DE4000534A1 - New 1,4-di-substd. 2,6-di:fluoro:benzene derivs. - used in components of liq. crystal media as dielectric giving good stability to UV and temp. - Google Patents

Abstract

1,4-Di-substd. 2,6-difluorobenzene cpds. of formula (I) are new. In (I) R1, R2 = H or 1-15C alk(en)yl (opt. substd. by halogen), where 1 or more CH2 gps. may be replaced by -O-. -S-, gps. (i),(ii) -CO-, -CO-O-, -O-CO- or -O-CO-O, that O atoms are not directly linked to one another; A1,A2 = (a) trans-1,4-cyclohexylene, where 1 or more non-vicinal CH2 gps. may be replaced by -O- and/or -S-, (b) 1,4-phenylene, where 1 or 2 CH gps. may be replaced by N, or (c) 1,4-cyclohexenylene, 1,4-bicyclo (2,2,2)-octylene, piperidin-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydro naphthalene-2,6-diyl, and where gps. (a) and (b) may be substd. by CN or F; Z1,Z2 = -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH2CH2-, -CH=CH-, -C=C- or a simple bond; m,n = 0-2; m+n = 1-3; and at least 1 of Z1 and Z2 = -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH2CH2-, -CH=CH- or -C=C-, and/or at least 1 of A1 and A2 = gps. (iii) or (iv) and/or n = 1 or 2, and if n = 2, then -(Z2-A2)n is not gp. (v). USE/ADVANTAGE - (I) are components of liq. crystal media, and liq. crystal media contg. at least 2 liq. crystal components, at least 1 being (I). Liq. crystal recording units contain the liq. crystal media, and electro-optical recording units contain liq. crystal media as dielectric. (I) are colourless, liq. crystalline or mesogenic cpds., with low viscosity, hgih dielectric anisotropy, and excellent stability to UV and temp.

Description

The invention relates to novel 1,4-disubstituted 2,6-difluorobenzene compounds of the formula I,

wherein
R¹ and R² are each independently H or an unsubstituted or at least monosubstituted by halogen alkyl or alkenyl radical having 1 to 15 carbon atoms, wherein in these radicals also one or more CH₂ groups each independently

may be replaced so that O atoms are not directly linked to each other,
A¹ and A² each independently

• (a) trans-1,4-cyclohexylene radical, wherein also one or more non-adjacent CH₂ groups replaced by -O- and / or -S- could be,
• (b) 1,4-phenylene radical, wherein also one or two CH groups have to be replaced by N. can,
• (c) radical from the group 1,4-cyclohexenylene, 1,4-bicyclo (2,2,2) octylene, piperidine-1,4-diyl, Naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,

where radicals (a) and (b) may be substituted by CN or fluorine,
Z¹ and Z² are each independently of one another -CO-O-, -O-CO-, -CH₂O-, -OCH₂-, -CH₂CH₂-, -CH = CH-, -C≡C- or a single bond,
m and n are each independently 0, 1 or 2, wherein
(m + n) is 1, 2 or 3,
with the proviso that at least one of the radicals Z¹ and Z² present in the molecule is -CO-O-, -O-CO-, -CH₂O-, -OCH₂-, -CH₂CH₂-, -CH = CH- or -C≡C- means and / or at least one of the radicals A¹ and A² present in the molecule

and / or n is 1 or 2, wherein in the case n = 2 - (Z²-A²) _n of

is different.

The invention further relates to the use of these Compounds as components of liquid-crystalline media and liquid crystal and electro-optical display, the contain the liquid-crystalline media according to the invention.

The compounds of the formula I can be used as components liquid crystalline media are used, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation more upright Phases or the effect of the dynamic Scattering based.

The invention was based on the object new stable to find liquid-crystalline or mesogenic compounds as components of liquid-crystalline media are suitable and in particular at the same time a comparatively have low viscosity and a relatively high dielectric anisotropy.

