DE4445224A1 - Liq. crystalline or mesogenic fluoro:cyclohexenyl benzene(s( and fluoro:di:phenyl(s) - Google Patents

Abstract

4,4'-substd.-1-(2-fluorocyclohex-1-enyl)-benzene and 4,4'-substd.-2'-fluoro-diphenyl cpds. of formula (I) are new. In (I), R = 1-18C alk(en)yl opt. substd. by CN or halogen(s) in which non-adjacent -CH2- gp(s). may be replaced by -O-, -S-, -CO-, -O-CO-, -CO-O- and -C=C-; ring A = 2-fluorocyclohex-1-en-1,4-diyl or 2-fluoro-1,4-phenylene; A<1> = (a) 1,4-phenylene, in which 1 or 2 CH gps. may be replaced by N; (b) 1,4-cyclohexylene, in which 1 or 2 non-adjacent CH2 gps. may be replaced by -O- or -S-; or (c) 1,4-cyclohexenylene, piperidin-1,4-diyl, 1,4-bicyclo(2,2,2)-octylene or naphth-2,6-diyl; and gps. (a) and (b) may be mono- or poly-substd. by halogen, CN and/or Me; Z<1> = -CH2CH2-, -CO-O-, -O-CO-, -CH=CH-, -OCH2-, -CH2O-, -C=C-, -(CH2)4-; -CH=CH-CH2CH2- or a single bond; X = 1-12 C alkyl or alkoxy, NCS or Q-Y (Q = -O-, -S- or a single bond; Y = CN, F, Cl or 1-5 C (halo)alk(en)yl; L<1> and L<2> = H or F; and m = 0, 1 or 2.

Description

The present invention relates to fluorinated benzene derivatives of the formula I,

in which
R is an unsubstituted or substituted by CN or at least one halogen alkyl or alkenyl radical having up to 18 carbon atoms, wherein one or more non-adjacent CH₂ groups by a radical selected from the group -O-, -S-, -CO -, -O-CO-, -CO-O- and -C≡C- may be replaced,

A¹ a) a 1,4-phenylene radical in which one or two CH groups may be replaced by N,
b) a 1,4-cyclohexylene radical in which one or two non-adjacent CH₂ groups may be replaced by -O- or -S-,
c) a 1,4-cyclohexenylene, a piperidine-1,4-diyl, a 1,4-bicyclo [2,2,2] -octylene or a naphthalene-2,6-diyl radical
where the radicals a) and b) may be mono- or polysubstituted by halogen atoms, cyano and / or methyl groups,
Z¹ is -CH₂CH₂-, -CO-O-, -O-CO-, -CH = CH-, -OCH₂-, -CH₂O-, -C≡C-, - (CH₂) ₄-, -CH = CH-CH₂CH₂ - or a single bond,
X is alkyl or alkoxy having 1-12 C atoms, NCS or QY, where Q is -O-, -S- or a single bond and Y is CN, F, Cl or halogenated alkyl or alkenyl having 1-5 C atoms,
L 1 and L 2 are each independently H or F, and
m is 0.1 or 2
mean.

The invention further relates to the use of these compounds as Components of liquid-crystalline media as well as liquid crystal and electro optical display elements comprising the liquid-crystalline Media included.

The compounds of the formula I can be used as components of liquid-crystalline Media are used, especially for displays based on the principle the twisted cell including their hochverdrillten variants, such as. B. STN or SBE, the guest-host effect, the effect of deformation upright phases or the effect of dynamic dispersion especially for matrix liquid crystal displays (MFK displays).

The invention was based on the object new stable liquid crystalline or to find mesogenic compounds that are liquid as components crystalline media are suitable and in particular a comparatively have low viscosity and a high positive dielectric Anisotropy.

Compounds of the formula

be in the JO 5310616 described.

4,4'-disubstituted 2 ', 3-difluorobiphenyls are known from DE 40 07 863 known.

It has now been found that compounds of the formula I as Komponen th liquid-crystalline phases are excellently suitable. In particular they have comparatively low viscosities. With your help can be stable liquid-crystalline phases with broad mesophases range of advantageous values for the optical and dielectric anisotropy received, which at the same time by very favorable values for the specific resistance. This can be especially ins for media for matrix liquid crystal displays (MFK displays) or Supertwist displays achieve significant benefits.

With the provision of compounds of formula I is also completely In general, the range of liquid-crystalline substances that are under various application-technical aspects for the production liquid-crystalline mixtures, significantly widened.

