＨＦ ５００ml中に溶解し、次いでＢＨ₃・ＴＨＦ錯体２４０mlを、＋２℃で０.５時間にわたり添加する。この混合物を＋２℃で、さらに１時間撹拌し、室温まで温め、次いでさらに１時間撹拌する。エタノール６０mlを添加し、この混合物を３０℃に温め、次いで先ず６Ｎ ＮａＯＨ ４０mlを、次に３０％Ｈ₂Ｏ₂ ８０mlを添加する。この混合物を２時間還流させ、室温まで冷却し、次いで加水分解する。この水性相は分離し、この有機相をメチル tert−ブチルエーテル２５０mlにより稀釈する。この有機相を５％ＮａＨＳＯ₃溶液および水により洗浄し、次いでＮａ₂ＳＯ₄上で乾燥させる。この溶剤をロータベーパーで除去し、残留物をｎ−ヘキサンから再結晶させる。

0.2 mol of the cyclohexene derivative from 1a) is dissolved in 500 ml of THF and then 240 ml of BH ₃ .THF complex are added at + 2 ° C. over 0.5 hours. The mixture is stirred at + 2 ° C. for a further hour, warmed to room temperature and then stirred for a further hour. 60 ml of ethanol are added and the mixture is warmed to 30 ° C., then 40 ml of 6N NaOH and then 80 ml of 30% H ₂ O ₂ are added. The mixture is refluxed for 2 hours, cooled to room temperature and then hydrolyzed. The aqueous phase is separated and the organic phase is diluted with 250 ml of methyl tert-butyl ether. The organic phase is washed with 5% NaHSO ₃ solution and water and then dried over Na ₂ SO ₄ . The solvent is removed with a rotor vapor and the residue is recrystallized from n-hexane.

ｂ）からのシクロヘキサノール誘導体０.０９４モルを、窒素雰囲気の下に、ジクロロメタン２５０ml中に溶解し、次いでピリジニウム クロロクロメート０.１４モルを添加する。この反応混合物を２時間還流させ、次いで蒸発させる。この残留物をＡｌ₂Ｏ₃／シリカゲルカラムにおいて精製する。

0.094 mol of the cyclohexanol derivative from b) is dissolved in 250 ml of dichloromethane under a nitrogen atmosphere and then 0.14 mol of pyridinium chlorochromate is added. The reaction mixture is refluxed for 2 hours and then evaporated. The residue is purified on an Al ₂ O ₃ / silica gel column.

ジクロロメタン２０ml中のｃ）からのシクロヘキサノン誘導体（０.０２モル）を、室温で、ジクロロメタン１５ml中のＤＡＳＴ ０.０３８２モルに添加する。この混合物を４時間還流させ、この反応溶液を一夜にわたって、室温まで冷却させる。この混合物を氷冷却して加水分解し、引き続いて慣用の方法により仕上げ処理する：

Cyclohexanone derivative (0.02 mol) from c) in 20 ml of dichloromethane is added at room temperature to 0.0382 mol of DAST in 15 ml of dichloromethane. The mixture is refluxed for 4 hours and the reaction solution is allowed to cool to room temperature overnight. The mixture is hydrolyzed with ice cooling and subsequently worked up by conventional methods:

この生成物（０.０１モル）は、さらに精製することなく、ＴＨＦ ５０ml中に溶解し、カリウム tert−ブトキシド０.０３モルを添加し、この混合物を次いで、Ｎ₂雰囲気の下に、５０℃で１１時間撹拌する。この混合物を室温まで冷却させ、氷水および濃ＨＣｌを添加し、この混合物をメチル tert−ブチルエーテルにより抽出し、引き続いて慣用の方法により仕上げ処理に付する。
Ｃ ４０ Ｎ １２４.５ Ｉ；△ｎ＝＋０.１０６；△ε＝６.７６

This product (0.01 mol) is dissolved in 50 ml of THF without further purification, 0.03 mol of potassium tert-butoxide is added and the mixture is then placed under N ₂ atmosphere at 50 ° C. For 11 hours. The mixture is allowed to cool to room temperature, ice water and concentrated HCl are added, the mixture is extracted with methyl tert-butyl ether and subsequently worked up by conventional methods.
C 40 N 124.5 I; Δn = + 0.106; Δε = 6.76

で表わされる、次の化合物を製造する： Similarly, the following formula:

The following compounds represented by:

