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WO1991017134A1 - Phenyl cyclohexanes and liquid cristal medium - Google Patents

Phenyl cyclohexanes and liquid cristal medium Download PDF

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Publication number
WO1991017134A1
WO1991017134A1 PCT/EP1991/000662 EP9100662W WO9117134A1 WO 1991017134 A1 WO1991017134 A1 WO 1991017134A1 EP 9100662 W EP9100662 W EP 9100662W WO 9117134 A1 WO9117134 A1 WO 9117134A1
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Prior art keywords
formula
compounds
cyclohexyl
phenylcyclohexanes
liquid
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German (de)
French (fr)
Inventor
Volker Reiffenrath
Reinhard Hittich
Ulrich Finkenzeller
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
    • C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to phenylcyclohexanes of the formula I
  • the compounds B are characterized only by a moderate dielectric anisotropy, which often leads to relatively high threshold voltages in mixtures.
  • the compounds of formula I can be prepared like similar e.g. Compounds known from DE-OS 32 11 601 are used as components of liquid-crystalline media, in particular for displays which are based on the principle of the twisted cell.
  • the substances previously used for this purpose all have certain disadvantages, for example melting points that are too high, clearing points that are too low, stability that is poor with respect to the action of heat, light or electrical fields, electrical resistance that is too low, temperature dependence of the threshold voltage that is too high.
  • the materials used to date have disadvantages, particularly in the case of displays of the supertwist type (STN) with twist angles of significantly more than 220 ° C. or in the case of displays with an active matrix.
  • STN supertwist type
  • the object of the invention was to find new liquid-crystalline compounds which are suitable as components of liquid-crystalline media, in particular for nematic media with positive dielectric anisotropy, and which do not show the disadvantages of the known compounds or only show them to a lesser extent.
  • This object was achieved by the provision of the new compounds of the formula I.
  • the compounds of the formula I are particularly suitable as components of liquid-crystalline media.
  • liquid-crystalline media with wide nematic ranges, high clearing points, excellent nematogenicity to low temperatures, excellent chemical stability are pronounced with their help available with positive electrical anisotropy, low temperature dependence of the threshold voltage and / or small optical anisotropy.
  • the new compounds also show good solubility for other components of such media and high positive dielectric anisotropy with a favorable viscosity.
  • the compounds of the formula I enable STN displays with a very high steepness of the electro-optical characteristic as well as displays with an active matrix with excellent long-term stability.
  • the compounds of the formula I are colorless in the pure state and form liquid-crystalline mesophases in a temperature range which is favorable for electro-optical use.
  • the invention thus relates to the compounds of the formula I and the use of the compounds of the formula I as components of liquid-crystalline media, liquid-crystalline media containing at least one compound of the formula I and electro-optical displays which contain such media.
  • n, R, L 1 , L 2 , Q, X, Y and Z have the meaning given, unless expressly stated otherwise.
  • R is an alkyl radical and / or an alkoxy radical
  • this can be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly preferably means ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, furthermore methyl , Octyl, nonyl, decyl, undecyl,
  • R is an alkenyl radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Accordingly, it means especially vinyl, prop-1-, or prop-2-enyl, but-1-, 2- or but-3-enyl,
  • R is an alkyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain and halogen is preferably F or Cl. In the case of multiple substitution, halogen is preferably F.
  • the resulting residues also include perfluorinated residues. In the case of single substitution, the fluorine or chlorine substituent can be in any position, but preferably in the ⁇ position.
  • branched alkyl groups can occasionally be of importance because of their better solubility in the customary liquid-crystalline base materials, but in particular as chiral dopants if they are optically active.
  • Branched groups of this type usually contain no more than one chain branch.
  • X is preferably F, Cl, -CF 3 , -OCHF 2 or -OCF 3 .
  • the compounds of the following partial forms are particularly preferred:
  • n 1 to 7 and L 1 , L 2 , A, Y and Z have the meaning entered.
  • Particularly preferred individual compounds of sub-formula la are:
  • Particularly preferred individual compounds of sub-formula Ib are:
  • Particularly preferred individual compounds of sub-formula Ic are:
  • the compounds of the formula I are otherwise prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart), under reaction conditions who are known and suitable for the implementations mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail.