The compounds of the formula I have a broad application Area. Depending on the choice of substituents, these may Compounds serve as base materials from which liquid crystalline Phases are composed for the most part; but it can also compounds of formula I liquid-crystalline base materials be added to other classes of compounds, for example, the dielectric and / or optical anisotropy of such a dielectric to influence and / or the threshold voltage and / or to optimize its viscosity and / or its resistivity ren.  

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

The invention thus relates to the compounds of the formula I in particular the compounds of the formula I in which n is L¹ and / or L² is fluorine mean.

The invention further relates to the use of this verbin tions as components of liquid-crystalline media.

The invention further liquid-crystalline media with a Content of at least one compound of formula I and liquid crystal display elements, in particular electro-optical display elements, in particular special matrix liquid crystal displays containing such media.

For the sake of simplicity, A² means in the following

Cyc is a 1,4-cyclohexylene or a 1,4-Cyclohexenylenrest, Dio a 1,3-dioxane-2,5-diylrest, Dit a 1,3- Dithian-2,5-diyl, Phe a 1,4-phenylene, Pyd a pyridine-2,5- diyl radical, Pyr is a pyrimidine-2,5-diyl radical and Bi is a bicyclo (2,2,2) octylene radical, wherein Cyc and / or Phe unsubstituted or on or may be substituted twice by F or CN.

The compounds of the formula I accordingly comprise Ver Compounds with two or three rings of the subformulae Ia to In:

R-Cyc-A²-Phe-X Ia

R-Phe-A²-Phe-X Ib

R-dio-A²-Phe-X Ic

R-Dit-A²-Phe-X Id

R-Pyd-A²-Phe-Xe

R-Pyr-A²-Phe-X If

R-Bi-A²-Phe-X Ig

R-Phe-Z¹-A²-Phe-XIh

R-Cyc-Z¹-A²-Phe-XIi

R-Dio-Z¹-A²-Phe-X Ij

R-Dit-Z¹-A²-Phe-X Ik

R-Pyd-Z¹-A²-Phe-X II

R-Pyr-Z¹-A²-Phe-X Im

R-Bi-Z¹-A²-Phe-X In

Compounds with four rings of the subformulae Io to Ig:

R-A¹-A¹-A²-Phe-X Io

R-A¹-Z¹-A¹-A²-Phe-X Ip

R-A¹-Z¹-A¹-Z¹-A²-Phe-X Iq

In the compounds of the sub-formulas Ia to Ig, one or more Bridges have Z¹, the bridge members are preferably -CH₂CH₂-, -CO-O-, -O-CO-, -CH₂O-, -OCH₂- or -C≡C-, in particular -CH₂CH₂-.

R is preferably straight-chain alkyl, furthermore alkoxy and alkenyl.

The compounds of the formula I preferably contain no more than one the radicals Bi, Pyd, Pyr, Dio or Dit.

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

In the compounds of the formula I, X is preferably CN, NCS, OCN, F, Cl, CF₃, OCF₃, CF₂H, CHF₂, CF₂Cl, OCF₂H, OCF₂Cl, OCH₂CF₃, OCHFCF₃, OCF₂CF₃, OCH₂CF₂H, OCH = CF₂, OCF = CF₂, OCF = CCl₂, OCH₂CF₂Cl, CH₂CF₃, CH₂CF₂H, OCF = CH₂, CH = CF₂, CF = CF₂, CF = CH₂, OCH₃ or C₂H₅.

Particularly preferred are compounds wherein X is F, Cl, CN, OCF₃, OCHFCF₃, OCHF₂, OCH₂CF₃, OCF = CF₂ or OCH = CF₂ means.  

Preference is also given to compounds of the formula I in which those in the molecule contained 1,4-phenylene rings one or two times substituted by fluorine are. In particular, these are 2-fluoro-1,4-phenylene and 2,6-difluoro-1,4- phenylene.

If R is an alkyl radical or an alkoxy radical, this may straight-chain or branched. Preferably it is straight-chain, has 2, 3, 4, 5, 6 or 7 carbon 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 (= methoxy methyl), 2- = ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxa heptyl, 2-, 3-, 4-, 5-, 6- or 7-oxo-octyl, 2-, 3-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

If R is an alkenyl radical, it may be straight-chain or be branched. It is preferably straight-chain and has 2 to 10 C atoms. It therefore 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 R is an alkyl radical in which a CH₂ group by -O- and one replaced by -CO-, 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 to 6 C atoms. They therefore mean especially acetyloxy, propionyloxy, Butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxy methyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-Pro pionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl,  4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, Butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxy carbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 4- (methoxy carbonyl) -butyl.