エーテル６０ml中のマグネシウム片０.２５モルの懸濁液に、臭素２滴を添加する。引き続いて、エーテル６０ml中の３,５−ジフルオロ−４−トリフルオロメトキシブロモベンゼン０.２モルの溶液を、滴下して添加する。この混合物をさらに０.５時間撹拌し、次いでこのグリニアル試薬に、２０〜２５℃で、エーテル５０ml中の４−トランス−４−プロピルシクロヘキシルシクロヘキサノン０.２モルの溶液を滴下して添加する。この混合物をさらに２時間撹拌し、水５００ml中に注ぎ入れ、酸性にし、次いでエーテルと振り混ぜることによって抽出する。この有機相を蒸発乾燥させる。この残留物を、トルエン中に溶解し、次いで水分離器上で、ｐ−トルエンスルホン酸とともに、５時間還流させる。この混合物を引き続いて、室温まで冷却させ、中和し、次いで慣用の方法で仕上げ処理に付する。 Example 2

Two drops of bromine are added to a suspension of 0.25 moles of magnesium pieces in 60 ml of ether. Subsequently, a solution of 0.2 mol of 3,5-difluoro-4-trifluoromethoxybromobenzene in 60 ml of ether is added dropwise. The mixture is stirred for a further 0.5 hours and then a solution of 0.2 mol of 4-trans-4-propylcyclohexylcyclohexanone in 50 ml of ether is added dropwise to the Grignard reagent at 20-25 ° C. The mixture is stirred for a further 2 hours, poured into 500 ml of water, acidified and then extracted by shaking with ether. The organic phase is evaporated to dryness. This residue is dissolved in toluene and then refluxed with p-toluenesulfonic acid for 5 hours on a water separator. This mixture is subsequently allowed to cool to room temperature, neutralized and then worked up in a conventional manner.

例１ａ）からのシクロヘキセン誘導体０.２モルを、ＴＨＦ ２００ml中に溶解し、次いでホウ水素化ナトリウム０.２ｇを添加する。この混合物にＢＦ₃・エーテレート０.２４モルを滴下して添加する。この期間中、反応混合物の温度は、１０℃を越えてはならない。この混合物を引き続いて室温で、さらに２時間撹拌する。加水分解の後に、さらに仕上げ処理することなく、この反応混合物に、ナトリウムジクロメートの硫酸溶液を直接に添加する。この酸化期間中、反応温度は、１５℃を越えてはならない。この混合物を、室温でさらに１時間撹拌し、次いで３０℃でさらに０.５時間撹拌する。この混合物を濾過し、エーテルにより抽出し、次に水により洗浄し、引き続いて溶剤を減圧の下に除去する。この残留物をクロマトグラフィにより精製する。

0.2 mol of the cyclohexene derivative from example 1a) is dissolved in 200 ml of THF and then 0.2 g of sodium borohydride is added. To this mixture, 0.24 mol of BF ₃ .etherate is added dropwise. During this period, the temperature of the reaction mixture should not exceed 10 ° C. The mixture is subsequently stirred at room temperature for a further 2 hours. After hydrolysis, sodium dichromate in sulfuric acid is added directly to the reaction mixture without further workup. During this oxidation period, the reaction temperature must not exceed 15 ° C. The mixture is stirred at room temperature for a further hour and then at 30 ° C. for a further 0.5 hour. The mixture is filtered and extracted with ether, then washed with water and the solvent is subsequently removed under reduced pressure. The residue is purified by chromatography.

ｂ）からのケトン０.０１モルを、６０℃で１５時間、ジエチルアミノサルファトリフルオライド０.０２５モルにより処理する。この混合物を次いで、氷水中に、撹拌しながら滴下して導入する。エーテルの添加後に、この有機相を分離採取し、次いで慣用の仕上げ処理に付する。

0.01 mol of the ketone from b) is treated with 0.025 mol of diethylaminosulfur trifluoride at 60 ° C. for 15 hours. This mixture is then introduced dropwise into ice water with stirring. After the ether addition, the organic phase is separated off and then subjected to conventional work-up.