  • the starting materials can also be formed in situ in such a way that they are not isolated from the reaction mixture, but instead are immediately converted further into the compounds of the formula I.
  • the compounds of the formula I can be prepared, for example, according to the following synthesis schemes: 0
  • bromobenzene derivatives used as starting materials are known, and some of them can be prepared from literature-related compounds without difficulty using standard organic chemistry processes.
  • the OCF 3 or OCHF 2 compounds can be obtained from the corresponding phenols by known methods or the CF 3 or CN compounds can be obtained from the corresponding benzoic acids.
  • the liquid-crystalline media according to the invention preferably contain 2 to 40, in particular 4 to 30, components as further constituents. These media very particularly preferably contain 7 to 25 components in addition to one or more compounds according to the invention.
  • These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of the biphenyls, terphenyls, phenyl or cyclohexyl benzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters of cyclohexyl benzoic acid, Phenyl or cyclohexyl ester of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl ester of benzoic acid, cyclohexanecarboxylic acid, or cyclohexylic acid, or cyclohex
  • L and E which may be the same or different, each independently represent a bivalent radical from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe- Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- as well as their mirror images formed group, whereby Phe unsubstituted or substituted by fluorine-substituted 1,4-phenylene, Cyc- 1,4-cyclohexylene or 1,4-cyclohexenylene, pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, dio 1,3-dioxane-2,5-diyl and G 2- (trans-1, 4-Cyclohexyl) ethyl, pyrimidine-2,5-diyl, pyridine-2
  • One of the radicals L and E is preferably Cyc, Phe or Pyr.
  • E is preferably Cyc, Phe or Phe-Cyc.
  • the media according to the invention preferably contain one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which L and E are selected from the group Cyc, Phe and Pyr and at the same time one or more components from selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which one of the radicals L and E is selected from the group Cyc, Phe and Pyr and the other radical is selected from the group -Phe-Phe-, -Phe -Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which the radicals L and E are selected from the group -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and
  • R 'and R each independently represent alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. In most of these compounds, R' and R" are different from one another different, one of these radicals is usually alkyl or alkenyl.
  • R " is particularly preferably selected from the group consisting of F, Cl, -CF 3 and -OCF 3 .
  • R is particularly preferably selected from the group consisting of F, Cl, -CF 3 and -OCF 3 .
  • R " is particularly preferably selected from the group consisting of F, Cl, -CF 3 and -OCF 3 .
  • other variants of the proposed substituents in the compounds of the formulas 1, 2, 3, 4 and 5 are also common. Many such substances or mixtures thereof are commercially available. All of these substances can be obtained by methods known from the literature or by analogy.
  • the media according to the invention preferably also contain components from the group of compounds 1b, 2b, 3b, 4b and 5b (group 2), the proportions of which are preferably as follows are: 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 of the compounds from groups 1 and 2 giving up to 100%.
  • the media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30%, of compounds according to the invention. Also 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 compounds according to the invention.
  • the media according to the invention are produced in a conventional manner.
  • the components are dissolved in one another, advantageously at elevated temperature.
  • the liquid-crystalline phases according to the invention can be modified so that they can be used in all types of liquid-crystal display elements which have hitherto become known.
  • pleochroic dyes for producing colored guest-host systems or substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases can be added.
  • mp. Melting point
  • cp. Clearing point.
  • Percentages above and below mean percentages by weight; all temperatures are given in degrees Celsius.
  • Conventional work-up means: water is added, the mixture is extracted with methylene chloride, the mixture is separated off, the organic phase is dried, evaporated and the product is purified by crystallization and / or chromatography.
  • K crystalline solid state
  • S smectic phase (the index indicates the phase type)
  • N nematic state
  • Ch nematic state
  • cholesteric phase I: isotropic phase. The number between two symbols indicates the transition temperature in degrees Celsius.
  • the 1- (3,4-difluorophenyl) -4- (p-n-propylphenyl) cyclohexene obtained according to Scheme 1 is hydrogenated in a manner known per se on Pd-C at room temperature. After customary working up by chromatography and crystallization, trans-1- (3,4-difluorophenyl) -4- (p-n-propylphenyl) cyclohexane is obtained.