If R is an alkenyl radical in which a CH₂ group by CO or CO-O or O-CO- is replaced, it may be straight-chain or be branched. Preferably, it is straight-chain and has 4 to 13 carbon atoms. It therefore particularly means acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyl oxyhexyl, 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 presentation liquid crystalline polymer.

Compounds of formulas I with branched wing groups R can occasionally due to better solubility in the usual liquid crystalline base materials, but especially as chiral dopants when they are optically active. Smectic compounds These types 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 type usually contain no more than one Chain branching. 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-methyl butoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methyl hexoxy, 1-methylheptoxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyl octaroyloxy, 5-methylheptyloxycarbonyl, 2-methylbutyryloxy, 3-methyl valeryloxy, 4-methylhexanoyloxy, 2-chloropropionyloxy, 2-chloro-3-methyl butyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl.

If R represents an alkyl radical in which two or more CH₂ groups replaced by -O- and / or -CO-O-, it may be straight-chain or be branched. Preferably, it is branched and has 3 to 12 carbon atoms.

It therefore means especially bis-carboxymethyl, 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-biscarboxy-heptyl, 8,8-bis-carboxy octyl, 9,9-bis-carboxynonyl, 10,10-bis-carboxydecyl, bis (methoxy carbonyl) -methyl, 2,2-bis (methoxycarbonyl) -ethyl, 3,3-bis (methoxy carbonyl) -propyl, 4,4-bis (methoxycarbonyl) -butyl, 5,5-bis (methoxy carbonyl) pentyl, 6,6-bis (methoxycarbonyl) hexyl, 7,7-bis (methoxy carbonyl) 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 suitable via the polycondensations Have wing groups R, are suitable for the preparation of liquid crystalline Polycondensates.

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

Among these compounds of formula I and the sub-formulas are those in which at least one of them contains Rests has one of the preferred meanings given.  

In the compounds of formula I, those stereoisomers are forthcoming zugt, in which the rings Cyc and piperidine are trans-1,4-disubstituted. Those of the above formulas containing one or more Groups Pyd, Pyr and / or Dio contain, 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 prepared by methods known per se as described in the literature (eg in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart), under reaction conditions suitable for the said reactions are known and suitable. You can do that also known per se, not mentioned here variants Make use.

The novel fluorocyclohexene derivatives of the formula I can z. B. be prepared as follows:  

Scheme 1

Scheme 2

Scheme 3

Scheme 4

The synthesis of some particularly preferred compounds is in following specified:  

Scheme 5

Scheme 6

Scheme 7

Scheme 8

Scheme 9

Scheme 10

Scheme 11

The liquid-crystalline media of the invention preferably contain in addition to one or more compounds according to the invention as further Ingredients 2 to 40, in particular 4 to 30 components. Very special These preferably contain these media in addition to one or more inventions compounds according to the invention 7 to 25 components. These others Ingredients are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular Substances from the classes of the azoxybenzenes, Benzylidenaniline, Biphenyls, terphenyls, phenyl or cyclohexyl benzoates, cyclohexane carboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclo hexylcyclohexanecarboxylic acid, cyclohexylphenyl ester of benzoic acid, cyclohexanecarboxylic acid or cyclohexylcyclohexanecarboxylic acid, Phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes,  Cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclohexylcyclohexyl cyclohexenes, 1,4-biscyclohexylbenzenes, 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-cyclohexyl ethane, 1-cyclohexyl-2- (4-phenyl-cyclohexyl) -ethanes, 1-cyclohexyl-2-one biphenylylethane, 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 of inventive media in Questioning compounds can be represented by the formulas 1, 2, 3, 4 and 5 characterize:

R'-L-E-R "1

R'-L-COO-E-R "2

R'-L-OOC-E-R "3

R'-L-CH₂CH₂-E-R "4

R'-L-C≡C-E-R "5

In the formulas 1, 2, 3, 4 and 5, L and E denote the same or ver can be separate, each independently a bivalent The residue of -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio, -G-Phe and -G-Cyc and their mirror images formed group, where Phe is unsubstituted or 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-diyl) Cyclohexyl) -ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5- mean diyl.