It has now been found that compounds of the formula I as Components of liquid-crystalline media excellently suitable are. In particular, they have comparatively low viscosities. With their help can be liquid crystalline Media with a broad mesophase range and advantageous values for the optical and dielectric Anisotropy with excellent UV and temperature stability receive.

Liquid crystals of the formula

are already known from WO 89/02 425 and are distinguished due to high birefringence and relatively high viscosity out.

With regard to a wide variety of applications of such compounds with positive Δε it was desirable have further compounds available tailor-made to the respective applications Have properties.

With the provision of compounds of the formula I is also quite generally the range of liquid crystalline Substances that differ in various application Aspects for the production of liquid crystalline Mixtures are suitable, considerably widened.

The compounds of the formula I have a broad Scope of application. Depending on the selection of the Substituents may use these compounds as base materials serve, from which liquid-crystalline media for are composed predominantly; but it can also compounds of the formula I liquid-crystalline base materials added from other classes of compounds be, for example, the dielectric and / or optical anisotropy of such a dielectric affect and / or at its threshold voltage and / or to optimize its viscosity.  

The compounds of the formula I are in a pure state colorless and form liquid crystalline mesophases in a conveniently located for the electro-optical use Temperature range. Chemical, thermal and against Light are they stable.

The invention thus relates to the compounds of Formula I and the use of these compounds as Components of liquid-crystalline media. Subject of the invention are also liquid crystalline media with a Content of at least one compound of the formula I and Liquid crystal display elements, in particular electro-optical Display elements containing such media.

For the sake of simplicity, A³ will mean one below Remainder of the formula

Cyc is a 1,4-cyclohexylene radical,
A⁴ is a radical of the formula

Che is a 1,4-cyclohexenylene radical, Dio is a 1,3-dioxane-2,5-diyl radical, With a 1,3-dithiane-2,5-diyl radical, Phe a 1,4-phenylene radical, Pyd a pyridine-2,5-diyl radical, Pyr is a pyrimidine-2,5-diyl radical and Bi is a Bicyclo (2,2,2) octylene.

The compounds of the formula I accordingly comprise the preferred compounds with two rings of the sub-formulas Ia and Ib:

R¹-A³-A²-R² (Ia)
R¹-A³-Z²-A²-R² (Ib)

Compounds with three rings of subformulae Ic to If:

R¹-A³-Z²-A²-Z²-A²-R² (Ic)
R¹-A¹-Z¹-A³-Z²-A²-R² (Id)
R¹-A¹-Z¹-A⁴-Z¹-A³-R² (Ie)
R¹-A⁴-Z¹-A¹-Z¹-A³-R² (If)

as well as compounds with four rings of the subformulae Ig to Ij:

R¹-A¹-Z¹-A³-Z²-A²-Z²-A²-R² (Ig)
R¹-A¹-Z¹-A¹-Z¹-A³-Z²-A²-R² (Ih)
R¹-A¹-Z¹-A¹-Z¹-A⁴-Z¹-A³-R² (Ii)
R¹-A¹-Z¹-A⁴-Z¹-A¹-Z¹-A³-R² (Ij)

Among them are especially those of the sub-formulas Id, Ie, Ih and Ii are preferred.

Some particularly preferred, smaller group of compounds are given below:

In the compounds of the formulas above and below R¹ and R² are preferably alkyl or alkoxy. A¹ and / or A² are preferably Phe, Cyc, Che, Pyr or dio. Preferably, the compounds of the Formula I is not more than one of the radicals Bi, Pyd, Pyr, Dio or Dit.

Preference is also given to compounds of the formula I and of all Partial formulas in which A¹ and / or A² once or twice  by F or simply by CN substituted 1,4-phenylene means. In particular, these are 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene and 2,3-difluoro-1,4-phenylene as well 2-cyano-1,4-phenylene and 3-cyano-1,4-phenylene.