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

The invention concerns phenyl cyclohexanes of formula (I) in which: Q is (a), (b) or (c); R is alkyl, alkoxy, oxaalkyl or haloalkyl, each with up to 12 C atoms; r is 0 or 1; X is F, Cl, CF3, OCF3 or OCHF2; and L<1>, L<2>, Y and Z are independently H or F, with the proviso that, if Y = Z = H and at the same time r = o and Q = (a), X is CF3, CHF2, OCF3 or OCHF2 and /or L<1> and/or L<2> is F.

Description

Phenylcyclohexane und  Phenylcyclohexanes and

flüssigkristallines Medium  liquid crystalline medium

Die Erfindung betrifft Phenylcyclohexane der Formel I, The invention relates to phenylcyclohexanes of the formula I

Figure imgf000003_0001
worin
Figure imgf000003_0001
wherein

Q Y /Q Y /

Figure imgf000003_0002
Figure imgf000003_0002

R Alkyl, Alkoxy, Oxaalkyl, Alkenyl oder Haloalkyl mit jeweils bis zu 12 C-Atomen, r 0 oder 1,  R alkyl, alkoxy, oxaalkyl, alkenyl or haloalkyl, each with up to 12 carbon atoms, r 0 or 1,

X F, Cl, CF3, CHF2, OCF3 oder OCHF2, und L1, L2, Y und Z jeweils unabhängig voneinander H oder F bedeuten, mit der Maßgabe, daß im Falle Y = Z = H und gleichzeitig r = o und Q = X CF3, CHF2, OCF3 oder OCHF2

Figure imgf000003_0003
XF, Cl, CF 3 , CHF 2 , OCF 3 or OCHF 2 , and L 1 , L 2 , Y and Z each independently represent H or F, with the proviso that in the case Y = Z = H and simultaneously r = o and Q = X CF 3 , CHF 2 , OCF 3 or OCHF 2
Figure imgf000003_0003

und/oder L1 und/oder L2 F bedeutet. Aus der DE-OS 31 39 130 sind Flüssigkristalle der Formel B bekannt (n = 3-7):

Figure imgf000004_0001
and / or L 1 and / or L 2 F. From DE-OS 31 39 130 liquid crystals of the formula B are known (n = 3-7):
Figure imgf000004_0001

Die Verbindungen B zeichnen sich nur durch eine moderate dielektrische Anisotropie aus, die in Mischungen oft zu relativ hohen Schwellenspannungen führt. The compounds B are characterized only by a moderate dielectric anisotropy, which often leads to relatively high threshold voltages in mixtures.

Die Verbindungen der Formel I können wie ähnliche, z.B. aus der DE-OS 32 11 601 bekannte Verbindungen als Komponenten flüssigkristalliner Medien verwendet werden, insbesondere für Anzeigen, die auf dem Prinzip der verdrillten Zelle beruhen. Die bisher für diesen Zweck eingesetzten Substanzen besitzen sämtliche gewisse Nachteile, beispielsweise zu hohe Schmelzpunkte, zu niedrige Klärpunkte, zu geringe Stabilität gegenüber der Einwirkung von Wärme, Licht oder elektrischen Feldern, zu niedrigen elektrischen Widerstand, zu hohe Temperaturabhängigkeit der Schwellenspannung. The compounds of formula I can be prepared like similar e.g. Compounds known from DE-OS 32 11 601 are used as components of liquid-crystalline media, in particular for displays which are based on the principle of the twisted cell. The substances previously used for this purpose all have certain disadvantages, for example melting points that are too high, clearing points that are too low, stability that is poor with respect to the action of heat, light or electrical fields, electrical resistance that is too low, temperature dependence of the threshold voltage that is too high.

Insbesondere bei Anzeigen vom Supertwisttyp (STN) mit Verdrillungswinkeln von deutlich mehr als 220 °C oder bei Anzeigen mit aktiver Matrix weisen die bisher eingesetzten Materialien Nachteile auf. The materials used to date have disadvantages, particularly in the case of displays of the supertwist type (STN) with twist angles of significantly more than 220 ° C. or in the case of displays with an active matrix.

Der Erfindung lag die Aufgabe zugrunde, neue flüssigkristalline Verbindungen aufzufinden, die als Komponenten flüssigkristalliner Medien geeignet sind, insbesondere für nematische Medien mit positiver dielektrischer Anisotropie, und die die Nachteile der bekannten Verbindungen nicht oder nur in geringerem Maße zeigen. Diese Aufgabe wurde durch die Bereitstellung der neuen Verbindungen der Formel I gelöst. Es wurde gefunden, daß die Verbindungen der Formel I vorzüglich als Komponenten flüssigkristalliner Medien geeignet sind. Insbesondere sind mit ihrer Hilfe flüssigkristalline Medien mit weiten nematischen Bereichen, hohen Klärpunkten, hervorragender Nematogenität bis zu tiefen Temperaturen, hervorragender chemischer Stabilität, ausgeprägtem