Preferably, one of L and E is Cyc, Phe or Pyr.  

E is preferably Cyc, Phe or Phe-Cyc. Preferably, the contain Media selected one or more components according to the invention from the compounds of the formulas 1, 2, 3, 4 and 5, wherein L and E are selected from are selected from the group Cyc, Phe and Pyr and at the same time one or several 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 Group Cyc, Phe and Pyr and the other radical is selected from the -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 from are selected from the group -Phe-Cyc, -Cyc-Cyc, -G-Phe and -G-Cyc-.

R 'and R "in the compounds of sub-formulas 1a, 2a, 3a, 4a and 5a each independently represent alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy of up to 8 carbon atoms. For most of these Compounds R 'and R "are different from each other, with one of these Radicals are usually alkyl or alkenyl. In the compounds of the sub-formulas 1b, 2b, 3b, 4b and 5b represents R "-CN, -CF₃, F, Cl or -NCS; R has it the meaning given for the compounds of sub-formulas 1a to 5a tung and is preferably alkyl or alkenyl. But other variants the intended substituents in the compounds of the formulas 1, 2, 3, 4 and 5 are in use. Many such substances or mixtures of which are commercially available. All these substances are according to literature known methods or in analogy available.

In addition to components from the group of compounds 1a, 2a, 3a, 4a and 5a (group 1), the media according to the invention preferably also contain 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%,
the sum of the proportions of the compounds according to the invention and the compounds of groups 1 and 2 being up to 100%.

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

The preparation of the media according to the invention takes place in per se Wise. In general, the components are dissolved in each other, purpose moderately at elevated temperature. By suitable additives, the liquid crystalline phases according to the invention are modified so that they are in all hitherto known types of liquid crystal display elements can be used. Such additives are the subject known and described in detail in the literature (H. Kelker / R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic dyes for producing colored Guest host systems or substances for changing the dielectric Anisotropy, viscosity and / or orientation of the nematic Phases are added.

In particular, the media according to the invention are suitable for use in MFK displays.

In the present application and in the following examples, the structures of the liquid crystal compounds are indicated by acronyms, wherein the transformation into chemical formulas according to following Tables A and B takes place. All radicals C _n H _{2n + 1} and C _m H _{2m + 1} are straight-chain alkyl radicals with n or m C atoms. The coding according to Table B is self-evident. In Table A, only the acronym for the basic body is given. In the individual case, a code for the substituents R 1, R 2, L 1 and L 2 follows separately from the acronym for the main body with a dash:

Table A

Table B

The following examples are intended to illustrate the invention without going to limit. Above and below are percentages by weight percent. All temperatures are in degrees Celsius. Mp means Melting point, bp. = Clearing point. Furthermore, K = crystalline state, N = nematic phase, S = smectic phase and I = isotropic phase. The Indications between these symbols represent the transition temperatures An means optical anisotropy (589 nm, 20 ° C) and viscosity (mm² / sec) was determined at 20 ° C.  

"Usual workup" means: you add water, extracted with Dichloromethane, methyl tert-butyl ether or diethyl ether, separates, the organic phase is dried, evaporated and the product is purified Crystallization and / or chromatography.

DAST diethylaminosulfur DCC dicyclohexylcarbodiimide DDQ dichlorodicyanobenzoquinone DIBALH diisobutylaluminum DMSO dimethyl sulfoxide KOT Potassium tert-butoxide THF tetrahydrofuran pTsOH p-toluenesulfonic acid

example 1

To a suspension of 1 mole of magnesium turnings in 250 ml THF you get a few drops of bromine. Subsequently, a solution of 1 mol 1-bromo-4-fluorobenzene in 250 ml of THF was added dropwise in portions. You cook Reflux for 1.5 h and add 0.9 mol of 4-trans-4-propyl in the boiling point cyclohexylcyclohexanone in 500 ml of THF to the Grignard reagent. It is refluxed for 1.5 h and at 30 ° C with 1.5 l of water and 200 ml conc. HCl added. The mixture is stirred for 1/4 h, separating the organic Phase, extracted the aqueous phase with methyl tert-butyl ether and The combined organic phases work up as usual.

