DD274233A5 - LIQUID CRYSTALLINE COMPOSITION CONTAINING GLUORIZED OLIGOPHENYLE - Google Patents

Abstract

A liquid-crystalline composition having at least two liquid-crystalline components, characterized in that at least one component is a fluorinated oligophenyl of the formula I in which a is 1 and in which the terminal substituents R 1, R 2 and R 3 are each independently one, optionally with CN or with at least one halogen atom substituted, alkyl or alkenyl radical having up to 15 carbon atoms, wherein one or more non-adjacent CH2 groups of these radicals may also be replaced by O, S, CO, OCO, COO, OCO or CC, one of these radicals R1 and R2 also a group of formula, in one of the following pairs of lateral substituents both fluorine: (A, B), (C, D), (D, E), (C, E), (B, C), (D , J), (D, K), (A, C), (C, J), (C, D), (DE), (D, A), (C, E), (C, A), (D, J), (D, K), (D, J), (B, G), (A, G), and all other lateral substituents are hydrogen or fluorine. Formula and Formula I

Description

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Liquid crystal composition containing fluorinated oligophenyls

Application of the invention

The invention relates to liquid crystalline compositions containing fluorinated oligophenyls.

Liquid crystalline materials are well known and generally utilize the electro-optic circuit properties of the nematic (N) smectic, in particular the chiral smectic C (S *) or smectic I (S *), phase, where the asterisk (*) indicates a chiral phase. Their use in electro-optical display elements is widespread.

Such materials are generally mixtures of compounds so selected that this mixture has the desired properties. Such properties include in particular:

a) A wide temperature range over which the suitable liquid-crystalline phase, for. B. S _A , S _c , S *, S ₁ , S * or N stable, said area preferably

the room temperature includes (about 20 ⁰ C).

b) Low viscosity

c) Easy to produce

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d) Good electro-optical reaction

e) In the case of Verb.ungen or mixtures having a Sp phase, miscibility with one or more optically active substances, ie those which have an asymmetrically substituted carbon atom and so can form a helical, chiral phase, which has a large pitch and has a high spontaneous polarization (P _g ). It is also favorable if the compound or mixture has an S. phase at a higher temperature than the S.sub.3 phase, since this facilitates the orientation of the S.sub.3 phase with the electrodes of the liquid-crystalline electro-optical display elements.

Characteristic of the known chemical solutions

Fluorinated terphenyls are known for use in liquid crystalline materials. European Patent Application EP-A-8430494.3 describes the preparation and use of monofluorinated terphenyls of the general formula

R ¹ -

wherein R and R are independently alkyl or alkoxy in nematic liquid crystalline materials. British Patent Application GB-A-8725928 and International Patent Application WO / 07890 disclose the use of these monofluorinated terphenyls in S ^ mixtures.

European Patent Application EP-A-0084194 contains a wholly speculative citation on laterally difluorinated terphenyls, including a theoretical reference citation of the compound:

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for use in nematic mixtures.

PCT / EP 87/00515 unpublished at the time of application of this invention contains the speculative formula which encompasses difluoroterphenyls, and also cites two specific compounds:

C ₂ H ₅₁

FF

.J

which are to be used exclusively in nematic liquid-crystalline mixtures.

Object of the invention

The object of the present invention was to find other useful fluorinated oligophenyls, and in particular to study their use in smectic liquid crystal materials.

Explanation of the essence of the invention

Inventive fluorinated oligophenyls of the formula I have been found

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A B

_ Yes

-R '

wherein a is 0 or 1 and the terminal substituents

R \ and

I ² ^ 3

each independently of one another, optionally substituted by CN or at least by a halogen atom, alkyl or alkylene radical having up to 15 carbon atoms, wherein one or more non-adjacent CH ₂ groups of these radicals may be replaced by -0-, - S, -CO-, -O-C0-, -CO-O-, -O-CO-O- or -C = C-,

1 2 one of the rights R and R can also be a group of the formula

C ¹ D ¹

R ³ - <o

J ¹ K ¹

mean, and

in one of the following pairs of lateral substituents, the two substituents are fluorine: (A, B), (C, D), (D, E), (C, E), (B, C), (D, J), (D, K), (A, C), (C, J), (C, D ¹ ), (D ', E), (D ¹ , A), ( ¹ C, E), (C ¹ , A), (D ¹ , J ¹ ), (D ¹ , K ¹ ), (C, J ¹ ), (B, Q), (A, G),

all other lateral substituents are either hydrogen or fluorine.

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The structural preferences discussed later are based, inter alia, on the utility in liquid crystalline mixtures and / or their accessibility.

Preferred structures for difluorinated terphenyls of the formula I are those of the sub-formulas 1.1 to 1.6

F F

FFR ¹ ^ -W M- (O) -R "1,2

R ^]

FR ¹ - / ^ - / (Λ - / oV-R ⁴ 1.6

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Preferred structures of the trifluorinated terphenyls are those of the partial formulas I, 7 to I, 12:

FF F

^ R ² 1,7

FF F

-R ² 1.8

FFF

FF FR ¹ - ^ ö) - (ö} - ^ ö \ -R ² 1,10

FFF

r.1 / \ / \. / \ ri2 TIi

R - (O) - (o) - (o) - R 1.11

FF F

R ^x - ^ MoV (O) -R "1,12

-0-0-0-1

Mixtures with sm-catalytic C-phases which contain compounds of the formula I in which a is O are particularly preferred. Preferred structures of the difluorinated biphenyls of the formula I (a = O) are those of the sub-formulas 1.13 to 1.19:

F F

^ R ² 1,13

F F

² 1,14

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F F

1.16

R ¹ - (OJ- (Oy-R ² 1,17

F

R ² 1,19

\ F

For the sake of simplicity, in the following Phe, a 1,4-phenylene group, PheF means a group of the formula

and

F ₂ PheF _{2 is} a group of the formula -ZiV

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

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Compounds of formula I having a negative anisotropy of dielectric constant (Δε = ε -. £ j_ <0, where ε ^ to mean the dielectric constant along the longitudinal molecular axis and ej_ the dielectric constant perpendicular) to be in an electric field with their long molecular axes oriented perpendicular to the field direction. This effect is known and exploited to control the optical transparency in various liquid crystal displays, such. In liquid crystal cells of the light scattering type (dynamic scattering), of the so-called DAP type (deformation of upright phases) or of the guest / host type (guest host interaction).

The ECB effect (electrically controlled birefringence) or DAP effect (deformation of upright phases) was first described in 1971 (M.F. Schieckel and

K. Fahrenschon, "Deformation of nematic liquid crystals with vertical orientation in electrical fields", Appl. Phys. Lett. 19 (1971), 3912). This was followed by works by J.F. Kahn Appl. Phys. Lett. 20 (1972), 1193) and

G. Labrunie and J. Robert (J. Appl. Phys. 44 (1973), 4869).

The work of J. Robert and F. Clerc (SID 80 Digest Techn. Papers (1980), 30), J. Duchene (Displays 7 (1986), 3) and H. Schad (SID 82 Digest Techn. Papers (1982). , 244) have shown that liquid-crystalline phases must have high fourths for the ratio of the elastic constants Kg / K ,, high values for the optical anisotropy Δη and values for the dielectric anisotropy Δε values -0.5 and -5 in order to be highly informative Display elements based on the ECB effect can be used.

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ECO effect based electro-optic display elements have a homeotropic edge orientation, i. H. the liquid crystalline phase has a negative dielectric anisotropy.

For the technical application of this effect in electro-optical display elements FK phases are needed, which must meet a variety of requirements. Particularly important here are the chemical resistance to moisture, air and physical influences such as heat, radiation in the infrared, visible and ultraviolet range and electrical alternating and alternating fields. Furthermore, technically usable LC phases require a liquid-crystalline mesophase in a suitable temperature range and a low viscosity.

There is thus still a great need for liquid-crystalline phases with favorable meso ranges, high values for Ko / K, high optical anisotropy Δη, negative dielectric anisotropy Δε and high long-term stability.

Furthermore, compounds of the formula I are suitable as components chiral tilted smectic phases.

Chiral tilted smectic liquid crystalline phases with ferroelectric properties can be prepared by adding base mixtures with one or more tinted smectic phases to a suitable chiral dopant (LA Veresnev et al., Mol. Cryst. Liq. Cryst. 89, 327 (Mol. 1982), HR Brand et al., J. Physique 44 (Lett.), L-771 (1983). Such phases can be used as dielectrics for fast switching displays based on the principle of SSFLC technology described by Clark and Lagerwall

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(N.A. Clark and S. T. Lagerwall, Appl. Phys., Lett., 3J, 899 (1980); USP 4,367,924) based on the ferroelectric properties of the chirally-tilted phase.

It has been found that the fluorinated Oliqonhcriyle of formula I are particularly suitable as components of liquid crystalline phases. In particular, stable liquid-crystalline phases with a broad mesophase range and comparatively low viscosity can be produced with their help.

Furthermore, the compounds of the formula I are suitable as components of chirally tilted smectic liquid-crystalline phases.

The compounds of the formula I have a wide range of applications. Depending on the choice of substituents, these compounds may serve as base materials from which liquid crystalline phases are predominantly composed; However, it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compounds, for example the dielectric and / or optical anisotropy and / or the viscosity and / or the spontaneous polarization and / or the phase ranges and / or the tilt angle and / or or to vary the pitch of such a dielectric.

The compounds of the formula I are furthermore suitable as intermediates for the preparation of other substances which can be used as constituents of liquid-crystalline dielectrics.

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The compounds of the formula I are colorless in the pure state and form liquid-crystalline mesophases in a temperature range which is favorably located for the electro-optical use. Chemically, thermally and against light, they are very stable.

The invention thus relates to liquid-crystalline compositions having at least two liquid-crystalline components, where at least one component is a fluorinated oligophenyl of the formula I in which a is I, in particular compositions containing at least one oligophenyl of the formula I '

wherein

R and R are each independently of one another an optionally substituted by CN or at least one halogen atom, alkyl or alkenyl radical having up to 15 carbon atoms, wherein one or more non-adjacent CH ₂ groups of these radicals may be replaced by -0-, -S-, -CO-,

-O-C0-, -CO-O-, -O-CO-O- or -C ^ C-,

Each of A and A independently represents an unsubstituted or fluorine-mono- to tetra-substituted 1,4-phenylene group,

m is 0 or 1,

η is 1, 2 or 3, and (m + n) is 2 or 3.

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The invention furthermore relates to chiral c / unsaturated smectic compositions containing at least one. Oligophenyl of the formula I, wherein a is O or.

Before and after R ¹ , R ² , R ³ , A ¹ , A ² , in and η have the meaning given, unless expressly stated otherwise.

The compounds of the formula I accordingly comprise

Compounds with three rings of subformulae Ia and Id:

R ¹ -Phe-Phe-PheF ₂ -R ³ Ia

R ¹ -Phe-PheF ₂ -Phe-R ² Ib

R ¹ -PheF-Phe-PheF-R ² Ic

R ^ PheF-PheF-Phe-R ² Id,

Compounds with four rings of sub-formulas Ie to Ij

R ¹ -Phe-Phe-Phe-PheF ₂ -R ² Ie

R ¹ -Phe-Phe - PheF ₂ -Phe-R ² If

R ¹ -PheF-Phe-Phe-PheF-R ² Ig

R ¹ -PheF-Phe-PheF-Phe-R ² Ih

R ¹ -PheF-PheF-Phe-Phe-R-Ii

R ¹ -Phe-PheF-PheF-Phe-R ² Ij

and those with 2 rings of the subformula Ik

R ¹ -PheF ₂ -Pb.iR ² . Ik

In the compounds of the formulas above and below, R ¹ and R ^{2 are} preferably alkyl, furthermore alkoxy.

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1 2 A and A are Phe, PheF and PheF, preferably the compound of formula I contains no more than one of the radicals

η is preferably 1, 2 or 3, especially preferably 1.

m is preferably 0 or 1.

In the formulas above and below, R, R and R preferably have 1-13 C atoms, in particular 3-12 C atoms.

1 ? 3 Compounds of the formulas I in which R, R and R have 1-7 C atoms, preferably 1-5 C atoms, are particularly suitable for liquid-crystalline phases for display elements based on the ECB effect. Links of the For-

1 ? In contrast, 3 mel I in which R, R and R have 5-15 C atoms, preferably 5-12 C atoms, in particular 5-9 C atoms, are suitable for liquid-crystalline phases mil

12 3 ferroelectric properties. In R, R and R, one or two CH ₉ groups may be substituted. Preferably, only one CH ₂ group is replaced by -O-, -CO-, -C = C-, -S-, -CO-O-, -0-C0- or -O-CO-O-, in particular by -0-, -0-C0-, -CO-O- or -C = C-.

1 ? 3 If R, R and R are alkyl radicals in which one ("alkoxy" or "oxaalkyl") or two ("alkoxylakoxy" or "dioxaalkyl") non-adjacent CH ₂ groups may be replaced by O atoms, mean so they can be straight or branched. They are preferably straight-chain, have 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and accordingly preferably represent ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethoxy, Propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy or decoxy, furthermore methyl, Ur.iecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.

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Oxaalkyl is preferably straight-chain 2-oxyprc / 1 (- methoxymethyl), 2- (= ethoxymethyl) or 3-oxabutyi (- 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, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl, 1,3-dioxabutyl (= methoxymethoxy), 1,3- , 1,4-, 2,4-dioxapentyl, 1,3-, 1,4-, 1,5-, 2,4-, 2,5- or 3,5-dioxahexyl, 1,3-, 1, 4, 1,5, 1,6, 2,4, 2,5, 2,6, 3,5, 3,6 or 4,6-dioxaheptyl.