Figure imgf000005_0001
bei positiver dieelektrischer Anisotropie, geringer Temperaturabhängigkeit der Schwellenspannung und/oder kleiner optischer Anisotropie erhältlich. Die neuen Verbindungen zeigen außerdem eine gute Löslichkeit für andere Komponenten derartiger Medien und hohe positive dielektrische Anisotropie bei gleichzeitig günstiger Viskosität. The object of the invention was to find new liquid-crystalline compounds which are suitable as components of liquid-crystalline media, in particular for nematic media with positive dielectric anisotropy, and which do not show the disadvantages of the known compounds or only show them to a lesser extent. This object was achieved by the provision of the new compounds of the formula I. It has been found that the compounds of the formula I are particularly suitable as components of liquid-crystalline media. In particular, liquid-crystalline media with wide nematic ranges, high clearing points, excellent nematogenicity to low temperatures, excellent chemical stability, are pronounced with their help
Figure imgf000005_0001
available with positive electrical anisotropy, low temperature dependence of the threshold voltage and / or small optical anisotropy. The new compounds also show good solubility for other components of such media and high positive dielectric anisotropy with a favorable viscosity.

Die Verbindungen der Formel I ermöglichen sowohl STN-Anzeigen mit sehr hoher Steilheit der elektrooptischen Kennlinie als auch Anzeigen mit aktiver Matrix mit hervorragender Langzeitstabilität. The compounds of the formula I enable STN displays with a very high steepness of the electro-optical characteristic as well as displays with an active matrix with excellent long-term stability.

Die Verbindungen der Formel I sind in reinem Zustand farblos und bilden flüssigkristalline Mesophasen in einem für die elektrooptische Verwendung günstig gelegenen Temperaturbereich. The compounds of the formula I are colorless in the pure state and form liquid-crystalline mesophases in a temperature range which is favorable for electro-optical use.

Gegenstand der Erfindung sind somit die Verbindungen der Formel I sowie die Verwendung der Verbindungen der Formel I als Komponenten flüssigkristalliner Medien, flüssigkristalline Medien mit einem Gehalt an mindestens einer Verbindung der Formel I und elektrooptische Anzeigen, die derartige Medien enthalten. Vor- und nachstehend haben n, R, L1, L2, Q, X, Y und Z die angegebene Bedeutung, sofern nicht ausdrücklich etwas anderes vermerkt ist. The invention thus relates to the compounds of the formula I and the use of the compounds of the formula I as components of liquid-crystalline media, liquid-crystalline media containing at least one compound of the formula I and electro-optical displays which contain such media. Above and below, n, R, L 1 , L 2 , Q, X, Y and Z have the meaning given, unless expressly stated otherwise.

Falls R einen Alkylrest und/oder einen Alkoxyrest bedeutet, so kann dieser geradkettig oder verzweigt sein. Vorzugsweise ist er geradkettig, hat 2, 3, 4, 5, 6 oder 7 C-Atome und bedeutet demnach bevorzugt Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Ethoxy, Propoxy, Butoxy, Pentoxy, Hexoxy oder Heptoxy, ferner Methyl, Octyl, Nonyl, Decyl, Undecyl, If R is an alkyl radical and / or an alkoxy radical, this can be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly preferably means 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, ündecoxy, Dodecoxy, Tridecoxy oder Tetradecoxy. Dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, ündecoxy, dodecoxy, tridecoxy or tetradecoxy.

Oxaalkyl bedeutet vorzugsweise geradkettiges 2-Oxapropyl (= Methoxymethyl), 2- (= Ethoxymethyl) oder 3-Oxabutyl Oxaalkyl preferably means straight-chain 2-oxapropyl (= methoxymethyl), 2- (= ethoxymethyl) or 3-oxabutyl

(= 2-Methoxyethyl), 2-, 3- oder 4-Oxapentyl, 2-, 3-, 4- oder 5-Oxahexyl, 2-, 3-, 4-, 5- oder 6-Oxaheptyl, 2-, 3-, 4-, 5-, 6- oder 7-Oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- oder 8-Oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- oder 9-Oxadecyl.  (= 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.