0.2 mol of the cyclohexene derivative from 1a) are dissolved in 500 ml of THF and at + 2 ° C with 240 ml BH₃ THF complex within 0.5 h. you stirred for 1 h at + 2 ° C, allowed to warm to room temperature and stirred another hour. After adding 60 ml of ethanol to 30 ° C heated and first with 40 ml of 6N NaOH and then with 80 ml of 30% H₂O₂ added. The mixture is refluxed for 2 h, allowed to reach room temperature cool and hydrolyzed. The aqueous phase is separated and the organic phase diluted with 250 ml of methyl tert-butyl ether. The organic phase is washed with 5% NaHSO₃ solution and water washed and dried over Na₂SO₄. The solvent is dissolved on Rotavapor removed and the residue is recrystallized in n-hexane.

In a nitrogen atmosphere, 0.094 mol of the cyclohexanol derivative from b) dissolved in 250 ml of dichloromethane and with 0.14 mol of pyridiniumchloro chromated. The reaction mixture is refluxed for 2 h and concentrated. The residue is over a Al₂O₃ / silica gel column cleaned.

0.0382 mol DAST in 15 ml of dichloromethane are at room temperature with the cyclohexanone derivative (0.02 mol) from c) in 20 ml of dichloromethane ver puts. The mixture is refluxed for 4 h and the reaction solution is allowed to stand Cool night to room temperature. Under ice-cooling is hydrolyzed and then work up as usual:

The product (0.01 mol) is dissolved without further purification in 50 ml of THF, treated with 0.03 mol of potassium tert-butoxide and stirred for 11 h at 50 ° C in a N₂ atmosphere. The mixture is allowed to cool to room temperature, mixed with ice-water and conc. HCl and extracted with methyl tert-butyl ether. Then it is worked up as usual.
K 40 N 124.5 l; Δn = + 0.106; Δ∈ = 6.76

Analogously, the following compounds of the formula

manufactured:

Example 2

To a suspension of 0.25 mol of magnesium turnings in 60 ml of ether you have two drops of bromine. Subsequently, a solution of 0.2 mol Added dropwise 3,5-difluoro-4-trifluoromethoxybromobenzene in 60 ml of ether. you stirred for 0.5 h and then added dropwise at 20-25 ° C, a solution of 0.2 mol 4-trans-4-propylcyclohexylcyclohexanone in 50 ml of ether for Grignard Reagent. It is stirred for 2 h, poured into 500 ml of water, ange acidified and shaken with ether. The organic phase becomes the Residue evaporated. The residue is dissolved in toluene and washed with  p-toluenesulfonic acid for 5 hours under reflux at the water cooked. Then allowed to cool to room temperature, neutra lisiert and works as usual.

0.2 mol of the cyclohexene derivative from Example 1a) are dissolved in 200 ml of THF dissolved and mixed with 0.2 g of sodium borohydride. To be the mixture 0.24 mol of BF₃ etherate was added dropwise, the temperature of the reaction should not exceed 10 ° C. Then it is added 2 h Room temperature stirred. After hydrolysis, the reaction Mixture without further workup directly with sulfuric acid sodium di chromatic solution added. During the oxidation, the reaction temperature should be not higher than 15 ° C. It is stirred for one hour at room temperature after and a further 0.5 h at 30 ° C. It is filtered off, extracted with ether, Wash with water and remove the solvent in vacuo. The return stand is purified by chromatography.

0.01 mol of the ketone from b) are mixed with 0.025 mol of diethylaminosulfur trifluoride treated at 60 ° C for 15 h. Thereafter, the mixture is under Stirring dripped into ice water. After addition of ether, the organi separated phase and worked up as usual.

To 13.5 mol BuLi (15% in n-hexane) in 10 ml THF are added at -20 ° C 13.5 mol of diisopropylamine was added dropwise. Then the solution becomes Stirred for 10 min and to a mixture consisting of 10 ml of THF and 13.5 mol of the geminal difluoro compound from c) under protective gas -40 ° C added dropwise.

The mixture is first 0.5 h at -40 ° C and then over Stirred at room temperature overnight. After the hydrolysis is as usual worked up. Δε = 15.5; Δn = + 0.079.

Example 3 Step 3.1

To 1.2 moles of 4- (trans-4-propylcyclohexyl) -2-fluorobenzene, 1.2 moles of potassium Tert-butylate and 3 L of THF are at -100 ° C in a nitrogen atmosphere 1.32 mol of n-butyllithium (15% in n-hexane) was added dropwise within 1 h. The mixture is stirred for 1 h and added dropwise at -100 ° C 1.38 mol trimethyl borate to the Reaction mixture and stirred for a further 1.5 h. After adding 3.6 l of 18%  HCl, the organic phase is separated and the aqueous phase with Extracted toluene. The combined organic extracts are followed Working up as usual.