Z 1 and Z 2 are preferably a single bond, -CO-O-, -O-CO- and -CH₂CH₂-, secondarily preferred -CH₂O- and -OCH₂-. Preferably, only one of them is in the molecule existing group Z¹ and Z² from the single bond different.

If R¹ or R² is an alkyl radical and / or an alkoxy radical means it can be straight or branched his. Preferably, it is straight-chain, has 2, 3, 4, 5, 6 or 7 C atoms and therefore preferably denotes ethyl, Propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, Butoxy, pentoxy, hexoxy or heptoxy, furthermore methyl, Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Pentadecyl, methoxy, octoxy, nonoxy, decoxy, Undecoxy, dodecoxy, tridecoxy or tetradecoxy.

Oxaalkyl is preferably straight-chain 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-oxo-octyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

If R¹ or R² is an alkyl radical in which a CH₂ group is replaced by -CH = CH-, so this can straight-chain or branched. Preferably, he is straight-chain and has 2 to 10 carbon atoms. He means especially vinyl, prop-1, or prop-2-enyl, But-1-, 2- or but-3-enyl, pent-1, 2-, 3- or pent-4-enyl, Hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1, 2-, 3-, 4-, 5- or hept-6-enyl, Oct-1, 2-, 3-, 4-, 5-, 6-  or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or Non-8-enyl, Dec-1, 2-, 3-, 4-, 5-, 6-, 7-, 8- or Dec-9-enyl.

If R¹ or R² is an alkyl radical in which a CH₂ group replaced by -O- and one by -CO-, so these are preferably adjacent. Thus, these include an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. Preferably, these are straight-chain and have 2 up to 6 C atoms.

They therefore mean especially acetyloxy, propionyloxy, Butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, Propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, Pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, Propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 4- (methoxycarbonyl) -butyl.

If R¹ or R² is an alkyl radical in which a CH₂ group by unsubstituted or substituted -CH = CH- and an adjacent CH₂ group by CO or CO-O or O-CO is replaced, this can be straight-chain or be branched. Preferably, it is straight-chain and has 4 to 13 C-atoms. He therefore means special Acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl,  6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl, 9-Methacryloyloxynonyl.

Compounds of the formula I which are required for polymerization reactions suitable wing groups R are suitable for the preparation of liquid-crystalline polymers.

Compounds of the formulas I with branched wing groups R¹ or R² can sometimes be for a better Solubility in the usual liquid-crystalline base materials be important, but especially as chiral dopants when they are optically active. Smectic compounds of this type are suitable as Components for ferroelectric materials.

Compounds of the formula I with S _A phases are suitable, for example, for thermally addressed displays.

Branched groups of this kind usually contain no more than a chain branch. Preferred branched Radicals R are isopropyl, 2-butyl (= 1-methylpropyl), Isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 1-methylheptoxy.

If R¹ or R² represents an alkyl radical in which two or more CH₂ groups replaced by -O- and / or -CO-O- are, this can be straight-chain or branched. Preferably, it is branched and has 3 to 12 carbon atoms. It therefore particularly means bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxyhexyl, 7,7-bis-carboxyheptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, bis (methoxycarbonyl) -methyl,  2,2-bis- (methoxycarbonyl) -ethyl, 3,3-bis- (methoxycarbonyl) -propyl, 4,4-bis (methoxycarbonyl) -butyl, 5,5-bis- (methoxycarbonyl) -pentyl, 6,6-bis (methoxycarbonyl) hexyl, 7,7-bis (methoxycarbonyl) heptyl, 8,8-bis- (methoxycarbonyl) -octyl, Bis (ethoxycarbonyl) methyl, 2,2-bis (ethoxycarbonyl) ethyl, 3,3-bis- (ethoxycarbonyl) -propyl, 4,4-bis (ethoxycarbonyl) -butyl, 5,5-bis (ethoxycarbonyl) -hexyl.

Compounds of the formula I which are more than suitable for polycondensations suitable wing groups R¹ and R² have, are suitable for the preparation of liquid-crystalline polycondensates.