Falls R einen Alkenylrest bedeutet, so kann dieser geradkettig oder verzweigt sein. Vorzugsweise ist er geradkettig und hat 2 bis 10 C-Atome. Er bedeutet demnach besonders Vinyl, Prop-1-, oder Prop-2-enyl, But-1-, 2- oder But-3-enyl, If R is an alkenyl radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Accordingly, it means especially vinyl, prop-1-, or prop-2-enyl, but-1-, 2- or but-3-enyl,

Pent-1-, 2-, 3- oder Pent-4-enyl, Hex-1-, 2-, 3-, 4- oder Hex-5-enyl, Hept-1-, 2-, 3-, 4-, 5- oder Hept-6-enyl, Oct-1-, 2-, 3-, 4-, 5-, 6- oder Oct-7-enyl, Non-1-, 2-, 3-, 4-, 5-, 6-, 7- oder Non-8-enyl, Dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- oder Dec-9-enyl. Falls R einen mindestens einfach durch Halogen substituierten Alkylrest bedeutet, so ist dieser Rest vorzugsweise geradkettig und Halogen ist vorzugsweise F oder Cl. Bei Mehrfachsubstitution ist Halogen vorzugsweise F. Die resultierenden Reste schließen auch perfluorierte Reste ein. Bei Einfachsubstitution kann der Fluor- oder Chlorsubstituent in beliebiger Position sei, vorzugsweise jedoch in ω-Position. 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 which is at least monosubstituted by halogen, this radical is preferably straight-chain and halogen is preferably F or Cl. In the case of multiple substitution, halogen is preferably F. The resulting residues also include perfluorinated residues. In the case of single substitution, the fluorine or chlorine substituent can be in any position, but preferably in the ω position.

Verbindungen der Formel I mit verzweigten Alkylgruppen können gelegentlich wegen einer besseren Löslichkeit in den üblichen flüssigkristallinen Basismaterialien von Bedeutung sein, insbesondere aber als chirale Dotierstoffe, wenn sie optisch aktiv sind. Verzweigte Gruppen dieser Art enthalten in der Regel nicht mehr als eine Kettenverzweigung. Bevorzugte verzweigte Alkylreste sind Isopropyl, 2-Butyl (= 1-Methyl- propyl), Isobutyl (= 2-Methyl-propyl), 2-Methyl-butyl, Iso- pentyl (= 3-Methylbutyl), 2-Methylpentyl, 3-Methylpentyl oder 2-Heptyl (= 1-Methylhexyl). Compounds of the formula I with branched alkyl groups can occasionally be of importance because of their better solubility in the customary liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Branched groups of this type usually contain no more than one chain branch. Preferred branched alkyl radicals are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3- Methylpentyl or 2-heptyl (= 1-methylhexyl).

Figure imgf000007_0001
Figure imgf000007_0001

X ist vorzugsweise F, Cl, -CF3, -OCHF2 oder -OCF3. Besonders bevorzugt sind die Verbindungen der folgenden Teilformein: X is preferably F, Cl, -CF 3 , -OCHF 2 or -OCF 3 . The compounds of the following partial forms are particularly preferred:

Figure imgf000008_0001
Figure imgf000008_0001

worin n 1 bis 7 und L1, L2, A, Y und Z die eingegebene Bedeutung haben. Besonders bevorzugte Einzelverbindungen der Teilformel la sind:where n 1 to 7 and L 1 , L 2 , A, Y and Z have the meaning entered. Particularly preferred individual compounds of sub-formula la are:

Figure imgf000009_0001
Besonders bevorzugte Einzelverbindungen der Teilformel Ib sind:
Figure imgf000009_0001
Particularly preferred individual compounds of sub-formula Ib are:

L  L

) Λ Λ) Λ Λ

Figure imgf000010_0001
Figure imgf000011_0001
Besonders bevorzugte Einzelverbindungen der Teilformel Ic sind:
Figure imgf000010_0001
Figure imgf000011_0001
Particularly preferred individual compounds of sub-formula Ic are:

Figure imgf000011_0002
Figure imgf000012_0001
Besonders bevorzugte Einzelverbindungen der Teilformel Id sind:
Figure imgf000011_0002
Figure imgf000012_0001
Particularly preferred individual compounds of sub-formula Id are:

/ Λ

Figure imgf000013_0001
Besonders bevorzugte Einzelverbindungen der Teilformel le sind: / Λ
Figure imgf000013_0001
Particularly preferred individual compounds of the sub-formula are:

Figure imgf000013_0002
Xj v \ ;
Figure imgf000014_0001
Figure imgf000013_0002
Xj v \;
Figure imgf000014_0001

Besonders bevorzugte Einzelverbindungen der Teilformel If sind: Particularly preferred individual compounds of the sub-formula If are:

Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000014_0002
Figure imgf000015_0001

Die Verbindungen der Formel I werden im übrigen nach an sich bekannten Methoden hergestellt, wie sie in der Literatur (z.B. in den Standardwerken wie Houben-Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart) beschrieben sind, und zwar unter Reaktionsbedingungen, die für die genannten Umsetzungen bekannt und geeignet sind. Dabei kann man auch von an sich bekannten, hier nicht näher erwähnten Varianten Gebrauch machen. The compounds of the formula I are otherwise prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart), under reaction conditions who are known and suitable for the implementations mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail.