Step 3.2

0.13 mol of 4- (trans-4-propylcyclohexyl) -2-fluorophenylboronic acid, 0.13 mol 2,3,4-trifluorobromobenzene, 325 ml of toluene and 130 ml of ethanol are pre-filtered and with 1.6 g Tetrakistriphenylphosphinpalladium (0) and a Sodium carbonate solution (41.66 g Na₂CO₃ in 150 ml H₂O). One lets Cool to room temperature and separates the organic phase. The aqueous phase is extracted with toluene and the combined organic Extracts are then worked up as usual. K 42 N 57.1 l; Δn = +0.131; Δε = 10.01.

Analogously, the following compounds of the formula

manufactured:

Example 4 Step 4.1

Under nitrogen, 1.0 mol of sodium hydride (60%) in 200 ml of THF and suspended at 0 ° C with 1.0 mol of 4-bromo-2-fluorophenol dissolved in 400 ml of THF are added dropwise. It is allowed to reach room temperature warm, stir for 0.5 h and filtered. The filtrate is concentrated, in toluene dissolved and concentrated until crystallization. The residue is with Petroleum ether precipitated. The crystals are filtered off with suction and dried.  

Step 4.2

0.08 mol of the phenolate from 2.1 are presented in 80 ml of DMEU and on Heated to 50 ° C. After addition of 0.088 mol of 1,2,2,2-tetrafluoro-1-iodoethane is stirred for 16 h at 50 ° C. It is allowed to cool to room temperature and mixed with water. It is acidified with dil. HCl, extracted with methylene chloride. tert-butyl ether, then with 10% NaOH and water, dried Na₂SO₄ and filtered. The filtrate is concentrated and in the Kugelrohr at Distilled 800 mbar.

Step 4.3

0.013 mol of 1 - [(1,2,2,2-tetrafluoroethoxy] -2-fluoro-4-bromobenzene are dissolved in Dissolved 50 ml of THF, heated to 60 ° C, and with 0.012 mol of 4- (trans-4-propyl cyclohexyl) -2-fluorophenylboronic acid and with a solution consisting of 0.013 mol KH₂PO₄, 0.025 mol Na₂HPO₄ and 25 ml of water. To Add 0.012 mol of tetrakistriphenylpalladium (0) overnight 70 ° C stirred. It is allowed to cool to room temperature and works as usual on.

Analogously, the following compounds of the formula

manufactured:

Example 5 Step 5.1

In a nitrogen atmosphere, 0.05 mol of sodium 1-bromo-3,5-difluoro phenolate in 50 ml of DMEU and heated to 50 ° C. While stirring 0.05 ml of 1-bromo-2,2-difluoroethane are added dropwise. Subsequently, will stirred overnight at 50 ° C. After addition of 0.005 mol of 1-bromo-2,2- difluoroethane are stirred at 70 ° C for a further 24 h. One leaves on space Cool the temperature, mix with water and work up as usual.

Step 5.2

To 4.8 g of NaOH in 30 ml of water are added 0.03 mol of p-trans- [4-propyl-cyclo hexyl] -2-fluoro-phenylboronic acid in 60 ml of toluene and stirred at 45 ° C for 0.5 h. To the solution are added 0.03 mol of 1- (2,2-difluoroethoxy) -4-bromo-2,6-difluorobenzene and 0.7 g of tetrakis (triphenylphosphine) palladium (0) and stirred at 100 ° C overnight. It is cooled to room temperature and separates the organic phase. The solvent is removed on a rotary evaporator and the residue is filtered through a pebble gel with petroleum ether 50-70 °. The filtrate is concentrated and the residue is recrystallized from n-hexane.
K 56 N 97.2 l; Δn = +0.139; Δε = 12.34.

Analogously, the following compounds of the formula

manufactured:

Example 6 Step 6.1

0.085 mol of 4-bromo-2-fluorophenolate are dissolved in 100 l of 1,3-dimethyl-2-imida zolidinone, heated to 140 ° C and dropwise with 0.09 mol 2,2,2-Trifluorethylmethylsulfonat added. The solution is at 140 ° C for 24 h touched. Then it is mixed with 500 ml of ice water and as usual worked up.  