1 2 If R and R are an alkyl radical in which a CH ^ group is replaced by -S-, this may be straight-chain and branched. Preferably, this thiaalkyl radical is straight-chain and is 2-thiapropy.l, 2 or 3-thiabutyl, 2-, 3- or 4-thiapentyl, 2-, 3-, 4- or 5-thiahexyl, 2-, 3-, 4- , 5- or 6-thiaheptyl, 2-, 3-, 4-, 5-, 6- or 7-thiaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-thianonyl or 2 -, 3-, 4-, 5 ~, 6-, 7-, 8- or 9-thiadecyl.

1 2 Particularly preferred are alkyl radicals R or R, in which

1 7 3

the CH ₂ group adjacent to the group A, A and / or A is replaced by -S- and thus preferably denotes methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylihio, heptylthio, octylthio, nonylthio or decylthio,

If R and R are an alkyl radical in which a CH ~ group is replaced by -CH = CH-, this may be straight-chain or 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-J-, 2-, 3, 4, 5, 6

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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.

1 7 If R and R is an alkyl radical in which one CH ₂ group is replaced by -0-C0- or -CO-O-, this may be linear or branched. It is preferably straight-chain and has 2 to 6 C atoms. It accordingly particularly denotes 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, methoxycarbonylnylthyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 4- (methoxycarbonyl) -butyl.

Compounds of the formula I with branched wing groups

1 ? R and / or R may occasionally be of importance for better solubility in the usual liquid crystalline base materials, but especially as chiral dopants when optically active. Smectic compounds of this type are useful as components of ferroelectric materials.

Branched groups of this type usually contain no more than one chain branch. Preferred branched radicals R ¹ and / or R ² are isopropyl, 2-putyl (= 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,

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2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxycarbonyl, 2-methylbutylyloxy, 3 Methyl valeryloxy, 4-methylhexanoyloxy, 2-chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl _; 2-fluoro-3-methylvaleryloxy, 2-fluoro-3-methylbutoxy.

1 2 If R and R represent an alkyl radical in which two or more CH ₂ groups have been replaced by -O- and / or -CO-O-, this may be straight-chain or branched. Preferably, it is branched and has 3 to 12 carbon atoms. It therefore particularly denotes 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-biscarboxy-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, o-bis-f-methycarbonyl) 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) pentyl.

Compounds of the formula I which are known for polycondensation

1 2

Suitable wing groups R and / or R are suitable for representing liquid crystal polycondensates.

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

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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), namely under Reaction conditions which are known and suitable for the said reactions. One can also make use of known per se, not mentioned here variants.

If desired, the starting materials can also be formed in situ, such that they are not isolated from the reaction mixture, but immediately reacted further to give the compounds of the formula I.

Compounds of the formula I are accessible starting from 1,2-difluorobenzene.

This is metallated by a known method (eg BAM Roe et al., J. Chem. Soc. Chem. Comm., 2_2, 582 (1965)) and reacted with the appropriate electrophile. With the thus obtained 1-substituted 2,3-diflurobenzene, this reaction sequence can be carried out a second time and thus one arrives at the 1,4-disubstituted 2,3-difluorobenzene derivatives of the formula I. 1,2-Difluorobenzene or 1 substituted 2,3-difluorobenzene is added in an inert solvent such as: diethyl ether, tetrahydrofuran (THF), dimethoxyethane, tert-butyl methyl ether or dioxane, hydrocarbons, such as hexane, heptane, cyclohexane, benzene or toluene, or mixtures of these solvents a ^ omplexierungsmittels such as N, N-dimethylpropyleneurea (DMPH), tetramethylethylenediamine (TMEDA) or hexamethylphosphoric triamide (HMPA) with phenyllithium, lithium tetramethylpiperidide, n-, sec- or tert-butyl lithium at temperatures of from -100 ⁰ C to +50 ⁰ C, preferably - 78 ⁰ C implemented to 0 ⁰ C.

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The lithium-2,3-difluorophenyl compounds are reacted at -100 ⁰ C to 0 ⁰ C, preferably at -50 ⁰ C with the corresponding electrophiles. Suitable electrophiles are aldehydes, ketones, nitriles, epoxides, carboxylic acid derivatives such as esters, anhydrides or halides, haloformate or carbon dioxide. Particularly suitable are cyclohexanone derivatives.

For reaction with aliphatic halogen compounds, the potassium-2,3-difluorophenyl compound are suitable. These are tertiary by transmetallation of the lithium compounds with potassium. butoxide at -80 ° to -120 ⁰ C.

For reaction with aromatic halogen compounds, the lithium-2,3-difluorophenyl compounds are transmetallated and coupled under transition metal catalysis. Particularly suitable for this purpose are the zinc (see DE OS 36 32 410), the titanium-2,3-difluorophenyl compounds (cf., DE OS 37 36 489).

The p-ter and p-quaterphenyls of the formula I can be prepared, for example, according to synthesis methods 1 to 10, which are shown schematically in Figs. 1 to 8 of the accompanying drawing.

Although this is illustrated illustratively for the cases where R and R represent alkyl or alkoxy, these reactions can of course also be carried out with the perfluoroalkyl or perfluoroalkoxy analog. Other methods for producing these substances are familiar to the person skilled in the art. Wherein in one of the pairs (D, K) or (C, J) denote terphenyls of the formula I _{1 are} both fluorine substituents, can be prepared, for example, the difluorophenol Route 9 as a starting material or from the known l, 3-difluoro-2 -aminophenol by adding

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suitable 4-substituted phenyl rings to these precursors.

These rings can be linked together, for example, via the known phenylboronic acids.

Difluorobiphenyls of formula I can be prepared by modifications of routes 1 to 10, in which the various intermediates are coupled with phenyl groups, e.g. B .:

10 / RO ^- Na ⁺

2

/ Br - <(Ö) - (Ö) -R

F F

(IF)

F F FF

15 _ / / OH

R - ^ W + Br- (O) -R ^ * R '- <0) - <0> -R <

OH (5B) (5A)

F F FF

R '- (0> -Br +

H'

(5A) (5B)

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X) H (8C)

7 4 2 3

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/ OH R '- ^ oVb. + Er- (OJ-I

R ¹ -

Trifluoro-phenols may also be prepared by modifications of routes 1 to 9 by coupling the corresponding intermediates, e.g. B .:

F F

FFF

R ¹ - (O) - ^ - B (OH) ₂ + Br - ^) - R ² - * R '- (o) -

(6C)

The compounds of formula I often have nematic or smectic C phases, which are stable over a broad range of temperatures, and are useful components of liquid crystalline mixtures. Therefore, liquid-crystalline mixtures of compounds wherein at least one is a compound of formula I, preferably selected from the sub-formulas 1,1 to 1,10, also constitute a further subject of the invention.

The liquid-crystalline phases according to the invention consist of 2 to 25, preferably 3 to 15 components, including at least one compound of the formula I. The other constituents are preferably selected from among

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nematic or nematogenic substances, in particular the known substances, from the classes of azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenylcyclohexanes, cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalenes, 1,4-biscyclohexylbenzenes , 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyldithiane, 1,2-bis-phenylethanes, 1,2-bis-cyclohexylethane, 1-phenyl-2-cyclohexylethane, optionally halogenated stilbenes, benzylphenyl ethers, tolans uno substituted cinnamic acids.

The most important as components of such flüs. igkristalliner phases in question / erbindunaen can be characterized by the formula 2,

R'-L-G-E-R "2

wherein L and E are each a carbo- or heterocyclic ring system of the 1,4-disubstituted benzene, 2 (3) -fluorobenzene and cyclohexane rings, 4,4'-disubstituted biphenyl, phenylcyclohexane and cyclohexylcyclohexane systems, 2,5- disubstituted pyrimidine and 1,3-dioxane rings, 2,6-disubstituted naphthalene, di- and tetrahydronaphthalene, quinazoline and tetrahydroquinazoline,

G -CH = CH- -N (O) = N-

-CH = CY- -CH = N (O) -

-C = C- CH ₉ -CH ₉ -

-CO-O- -CH ₂ -O-

-CO-S- -CH ₂ -S-

-CH = N- -COO-Phe-COO-

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or a CC single bond, Y is halogen, preferably chlorine, or -CN, and R 'and R "are alkyl, alkoxy, alkanoyloxy or alkoxycarbonyloxy having up to 18, preferably up to 8 carbon atoms, or one of these radicals also CN, NC, NO ₂ , CF ₃ , F, Cl or Br mean.

In most of these compounds, R 'and R "are different from one another, one of these radicals usually being an alkyl or alkoxy group. But other variants of the proposed substituents are gebräuchlieh. Many such substances or mixtures thereof are commercially available. All these substances can be prepared by literature methods.

The preparation of the liquid-crystalline phases according to the invention takes place in a conventional manner. In general, the components are dissolved in each other, useful at elevated temperature.

By means of suitable additives, the liquid-crystalline phases according to the invention can be modified so that they can be used in all hitherto known types of liquid-crystal display elements.

Such additives are known in the art and described in detail in the literature. For example, conducting salts, preferably ethyldimethyldodecylammonium-4-hexyloxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf., for example, Haller, Z., Mol.Cryst.LLq.Cryst., Volume 24, pages 249-258 (1973)), conductivity enhancers, dichroic dyes for producing colored guest-host systems, or substances for modifying the dielectric anisotropy, viscosity and / or orientation of the nematic phases. Such substances

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are ζ. For example, in DE-OS 2209127, 2240864, 2321632, 2338281, 2450088, 2637430, 2853728 and 2902177 described.

When the liquid crystalline material is nematic, the other components of these materials can be selected from a wide variety of compounds known as useful components for nematic liquid crystalline materials, e.g. B. the compounds of sub-formulas 2.1 to 2.6, wherein R and R,

a D

independently of one another are alkyl or alkoxy: 10

v0-0- ^{CN 2} ' ²

^{CN 2} ' ³

v_ ^ z. w ^ ^R b ² ' ⁴

F

^R aU ^COO -i £> - ^R b ² ' ⁵

_Rb 2.6

In general, a nematic liquid crystalline material contains up to 25%, in some cases up to 60% of one or more compounds of formula I.

For display elements which are based on the principle of the "twisted nematic cell" (TN) the Freedericksz effect or the phase change cholesteric / nematic, the majority of the materials preferably consists of compounds selected from the formulas 2.1 to 2.6. When a cholesteric phase is required, one or more of the alkyl groups R _a or R 1 may be asymmetric

PAT LOG 7/1 150888

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Contain C atom, ζ. B. be used in the form of a 2-methylbutyl group _/.

Certain compounds of formula I are found to be particularly suitable for materials based on the effect of electrically controlled birefringence (ECB).

In such materials, one or more compounds of formula I may contain up to 50%, preferably up to 25%. In addition, such mixtures preferably contain compounds of the sub-formulas 3.1 to 3.6

F

3,1 ³ ' ²

R _a - (o> - <o> - (> - R _K 3.3

R _a - (> - (o> - <o> - <> - R _K 3,4

CN

3.6 R _b

Certain fluorinated oligophenyls of the formula I are found to be suitable for liquid-crystalline materials which have ferroelectric properties. Some terphenyls of formula I have smectic C phases that are stable over a broad temperature range.

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The chirally tilted smectic phases according to the invention preferably contain one or more, in particular at least two or more, bi- or terphenyls of the formula I. Mixtures with an S _p phase which, in addition to one or more terphenyls of the formula I, one or more biphenyls of the formula I. are further preferred. Particularly preferred according to the invention chiral tilted smectic liquid-crystalline phases, the achiral base mixture with another component magnitude smaller dielectric anisotropy, low viscosity and wide S contain, in addition compounds of the formula I, at least _c ~ phase range is. This further component (s) of the achiral base mixture may, for example, comprise 40 to 90%, preferably 50 to 80%, of the base mixture.

Ij. Suitable components are in particular compounds of the sub-formulas 4.1 to 4.8 in question:

4.1

^R b ⁴ ' ²

a0®0 ^R b ⁴ ' ³

_N

a () ® (> ^R k ⁴ ' ⁵

^N

0 ⁴ ' ⁶

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V (> b ⁴ ' ⁷

^R b ⁴ ' ⁸

R _a and R are each preferably alkyl, alkoxy, alkanoyloxy or alkoxycarbonyl having in each case 3 to 12 C atoms. X is 0 or S, preferably 0. In the compounds of the formulas 4.1 to 4.8, a 1,4-phenylene group can also be substituted laterally by halogen, particularly preferably by fluorine. Preferred components of this type are those of the following formulas:

⁴ ' ^{9 4} ' ¹⁰

Preferably, one of the groups is R and R, alkyl and the other group is alkoxy.

Particularly preferred are the compounds of the sub-formulas 4.1 to 4.10, wherein R ^ and R _{K are} each straight-chain alkyl

egg yy

or alkoxy each having 5 to 10 carbon atoms.

Further preferred are phases according to the invention which, in addition to components of the formula] η 4.1 to 4.8, also contain at least one component with clearly negative dielectric anisotropy (Δε < -2). Particularly suitable here r.iiid compounds of formulas 5.1 to 5.3,

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5.2

CN

⁵ ' ³

1 p

In an S * blend of this invention, R and R are preferably of greater C chain length than would be used with a nematic material, e.g. B.

1 2, a radical R or R preferably contains five or more carbon atoms.

1 2 R and R are preferably n-alkyl or n-alkoxy.

The fact that S * mixtures can be prepared with oligophenylene of formula I and their advantages, ie good S _c phases and fast switching times, is completely unexpected since the prior art only deals with nematic and ECB mixtures.

Preferred compounds with asymmetric ir. Carbon atom in an S * material of the present invention are the 1-methylheptyl esters disclosed in EP-A-0110299, or one or more of the compounds containing a -COO-C 1 -C 5N) group disclosed in WO 87/07890 or in U.S. Pat British Patent Applications 8729502, 8729503, 8729865 or 8729982.