Die Ausgangsstoffe können gewünschtenfalls auch in situ gebildet werden, derart, daß man sie aus dem Reaktionsgemisch nicht isoliert, sondern sofort weiter zu den Verbindungen der Formel I umsetzt. If desired, the starting materials can also be formed in situ in such a way that they are not isolated from the reaction mixture, but instead are immediately converted further into the compounds of the formula I.

Die Verbindungen der Formel I können beispielsweise gemäß folgender Syntheseschemata hergestellt werden:

Figure imgf000016_0001
0 The compounds of the formula I can be prepared, for example, according to the following synthesis schemes:
Figure imgf000016_0001
0

ll

Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000017_0001
Figure imgf000018_0001

~ ~

Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000019_0001
Figure imgf000020_0001

Die als AusgangsStoffe verwendeten Brombenzolderivate sind zum Teil bekannt, zum Teil können sie ohne Schwierigkeiten nach Standardverfahren der organischen Chemie aus literaturbedingten Verbindungen hergestellt werden. Beispielsweise sind die OCF3- oder OCHF2-Verbindungen nach bekannten Verfahren aus den entsprechenden Phenolen bzw. die CF3- oder CN- Verbindungen aus den entsprechenden Benzoesäuren erhältlich. Some of the bromobenzene derivatives used as starting materials are known, and some of them can be prepared from literature-related compounds without difficulty using standard organic chemistry processes. For example, the OCF 3 or OCHF 2 compounds can be obtained from the corresponding phenols by known methods or the CF 3 or CN compounds can be obtained from the corresponding benzoic acids.

Verbindungen der Formel Compounds of the formula

Figure imgf000020_0002
Figure imgf000020_0002

oder auch entsprechende monofluorierte Verbindungen sind beispielsweise aus den bekannten Vorstufen mit X = H durch Lithiierung bei tiefen Temperaturen und anschließende ümsetzung mit einem geeigneten Elektrophil erhältlich. Weitere Synthesevarianten sind dem Fachmann bekannt. Alle Ausgangsmaterialien sind entweder bekannt oder können in Analogie zu bekannten Verbindungen hergestellt werden. or corresponding monofluorinated compounds can be obtained, for example, from the known precursors with X = H by lithiation at low temperatures and subsequent reaction with a suitable electrophile. Further synthesis variants are known to the person skilled in the art. All starting materials are either known or can be prepared analogously to known compounds.

Einige besonders bevorzugte Verbindungen sind Some particularly preferred compounds are

Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
wobei R die in Anspruch 1 angegebene Bedeutung besitzt.
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
wherein R has the meaning given in claim 1.