ＴＨＦ １０ml中のＢｕＬｉ（ｎ−ヘキサン中の１５％）１３.５モルに、−２０℃において、ジイソプロピルアミン１３.５モルを滴下して添加する。この溶液を次いで、１０分間撹拌し、次いでＴＨＦ １０mlおよびｃ）からのジェムのジフッ素化合物１３.５モルからなる混合物に、保護気体の下に−４０℃で、滴下して添加する。
この混合物を先ず−４０℃で０.５時間、引き続いて室温で一夜にわたり、撹拌する。加水分解の後に、この生成物を慣用の仕上げ処理に付する。
△ε＝１５.５；△ｎ＝＋０.０７９

To 13.5 mol BuLi (15% in n-hexane) in 10 ml THF is added dropwise at -20 ° C 13.5 mol diisopropylamine. This solution is then stirred for 10 minutes and then added dropwise at −40 ° C. under a protective gas to a mixture consisting of 10 ml of THF and 13.5 mol of gem difluoride compound from c).
The mixture is first stirred at −40 ° C. for 0.5 hour and subsequently at room temperature overnight. After hydrolysis, the product is subjected to conventional finishing.
Δε = 15.5; Δn = + 0.079

Example 3

４−（トランス−４−プロピルシクロヘキシル）−２−フルオロベンゼン１.２モル、カリウム tert−ブトキシド１.２モルおよびＴＨＦ ３リットルに、窒素雰囲気の下に−１００℃で１時間にわたり、ｎ−ブチルリチウム（ｎ−ヘキサン中の１５％）１.３２モルを滴下して添加する。この混合物をさらに１時間撹拌し、次いでこの反応混合物に、−１００℃で、ホウ酸トリメチル１.３８モルを滴下して添加し、この反応混合物をさらに１.５時間撹拌する。１８％ＨＣｌ ３.６リットルを添加し、この有機相を分離採取し、この水性相はトルエンにより抽出する。有機抽出液を集め、引き続いて慣用の仕上げ処理に付する。 Step 3.1

4- (trans-4-propylcyclohexyl) -2-fluorobenzene, 1.2 mol of potassium tert-butoxide and 3 liters of THF, at −100 ° C. under nitrogen atmosphere for 1 hour, 1.32 mol of lithium (15% in n-hexane) is added dropwise. The mixture is stirred for a further hour, then 1.38 mol of trimethyl borate are added dropwise to the reaction mixture at −100 ° C. and the reaction mixture is stirred for a further 1.5 hours. 3.6 l of 18% HCl is added, the organic phase is separated off and the aqueous phase is extracted with toluene. The organic extract is collected and subsequently subjected to conventional finishing.

４−（トランス−４−プロピルシクロヘキシル）−２−フルオロフェニルボロン酸０.１３モル、３,４−ジフルオロブロモベンゼン０.１３モル、トルエン３２５mlおよびエタノール１３０mlに、テトラキス（トリフェニルホスフィン）パラジウム(Ｏ)１.６ｇおよび炭酸ナトリウム溶液（Ｈ₂Ｏ １５０ml中のＮａ₂ＣＯ₃ ４１.６６ｇ）を添加する。この混合物を室温まで冷却させ、この有機相を分離採取する。水性相はトルエンにより抽出し、これらの有機抽出液を集め、次いで慣用の仕上げ処理に付する。
Ｃ ４２ Ｎ ５７.１ Ｉ；△ｎ＝＋０.１３１；△ε＝１０.０１ Step 3.2

To 0.13 mol of 4- (trans-4-propylcyclohexyl) -2-fluorophenylboronic acid, 0.13 mol of 3,4-difluorobromobenzene, 325 ml of toluene and 130 ml of ethanol were added tetrakis (triphenylphosphine) palladium (O ) 1.6 g and sodium carbonate solution (41.66 g Na ₂ CO _{3 in} 150 ml H ₂ O). The mixture is allowed to cool to room temperature and the organic phase is separated off. The aqueous phase is extracted with toluene and these organic extracts are collected and then subjected to conventional finishing.
C 42 N 57.1 I; Δn = + 0.131; Δε = 1.01

で表わされる次の化合物を製造する：
Similarly, the following formula:

The following compounds represented by:

Example 4

水素化ナトリウム（６０％）１.０モルを、窒素雰囲気の下に、ＴＨＦ２００ml中に懸濁し、次いでＴＨＦ４００ml中に溶解した４−ブロモ−２−フルオロフェノール１.０モルを０℃で、滴下して添加する。この混合物を室温まで温め、０.５時間撹拌し、次いで濾過する。この濾液を蒸発させ、トルエン中に溶解し、次いで結晶形態まで蒸発させる。この残留物を、石油エーテルを用いて沈殿させる。この結晶を吸引濾別し、次いで乾燥させる。 Step 4.1

1.0 mol of sodium hydride (60%) is suspended in 200 ml of THF under a nitrogen atmosphere, and then 1.0 mol of 4-bromo-2-fluorophenol dissolved in 400 ml of THF is added dropwise at 0 ° C. Add. The mixture is warmed to room temperature, stirred for 0.5 hour, and then filtered. The filtrate is evaporated, dissolved in toluene and then evaporated to crystalline form. This residue is precipitated using petroleum ether. The crystals are filtered off with suction and then dried.