Derivatives of optically active lactic acid are described in WO 86/02938 or PCT / GB 87/00132. WO 86/04328 describes derivatives of the terperoids, in WO 87/06577 naphthalic acid esters, in WO 88/02390 mandelic acid esters and in WO 86/02937 derivatives of the optically active amino acid.

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The chiral dopants of sub-formulas 6.1 to 6.6, wherein X is an alkoxy or Alkylaminoresst, YH, CF- or CH ₃ , m 0 or ι. η is 1 or 2 and ρ is 0 or 1, are particularly preferred.

R _a - (Phe) -Phe-COO-2Oct * 6.1

CN

R - (Phe) -Phe -COO-CH-R. C, 2

at D

R _a - (Phe) _n -Phe- (CO) -O-CH-CO-X 6.3

CH ₃

_T , -pne-CH _o CH _o -C00-20ct * 6.4

R - (Phe) - (COO) -Phe- (CO) -OCH 1 -CF -alkyl 6,5

a η πι ρ ζ ι

Y

R- (PtIe) - (COO) -Plete- (CO J-OC (CN) R ¹ R ² 6,6

ei IU ρ

In the compounds of the formulas 6.1 to 6.6, one or more groups Phe can also be substituted by fluorine

R, R and R have the meanings given above and a D

R ₁ is preferably C ₁ -C ₄ n-alkyl, cycloalkyl or branched alkyl.

R in the abovementioned formulas is preferably C 1 -C 4 -n-alkyl or n-alkoxy, in particular n-octyloxy, R is particularly preferably methyl or a group of the formula

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/ ^C b ^H 2b + l

- (CH _? ) -CH

^C c ^H 2c + l

wherein a is 0 to 6, and b and c are each independently 1 to 6.

R and R each have a different number of carbon atoms or taken together preferably represent an alicyclic radical, e.g. B. the formula

When the S * mixtures according to the invention contain two or more compounds having an asymmetric carbon atom, two or more of these compounds may preferably have opposite optical directions of rotation, i. H. have a (+) - and (-) - sense of rotation or a D and L stereoisomerism. In this way, the length of the helical S * pitch can be controlled, and / or a useful S, phase generated, which facilitates the alignment of the liquid crystalline material with the electrodes of the electro-optical arrangement.

The S * mixtures according to the invention preferably contain 1 to 30% by weight of chiral dopant (s).

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The remainder of the mixture can consist of one or more compounds of the formula I, in particular of the formulas 1.1 to 1.6 or 1.13 and 1.17 to 1.19, ie together 100% by weight.

In addition, the mixture according to the invention can contain 1 to 30% by weight of chiral dopant (s) and the remaining mixture of compounds of the formula I in addition to one or more compounds of the formulas 4.1 to 4.10 or 5.1 to 5.3 contain and / or other known smectic components. The mixtures according to the invention preferably contain no more than 80% of the compounds of the formulas 4.1 to 4.10 or 5.1 to 5.3.

The liquid-crystalline materials according to the invention can be used in liquid-crystalline electro-optical display elements of known construction.

embodiments

The following examples as well as appended Figs. 1-8 with the preparative routes 1-10 are intended to illustrate the invention without limiting it. The following coolings are used.

K = crystalline N = nematic liquid crystal S _A = smectic A liquid crystal ^ S _c = smectic C liquid crystalline I = isotropic liquid

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- 31 Example 1

Preparation of 4-hexyloxy-4-pentyl-2 ', 5'-difluoropterphenyl

IA 4-hexyloxybromobenzene

A solution of bromohexane (60 g) in acetone (150 ml) is added to a mixture of p-bromophenol (71 g) and K ₂ CO ₃ (120 g) in acetone (600 ml) at room temperature. The mixture is heated to boiling for 43 h. The product is extracted twice with ether, the combined ethereal extracts are washed with water and 5% sodium hydroxide solution and dried. After removal of the solvent, the residue is distilled (bp 100-110 ⁰ C / 0.1 torr) to give a colorless liquid.

IB 4 ~ hexyloxyphenylboronic acid

Of IA (72 g) with magnesium (7.75 g) in THF (250 mL), the Grignard reagent which at -78 ⁰ C to a solution of triisopropyl borate (109.1 g) in THF (40 ml) is given. After warming to room temperature, 10% hydrochloric acid (320 ml) is added and stirred for 1 h at room temperature. After usual workup, a colorless solid, mp 80-85 ⁰ C.

IC 4-amino-2,5-difluorobromobenzene

N-bromosuccinimide (42 g) is added in 1.5 h to a stirred solution of 2,5-difluoroaniline (31.0 g) in CH ₂ Cl ₂ (180 mL). The mixture is stirred at 0 ^° C. for 2 h. The solution is washed with water and dried. The solvent is removed, and you get a red solid, mp 74-75 ⁰ C.

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- 32 ID 2,5-difluoro-4-bronibiphenyl

A solution of IC in benzene (200 ml) is added in 1.5 hours to a solution of isopentyl nitrite (33.6 g) in benzene. The mixture is heated to boiling for 1.5 h. After cooling, usual work-up and chromatographic purification (silica gel / CH ₂ Cl ₂ ) gives a low-melting dark brown product.

IE 4'-pentanoyl-2,5-difluoro-4-bromobiphenyl

AlCl ₃ (25.4 g) (34.9 g) in CH ₂ Cl ₂ (120 ml) at 0 ⁰ C to a stirred solution of valeroyl chloride. A solution of ID (13.2 g) in CH ₂ Cl (120 mL) is added in 2 h at 0 ^° C. The mixture is stirred at room temperature for 48 h and then poured onto an ice / hydrochloric acid mixture. After usual work-up, a low-melting red-brown solid is obtained.

J ₁ F 4'-pentyl-2,5-difluoro-4-bromobiphenyl

Triethylsilane (7.0 g) is added at 0 ^° C ii kh to a solution of IE (8.0 g) in trifluoroacetic acid (40 ml). After stirring for 16 hours at room temperature, the mixture is poured into a NaHCOO solution. After usual workup, a solid oil, bp 110-120 ° C / 0.01 torr.

IG 4-hexyloxy-4 "-pentyl-2 ', 5' --diriuor-p-terphenyl

A solution of IB (0.98 g) in ethanol at 20 ⁰ C to a solution of IF (1.25 g) and tetrakis (triphenylphosphine) palladium (O) (0.14 g) (in a Lösüngsmittelgemisch from benzene 20 ml) and ^ M-Na ₂ CO ₃ (20 ml). The mixture is heated to 95 ^° C. for 23 h. Nacn will cool off

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the mixture was stirred for 1 h with 30% H ₂ O ₂ (2 mL) at room temperature. After customary work-up and recrystallization from ethanol to give a colorless solid, K 53.0 N 118.0 I.

Example 2

Preparation of 4,4 "-dipentyl-2 ', 5'-difluoro-p-terphenyl 2A 4-pentanoylbromobenzene

Valeroyl chloride (50 g) (20 g) at 0 ⁰ C to a mixture of bromobenzene (150 ml) and aluminum chloride. The mixture is stirred for 1 h at 0 ⁰ C, heated to 80 ⁰ C for 2 h, cooled and poured onto 18% hydrochloric acid. After customary work-up and distillation (180-184 ° C / 20 torr) to obtain a colorless solid.

For example, 4-pentylbromobenzene

A mixture of 2A (77.1 g), hydrazine hydrate (46.4 g) and KOH (590 g) in diethylene glycol (250 ml) is heated to 130 ^° C. for 2 h. After removal of the excess hydrazine hydrate by heating call 200 ⁰ C, the mixture is poured onto 18% HCl. Still usual work-up and distillation (145-148 ° C / 20 torr) gives a colorless liquid.

2_C 4-pentylphenylboronic acid

The Grignard Reag. ^ Nz from 2B is converted according to Example IB with triisopropyl borate i η the corresponding phenylboronic acid.

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This is coupled with the product of IF analogous to Example IG. This gives 4,4 "-dipentyl-2 ', 5'-difluoropterphenyl, K 65.0 N 86.0 I.

Example 3

Preparation of 4-hexyloxy-4 "-pentyl-2,2-difluoro-pterphenyl

3A 4-hexyloxy-2-fluorobromobenzene

Bromhexane is reacted with 4-bromo-3-fluorophenol analogously to Example IA. After customary work-up and distillation (100-105 ° C / 0, l torr), the product is obtained as a colorless liquid.

3B 4-hexyloxy-2-fluorophenyiboronic acid

A solution of n-butyllithium (10.0 M in hexane, 3.30 ml) is added to a cooled to -78 ⁰ C solution of 3A (9.0 g) in THF (70 ml). A solution of triisopropyl borate is after 2.5 h (19.30 g) in THF (50 mL) at -78 ⁰ C. After warming to room temperature, it is stirred for 1 h with 10% HCl (50 ml). After usual work-up, a white solid is obtained as product.

3C 4-hexyloxy-4 "-pentyl-2,2" -difluoro-p-terphenyl

The product of 3B is coupled with 4 ¹ -bromo-2-fluoro-4-pentylbiphenyl analogously to Example IC. After chromatographic purification (silica gel / petroleum ether (40-60 ⁰ C) CH ₂ Cl ₂ 3: 1) and recrystallization from ethanol to give the product as a colorless solid, K 45.0 N 131.0 I.

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- 35 Example 4

Preparation of 4-n-octyloxy-4'-pentyl-2,2'-difluoropterphenyl

4A 4-n-Octyloxy-2-fluorobromobenzene Method used: 3 A

amounts

4-Bromo-4-fluorophenol 6.00 g

1-bromooctane 7.40 g

K ₂ CO ₃ 10.00 g

The product is distilled under reduced pressure (140-142 ° C / 0.5 torr). A colorless liquid is obtained.

4B 4'-Pentyl-2'-fluorobiphenyl-4-ylboronic acid Method used: 3B

amounts

3'-Bromo-2-fluoro-4-n-pentylbiphenyl 9.90 g magnesium 0.871 g

Tri-isopropylborate 11.66 g

4C 4-Octyloxy-4'-pentyl-2,2'-difluoro-p-terphenyl Method used: IG

amounts

4A 6.00 g

4B 1.75 g

Tetrakis (triphenylphosphine) palladium (0) 0.2979 g

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After chromatographic purification, the product is obtained as a colorless solid, K 42.5 N 121.5 I.

Example 5

Preparation of 4 "hexyloxy-4" -n-pentyl ~ 3,2 "-difluoropterphenyl

4-Hexyloxy-3-fluorophenylboronic acid is coupled with 4'-bromo-2-fluoro-4-n-yentylbiphenyl analogously to Example IG.

After chromatographic purification, the product is obtained as a colorless solid, K 96.0 S _c 105.5 N 139.0 I.

Example 6

Preparation of 4-hexyloxy-4 "-pentyl-2'3'-difluoropterphenyl

6A 2,3-Di-fluorophenylboronic acid

1,2-Difluorobenzene is converted with triisopropyl borate in 6A analogously to Example 3B.

6B 4-pentyl-2 ', 3'-difluorobiphenyl Method used: IG.

amounts

1-Bromo-4-pentylbenzene, 3.80 g

6A 3.50 g

Tetrakis (triphenylphosphine) palladium (O) 0.651 g

After chromatographic purification, the product is obtained as a colorless liquid.

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5C 4'-pentyl-2,3-di-4-fluorobiphenyl-4-ylboronic acid Method used: 3B.

amounts

6B 4.00 g

n-Butyllithium 1.50 ml, 10.0 M in hexane

Triisopropyl borate C, 70 g

6D 4-hexyloxy-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl. Method used: IG.

amounts

IB 1.30 g

6C 2.0 g

Tetrakis (triphenylphosphiri) palladium (0) 0.312 g

After chromatographic purification, the product is obtained as a colorless solid, K 53 ° _C 65.5 ° N 149 °

The analogous connection jjEj

4-octyloxy-4 "-pentyl-2'3'-difluoro-p-terphenyl

is prepared using 1-bromo-4-octyloxybenzene instead of IB.

amounts

4-bromophenol 64.54 g

1-eromoctane 60.00 g

K ₂ CO ₃ 103.5 g

Colorless liquid Sdp 145 ° C / 0, l torr.

PAT LOG 7/1 150888

- 38 6E is made by coupling analog 6D:

amounts

1-Bromo-4-octoxybenzene 1.40 g

6C 1.90 g

TeLrakis (triphenylpnosphine) palladium (0) 0.3102 g

After chromatographic purification, the product is contained as a colorless solid, K 48.5 S _c 95.1 N 141.5

Example 7

Preparation of 4,4 "-di-pentyl-2 ', 3'-difluoro-p-terphenyl Method used: IG.

amounts

.? B 1.30 g

6C 2.10 g

Tetrakis (triphenylphosphine) palladium (0) 0.28 g

After recrystallization from ethanol, the product is obtained as a colorless solid, K 60 N 120 I.

Example 8

Preparation of 4-hexyloxy "4" -n-pentyl-2,3-difluoro-phenyl

8A 2,3-difluorophenol

Method used: M.F. Hawthorne, J. Org. Chem. (1957), 22, 1001.

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amounts

6A 4.40 g

10% H ₂ O ₂ 30 ml

Mp 34-36 ⁰ C, white solid.

8B 2,3-Difluorohexyloxybepzol Method used: 3A.

amounts

8A 7.00 g

1-bromohexane 10.72 g

K ₂ CO ₃ 17.40 g

After distillation (122 ° C / 15 torr) to give a colorless liquid.