Die erfindungsgemäßen flüssigkristallinen Medien enthalten vorzugsweise neben einer oder mehreren erfincungsgemäßen Verbindungen als weitere Bestandteile 2 bis 40, insbesondere 4 bis 30 Komponenten. Ganz besonders bevorzugt enthalten diese Medien neben einer oder mehreren erfincungsgemäßen Verbindungen 7 bis 25 Komponenten. Diese weiteren Bestandteile werden vorzugsweise ausgewählt aus nematischen oder nematogenen (monotropen oder isotropen) Substanzen, insbesondere Substanzen aus den Klassen der Biphenyle, Terphenyle, Phenyl- oder Cyclohexylbenzoate, Cyclohexan-carbonsäure- phenyl- oder cyclohexyl-ester, Phenyl- oder Cyclohexylester der Cyclohexylbenzoesäure, Phenyl- oder Cyclohexylester der Cyclohexylcyclohexancarbonsäure, Cyclohexylphenylester der Benzoesäure, der Cyclohexancarbonsäure, bzw. der Cyclohexyl- cyclohexancarbonsäure, Phenylcyclohexane, Cyclohexyl- biphenyle, Phenylcyclohexylcyclohexane, Cyclchexylcyclo- hexane, Cyclohexylcyclohexene, Cyclohexylcyclohexylcyclohe- xene, 1,4-Bis-cyclohexylbenzole, 4,4'-Bis-cyclohexyl- biphenyle, Phenyl- oder Cyclohexylpyrimidine, Phenyl- oder Cyclohexylpyridine, Phenyl- oder Cyclohexyldioxane, Phenyl- oder Cyclohexyl-1,3-dithiane, 1,2-Diphenylethane, 1,2-Dicy- clohexylethane, 1-Phenyl-2-cyclohexylethane, 1-Cyclohexyl- 2-(4-phenyl-cyclohexyl)-ethane, 1-Cyclohexyl-2-biphenylyl- ethane, 1-Phenyl-2-cyclohexylphenylethane und Tolane. Die 1,4-Phenylengruppen in diesen Verbindungen können auch fluoriert sein. In addition to one or more compounds according to the invention, the liquid-crystalline media according to the invention preferably contain 2 to 40, in particular 4 to 30, components as further constituents. These media very particularly preferably contain 7 to 25 components in addition to one or more compounds according to the invention. These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of the biphenyls, terphenyls, phenyl or cyclohexyl benzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters of cyclohexyl benzoic acid, Phenyl or cyclohexyl ester of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl ester of benzoic acid, cyclohexanecarboxylic acid, or cyclohexylcyclohexanecarboxylic acid, phenylcyclohexane, cyclohexylbiphenyls, phenylcyclohexylcyclohexane, cyclchexylcyclohexylhexyl, cyclohexylhexyl, cyclohexylhexyl, cyclohexylhexyl, cyclohexylhexyl, cyclohexylhexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, '-Bis-cyclohexyl-biphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithiane, 1,2-diphenylethane, 1,2-dicyclohexylethane, 1- Phenyl-2-cyclohexylethane, 1-cyclohexyl- 2- (4-phenyl-cyclohexyl) -ethane, 1- Cyclohexyl-2-biphenylylethane, 1-phenyl-2-cyclohexylphenylethane and tolane. The 1,4-phenylene groups in these compounds can also be fluorinated.

Die wichtigsten als weitere Bestandteile erfindungsgemäßer Medien in Frage kommenden Verbindungen lassen sich durch die Formeln 1, 2, 3, 4 und 5 charakterisieren: The most important compounds which are suitable as further constituents of media according to the invention can be characterized by the formulas 1, 2, 3, 4 and 5:

R' -L-E-R" 1 R '-L-E-R "1

R' -L-COO-E-R" 2  R '-L-COO-E-R "2

R' -L-OOC-E-R" 3  R '-L-OOC-E-R "3

R' -L-CH2CH2-E-R" 4 R '-L-CH 2 CH 2 -ER "4

R' -L-C≡C-E-R" 5  R '-L-C≡C-E-R "5

In den Formeln 1, 2, 3, 4 und 5 bedeuten L und E, die gleich oder verschieden sein können, jeweils unabhängig voneinander einen bivalenten Rest aus der aus -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- und -G-Cyc- sowie deren Spiegelbilder gebildeten Gruppe, wobei Phe unsubstituiertes oder durch Fluor substituiertes 1,4-Phenylen, Cyc trans-1,4-Cyclohexylen oder 1,4-Cyclohexenylen, Pyr Pyrimidin-2,5-diyl oder Pyridin-2,5-diyl, Dio 1,3-Dioxan-2,5-diyl und G 2-(trans-1,4-Cyclohexyl)-ethyl, Pyrimidin-2,5-diyl, Pyridin-2,5-diyl oder 1,3-Dioxan-2,5-diyl bedeuten. In formulas 1, 2, 3, 4 and 5, L and E, which may be the same or different, each independently represent a bivalent radical from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe- Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- as well as their mirror images formed group, whereby Phe unsubstituted or substituted by fluorine-substituted 1,4-phenylene, Cyc- 1,4-cyclohexylene or 1,4-cyclohexenylene, pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, dio 1,3-dioxane-2,5-diyl and G 2- (trans-1, 4-Cyclohexyl) ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.

Vorzugsweise ist einer der Reste L und E Cyc, Phe oder Pyr. E ist vorzugsweise Cyc, Phe oder Phe-Cyc. Vorzugsweise enthalten die erfindungsgemäßen Medien eine oder mehrere Komponenten ausgewählt aus den Verbindungen der Formeln 1, 2, 3, 4 und 5, worin L und E ausgewählt sind aus der Gruppe Cyc, Phe und Pyr und gleichzeitig eine oder mehrere Komponenten aus gewählt aus den Verbindungen der Formeln 1, 2, 3, 4 und 5, worin einer der Reste L und E ausgewählt ist aus der Gruppe Cyc, Phe und Pyr und der andere Rest ausgewählt ist aus der Gruppe -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- und -G-Cyc-, und gegebenenfalls eine oder mehrere Komponenten ausgewählt aus den Verbindungen der Formeln 1, 2, 3, 4 und 5, worin die Reste L und E ausgewählt sind aus der Gruppe -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- und -G-Cyc-. One of the radicals L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. The media according to the invention preferably contain one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which L and E are selected from the group Cyc, Phe and Pyr and at the same time one or more components from selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which one of the radicals L and E is selected from the group Cyc, Phe and Pyr and the other radical is selected from the group -Phe-Phe-, -Phe -Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which the radicals L and E are selected from the group -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-.