Formula I includes both the racemates of these compounds as well as the optical antipodes and their mixtures.

Among these compounds of the formula I and the sub-formulas those are preferred in which at least one of the radicals contained therein one of the specified has preferred meanings.

In the compounds of formula I are those stereoisomers preferred in which the rings cyc and piperidine trans-1,4-disubstituted. Those of the above named formulas containing one or more groups Pyd, Pyr and / or Dio, each enclosing the two 2,5-positional isomers.

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

The compounds of the formula I are known per se Methods presented in the literature (eg. in the standard works such as Houben-Weyl, Methods of the Organic Chemistry, Georg-Thieme-Verlag, Stuttgart Vol. IX, P. 867 ff.), Under reaction conditions, the known for the above reactions and are suitable. It can also be known by itself, here unspecified variants make use.

The compounds of the invention may, for. B. manufactured, by dissolving a compound of formula II,

wherein R¹, A¹, Z¹ and m are as defined, according to the following reaction schemes:

Other synthetic methods will be apparent to those skilled in the art. For example, in the 5-position correspondingly substituted 1,3-difluorobenzene compounds can be converted according to the above scheme into the 2-substituted 1,3-difluoro compounds and the radical R 1 - (A 1 -Z 1) _m - subsequently by reactions customary in liquid-crystal chemistry ( For example, esterification, etherification or couplings, for example, according to the article E. Poetsch, contacts (Darmstadt) 1988 (2), p 15) or vice versa.

The compounds of the formula II can be, for example be prepared according to the following synthesis schemes:

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

The starting materials are either known or can be prepared in analogy to known compounds.

Esters of the formula I can also be obtained by esterification of corresponding Carboxylic acids (or their reactive derivatives) with alcohols or phenols (or their reactive  Derivatives) or by the DCC method (DCC = dicyclohexylcarbodiimide) to be obtained.

The corresponding carboxylic acids and alcohols or phenols are known or can be analogous to known methods or by reaction of metallated II with suitable electrophiles (B (OH) ₃ / H₂O₂ or CO₂) getting produced.

The synthesis of some particularly preferred compounds is specified below (Y = H or F):

Scheme 6 (Y = H or F)

In a further process for the preparation of the compounds of formula I is an aryl halide with a Olefin in the presence of a tertiary amine and a Palladium catalyst (see R.F. Heck, Acc. Chem. Res (1979) 146). Suitable aryl halides are, for example Chlorides, bromides and iodides, especially bromides and Iodide. The necessary for the success of the coupling reaction tertiary amines, such as. For example, triethylamine, are suitable also as a solvent. As palladium catalysts are, for example, its salts, in particular Pd (II) acetate, with organic phosphorus (III) compounds such. B. Triarylphosphanen suitable. You can do it in the presence or absence of an inert solvent at temperatures between about 0 ° and 150 °, preferably between 20 ° and 100 °, work; as a solvent come z. B. Nitriles such as acetonitrile or hydrocarbons such as benzene or toluene. The used as starting materials Aryl halides and olefins are often in the Available commercially or can by literature methods be prepared, for example by halogenation corresponding parent compounds or by elimination reactions at appropriate alcohols or Halides.

In this way, for example stilbene derivatives can be produced. The style levels can still be made by reacting a 4-substituted benzaldehyde with a corresponding phosphorylide according to Wittig. you but can also produce tolans of formula I by instead of the olefin monosubstituted acetylene is used (Synthesis 627 (1980) or Tetrahedron Lett. 27, 1171 (1986)).

Furthermore, for the coupling of aromatics aryl halides be reacted with Arylzinkverbindungen. To be favoured these reactions with the addition of a catalyst such  z. B. a palladium (0) complex in inert solvents such as hydrocarbons at high temperatures, eg. In boiling xylene, carried out under protective gas.