２.１からのフェノキシド０.０８モルを、ＤＭＥＵ８０ml中に導入し、この混合物を５０℃に加熱する。１,２,２,２−テトラフルオロ−１−ヨウドエタン０.０８８モルを添加し、この混合物を次いで、５０℃で１６時間撹拌する。この混合物を室温まで冷却させ、次いで水を加える。この混合物を、稀ＨＣｌを用いて酸性にし、メチル tert−ブチルエーテルにより、次いで１０％ＮａＯＨおよび水により抽出し、Ｎａ₂ＳＯ₄上で乾燥させ、次いで濾過する。この濾液を蒸発させ、残留物を次いでバルブチューブ中で８００ミリバールにおいて、蒸留する。 Step 4.2

0.08 mol of phenoxide from 2.1 is introduced into 80 ml of DMEU and the mixture is heated to 50 ° C. 0.088 mol of 1,2,2,2-tetrafluoro-1-iodoethane is added and the mixture is then stirred at 50 ° C. for 16 hours. The mixture is allowed to cool to room temperature and then water is added. The mixture is acidified with dilute HCl, extracted with methyl tert-butyl ether, then with 10% NaOH and water, dried over Na ₂ SO ₄ and then filtered. The filtrate is evaporated and the residue is then distilled in a valve tube at 800 mbar.

１−（１,２,２,２−テトラフルオロエトキシ）−２−フルオロ−４−ブロモベンゼン０.０１３モルをＴＨＦ５０mlに溶解し、この溶液を６０℃に加熱し、次いで４−（トランス−４−プロピルシクロヘキシル）−２−フルオロフェニルホウ酸０.０１２モルおよびＫＨ₂ＰＯ₄ ０.０１３モル、Ｎａ₂ＨＰＯ₄ ０.０２５モルおよび水２５mlからなる溶液を添加する。テトラキストリフェニルパラジウム（Ｏ）０.０１２モルを添加し、この混合物を７０℃で一夜にわたり撹拌し、室温まで冷却させ、次いで慣用の仕上げ処理に付する。 Step 4.3

0.013 mol of 1- (1,2,2,2-tetrafluoroethoxy) -2-fluoro-4-bromobenzene is dissolved in 50 ml of THF, the solution is heated to 60 ° C. and then 4- (trans-4 - adding a solution consisting of propyl cyclohexyl) -2-fluorophenyl borate 0.012 mol and KH ₂ PO ₄ 0.013 mol, Na ₂ HPO ₄ 0.025 mol and water 25 ml. Tetrakistriphenylpalladium (O) 0.012 mol is added and the mixture is stirred at 70 ° C. overnight, allowed to cool to room temperature and then subjected to conventional workup.

で表わされる次の化合物を製造する： Similarly, the following formula

The following compounds represented by:

Example 5

ナトリウム １−ブロモ−３,５−ジフルオロフェノキシド０.０５モルを、窒素雰囲気の下に、ＤＭＥＵ５０ml中に導入し、この混合物を次いで、５０℃に加熱する。１−ブロモ−２,２−ジフルオロエタン０.０５mlを撹拌しながら、滴下して添加する。この混合物を引き続いて、５０℃で一夜にわたり撹拌する。１−ブロモ−２,２−ジフルオロエタン０.００５モルを加え、この混合物を７０℃でさらに２４時間撹拌し、次いで室温まで冷却させ、水を加え、この混合物を次いで、慣用の仕上げ処理に付する。 Step 5.1

0.05 mol of sodium 1-bromo-3,5-difluorophenoxide is introduced into 50 ml of DMEU under a nitrogen atmosphere and the mixture is then heated to 50 ° C. Add 0.05 ml of 1-bromo-2,2-difluoroethane dropwise with stirring. The mixture is subsequently stirred at 50 ° C. overnight. 0.005 mol of 1-bromo-2,2-difluoroethane is added and the mixture is stirred at 70 ° C. for a further 24 hours, then allowed to cool to room temperature, water is added and the mixture is then subjected to conventional workup. .