8C 4-Hexyloxy-2,3-difluorophenyl boric acid Method used: 3B.

amounts

8B 10.0 g

n-Butyllithium 4.70 ml, 10.0 M in hexane

Triisopropyl borate 17.70 g

8D 4-hexyloxy-4 "-pentyl-2,3-difluoro-p-terphenyl Method used: IG.

amounts

4-Bromo-4'-pentylbiphenyl 1.40 g

8C 1/50 g

Tetrakis (triphenylphosphine) palladium (O) 0.2868 g

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N / A- . "Iiroma tographic shear purification gives the product as a colorless solid, K 97.5 ° _C 145.5 ° N 166 °

Example 8b

Preparation of 4-octyloxy-4'-pentyl-2,3-difluoro-pterphenyl

This compound is prepared analogously using 1,2-difluoro-3-octoxybenzene instead of 8B.

amounts

8A 7.00 g

1-bromooctane 12, 5 g

K ₂ CO ₃ 17.40 g

After distillation (150 ° C / 15 torr) to obtain a colorless liquid.

3e 4-octyloxy-2,3-difluorophenylboronic acid Method used: 8C.

amounts

l, 2-Difluoro-3-octoxybenzene 7.50 g

n-Butyllithium 3.10 ml 10.0 M in hexane

Triisopropyl borate 11.66 g

A colorless solid is obtained.

8F 4-octyloxy-4 "-pentyl-2,3-difluoro-p-terphenyl. Method used: 8D

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amounts

4-Bromo-4-pentylbiphenyl 1.54 g

2,3-difluoro-4-octoxyphenylboronsäure \, 75 g

Tetrakis (triphenylphosphine) palladium (0) 0.309 g

After chromatographic purification, the product is obtained as a colorless solid, K 93.5 S _c 144 S _A 148 N 159 I.

Example 9

Preparation of 4,4 "-di-pentyl-2,6-difluoro-p-terphenyl

9A 1,3-Difluoro-5- (1-hydroxypentyl) benzene

A solution of pentanal (19.0 g) in ether (75 ml) is added to a solution of the Grignard reagent prepared from 1-3-rom-3,5-difluorobenzene (50.2 g) in THF (100 ml). After 2 hours of heating, the mixture is added to the saturated NH ₄ Cl solution. After customary work-up and chromatographic purification, the product is obtained as a colorless liquid, bp 90 ° C / 0.5 torr.

9B 1,3-Difluoro-5-pent-1-enylbenzene

Phosphorus (V) oxide (64.5 g) is added to a solution of 9A (35.0 g) in dry pentane (150 ml) The mixture is stirred and filtered.

9C 1,3-Difluoro-5-pentylbenzene

5% palladium / carbon (4.0 g) is added to the filtrate of 9B. The mixture is hydrogenated at normal pressure and room temperature. After usual work-up and distillation under reduced pressure, the product is obtained as a colorless liquid, bp 200 ° C / 760 torr.

PAT LOG 7/1 150888

- 42 9_D 2, 6-difluoro-5-pentylphenylbcronsäure

A solution of n-butyllithium (10.4 M in hexane, 2.70 ml) at -78 ⁰ C to a solution of 9C (9.0 g) (50 mL) in THF and stirred for 2.5 h. With triisopropylborate (10.22 g) is converted according to Example 3B in the phenylboronic acid. This gives a colorless solid, mp 95-100 ⁰ C.

9E 3-Pentyl-4 "-hexyloxy-2,6-difluoro-p-terphenyl. Method used: IG.

amounts

4-Bromohexoxybiphenyl 1.30 g

9D 1.10g

Tetrakis (triphenylphosphine) palladium (0) 0.157 g

After recrystallization from ethanol, the product is obtained as a colorless solid, K 62 ° N 123 ° I.

9F 4,4 "-dipentyl-2,6-difluoro-p-terphenyl Method used: IG.

amounts

4-Bromo-4-pentylbiphenyl 1.40 g

9D 1.37 g

Tetrakis (triphenylphosphine) palladium (0) 0.157 g

r-

After recrystallization from ethanol, the product is obtained as a colorless solid, K 50 N 82 I.

PAT LOG 7/1 150888

- 43 Example 10

4,4 "-dialkyl-2 ', 3'-difluorophenyls a) 4-alkyl-1- (2,3-difluorophenyl) -cyclohex-1-ene

A mixture of 0.3 mol of 1,2-difluorobenzene, 600 ml of tetrahydrofuran and 0.3 mol of tetramethylethylenediamine is added at -60 ⁰ C to -70 ⁰ C with a solution of 0.3 mol of n-butyllithium in 188 ml of hexane. After 3 hours of stirring at -60 ⁰ C, a solution of 0.32 mol of 4-pentylcyclohexanone in 100 ml of tetrahydrofuran is added. After customary workup, the residue is dissolved in 1000 ml of toluene and heated with 10 g of p-toluenesulfonic acid for 3 h in a water. After customary work-up, 4-pentyl-1- (2,3-difluorophenyl) -cyclohex-1-ene, bp: 123 ° C / 0.5 torr.

Analog are produced-

4-Ethyl-1- (2,3-difluorophenyl) -cyclohex-1-ene 4-propyl-1- (2,3-difluorophenyl) -cyclohex-1-ene 4-butyl-1- (2,3-difluorophenyl ) -cyclohex-1-ene 4-hexyl-1- (2,3-difluorophenyl) -cyclohex-1-ene 4-heptyl-1- (2,3-difluorophenyl) -cyclohex-1-ene 4-octyl-1 - (2,3-difluorophenyl) cyclohex-1-ene 4-nonyl-1- (2,3-difluorophenyl) -cyclohex-1-ene 4-decyl-1- (2,3-difluorophenyl) -cyclohex-1 4-dodecyl-1- (2,3-difluorophenyl) -cyclohex-1-ene-4-ethoxy-1- (2,3-difluorophenyl) -cyclohex-1-ene-4-propoxy-1- (2,3 -difluorophenyl) -cyclohex-1-ene 4-butoxy-1- (2,3-difluorophenyl) -cyclohex-1-ene 4-pentoxy-1- (2,3-difluorophenyl) -cyclohex-1-ene 4-hexoxy -l- (2,3-difluorophenyl) cyclohex-1-ene

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4-Heptoxy-1- (2,3-difluo-phenyl) -cyclohex-1-ene 4-Octoxy-1- (2,3-difluorophenyl) -cyclohex-1-ene-4-nonuxy-1- (2,3-difluorophenyl ) -cyclohex-1-en 4-decoxy-1- (1,3-difluorophenyl) -cyclohex-1-ene 4-undecoxy-1- (2,3-difluorophenyl) -cyclohex-1-ene

b) 4-alkyl-2 ·, 3'-difluorobiphenyls

A mixture of 0.1 mol of 4-phenyl-1- (2,3-difluorophenyl) -cyclohex-1-ene and 500 ml of toluene is mixed with 0.22 mol of 2,3-dichloro-5,6-dicyano-p- added benzoquinone and heated under reflux for 2 hours. After usual workup, 4-pentyl-2 ', 3'-difluorobiphenyl, b.p .: 125 ° C / 0.5 torr.

Analog are shown:

4-ethyl-2 ', 3'-difluorobiphenyl 4-p-propyl-2', 3'-difluorobiphenyl 4-butyl-2 ', 3'-difluorobiphenyl 4-hexyl-2', 3'-difluorobiphenyl 4-heptyl- 2 ·, 3'-difluorobiphenyl 4-octyl-2 ', 3'-difluorobiphenyl 4-nonyl-2', 3'-difluorobiphenyl 4-decyl-2 ', 3'-difluorobiphenyl 4-ethoxy-2', 3'- difluorobiphenyl 4-propoxy-2'.3'-difluorobiphenyl 4-butoxy-2 ', 3'-difluorobiphenyl 4-pentoxy-2', 3'-difluorobiphenyl 4-hexoxy-2 ', 3'-difluorobiphenyl 4-heptoxy-2 ', 3'-Difluorobiphenyl 4-octoxy-2', 3'-difluorobiphenyl 4-nonoxy-2 ', 3'-difluorobiphenyl 4-decoxy-2', 3'-difluorobiphenyl 4-dodecoxy-2 ', 3'-difluorobiphenyl

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- 45 -

4-octyloxy-4'-pentyl-2,3-difluorobiphenyl, K (N 13.5) I

4-octyloxy-4'-heptyl-2,3-difluorobiphenyl, K (S _c 6 S _A 13 N 23) I

4-Nonyloxy-4 ^l -decyl-2,3-difluorobiphenyl, K 47 I 4-ethoxy-4'-pentyl-2,3-difluorobiphenyl, K -10 I 4 -pentyloKy-4'-octyloxy-2,3- difluorobiphenyl, KS _A 12 N 18 I

4-Heptyloxy-4'-pentyl-2,3-difluorobiphenyl, K 0.5 I 4-nonyloxy-4'-octyloxy-2,3-difluorobiphenyl, K (S _c 11,5) S _A 33 N 34 I

c) 4,4 "dialkyl-2 ', 3'-difluoro-phenyle

0.1 mol of 4-pentyl-2 ', 3'-difluorobiphenyl are deprotonated according to Example 10a) with n-butyllithium in tetrahydrofuran / tetramethylethylenediamine and reacted with 0.1 mol of 4-propylcyclohexanone. After oxidation with 0.2 mol of 2,3-dichloro-5,6-dicyano-p-benzoquinone according to Example 10b) gives 4-pentyl-4 "-propyl-2 ', 3'-difluoro-phenyl.

Analog are shown:

4-ethyl-4 "-propyl-2 ', 3'-difluoro-phenyl 4-propyl-4" -propyl-2', 3'-difluoro-phenyl, K 94 N 133 I 4-butyl-4 "-propyl-2 ', 3'-difluoro-phenyl 4-pentyl-4 "-propyl-2 ', 3'-difluoro-phenyl 4-Hex" l-4 "-propyl-2', 3-difluoro-phenyl 4-heptyl-4" -propyl-2 ', 3 '-difluoro-phenyl 4-octyl-4'-propyl-2', 3'-difluoro-phenyl 4-nonyl-4'-propyl-2 ', 3'-difluoro-phenyl 4-decyl-4'-propyl-2', 3'- difluoro-phenyl 4-dodecyl-4 "-propyl-2 ', 3'-difluoro-phenyl

PAT LOG 7/1 150888

2742

- 46 -

4-Ethoxy-4 "-propyl-2 ', 3'-difluoro-phenyl 4-propoxy-4"-propyl-2',3'-difluoro-phenyl 4-butoxy-4 "-propyl-2 ', 3'-difluoro-phenyl 4 Pentoxy-4 "-propyl-2 ', 3'-difluoro-phenyl 4-hexoxy-4"-pro;->yl-2', 3 '-difluoro-phenyl 4-heptoxy-4 "-propyl-2', 3'-difluoro-phenyl 4-octoxy-4 "-propyl-2 ', 3'-difluorterphenyl 4-nonoxy-4"-propyl-2',3'-difluorterphenyl 4-decoxy ^4-r propyl 2 ', 3'-4- difluorterphenyl dodecoxy-4 "-propyl-2 ', 3'-difluorterphenyl

4-Ethyl-4 "-pentyl-2 ', 3'-difluoro-phenyl 4-propyl-4" -pentyl-2', 3'-difluoro-phenyl 4-butyl-4 "-pentyi-2 ', 3'-difluoro-phenyl 4 Pentyl-4'-pentyl-2 ', 3'-difluorophenyl, K 60.0 ° N 120.0 ° I

4-hexyl-4 "-pentyl-2 ', 3'-difluoro-phenyl 4-heptyl-4"-pentyl-2',3'-difluoro-phenyl, K 36.5 (S _c 24) N 110.5 I 4-octyl -4 "-pentyl-2 ', 3'-difluoro-phenyl 4-Nory: 4-pentyl-2', 3'-difluoro-phenyl-4-decyl-4" -pentyl-2 ', 3'-difluoro-phenyl 4-dodecyl 4 "-pent: vl-2 ', 3'-difluorophenyl 4-ethoxy-4"-pentyl-2',3'-difluoro-phenyl 4-prc / oxy-4"-per.tyl-2 ', 3' - difluoro-phenyl-4-butoxy-4'-pentyl-2 ', 3'-difluorotarphenyl.l 4-pentoxy-4'-pentyl-2', 3'-difluorophenyl 4-hexoxy-4i ^: -pentyl-2 ', 3 '-difluorophenyl, K 53.0 ° S _c 65, j ° N 149.0 ⁰ I 4-Heptoxy 4 "-pentyl-2', 3 ', - difluoro-phenyl 4-octoxy-4"-pentyl-2', 3 '-difluoro-phenyl, K 48.6 ° _C 95.1 ° N 141.5 ° I 4-nonoxy-4'-pentyl-2', 3'-difluoro-phenyl 4-decoxy-4'-pentyl-2 ', 3'- difluoro-phenyl 4-dodecoxy-4'-pentyl-2 ', 3'-difluoro-phenyl

PAT LOG 7 Λ 150883

- 47 -

4-nonyl-4 "-heptyl-2 ', 3'-difluorophenyl K 49.0 S _c 77.0 S _A 93.0 N 108.5 I

4-ethyl-4 "-octyl-2 ', 3'-difluoro-phenyl 4-propyl-4"-octyl-2',3'-difluoro-phenyl 4-butyl-4 "-octyl-2 ·, 3'-difluoro-phenyl 4 Pentyl 4 "octyl-1 ', 3' -difluoro-phenyl 4-hexyl-4" -octyl-2 ', 3' -difluoro-phenyl 4-heptyl-4 "-octyl-2 ', 3'-difluoro-phenyl 4 -Octyl-4 "-octyl-2 ', 3'-difluoro-phenyl-4-nonyl-4" -octyl-2 ·, 3'-difluoro-phenyl 4-decyl-4 "-octyl-2', 3'-difluoro-phenyl 4-dodecyl 4 "-octyl-2 ·, 3'-difluoro-phenyl 4-ethoxy-4" -octyl-2 ', 3'-difluoro-phenyl 4-propoxy-4 "-octyl-2', 3'-difluoro-phenyl 4-butoxy-4 "-octyl-2 ', 3'-difluoro-phenyl 4-pentoxy-4"-octyl-2',3'-difluoro-phenyl ^ -hexoxy-4 "-octy] -2 ', 3'-difluoro-phenyl 4-heptoxy-4" -octyl-2 ', 3'-difluoro-phenyl 4-octoxy-4 "-octyl-2', 3'-difluoro-phenyl 4-nonoxy-4" -octyl-2 ', 3'-difluoro-phenyl 4-decoxy-4 "-octyl -2 ', 3'-difluorterphenyl ^{4-dodecoxy-4'!} octyl-2 ', 3' -difluorterphenyl