Couplings of alkynyl compounds with aryl halides may be prepared analogously to A.O. King, E. Negishi, F.J. Villani and A. Silveira in J. Org. Chem. 43, 358 (1978) Procedures are performed.

Tolanes of the formula I can also over the Fritsch Buttenberg Wiechell rearrangement (Ann., 279, 319, 332, 1984) in which 1,1-diaryl-2-haloethylene be rearranged to diarylacetylenes in the presence of strong Bases.

Tolans of formula I can also be prepared by Brominate the corresponding stilbene and then subjected to dehydrohalogenation. One can at known, not mentioned here variants of this Apply implementation.

Ethers of the formula I are corresponding by etherification Hydroxy compounds, preferably corresponding phenols, obtainable, wherein the hydroxy compound expediently first in a corresponding metal derivative, for. B. by Treat with NaH, NaNH₂, NaOH, KOH, Na₂CO₃ or K₂CO₃ into the corresponding alkali metal alcoholate or alkali metal phenolate is transferred. This can then with the corresponding alkyl halide, sulfonate or dialkyl sulfate be reacted, suitably in an inert solvent, such as Acetone, 1,2-dimethoxyethane, DMF or Dimethyl sulfoxide or with an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° and 100 °.  

Particular preference is given to compounds of the formula Ia

wherein R¹, Z¹, Z² and R² have the meanings indicated, m is 1 or 2 and L 1 and L 2 are each independently Mean H or F. In the case of m = 2, the two are Z 21 radicals the same or different. Preferably, at least one of the molecules present in the molecule of formula Ia Z1 and Z2 are different from the single bond and is preferably -CH₂CH₂-, -C≡C- or -CO-O-.

Starting from the commercial

let the connections represent methods known per se. Except as listed in the diagram below Linking possibilities also result analogous Synthesis method via Friedel-Crafts acylation or Wittig reaction with subsequent reduction or hydrogenation for the construction of the CH₂-CH₂ linked substances.

The

containing compounds can be over a chlorination using PCl₅ too

and subsequent HCl elimination by means of base in the acetylenes convert. The transformation of the -CH = CH- bridged Substances that have Heck coupling or Wittig reaction can be produced, succeeds in conventional Way z. B. by bromination and double HBr cleavage.  

The introduction of the carboxylate group succeeds in analogy for the introduction of the CH₂CH₂ group (see Compound 7, following formula scheme) using CO₂. The intermediary formed acids can be with the appropriate Phenols esterify from 1 according to synthesis step ba are representable.

The compound 8 can be according to d) to 12 and analogously e) to convert 13. 12 is by means of vinyl bromide according to bc) and 13 converted by divinylzinc according to c) to 14. 15 leaves obtained from 12 and 1 by means of crosstalk according to h) or 13 and 3 by crosstalk.

By suitable combination of the building blocks leave 1-15 build up all the precursors of Ia, where Z equals C≡C or the single bond is. the CH = CH grouping is in the CH₂-CH₂ or -C≡C grouping convertible.

The introduction of final grouping

succeed either by using a coupling step with

or by introduction of R² in association with the end grouping

The production of also the CO₂ and / or C≡C intermediate links containing compounds can be analogously according to analogue formula schemes.

The liquid-crystalline media according to the invention contain preferably in addition to one or more inventive Compounds as further constituents 2 to 40, in particular 4 to 30 components. Very particularly preferably included these media in addition to one or more inventive Compounds 7 to 25 components. These others Ingredients are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, especially substances from the classes of Azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, Phenyl or cyclohexyl benzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters  cyclohexylbenzoic acid, phenyl or cyclohexyl esters cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl ester benzoic acid, cyclohexanecarboxylic acid, or cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, Cyclohexylbiphenyls, phenylcyclohexylcyclohexane, Cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclohexylcyclohexylcyclohexenes, 1,4-bis-cyclohexylbenzenes, 4,4'-biscyclohexylbiphenyls, Phenyl or cyclohexylpyrimidines, Phenyl- or cyclohexylpyridines, phenyl- or cyclohexyl-dioxanes, Phenyl or cyclohexyl-1,3-dithiane, 1,2-diphenylethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2- (4-phenyl-cyclohexyl) ethanes, 1-cyclohexyl-2-biphenylylethanes, 1-phenyl-2-cyclohexylphenylethanes, optionally halogenated stilbenes, Benzylphenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene groups in these compounds can also be fluorinated.