トルエン６０ml中のｐ−トランス〔４−プロピルシクロヘキシル〕−２−フルオロフェニルホウ酸０.０３モルを、水３０ml中のＮａＯＨ ４.８ｇに添加し、この混合物を４５℃で０.５時間撹拌する。この溶液に、１−（２,２−ジフルオロエトキシ）−４−ブロモ−２,６−ジフルオロベンゼン０.０３モルおよびテトラキス（トリフェニルホスフィン）パラジウム（Ｏ）０.７ｇを添加し、この混合物を１００℃で一夜にわたり撹拌する。この混合物を室温まで冷却させ、次いでこの有機相を分離採取する。溶剤をロータベーパー上で除去し、残留物を、５０〜７０℃で石油エーテルを用いて、シリカゲルフリットに通すことにより濾過する。この濾液を蒸発させ、次いで残留物をｎ−ヘキサンから再結晶させる。
Ｃ ５６ Ｎ ９７.２ Ｉ；△ｎ＝＋０.１３９；△ε＝１２.３４ Step 5.2

0.03 mol of p-trans [4-propylcyclohexyl] -2-fluorophenylboric acid in 60 ml of toluene is added to 4.8 g of NaOH in 30 ml of water and the mixture is stirred at 45 ° C. for 0.5 hour. . To this solution was added 0.03 mole of 1- (2,2-difluoroethoxy) -4-bromo-2,6-difluorobenzene and 0.7 g of tetrakis (triphenylphosphine) palladium (O) and the mixture was added. Stir at 100 ° C. overnight. The mixture is allowed to cool to room temperature and the organic phase is then separated off. The solvent is removed on a rotavapor and the residue is filtered by passing through a silica gel frit with petroleum ether at 50-70 ° C. The filtrate is evaporated and then the residue is recrystallized from n-hexane.
C 56 N 97.2 I; Δn = + 0.139; Δε = 12.34

で表わされる次の化合物を製造する： Similarly, the following formula:

The following compounds represented by:

Example 6

４−ブロモ−２−フルオロフェノキシド０.０８５モルを、１,３−ジメチル−２−イミダゾリジノン１００リットルに溶解し、この溶液を１４０℃に加熱し、次いで２,２,２−トリフルオロエチル メチルスルホネート０.０９モルを滴下して添加する。この溶液を、１４０℃で２４時間撹拌する。引き続いて、氷水５００mlを添加し、この混合物を慣用の仕上げ処理に付する。 Step 6.1

0.085 mol of 4-bromo-2-fluorophenoxide is dissolved in 100 liters of 1,3-dimethyl-2-imidazolidinone, the solution is heated to 140 ° C. and then 2,2,2-trifluoroethyl 0.09 mol of methyl sulfonate is added dropwise. The solution is stirred at 140 ° C. for 24 hours. Subsequently, 500 ml of ice water are added and the mixture is subjected to conventional finishing.

トランス−ｎ−ペプチルシクロヘキシル−２−フルオロフェニルホウ酸０.０５モル、トルエン２０ml、エタノール１０ml、Ｎａ₂ＣＯ₃ ０.０３０モルおよびテトラキス（トリフェニルホスフィン）パラジウム（Ｏ）０.８６モルを、４−ブロモ−２−フルオロフェニル ２,２,２−トリフルオロエチルエーテル０.０１５モルに添加し、この混合物を２時間還流させる。石油エーテル（４０〜８０°）１００mlを加え、この混合物を慣用の仕上げ処理に付する。 Step 6.2

0.05 mol of trans-n-peptylcyclohexyl-2-fluorophenylboric acid, 20 ml of toluene, 10 ml of ethanol, 0.030 mol of Na ₂ CO ₃ and 0.86 mol of tetrakis (triphenylphosphine) palladium (O) 4-Bromo-2-fluorophenyl 2,2,2-trifluoroethyl ether is added to 0.015 mol and the mixture is refluxed for 2 hours. 100 ml of petroleum ether (40-80 °) are added and the mixture is subjected to conventional finishing.