4-nonoxy-4 "-ethoxy-2 ', 3'-difluoro-phenyl 4-decoxy-4" -ethoxy-2', 3'-difluoro-phenyl 4-dodecoxy-4 "-ethoxy-2 ', 3'-difluoro-phenyl

4-ethyl-4 "-heptoxy-2 ', 3'-difluoro-phenyl 4-butyl-4" -heptoxy-2', 3'-difluoro-phenyl 4-hexyl-4 "-heptoxy-2 ', 3'-difluoro-phenyl 4-heptyl -4 "-heptoxy-2 ', 3'-difluoro-phenyl 4-nonyl-4" -heptoxy-2', 3'-difluoro-phenyl 4-dodecyl-4 "-heptoxy-2 ', 3'-difluoro-phenyl 4-ethoxy-4 "-Heptoxy-2 ', 3'-difluorterphenyl

PAT LOG 7/1 150888

7 Ί23

- 48 -

4-propoxy-4 "-heptoxy-2 ', 3'-difluoro-phenyl 4-butoxy-4" -heptoxy-2', 3'-difluoro-phenyl 4-pentoxy-4 "-heptoxy-2 ', 3'-difluoro-phenyl 4 -Hexoxy-4 "-heptoxy-2 ', 3'-difluoro-phenyl-4-heptoxy-4" -heptoxy-2', 3'-difluoro-phenyl-4-octoxy-4 "-heptoxy-2 ', 3'-difluoro-phenyl-4-nonoxy -4 "-heptoxy-2 ', 3'-difluorophenylyi 4-i: ecoxy-4" -heptoxy-2', 3'-difluoro-phenyl 4-doCecoxy-4 "-heptoxy-2 ', 3'-difluoro-phenyl

Example 11

4,4 '' '- dialkyl-2', 3'-difluorquaterphenyle

0.1 mol of 4-pentyl-2 ', 3'-difluorobiphenyl (prepared according to Example 10b) are dephosphatized according to Example 10a with η-butyllithium in tetrahydrofuran / tetramethylethylenediamine and depolyated with 0.1 mol of 4- (p-propylphenyl) - implemented cyclohexanone. After oxidation with 0.2 mol of 2,3-dichloro-5,6-dicyano-p-benzoquinone according to Example 10b gives 4-pentyl-4 '' '- propyl-2', 3'-difluorquaterphenyl.

Analog are produced:

4-ethyl-4 '''-propyl-2',3'-difluoroquaterphenyl 4-propyl-4 '''-propyl-2',3'-difluoroquaterphenyl 4-butyl-4 '''-propyl-2',3'-difluoroquaterphenyl 4- ^T .iexyl-4 '''-propyl-2',3'-difluororquaterphenyl 4-heptyl-4 '''-propyl-2',3'-difluoroquaterphenyl 4-octyl-4 '''-propyl-2',3'-difluoroquaterphenyl 4-nonyl-4 '''-propyl-2',3'-difluoroquaterphenyl 4-decyl-4 '''-propyl-2',3'-difluorquaterphenyl 4-dodecyl -4 '''-propyl-2',3'-difluoroquaterphenyl 4-ethoxy-4 '''-propyl-2',3'-difluoropaterphenyl 4-propoxy-4 '''-propyl-2',3'- difluorquaterphenyl

PAT LOG 7/1 150888

27423

- 49 -

4-butoxy-4 '' '- propyl-2', 3 '' difluoroquaterphenyl 4-pentoxy-4 '' '- propyl-2', 3'-difluoroquaterphenyl 4-hexoxy-4 · '' - propyl-2 ', 3'-Difluoroquaterphenyl 4-Heptoxy-4 '' '- propyl-2', 3'-difluoroquaterphenyl 4-octoxy-4 '' '- propyl-2', 3'-difluoroquaterphenyl 4-nonoxy-4 '' '- propyl -2 ', 3'-difluoroquaterphenyl 4-decoxy-4' '' - propyl-2 ', 3'-difluorquaterphenyl

4-ethyl-4 '''-octyl-2',3'-difluoroquaterphenyl 4-propyl-4 '''-octyl-2',3'-difluoroquaterphenyl 4-butyl-4 '''-octyl-2',3'-Difluoroquaterphenyl 4-Pentyl-4 '''--octyl-2',3'-difluoroquaterphenyl 4-hexyl-4 '''-octyl-2',3'-difluoroquaterphenyl 4-heptyl-4 '''- octyl -2 ', 3'-difluoroquaterphenyl 4-octyl-4''' octyl-2 ', 3'-difluoroquaterphenyl 4-nonyl-4''' - octyl-2 ', 3'-difluoroquaterphenyl 4-decyl-4''' -octyl-2 ^1, 3 'difluorquaterphenyl 4-dodecyl-4''' - octyl-2 ', 3'-di fluorquaterphenyl 4-ethoxy-4''' - octyl-2 ', 3'-difluorquaterphenyl 4 -Propoxy-4 '''-octyl-2',3'-difluoroquaterphenyl 4-butoxy-4 '''-octyl-2',3'-difluoroquaterphenyl 4-pentoxy-4 '''-octyl-2', 3 '-difluoroquaterphenyl 4-hexoxy-1''' - octyl-2 ', 3'-di-iororquaterphenyl 4-heptoxy-4''' - octyl-2 ', 3'-difluorquaterphenyl 4-octoxy-4''' - octyl-2 ', 3'-difluoroquaterphenyl 4-nonoxy-4' ^! '-octyl-2', 3'-difluoroquaterphenyl 4-decoxy-4 '''-octyl-2',3'-difluorquaterphenyl

4-ethyl-4 '' '- ethoxy-2', 3'-difluoroquaterphenyl 4-propyl-4 '' '- ethoxy-2', 3'-difluoropaterphenyl 4-butyl-4 '' '- ethoxy-2', 3'-Difluoroquaterphenyl 4-Pentyl-4 '' '- ethoxy-2', 3'-difluoroquaterphenyl 4-hexyl-4 '' '- ethoxy-2', 3'-difluoroquaterphenyl 4-heptyl-4 '' '- ethoxy -2 ', 3' "difluorquaterphenyl 4-octyl-4 '' '- ethoxy-2', 3'-difluoroquaterphenyl

PAT LOG 7/1 150888

27 4

- 50 -

4-nonyl-4 '' '- ethoxy-2', 3'-difluoroquaterphenyl 4-decyl-4 '' '- ethoxy-2', 3'-difluoroquaterphenyl 4-dodecyl-4 '' '- ethoxy-2', 3'-Difluoroquaterphenyl 4-Ethoxy-4 '' '- ethoxy-2', 3'-difluoroquaterphenyl 4-propoxy-4 '' '- ethoxy-2', 5'-difluoroquaterphenyl 4-butoxy-4 '' * -ethoxy -2 ', 3'-difluoroquaterphenyl 4-pentoxy-4' '' - ethoxy-2 ', 3'-difluoroquaterphenyl 4-hexoxy-4' '' - ethoxy-2 ', 3'-difluoroquaterphenyl 4-hcptoxy-4' '' -ethoxy-2 ', 3'-difluoroquaterphenyl 4-octoxy-4' '' - ethoxy-2 ', 3'-difluoroquaterphenyl 4-nonoxy-4' '' - ethoxy-2 ', 3'-difluorquaterphenyl 4- decoxy-4 '' '- ethoxy-2', 3'-difluorquaterphenyl

4-ethyl-4 '' '- heptoxy-2', 3'-difluoroquaterphenyl 4-propyl-4 '' '- heptoxy-2', 3'-difluoroquaterphenyl 4-butyl-4 '' '- heptoxy-2', 3'-Difluoroquaterphenyl 4-Pentyl-4 '' '- heptoxy-2', 3'-difluoroquaterphenyl 4-hexyl-4 '' '- heptoxy-2', 3'-difluoroquaterphenyl 4-heptyl-4 '' '- heptoxy -2 ', 3'-difluoroquaterphenyl 4-octyl-4' '' - heptoxy-2 ', 3'-difluoroquaterphenyl 4-nonyl-4' '' - heptoxy-2 ', 3-difluoroquaterphenyl 4-decyl-4' ' '-heptoxy-2', 3'-difluoroquaterphenyl 4-dodecyl-4 '' '- heptoxy-2', 3'-difluoroquaterphenyl 4-ethoxy-4 '' '- heptoxy-2', 3'-difluorquaterphenyl 4-propoxy -4 '' '- heptoxy-2', 3'-difluoroquaterphenyl 4-butoxy-4 '' '- heptoxy-2', 3'-difluoroquaterphenyl 4-pentoxy-4 '' '- heptoxy-2', 3'- difluorquaterphenyl 4-hexoxy-4 '' '- heptoxy-2', 3'-difluororquaterphenyl 4-heptoxy-4 '' '- heptoxy-2', 3'-difluoroquaterphenyl 4-octoxy-4 '' '-heptoxy-2' , 3'-dj, f luorquaterphenyl

30 4-nonoxy-4 '' '- heptoxy-2', 3'-difluoroquaterphenyl 4-decoxy-4 '' '- heptoxy-2', 3'-difluorquaterphenyl

PAT LOG 7/1 150888

27 ^ 233

Example 12 4,4 "-dialkyl-2,3-difluorophenyls

a) 1- (2,3-Difluorophenyl) -4- (p-alkylphenyl) -crylohex-1-ene

A mixture of 0.1 mol of 1,2-difluorobenzene and 200 ml of tetrahydrofuran is treated at -70 ⁰ C and 0.105 mol of n-butyllithium in 60 ml of hexane. After stirring for 6 hours, a mixture of 0.1 mol of 4- (p-propylphenyl) cyclohexanone and 50 ml of tetrahydrofuran is added. After 2 hours of stirring, warming to room temperature and usual workup gives 1- (2,3-di-fluorophenyl) -4- (p-propylphenyl) cyclohex-1-ene

Analog are produced:

1- (2,3-di-fluorophenyl) -4- (p-ethylphenyl) -cyclohex-1-ene

1- (2,3-di-fluorophenyl) -4- (p-butylphenyl) -cyclohex-1-ene

1- (2,3-difluorophenyl) -4- (p-pentylphenyl) cyclohex-1-ene

1- (2,3-di-fluorophenyl) -4- (p-hexylphenyl) -cyclohex-1-ene

1- (2,3-Difluorophenyl) -4- (p-heptylphenyl) -cyclohex-1-en- (2,3-difluorophenyl) -4-v (p-octylphenyl) -cyclohex-1-ene

1- (2,3-difluorophenyl) -4- (p-nonylphenyl) cyclohex-1-ene

1- (2,3-difluorophenyl) -4- (p-decylphenyl) cyclohex-1-ene

PAT LOG 7/1 150888

- 52 -

1- (2,3-di-fluorophenyl) -4- (p-dodecylphenyl) -cyclohex-1-ene

1- (2,3-difluorophenyl) -4- (p-ethoxyphenyl) cyclohex-1-ene

1- (2,3-difluorophenyl) -4- (p-pentoxyphenyl) cyclohex-1-ene

1- (2,3-difluorophenyl) -4- (p-octoxyphsnyl) cyclohex-1-ene

l- (2,3-difluorophenyl) -4- (p-dodecyloxyphenylj-cyclohex-l-en

With 4- (4-alkylbiphenyl-4'-yl) -cyciohexanonen as starting compounds one receives analogously:

1- (2,3-Difluorophenyl) -4- (4-ethylbiphenyl-4'-yl) -cyclohex-1-ene 1- (2,3-Di-fluorophenyl) -4- (4-pentyl-biphenyl-4'-yl ) cyclohex-1-ene

1- (2,3-difluorophenyl) -4- (4-octylbiphenyl-4'-yl) cyclohex-1-ene

1- (2,3-difluorophenyl) -4- (4-dodecylbiphenyl-4'-yl) cyclohex-1-ene

1- (2,3-Difluorophenyl) -4- (4-pentoxy-biphenyl-4-yl) -cyclohex-1-ene

b) 4 "-alkyl-2,3-difluoro-phenols

0.1 mol of 1- (2,3-difluorophenyl) -4- (p-propylphenyl) -cyclohex-1-ene are oxidized according to Example 10b with 0.2 mol of 2,3-dichloro-5,6-dicyanobenzoquinone. After customary working up, one obtains ^u K 4-propyl-2,3-difluorterphenyl, 121 I.