The most important as further constituents according to the invention Media in question compounds can be characterized by the formulas 1, 2, 3, 4 and 5:

R'-LER '' (1)
R'-L-COO-ER '' (2)
R'-L-OOC-ER "(3)
R'-L-CH₂CH₂-ER '' (4)
R'-LC≡CER '' (5)

In the formulas 1, 2, 3, 4 and 5, L and E, denote may be the same or different, each independently from each other a bivalent radical from the -Phe-, -Cyc, -Phe-Phe, -Phe-Cyc, -Cyc-Cyc, -Pyr-, -Dio, G-Phe and -G-Cyc and their mirror images formed Group, wherein Phe is unsubstituted or by Fluorine-substituted 1,4-phenylene, Cyc trans-1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, dio-1,3-dioxane-2,5-diyl and G  2- (trans-1,4-cyclohexyl) -ethyl, pyrimidine-2,5-diyl, Pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.

Preferably, one of the radicals L and E is cyc, phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. Preferably contain the media of the invention one or several components selected from the compounds of Formulas 1, 2, 3, 4 and 5, wherein L and E are selected from the group Cyc, Phe and Pyr and at the same time one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, wherein one of the radicals L and E is selected from the group Cyc, Phe and Pyr and the other radical is selected from the group -Phe-Phe-, -Phe-Cyc, -Cyc-Cyc, -G-Phe and -G-Cyc-, and optionally one or more components selected from the Compounds of the formulas 1, 2, 3, 4 and 5, wherein the Radicals L and E are selected from the group -Phe-Cyc-, -Cyc-Cyc, -G-Phe and -G-Cyc.

R 'and R' 'in the compounds of the sub-formulas 1a, 2a, 3a, 4a and 5a each independently Alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy with up to 8 carbon atoms. For most of these compounds R 'and R' 'are different from each other, where one of these radicals is usually alkyl or alkenyl. In the Compounds of sub-formulas 1b, 2b, 3b, 4b and 5b means R "-CN, -CF₃, F, Cl or -NCS; R has the case at the compounds of the sub-formulas 1a to 5a specified Meaning and is preferably alkyl or alkenyl. But also other variants of the proposed substituents in The compounds of the formulas 1, 2, 3, 4 and 5 are customary. Many such substances or mixtures of which are commercially available. All these substances are by literature methods or in analogy available.  

The media according to the invention preferably contain in addition Components from the group of compounds 1a, 2a, 3a, 4a and 5a (group 1) also components from the group of Compounds 1b, 2b, 3b, 4b and 5b (group 2), their proportions preferably as follows:

Group 1: 20 to 90%, in particular 30 to 90%,
Group 2: 10 to 80%, in particular 10 to 50%,

wherein the sum of the proportions of the compounds of the invention and the compounds from groups 1 and 2 to 100% yield.

The media according to the invention preferably contain 1 to 40%, in particular preferably 5 to 30% of inventive Links. Further preferred Media containing more than 40%, in particular 45 to 90% of compounds of the invention. The media included preferably three, four or five according to the invention Links.

The preparation of the media according to the invention takes place in in the usual way. In general, the components are dissolved in each other, useful at elevated temperature. By suitable additives, the liquid-crystalline Phases modified according to the invention that in all hitherto known species of Liquid crystal display elements can be used. Such additives are known in the art and in the Literature described in detail (H. Kelker / R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic dyes for the production of colored guest host systems or substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic Phases are added.  