ＴＨＦ １０ml中のＢｕＬｉ（ｎ−ヘキサン中の１５％）１３.５ミリモルに、−２０℃において、ジイソプロピルアミン１３.５ミリモルを滴下して添加する。この溶液を引き続いて、１０分間撹拌し、次いでＴＨＦ １０ml、トランス−ｎ−ペンチルシクロヘキシルフェニル−２−フルオロフェニル ２,２,２−トリフルオロエチルエーテル１３.５ミリモルからなる混合物に、保護気体の下で−４０℃において滴下して添加する。この混合物を先ず、−４０℃で０.５時間、引き続いて室温で一夜にわたり、撹拌する。この添加後に、この混合物を慣用の仕上げ処理に付する。
Ｃ ４８ Ｎ ９６.６ Ｉ； △ｎ＝＋０.１４４； △ε＝８.２４ Step 6.3

To 13.5 mmol of BuLi (15% in n-hexane) in 10 ml of THF is added dropwise at -20 ° C. 13.5 mmol of diisopropylamine. The solution is subsequently stirred for 10 minutes, and then a mixture of 10 ml THF, 13.5 mmol trans-n-pentylcyclohexylphenyl-2-fluorophenyl 2,2,2-trifluoroethyl ether is added under protective gas. Add dropwise at -40 ° C. The mixture is first stirred at −40 ° C. for 0.5 hour and subsequently at room temperature overnight. After this addition, the mixture is subjected to conventional finishing.
C 48 N 96.6 I; Δn = + 0.144; Δε = 8.24

で表わされる化合物を製造する： In the same manner as in Example 3, by boric acid coupling, the following formula:

To produce a compound represented by:

１−トリフルオロメトキシ−２−フルオロ−４−ブロモベンゼン０.０５モルおよび４−（トランス−４−プロピルシクロヘキシル）−２−フルオロフェニルホウ酸０.０５モルを、トルエン１２５mlおよびエタノール５０ml中に溶解し、次いでテトラキス（トリフェニルホスフィン）パラジウム（Ｏ）０.６ｇおよびＮａ₂ＣＯ₃溶液（Ｈ₂Ｏ ６０ml中のＮａ₂ＣＯ₃ １５.９ｇ）を順次添加する。この混合物を、３時間還流させ、次いで室温まで冷却させ、この有機相を分離採取する。水性相はトルエンにより抽出し、有機抽出液を集め、次いで慣用の仕上げ処理に付する。
Ｃ ４３ Ｎ ６６.３ Ｉ；△ｎ＝＋０.１２４；△ε＝１２.５５ Example 7

0.05 mol of 1-trifluoromethoxy-2-fluoro-4-bromobenzene and 0.05 mol of 4- (trans-4-propylcyclohexyl) -2-fluorophenylboric acid are dissolved in 125 ml of toluene and 50 ml of ethanol. and then sequentially added tetrakis (triphenylphosphine) palladium (O) 0.6 g, and solution of Na ₂ CO ₃ (Na ₂ CO ₃ 15.9 g in H ₂ O 60 ml). The mixture is refluxed for 3 hours, then allowed to cool to room temperature and the organic phase is separated off. The aqueous phase is extracted with toluene, the organic extract is collected and then subjected to conventional finishing.
C 43 N 66.3 I; Δn = + 0.124; Δε = 12.55

で表わされる次の化合物を製造する： Similarly, the following formula:

The following compounds represented by:

Claims (7)

A benzene derivative represented by the following formula I:

[Where,
R is an alkyl group having up to 18 carbon atoms or an alkenyl group having one double bond, which groups are unsubstituted or substituted by CN or by at least one halogen And one CH ₂ group present in these groups or two or more non-adjacent CH ₂ groups are represented by —O—, —S—, —CO—, —O—CO—, —CO—. Optionally substituted by a group selected from the group of O- and -C≡C-

A ¹ is a 1,4-phenylene group which may be substituted with fluorine;
Z ¹ is a single bond,
X is NCS or OCH = CF _2,
L ¹ and L ² are each independently H or F, and m is 1.] 2. A compound according to claim 1 wherein L < ¹ > and / or L < ² > is fluorine. In the formula I according to claim 1, compounds wherein X is O CH = CF _2.   Use of a compound of formula I according to claim 1 as a component of a liquid crystal mixture for electro-optic display elements.   A liquid crystal mixture containing at least two components, wherein one or more components are compounds represented by formula I according to claim 1. An electro-optic display element comprising the liquid crystal mixture according to claim 5 as a dielectric. 6. A matrix liquid crystal display device comprising the liquid crystal mixture according to claim 5 as a dielectric.