PAT LOG 7/1 150888

- 53 analogue are produced:

4 "-ethyl-2 _: 3-difluoro-phenyl 4" -butyl-2,3-difluoro-phenyl-4 "-pentyl-2,3-difluoro-phenyl-4" -hexyl-2,3-difluoro-phenyl 4 "-heptyl-2,3-di fluorophenyl 4 "-0-octyl-2,3-difluoro-phenyl 4" -nucl-2,3-difluoro-phenyl 4 "-decyl-2,3-difluoro-phenyl 4" -dodecyl-2,3-di-fluoro-terphenyl 4 "-ethoxy-2,3 -difluoro-phenyl 4 "-pentoxy-2,3-difluoro-phenyl-4" -oxy-2,3-di-fluoro-fluorophenyl 4 "-dodecyloxy-2,3-difluoro-phenyl

With l- (2,3-difluorophenyl) -4- (4-alkylbiphenyl-4'-yl) -cyclohex-1-enes as starting compounds, the procedure is analogous:

4 '''- ethyl-2,3-difluorquaterpheny1 4 ^1' -pentyl-2,3-difluorquaterphenyl 4 '''- octyl-2,3-difluorquaterphenyl 4''' - dodecyl-2,3-difluorquaterpheny1 4 ''' - pentoxy-2,3-difluorquaterpheny1

c) 4,4 "dialkyl-2,3-difluoro-phenylene

To a mixture of 0.1 mol of 4 "-propyl-2,3-difluoro-phenyl, 0.1 mol of potassium tert-butoxide and 200 ml of tetrahydrofuran at -1'00 ⁰ C, a solution of 0.1 mol of n-butyllithium in 65 ml hexane was added dropwise. After stirring for 5 minutes at -100 ⁰ C a mixture of 0.1 mol of pentyl bromide and 0.1 mol of N, N-dimethylpropyleneurea is added. After warming to -30 ⁰ C.

PAT LOG 7/1 150888

7 4 2 3

- 54 -

and usual work-up gives 4 "-propyl-4-pentyl-2,3-difluoro-phenyl.

Analog are produced:

4 "-ethyl-4-pentyl-2,3-difluorterphenyl ^li 4-propyl-4-pentyl-2,3-difluorterphenyl 4" -butyl-4-pentyl-2,3-difluorterphenyl 4 "-pentyl-4-pentyl -2,3-difluoro-phenyl, K 80.0 S _c 115.5 S _A 131.5 N 142.0 I 4 "-Hexyl-4-pentyl-2,3-difluoro-phenylene-4-heptyl-4-pentyl-2 , 3-difluoro-phenyl, K 65.5 S _r 117.0 S. 135..0 N 136.0 I 4 "-Octyl-4-pentyl-2,3-difluorophenyl 4" -nonyl-4-pentyl-2, 3-difluoro-phenyl 4 "-decyl-4-pentyl-2,3-difluorophenyl 4" -dodecyl-4-pentyl-2,3-difluoro-phenyl-4 "-ethoxy-4-pentyl-2,3-difluoro-phenyl-4" -pentoxy- 4-pentyl-2,3-difluoro-phenyl, K 100.5 S _c 156.5 S _A 166.5 N 171.5 I 4 "-Octoxy-4-penty1-2,3-di-fluoro-pheny1, K 87.5 S _c 155.5 S _A 165.0 N 165.7 I 4 "- (4-methylhexyl) -4-pentyl-2,3-difluorophenyl, K 71.0 S _c 120.0 N 128.0 I 4" - dodecyloxy-4-pentyl-2,3-difluorterphenyl

4 "-ethyl-4-propyl-2,3-difluorophenyl 4" -propyl-4-propyl-2,3-difluoropterphenyl, K 133 N 150 I

4 "-butyl-4-propyl-2,3-difluoro-phenyl 4" -pentyl-4-propyl-2,3-difluoro-phenyl-4 "-hexyl-4-propyl-2,3-difluoro-phenyl 4" -heptyl-4-propyl -2,3-difluoro-phenyl 4- ^i: -octyl-4-propyl-2,3-difluoro-phenyl 4 "-nonyl-4-propyl-2,3-difluoro-phenyl

PAT LOG 7/1 150388

27423

- 55 -

4 "-decyl-4-propyl-2,3-difluoro-phenyl 4" -dodecyl-4-propyl-2,3-difluoro-phenyl 4 "-ethoxy-4-propyl-2,3-difluoro-phenyl 4 ^l! -Pentoxy-4 propyl 2,3-difluorophenyl 4 "-Octoxy-4-propyl-2,3-difluoro-phenyl 4" -dodecyloxy-4-propyl-2,3-difluoro-phenyl

4 "-ethyl-4-octy] -2,3-difluorterphenyl 4" -propyl-4-octyl-2,3-difluorterphenyl 4 "butyl-4-octyl-2,3-difluorterphenyl 4 ^& pentyl-4- octyl-2,3-difiphenylphenyl 4 "-hexyl-4-octyl-2,3-difluorophenyl 4" -heptyl-4-octyl-2,3-difluorophenyl 4 "-octyl-4-octyl-2,3- difluoro-phenyl 4 "-nonyl-4-octyl-2,3-difluoro-phenyl 4" -decyl-4-octyl-2,3-difluoro-phenyl 4 "-dodecyl-4-octyl-2,3-difluoro-phenyl 4" ~ ethoxy-4 Ocicyl-2 _/ 3-difluorophenyl 4 "-pentoxy-4-octyl-2,3-difluoro-phenyl 4" -octoxy-4-octyl-2,3-difluoro-phenyl 4 "-dodecyloxy-4-octyl-2,3-difluoro-phenyl

4 "-ethyl-4-dodecyl-2,3-difluoro-phenyl 4" -propyl-4-dodecyl-2 _; 3-difluoro-phenyl 4 "-butyl-4-dodecyl-2,3-difluorophenyl 4" -pentyl-4-dodecyl-2,3-difluoro-phenyl-4 "-hexyl-4-dodecyl-2,3-difluoro-phenyl-4" -heptyl- 4-dodecyl-2,3-difluoro-phenyl 4 "-octyl-dodecyl-2,3-difluoro-phenyl 4" -nonyl-4-dodecyl-2,3-difluoro-phenyl 4 "-decyl-4-dodecyl-2,3-difluoro-phenyl 4 "-dodecyl-l-dodecyl-2,3-difluorterphenyl 4 ^& pentyl-i-heptyl-2,3-difluorterphenyl, K 55.0 S _c 105.5 S _A 130.5 N 135.0 I

4 "-propyl-4-nonyl-2,3-difluoro-phenyl, K 63.0 S _c 84.5 S _A 116.5 N 129.0 I

PAT LOG 7/1 150888

"Joel & Ui

- 56 -

4 "-thoxy-4-dodecyl-2,3-difluoro-phenyl 4" -pentoxy-4-dodecyl-2,3-difluoro-phenyl 4 "-octoxy-4-dodecyl-2,3-difluoro-phenyl 4" -dodecyloxy-4-dodecyl -2,3-difluorterphenyl

With 4 '·' '- alkyl-2,3-difluorquaterphenylen as starting materials one receives analogously:

4 ¹ '' -Ethyl-4-propyl-2, '-. Difluorquatsrphenyl 41 t' - penty 1-4-propyl! * • .., 3-difluororquaterphenyl 1 4 ¹ '' -Octyl-4-propyl-2 , 3-difluorquaterpheny1 4 ¹ "-dodecyl-4-propyl-2,3-difluoroquaterphenyl-411'-pentoxy-4-propyl-2,3-difluoroquaterphenyl

4 ¹ '' -Ethyl-4-pentyl-2,3-difluoroquaterphenyl 411'-pentyl-4-pentyi-2,3-difluoroquaterphenyl1 4 ¹ '' -Octyl-4-pentyl-2,3-difluoroquaterphenyl 4 ¹ '' -Dodecyl-4-pentyl-2,3-difluoroquaterphenyl1 4 · 1'-pentoxy-4-pentyl-2,3-difluoroquaterphenyl1

4 ¹ '' -Ethyl-4-octyl-2,3-difluoroquaterphenyl1 4 '''- Pentyl-4-octyl-2,3-difluoroquaterphenyl1 4''' - Octyl-4-octyl-2,3-difluoroquaterphenyl1 4 ''' -dodecyl-4-octyl-2,3-difluorquaterpheny1 4 '' ^f pentoxy-4-octyl-2,3-difluorquaterpheny1

4 '''- Ethyl 4-dodecyl-2,3-difluoroquaterphenyl 4''' - Pentyl-4-dodecyl-2,3-difluoroquaterphenyl 4 '' ^l -Octyl-4-dodecyl-2 _/ 3-difluoroquaterphenyl 4 ''' - Dodecyl-4-dodecyl-2,3-difluoroquaterphenyl 4 ¹ • ^l -pentoxy-4-dodecyl-2,3-difluoroquaterphenyl

PAT LOG 7/1 150888

Example 13 4-Alkoxy-4 "-alkyl-2,3-difluoro-phenylene

0.2 mol l, 2-difluoro-3-ethoxybenzene are deprotonated at -60 ⁰ C in tetrahydrofuran, tetramethylethylenediamine with n-butyllithium according to Example 10a and reacted according to Example 10c mic 0.2 mol 4- (p-propylphenyl) cyclohexanone , Mach oxidation with 0.4 mol of 2,3-dichloro-5,6-dicyanobenzoquinone gives 4-Ethox_ • 4 ^ll -propyl-2,3-difluorterphenyl.

Analog are produced:

4-propoxy-4 "-propyl-2,3-difluoro-phenyl-4-butoxy-4" -propyl-2,3-di-fluoro-terphenyl 4-pentoxy-4 "-propyl-2,3-difluoro-phenyl-4-hexoxy-4" - propyl-2,3-difluoro-phenyl-4-heptoxy-4 "-propyl-2,3-difluoro-phenyl-4-octoxy-4" -propyl-2,3-difluoro-phenyl-4-nonoxy-4 "-propyl-2,3-difluoro-phenyl 4 -Decyloxy-4 "-propyl-2,3-difluoro-phenyl-4-dodecyloxy-4" -propyl-2,3-difluoro-phenyl

4 ~ Ethoxy-4 "-pentyl-2,3-difluoro-phenyl, K 105.0 S _c 135.0 N 185.1 l

4-Propoxy-4 "-pentyl-2,3-difluoro-phenyl-4-butoxy-4" -pentyl-2,3-difluoro-phenyl 4-pentoxy-4 "-pentyl-2,3-difluoro-phenyl 4-hexoxy-4" -pentyl -2,3-difluorophenyl, K 97.5 ° _C 145.5 ° N 166.0 ° I

4-Heptuxyl-4 "-pentyl-2,3-difluoro-phenyl-4-octo: y-4" -pentyl-2,3-difluoro-phenyl, K 93.5 °

S _c 144.0 ° S _A 148.0 ° N 159.0 ° I 4-Nonoxy-4 "-pentyl-2,3-difluoro-phenyl

PAT LOG 7/1 150888

- 58 -

4-Decyloxy-4 "-pentyl-2,3-difluoro-phenyl-4-dodecyloxy-4" -pentyl-2,3-difluoro-phenyl

4-Ethoxy-4 "-octyl-2,3-difluoro-phenyl-4-propoxy-4" -octyl-2,3-difluoro-phenyl-4-butoxy-4 "-octyl-2,3-difluoro-phenyl-4-pentoxy-4" -octyl -2,3-difluoro-phenyl 4-hexoxy-4 "-octyl-2,3-difluoro-phorphyl 4-heptoxy-4" -octyl-2,3-di-fluoro-terphenyl 4-octoxy-4 ^l! octyl-2,3-difluorophenyl 4-nonoxy-4 "-octyl-2,3-difluoro-phenyl-4-decyloxy-4" -octyl-2,3-difluoro-phenyl-4-dodecyloxy-4 "-octyl-2,3- difluorterphenyl

4-ethoxy-4 "dodecyl-2,3-difluorterphenyl 4-propoxy-4" dodecyl-2,3-difluorterphenyl 4-butoxy-4 ^M dodecyl-2,3-difluorterphenyl 4-pentoxy-4 "-dodecyl -2,3-difluorterphenyl 4-hexoxy-4 "dodecyl-2,3 ~ difluorterphenyl 4-heptoxy-4 ^M dodecyl-2,3-difluorterphenyl 4-octoxy-4" dodecyl-2,3-di fluorterphenyl 0 4-nonoxy-4 "-dodecyl-2,3-di-fluorophenyl 4-decylcoxy-4" -dodecyl-2,3-difluorophenyl 4-dodecyloxy-4 "-dodecyl-2,3-difluoro-phenyl

4-Ethoxy-4 "-ethoxy-2,3-difluoro-phenyl 4-propoxy-4" -ethoxy-2,3-difluoro-phenyl 4-butoxy-4 "-ethoxy-2,3-difluoro-phenyl 4-pentoxy-4" -ethoxy -2,3-difluoro-phenyl 4-hexoxy-4 "-ethoxy-2,3-difluoro-phenyl 4-heptoxy-4" -ethoxy-2,3-di-fluoro-terphenyl 4-octoxy-4 "-ethoxy-2,3-difluoro-phenyl 4 -Nonoxy-4 "-ethoxy-2,3-difluoro-phenyl-4-decyloxy-4" -ethoxy-2,3-difluoro-phenyl-4-dodecyloxy-4 "-ethoxy-2,3-difluoro-phenyl

PAT LOG 7/1 150888

- 59 · <

4-octoxy-4 "- (4-methylhexyl) -2,3-difluoro-phenyl, K 71.0 S _c 120.0 N 128.0 l

4-Ethoxy-4 "-pentoxy-2,3-di-fluoroperphenyl 4-propoxy-4" -pentoxy-2,3-difluoro-phenyl-4-butyl-4 "-pentoxy-2,3-di-fluoro-terphenyl 4-pentoxy-4 ^if -pentoxy-2,3-difluoro-terephthalyl 4-hexoxy-4 "-pentoxy-2,3-di-fluoro-terphenyl 4-heptoxy-4" -pentoxy-2,3-difluorophenyl 4-octoxy-4 "-pentoxy -: i, 3 -difloro-phenyl-4-nonoxy-4 "-pentoxy-2,3-difluorophenyl 4-decyloxy-4" -penoxy-2,3-di-fluoro-terphenyl 4-dodecyloxy-4 "-pentoxy-2,3 -difluorterphenyl