Step 6.2

0.015 mol of 4-bromo-2-fluorophenol (2,2,2-trifluoroethyl) ether are with 0.05 mol of trans-n-peptylcyclohexyl-2-fluorophenylboronic acid, 20 ml of toluene, 10 ml of ethanol, 0.030 mol of Na₂CO₃ and 0.86 mol of tetrakis (triphenylphos phin) palladium (0) and refluxed for 2 h. After adding of 100 ml of petroleum ether (40-80 °) is worked up as usual.

Step 6.3

13.5 mmol diisopropylamine are added dropwise at -20 ° C. to 13.5 mmol BuLi (15% in n-hexane) in 10 ml THF. The solution is then stirred for 10 minutes and to a mixture consisting of 10 ml of THF, 13.5 mmol of trans-n-pentylcyclohexylphenyl-2-fluorophenol (2,2,2-trifluoro ethyl) ether under inert gas at -40 ° C. dropwise. The mixture is first stirred for 0.5 h at -40 ° C and then overnight at room temperature. After the addition is worked up as usual.
K 48 N 96.6 l; Δn = +0.144; Δε = 8.24.

The following compounds of the formula

are prepared analogously to Example 3 by Boronsäurekopplung:

Example 7

0.05 mol of 1-trifluoromethoxy-2-fluoro-4-bromobenzene and 0.05 mol of 4- (trans-4-) Propylcyclohexyl-2-fluorohenylboronic acid are dissolved in 125 ml of toluene and Dissolved 50 ml of ethanol and successively with 0.6 g Tetrakistriphenylphophin palladium (0) and Na₂CO₃ solution (15.9 g Na₂CO₃ in 60 ml H₂O).

The mixture is heated for 3 h at reflux, allowed to cool to room temperature and burns off the organic phase. The aqueous phase is washed with toluene extracted, and the combined organic extracts are subsequently worked up as usual. K 43 N 66.3 l; Δn = +0.124; Δε = 12.55.

Analogously, the following compounds of the formula

manufactured:

Examples mix

Example A

Example B

Example C

Example D

Example E

Example F

Example G

Example H

Example I

Example J

Claims (9)

1. benzene derivatives of the formula I, in which
R is an unsubstituted or substituted by CN or at least one halogen alkyl or alkenyl radical having up to 18 carbon atoms, wherein one or more non-adjacent CH₂ groups by a radical selected from the group -O-, -S-, -CO -, -O-CO-, -CO-O- and -C≡C- may be replaced, A¹ a) a 1,4-phenylene radical in which one or two CH groups may be replaced by N,
b) a 1,4-cyclohexylene radical in which one or two non-adjacent CH₂ groups may be replaced by -O- or -S-,
c) a 1,4-cyclohexenylene, a piperidine-1,4-diyl, a 1,4-bicyclo [2,2,2] octylene or a naphthalene-2,6-diyl radical
where the radicals a) and b) can be substituted one or more times by halogen atoms, cyano and / or methyl groups,
Z¹ is -CH₂CH₂-, -CO-O-, -O-CO-, -CH = CH-, -OCH₂-, -CH₂O-, -C≡C-, - (CH₂) ₄-, -CH = CH-CH₂CH₂ - or a single bond,
X is alkyl or alkoxy having 1-12 C atoms, NCS or QY, where Q is O-, -S- or a single bond and Y is CN, F, Cl or halogenated alkyl or alkenyl having 1-5 C atoms,
L 1 and L 2 are each independently H or F, and
m 0, 1 or 2
mean. 2. benzene derivatives of the formula wherein R, X, L¹ and L² have the meaning given in claim 1. 3. Benzene derivatives of the formula wherein R, X, L¹ and L² and have the meaning given in claim 1. 4. Compounds of formula I, wherein L¹ and / or L² is fluorine. 5. Compounds of formula I, wherein X is CN, F, Cl, OCF₃, OCHF₂, CF₃, OCHFCF₃, OCH₂CF₃, OCH = CF₂ or OCF = CF₂ mean. 6. Use of the compounds of the formula I as components Liquid-crystalline media for electro-optical display elements. 7. Liquid-crystalline medium with at least two components, characterized in that one or more components a Compound of formula I are. 8. Electro-optical display element, characterized in that it as dielectric a liquid-crystalline medium according to claim 7 contains. 9. matrix liquid crystal display element according to claim 8, characterized characterized in that it is a liquid crystal as a dielectric Medium according to claim 7 contains.