The following examples are intended to illustrate the invention, without limiting it. Above and below mean Potencies percent by weight. All temperatures are in Degrees Celsius indicated. Mp means melting point Kp = clearing point. Furthermore, K = crystalline state, N = nematic Phase, S = smectic phase and I = isotropic Phase. The information between these symbols represents the Transition temperatures. Δn means optical anisotropy (589 nm, 20 ° C) and the viscosity (mm² / sec) was at 20 ° C determined.

"Usual work-up" means: one gives if necessary Add water, extracted with methylene chloride, diethyl ether or toluene, separates, the organic phase dries, evaporated and the product is purified by distillation under reduced pressure or crystallization and / or Chromatography. The following abbreviations are used:

DAST diethylaminosulfur DCC dicyclohexylcarbodiimide DDQ dichlorodicyanobenzoquinone DIBALH diisobutylaluminum KOT Potassium tert-butoxide THF tetrahydrofuran pTSOH p-toluenesulfonic acid TMEDA tetramethylethylenediamine

example 1

A mixture of 9.2 g of 2,6-difluoro-4- [2- (p -ethoxyphenyl) -ethyl] -phenylboronic acid (made by implementation of 3,5-Difluorobenzaldehyde with p-ethoxybenzyltriphenylphosphonium iodide after Wittig and subsequent hydrogenation of the obtained styrene derivative on Pd / C), 6.0 g of 1-bromo-4-n-propylbenzene, 38 ml of 2 ml of aqueous Na₂CO₃ solution, 0.6 g  Tetrakis (triphenylphosphine) palladium (0) and 75 ml of toluene is refluxed for two hours. The watery Phase is extracted twice with toluene and extracted with the org. Phase united. After usual aqueous workup and Chromatographic purification of the residue is obtained 4- [2- (p-ethoxyphenyl) ethyl] -2,6-difluoro-4'-n-propylbiphenyl.

Example 2 to 51

Similarly, one obtains from the corresponding precursors of Formula II the following compounds according to the invention:

Claims (6)

1. 1,4-disubstituted 2,6-difluorobenzene compounds of the formula I, wherein
R¹ and R² are each independently H or an unsubstituted or at least monosubstituted by halogen alkyl or alkenyl radical having 1 to 15 carbon atoms, wherein in these radicals also one or more CH₂ groups each independently may be replaced so that O atoms are not directly linked to each other,
A¹ and A² each independently

• (a) trans-1,4-cyclohexylene radical, in which also one or more non-adjacent CH₂ groups may be replaced by -O- and / or -S-,
• (b) 1,4-phenylene radical, in which also one or two CH groups may be replaced by N,
• (c) radical from the group consisting of 1,4-cyclohexenylene, 1,4-bicyclo (2,2,2) octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6- diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,

where radicals (a) and (b) may be substituted by CN or fluorine,
Z¹ and Z² are each independently of one another -CO-O-, -O-CO-, -CH₂O-, -OCH₂-, -CH₂CH₂-, -CH = CH-, -C≡C- or a single bond,
m and n are each independently 0, 1 or 2, wherein
(m + n) is 1, 2 or 3,
with the proviso that at least one of the radicals Z¹ and Z² present in the molecule is -CO-O-, -O-CO-, -CH₂O-, -OCH₂-, -CH₂CH₂-, -CH = CH- or -C≡C- means and / or at least one of the radicals A¹ and A² present in the molecule and / or n is 1 or 2, wherein in the case n = 2 - (Z²-A²) _n of is different. 2. Use of compounds of the formula I as components liquid-crystalline media. 3. Liquid-crystalline medium with at least two liquid-crystalline Components, characterized in that they contain at least one compound of the formula I contains. 4. Liquid crystal display element, characterized that it is a liquid-crystalline medium after Claim 3 contains. 5. Electro-optical display element, characterized that it is a liquid crystalline as a dielectric Medium according to claim 3 contains.