4-Ethoxy-4 "-dodecyloxy-2,3-difluoro-phenyl-4-propoxy-4" -dodecyl-O-y-?. 3-difluoro-phenyl 4-butoxy-4 "-dodecyloxy-2,3-difluoro-phenyl 4-pentoxy-4" -dodecyloxy -2,3-difluoro-phenyl 4-hexoxy-4 "-dodecyloxy-2,3-difluoro-phenyl 4-heptoxy-4" -dodecyloxy-2,3-di-fluoro-terphenyl 4-octoxy-4 "-dodecyloxy-2,3-difluoro-phenyl 4 Nonoxy-4 "-dodecyloxy-2,3-difluoro-phenyl-4-decyloxy-4" -dodecyloxy-2,3-difluoro-phenyl-4-dodecyloxy-4 "-dodecyloxy-2,3-difluoro-phenyl-4-octoxy-4" - pentyl-2,3,2 "trifluorophenyl, K 585 S _c 61.5 N 119.5 l

With 4- (4-alkylbiphenyl-4'-yl) -cyclohexanonen as starting products one receives analogously:

4-Ethoxy-4 '' '- propyl-2,3-difluoroquaterphenyl 4-propoxy-4' '' - propyl-2,3-difluoroquaterphenyl 4-butoxy-4 '' '- propyl-2,3-difluoroquaterphenyl] 4 Pentoxy-4 '' '- propyl-2,3-difluoroquaterphenyl 4-hexoxy-4' '' - propyl-2,3-difluoroquaterphenyl

PAT LOG 7/1 150888

- 60 -

4-heptoxy-4 '''- propyl-2,3-difluoroquaterphenyl 4-octoxy-4''' - propyl-2,3-difluoroquaterphenyl 4-nonoxy-4 '^;'-propyl-2,3-difluoroquaterphenyl4-decyloxy-4''' - propyl-2,3-difluoroquaterpheryl 4-dodecyloxy-4 '''- propyl-2,3-difluoroquaterphenyl

4-Ethoxy-4 '' '- pentyl-2,3-difluoroquaterphenyl 4-propoxy-4' '' - pentyl-2,3-difluoroquaterphenyl 4-butoxy-4 '' '- pentyl-2,3-difluoroquaterphenyl 4- Pentoxy-4 '' '- pentyl-2,3-difluoroquaterphenyl 4-hexoxy-4' '' - pentyl-2,3-difluoroquaterphenyl 4-heptoxy-4 · '' - pentyl-2,3-difluoroquaterphenyl 4-octoxy- 4 '' '- pentyl-2,3-difluoroquaterphenyl 4-nonoxy-4' '' - pentyl-2,3-difluoroquaterphenyl 4-decyloxy-4 '' '- pentyl-2,3-difluoroquaterphenyl 4-dodecyloxy-4' '' -pentyl-2,3-difluorquaterphenyl

4-Ethoxy-4 '' '- octyl-2,3-difluoroquaterphenyl 4-propoxy-4' '' - octyl-2,3-difluoroquaterphenyl 4-butoxy-4 '' '- octyl-2,3-difluoroquaterphenyl 4- Pentoxy-4 '' '- octyl-2,3-difluoroquaterphenyl 4-hexoxy-4' '' - octyl-2,3-difluoroquaterphenyl 4-heptoxy-4 '' '- octyl-2,3-difluoroquaterphenyl 4-octoxy- 4 '' '- octyl-2,3-difluoroquaterphenyl 4-nonoxy-4' '' - octyl-2,3-difluoroquaterphenyl 4-decyloxy-4 '' '- octyl-2,3-difluoroquaterphenyl 4-dodecyloxy-4' '' -octyl-2,3-difluorquaterphenyl

4-Ethoxy-4 '' · dodecyl-2,3-difluoroquaterphenyl 4-propoxy-4 '' '- dodecyl-2,3-difluoroquaterphenyl 4-butoxy-4' '' - dodecyl-2,3-difluoroquaterphenyl 4- Pentoxy-4 '' '- dodecyl-2,3-difluoroquaterphenyl 4-Hexoxy-4 ·' '- dodecyl-2,3-difluoroquaterphenyl 4-heptoxy-4' '' - dodecyl-2,3-difluoroquaterphenyl 4-octoxy- 4 '' '- dodecyl-2,3-difluorquaterphenyl

PAT LOG 7/1 150888

- 61 -

4-Nonoxy-4 '' '- dodecyl-2,3-difluoroquaterphenyl 4-decyloxy-4' '' - dodecyl-2,3-difluoroquaterphenyl 4-dodecyloxy-4 '' '- dodecyl-2,3-difluoroquaterphenyl

4-Ethoxy-4 '' '- ethoxy-2,3-difluoroquaterphenyl 4-propoxy-4' '' - ethoxy-2,3-difluoroquaterphenyl 4-butoxy-4 '' '- ethoxy-2,3-difluoroquaterphenyl 4- Pentoxy-4 '' '- ethoxy-2,3-difluoroquaterphenyl 4-hexoxy-4' '' - ethoxy-2,3-difluoroquaterphenyl 4-heptoxy-4 '' '- ethoxy-2,3-difluoroquaterphenyl 4-octoxy- 4 '' '- ethoxy-2,3-difluoroquaterphenyl 4-nonoxy-4' '' - ethoxy-2,3-difluoroquaterphenyl 4-decyloxy-4 '' '- ethoxy-2,3-difluoroquaterphenyl 4-dodecyloxy-4' '' -ethoxy-2,3-difluorquaterphenyl

4-Ethoxy-4 '''- pentoxy-2,3-difluoroquaterphenyl 4-propoxy-4''' - pentoxy-2,3-difluoroquaterphenyl 4-butoxy-4 '''- pentoxy-2,3-difluoroquaterphenyl 4- pentoxy-4 * '' pentoxy-2,3-difluorquaterphenyl 4-hexoxy-4 ^T '' pentoxy-2,3-difluorquaterphenyl 4-heptoxy-4 '''- pentoxy-2,3-difluorquaterphenyl 4-0ctoxy- 4 '''- pentoxy-2,3-difluoroquaterphenyl 4-nonoxy-4''' - pentoxy-2,3-difluoroquaterphenyl 4-decyloxy-4 '''- pentoxy-2,3-difluoroquaterphenyl 4-dodecyloxy-4''' pentoxy-2,3-difluorquaterphenyl

4-Ethoxy-4 '' '- dodecyloxy-2,3-difluoroquaterphenyl 4-propoxy-4' '' - dodecyloxy-2,3-difluoroquaterphenyl 4-butoxy-4 '' '- dodecyloxy-2,3-difluoroquaterphenyl 4- Pentoxy-4 '' '- dodecyloxy-2,3-difluoroquaterphenyl 4-hexoxy-4' '' - dodecyloxy-2,3-difluoroquaterphenyl 4-heptoxy-4 '' '- dodecyloxy-2,3-difluoroquaterphenyl 4-octoxy- 4 '' '- dodecyloxy-2,3-difluoroquaterphenyl 4-nonoxy-4' '' - dodecyloxy-2,3-difluoroquaterphenyl 4-decyloxy-4 '' '- dodecyloxy-2,3-difluoroquaterphenyl 4-dodecyloxy-4' '' -dodecyloxy-2,3-difluorquaterphenyl

PAT LOG 7/1 150888

27423

- 62 -

example

Ferroelectric smectic C liquid crystalline mixtures containing difluorophenyls:

Mix 14A

4-octyloxy-2,3-difluoro-4 "-n-pentyl-p-terphenyl 95% by weight of (+) - (1-cyano-2-methylpropyl) -4'-octyloxybiphenyl-4-ylcarboxylate 5% by weight. -%

The optically active compound in this mixture has L configuration.

The mixture shows the following liquid crystalline phase transitions. K 85.9 S _c 125.4 S _A 143.2 N 150.6 I

The S _c phase is supercooled to 76 ⁰ C.

Temp ( ⁰ C) Ps (nCcm " ² ) S "tilt (°) 125 4.0 16.0 122 6.6 120 7.8 18.0 115 9.8 113 10.6 110 11.4 22.5 105 13.1 100 14.6 25 95 16.0 27 90 16.9 28 87 17.6 85 18.1 82 18.8 80 19.0 130 1.0

PAT LOG 7/1 150888

2/4233

- 63 mix 14B

4-hexyloxy-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl 45% by weight 4-octyloxy-4" -pentyl-2', 3'-difluoro-p-terphenyl 45% by weight (+) - (1-Cyano-2-methylpropyl) -4'-octyloxybiphenyl-4-ylcarboxylate 6.25 wt%

(-) - (1-Cyano-2-methylpropyl) -4'-octyloxybiphenyl-4-yl carboxylate 3.75% by weight

The mixture shows the following liquid crystalline phase transitions ( ⁰ C):

> 20 S _c 84.7 S _A 98.6 N 128 I

Temp. ( ⁰ C) Ps (nCcm " ² ) S _c tilt (°)

9.0 10.0

75 2.93 14.0

15.0

84 12:12 82 1.12 80 2.0 75 2.93 70 3.75 65 4:32 60 4.87 55 5.4 50 5.83 45 6.4 40 6.9 35 7.28 30 7.74 25 8:08

18.0 50 5.83 20.0

22.5 22.5 23.5 25

In a liquid crystal display element of known type, the mixture 14B exhibits a switching time of 100 psec at 20 V and a layer thickness of 2 μηη with polyimide film for alignment.

PAT LOG 7/1 150888

- 64 Example 15

1: 1 mixture of:

4-hexyloxy-4 "-n-pentyl-2 ', 3'-difluoro-p-terphenyl and 4-octyloxy-4" -n-pentyl-2', 3'-difluoro-p-terphenyl

has an S _c phase, which is subcooled to 28 ⁰ C, 28 ⁰ C, S _c 79.1 N 142.4 I. The birefringence of the mixture is 0.19.

Pe play 16

A mixture consisting of the following liquid crystalline components is prepared:

4-Octyl-4 "-propyl-2'-fluoro-p-terphenyl 29.45%

4-heptyl-4 ^! · Propyl-2'-fluoro-p-terphenyl 19.80% L - (-) 4-hexoxy-4 · '- (2-methylbutyl) -2'-fluoro

p-terphenyl 29.40%

S - (+) - 2-Octyl-4'-octoxybiphenyl-4-yl carboxylate 6.45%

4-Octoxy-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl 5.00%

Example 17

A mixture consisting of the following liquid crystalline components is prepared:

4-octyl-4 '' - propyl-2'-fluoro-p-terphenyl 41.55% _T _ L (-) - 4-hexyloxy-4 '' - (2-methylbutyl) -2'-fluoro-pterphenyl 41.75 % S _ (+) _ 2-octyl-4'-octoxybiphenyl-4-yl carboxylate 11.70% 4-octoxy-4 '' - pentyl-2,3-difluoro-p-terphenyl 5.00%

PAT LOG 7/1 150888

27423

- 65 -

Example 18

A mixture consisting of the following liquid crystalline components is prepared:

4-octyl-4'-pentyl-2'-fluoro-p-terrhenyl 72.00%

S - (+) - 2-octyl-4'-octoxybiphenyl-4-ylcarboxylate 4.50%

2-fluoro-4-pentylphenyl-4-octoxybenzoate 13.50%

4-Octoxy-4 "-pentyl-2,3-difluoro-p-terphenyl 5.00%

4-Octoxy-4'-pentyl-2 ', 3'-difluoro-p-terphenyl 5.00%

Example 19

A mixture for ECB applications containing the following liquid crystalline components is prepared:

4.4'-Diprop / l-2,3-difluorobiphenyl 20%

4,4'-dipentyl-2,3-difluorobiphenyl 20%

4,4 "-dipropyl-2,3-difluoro-p-terphenyl 20%

4- (trans-4-propylcyclohexyl) methoxybenzene 15%

4- (trans-4-propylcyclohexyl) ethoxybenzene 15% 4,4'-bj.s (trans-4-propylcyclohexyl) -2-

fluorobiphenyl 4%

4 ~ ethyl 4'-methoxytolane 3%

4-methoxy-4'-methyltolane 3%

Clearing point 86 ⁰ C, Δε -1.5, Δη +0.185

 Example 20

A mixture for ECB applications containing the following liquid crystalline components is prepared:

4-propyloxy-4'-propyl-2,3-J-fluorobiphenyl 15% 4-pentyloxy-4'-pentyl-2,3-difluorobiphenyl 15%

PAT LOG 7/1 150888

4-pentyl-4 "-hexyloxy-2 ', 3'-difluoro-p-terphenyl 15%

4-pentyl-4 "-octyloxy-2 ', 3'-difluoro-p-terphenyl 15%

4- (trans-4-propylcyclohexyl) methoxybenzene 15% 4- (trans-4-propylcyclohexyl) ethoxybenzene 15% 4,4'-bis (trans-4-propylcyclohexyl) -2-fluorobiphenyl 4%

4,4'-bis (trans-4-pentylcyclohexyl) -2-fluorobiphenyl 3%

4- (trans-4-propylcyclohexyl) -4 '- (transpentylcyclohexyl) -2-fluorobiphenyl 3%

Clearing point 82 ⁰ C, Δε -1.7, Δη +0.17

 Example 21

A mixture for ECB applications containing the following liquid crystalline components is prepared:

4-propyloxy-4'-propyl-2,3-difluorobiphenyl 15% 4-pentyloxy-4'-pentyl-2,3-difluorobiphenyl Io % 4-pentyl-4 '' - hexyloxy-2,3'-difluoro-p -ter-

phenyl 15%

4-pentyl-4 "-octyloxy-2,3'-difluoro-p-terphenyl 15%

4- (trans-4-propylcyclohexyl) methoxybenzene 17% 4-ethyl-4'-methoxytolane 4%

4-ethoxy-4'-methyltolane. 4%

4- (trans-4-propylcyclohexyl) -4'-methoxytolane 5% 4- (trans-4-propylcyclohexyl) -4-ethoxytolane 5% 4- (trans-4-propylcyclohexyl) -4'-propoxytolane 5%

Clearing point 91 ⁰ C, Δε -1.5, Δη +0.23.

PAT LOG 7/1 150888

- 67 Example 22

Ferroelectric mixtures are prepared which produce difluorophenyls based on a base eutectic mixture (Host I). Host I contains:

4-hexyloxy-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl 37.25% by weight

4-hexyloxy-4 "-pentyl-2,3-difluoro-p-terphenyl 13.60% by weight

4-Octyloxy-4'-pentyl-2 ', 3'-difluoro-p-terphenyl 40.8% by weight

4-Octyloxy-4'-pentyl-2,3-difluoro-p-terphenyl 8.35% by weight

Mix 22A

Host I 70% by weight

4-Octyloxy-4'-pentyl-2,3-difluorobiphenyl 20% by weight

(+) - (l-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-yl-carboxylate 6.25% by weight

(-) - (1-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-yl-carboxylate 3.75% by weight

_C S 60 S _A 79.7 N 109.4 I and P ₅ 6.6 nC / cm ² (30 ⁰ C), S _c lit angle 21.5 °. Switching time: 40 [isec. (measured in Example 14 cell)

Mix 22B

Host I 90% by weight

(+) - (1-Cyano-2-methylpropyl) -4'-octyloxy-

biphenyl-4-yl-carboxylate 6.75% by weight

(-) - (1-Cyano-2-methylpropyl) -4'-octyloxybiphenyl-4-ylcarboxylate 3.75% by weight

K <20 S _c 90.4 S _A 109.6 N 133 I, P ₅ 8.9 nC / cm ² (30 ⁰ C),

_{c A} S _c tilt angle 23.5, switching time: 90 psec.

PAT LOG 7/1 150888

- 68 -

Mixture 22C

Host I 90% by weight

(+) - (l-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-yl-carboxylate 5.63% by weight

(-) - (l-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-yl-carboxylate 4.37 wt.%

_C S 93 S _A 109.6 N 133 I, P _g 4.24 nC / cm ² (30 ⁰ C), S _c tilt angle of 23.5 °, switching time: 260 psec.

Mix 22D

Host I 70% by weight

4-Octyloxy-4'-pentyl-2,3-difluorobiphenyl 20% by weight

(+) - (l-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-yl-carboxylate 5.63% by weight

(-) - (l-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-yl-carboxylate 4.37 wt.%

_C S 60 S _A 79.7 N 109.4 I, P _g 2.7 nC / cm ² (30 ⁰ C), S _c twist angle 19.5 °, switching time: 75 psec.

Mixture 22E

Host I 45% by weight

4,4 "-dipentyl-2 ', 3'-difluoro-p-terphenyl 45% by weight of (+) - (1-cyano-2-methylpropyl) -4'-octyloxy-

biphenyl-4-yl-carboxylate 6.25% by weight of (-) - (1-cyano-2-methylpropyl) -4'-octyloxy-

biphenyl-4-yl-carboxylate 3.75% by weight

S _c 60.5 S _A 87.1 N 114.7 I ₁ P _g 5.6 nC / cm ² , S _Q twist angle 22 °, switching time: 54 psec.

PAT LOG 7/1 150888

- 69 Example 23 Ferroelectric mixtures based on Host II:

4-heptyl-5 "-pentyl-2,3-difluoro-p-terphenyl 33.33% by weight of 4 ', 4" -dipentyl-2,3-difluoro-p-terphenyl 33.33% by weight of 4 ¹ , 4 "-diperityl-2 ', 3'-difluoro-p-terphenyl 33.33% by weight

Mixture 23A

Host II 90.00% by weight

(+) - (l-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-yl-carboxylate 6.25% by weight

(-) - (l-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-yl-carboxylate 3.75% by weight

_C S 60 S _A 105 N 115 I, P _g 7.2 nC / cm ² (30 ⁰ C), S _c twist angle 21.5 °, switching time: μεθΰ 17th

Mixture 23B

Host II 90.00% by weight

(+) - (1-Cyano-2-methylpropyl) -4'-octyloxybiphenyl-4-ylcarboxylate 10.00 wt%

_C S 59 S _A 105.4 N 116 IP _{g of} 30 nC / cm ² (30 ⁰ C), S _c twist angle 21.5 °, switching time: psec. 4

Mixture 23C

Host II 97.5% by weight

(+) - (1-Cyano-2-methylpropyl) -4'-octyloxybiphenyl-4-ylcarboxylate 2.5% by weight

S _c 86.7 S _A 107.1 N 124.7, P ₃ 7.0 nC / cm ² (30 ⁰ C) _c S twist angle of 23 °, switching time: 70 psec.

PAT LOG 7/1 150888

- 70 Example 24

Ferroelectric mixtures with different amounts of difluorophenylene and chiral dopants are prepared:

Mix 24A

4-Heptyl-4 "-nonyl-2,3-difluoro-p-terphenyl 97.5% by weight of (+) - (1-cyano-2-methylpropyl) -4'-octyloxybiphenyl-4-yl-carborane. ylate 2.5% by weight

K 48 S _n 62.6 S, 92.5 N 103.8 I, P _c 2.9 (50 ⁰ C), switching time: 15 psec.

Mix 24B

4-pentyl-4 '- (4-methylhexyl) -2,3-difluoro-p-

terphenyl 90% by weight

(+) - (l-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-yl-carboxylate 6.2% by weight

(-) - (1-Cyano-2-methylpropyl) -4'-octyloxybiphenyl-4-ylcarboxylate 3.8% by weight

K 56.1 S _c 80.9 S _A 82.7 N 89.4 I, S _c twist angle 26 °. Mix 24C

4-pentyl-4 "-heptyl-2 ', 3'-difluoro-p-terphenyl 29.25% by weight

4-heptyl-4 "-nonyl-2 ', 3'-difluoro _; -p-terphenyl 34.125% by weight

4-heptyl-4 "-pentyl-2,3-difluoro-p-terphenyl 19.50% by weight

4-Pentyl-4 "-heptyl-2,3-difluoro-p-terphenyl 14.625% by weight of (+) - 1-cyano-2-methylpropyl) -4'-octyloxy-

biphenyl-4-yl-carboxylate 2.50% by weight

PAT LOG 7/1 150888

45 5 Wt. /O 22 5 Wt. - ° / /O 22 Wt. - ° / / O

- 71 -

² (30 ⁰ C), S _c S 68 S _A 94.2 N 111 I, P _c 5.9 nC / cm _Q twist angle 22.5 °, switching time: psec 40th

Mix 24D

4,4 "-dipentyl-2 ', 3'-difluoro-p-terphenyl 4,4" -dipentyl-2,3-difluoro-p-terphenyl

4-heptyl-4 "-pentyl-2,3-difluoro-p-terphenyl (+) - 1-cyano-2-methylpropyl) -4'-octyloxy-

biphenyl-4-yl-carboxylate 6.2% by weight

(-) - 1-Cyano-2-methylpropyl) -4'-octyloxybiphenyl-4-ylcarboxylate 3.8% by weight

S _p p 43.6 95.5 N 109.5 I, P _Q 5.1 nC / cm ² (25 ⁰ C)

 Mix 24E

4-heptyl-4 "-pentyl-2 ', 3'-difluoro-p-terphenyl 48.5% by weight

4-heptyl-4 "-pentyl-2,3-difluoro-p-terphenyl 24.25% by weight

4, ^{/ | ll} -Dipentyl-2,3-difluoro-p-terphenyl 24.25 wt .-% (+) - l-cyano-2-methylpropyl) -4'-octyloxy

biphenyl-4-ylcarboxylate 3.0% by weight

_C S 75 S _A 91 N 116 I, P _g 7.9 nC / cm ² (30 ⁰ C), S _c twist angle 23 °.

7 LOG 7/1 150888

Claims (20)

2712 - Ji claims 1. liquid cryotalline composition having at least two liquid-crystalline components, characterized in that at least one component is a fluorinated oligophenyl of the formula I, -IT wherein a is 1, and wherein the terminal substituents R ¹ , and R ' each independently of one another, optionally substituted by CN or at least one halogen atom substituted alkyl or alkenyl radical having up to 15 carbon atoms, wherein one or more non-adjacent CH ^ groups of these radicals also by -0-, -S-, -CO- . -0-CO-, -CO-O-, -0-CO-O- or -C = C- replaced 1 2, one of these radicals R and R also a group of the formula, D ¹ K ¹ PAT LOG 19-B 160888 •? 3 ' in one of the following pairs of lateral subsituents, both substituents are fluorine: (A, B), (CD), (D ₁ E), (CE), (B ₇ C), (D, J), (D, K), (A, C), (CJ), (CD ¹ ), (D ¹ , E), (D ', A), (C ₁ E), (CA), (D ¹ , J ¹ ), (D', K ·), (D ¹ , J ¹ ), (B, G), (A, G), and all other lateral substituents are hydrogen or fluorine. 2. Composition according to claim 1, characterized 1 7 ^ net, that the terminal substituents R, R and R are each independently alkoxy, alkyl, perfluoroalkyl or perfluoroalkoxy each having up to 15 carbon atoms. 3. A composition according to claim 2, characterized in that the oligophenyls of the formula I, wherein 1 7 (C, D) both fluorine, R ethoxy and R n-pentyl signify 1 2 or wherein (B, C) are both fluorine, R is ethoxy and R is n-propyl. 4. The composition according to at least one of claims 1 to 3, characterized in that in the oligophenylene of the formula I only a pair of lateral substituents fluorine and the other lateral substituents are hydrogen. 5. The composition according to claim 4, characterized in that the oligophenyls of the formula I Difluorterphenyle are. PAT LOG 19-B 160888 Composition according to Claim 5, characterized in that the difluorophenyls are selected from the group of the following compounds of the formulas I, 1 to I, 6 F F O ) (O 1.1 1.2 1.3 1.4 R - (ο) - (ο> - ( ο VR 1.5 R - (ο) - (ο Υ- (ο 1.6 Composition according to at least one of Claims 1, 2 or 3, characterized in that, in the case of the oligophenylenes of the formula I, only one pair of lateral substituents is fluorine and one further lateral substituent is fluorine. PAT LOG 19-B 160888 8. The composition according to claim 7, characterized in that the Oligcphenyle of the formula I Trifluor terphenyle. 9. Composition according to claim 8, characterized characterized in that the Trifluorterphenyl a compound of formula is. 10. The composition according to any one of claims 1-9, characterized in that the terminal substituents of the oligophenyls of formula I are each independently n-alkyl ocer n-alkoxy having 5-12 C-atoms. 11. The composition according to any one of claims 1-9, characterized in that at least one terminal substituent of the oligophenyls of the formula I is a chiral alkyl or alkoxy group having 5-12 C-atoms. 12. The composition according to claim 1, characterized in that the oligophenyl of the formula I is a compound of formula I ', "/ ^F is wherein PAT LOG 19-B 160888 - U 1 2
A and A are each independently substituted or substituted by 1-4 fluorine atoms 1,4-phenylene group, 1 2
R and R are each independently optionally CN or at least one halo genatom substituted alkyl or alkenyl radical having up to 15 carbon atoms, wherein one or more non-adjacent CH ₂ groups of these radicals may also be replaced by -O-, -S-, -CO-, -O-CO-, - CO-O-, -O-CO-O- or -CsC-, m o or 1 η 1, 2 or 3, and the sum of m and η is 2 or 3. 13. A composition according to claim 12, characterized in that in the compound of formula I 'is the sum of m and η 2. 14. A composition according to any one of claims 1-11 or at least one of claims 12 or 13, characterized in that the terminal subituents of the oligophenyls of the formulas I and I ^{1 are} each independently n-alkyl or n-alkoxy with 1- 7 C atoms mean. 15. A composition according to any one of claims 1-14, characterized in that it is a nematic composition. PAT LOG 19-B 160888 -η- 16. A composition according to any one of claims 1-14, characterized in that it is a chiral c / etiltete smectic composition. 17. Composition having at least two liquid-crystalline components, characterized in that at least one component is an oligophenyl of the formula I according to claim 1 and / or an oligophenyl of the formula I. K G wherein a is 0 and R, R, A, B, C, D, E, G, J and K have the meaning given in claim 1 for use in ferroelectric display elements. 18. A composition according to claim 17, characterized in that in the oligophenylene of formula I a 0. 19. A composition according to claim 17, characterized in that the oligophenyl of the formula I is selected from the group of biphenyls of the formulas I, 13 to I, 19 F F F F R ¹ - 1.13 1.14 PAT LOG 19-B 160888 F F "^ R ² 1,16 * ² 1,17 R- (O) - (O) -R- 1.18 r i, i9 F. 20. Composition according to claim 17, characterized 15 records that in addition to at least one oligophenyl of the formula I in which a is O, at least one oligophenyl of the formula I in which a is I, contains. 21. A composition according to any one of claims 16-20, characterized in that it is in addition to minde- 20 least one oligophenyl of formula I a chiral dopant of the formula (F) (F) CN 25 contains PAT LOG 19-B 160888 · VJ - wherein R, alkyl or alkoxy and R _{ß are} alkyl, and (F) indicates that the rings may contain a lateral fluorine substituent, η is 1 or 2, with ict 0 or 22. The composition according to claim 21, characterized in that in the chiral dopant R _n n-alkyl having 1-4 C-atoms, cyclohexyl or a branched chiral alkyl group of the formula ^C b ^H 2b + l ~ c ^H 2c + l wherein a is 0 or 1-6 and b and c are each independently 1-6. For this. 8 Sohη c'cich now <j PAT LOG 19-B 160888