R' und R" bedeuten in den Verbindungen der Teilformeln 1a, 2a, 3a, 4a und 5a jeweils unabhängig voneinander Alkyl, Alkenyl, Alkoxy, Alkenyloxy oder Alkanoyloxy mit bis zu 8 Kohlenstoffatomen. Bei den meisten dieser Verbindungen sind R' und R" voneinander verschieden, wobei einer dieser Reste meist Alkyl oder Alkenyl ist. In den Verbindungen der Teilformeln 1b, 2b, 3b, 4b und 5b bedeutet R" -CN, -CF3, -OCF3. F, Cl oder -NCS; R hat dabei die bei den Verbindungen der Teilformeln la bis 5a angegebene Bedeutung und ist vorzugsweise Alkyl oder Alkenyl. Besonders bevorzugt ist R" ausgewählt aus der Gruppe bestehend aus F, Cl, -CF3 und -OCF3. Aber auch andere Varianten der vorgesehenen Substituenten in den Verbindungen der Formeln 1, 2, 3, 4 und 5 sind gebräuchlich. Viele solcher Substanzen oder auch Gemische davon sind im Handel erhältlich. Alle diese Substanzen sind nach literaturbekannten Methoden oder in Analogie dazu erhältlich. In the compounds of partial formulas 1a, 2a, 3a, 4a and 5a, R 'and R "each independently represent alkyl, alkenyl, alkoxy, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. In most of these compounds, R' and R" are different from one another different, one of these radicals is usually alkyl or alkenyl. In the compounds of sub-formulas 1b, 2b, 3b, 4b and 5b, R "means -CN, -CF 3 , -OCF 3. F, Cl or -NCS; R has the meaning and given for the compounds of sub-formulas Ia to 5a is preferably alkyl or alkenyl. R "is particularly preferably selected from the group consisting of F, Cl, -CF 3 and -OCF 3 . However, other variants of the proposed substituents in the compounds of the formulas 1, 2, 3, 4 and 5 are also common. Many such substances or mixtures thereof are commercially available. All of these substances can be obtained by methods known from the literature or by analogy.

Die erfindungsgemäßen Medien enthalten vorzugsweise neben Komponenten aus der Gruppe der Verbindungen 1a, 2a, 3a, 4a und 5a (Gruppe 1) auch Komponenten aus der Gruppe der Verbindungen 1b, 2b, 3b, 4b und 5b (Gruppe 2), deren Anteile vorzugsweise wie folgt sind: Gruppe 1: 20 bis 90 %, insbesondere 30 bis 90 %, 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), the proportions of which are preferably as follows are: Group 1: 20 to 90%, in particular 30 to 90%,

Gruppe 2: 10 bis 80 %, insbesondere 10 bis 50 %, wobei die Summe der Anteile der erfindungsgemäßen Verbindungen und der Verbindungen aus den Gruppen 1 und 2 bis zu 100 % ergeben. Group 2: 10 to 80%, in particular 10 to 50%, the sum of the proportions of the compounds according to the invention and of the compounds from groups 1 and 2 giving up to 100%.

Die erfindungsgemäßen Medien enthalten vorzugsweise 1 bis 40 %, insbesondere vorzugsweise 5 bis 30 % an erfindungsgemäßen Verbindungen. Weiterhin bevorzugt sind Medien, enthaltend mehr als 40 %, insbesondere 45 bis 90 % an erfindungsgemäßen Verbindungen. Die Medien enthalten vorzugsweise drei, vier oder fünf erfindungsgemäße Verbindungen. The media according to the invention preferably contain 1 to 40%, particularly preferably 5 to 30%, of compounds according to the invention. Also 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 compounds according to the invention.

Die Herstellung der erfindungsgemäßen Medien erfolgt in an sich üblicher Weise. In der Regel werden die Komponenten ineinander gelöst, zweckmäßig bei erhöhter Temperatur. Durch geeignete Zusätze können die flüssigkristallinen Phasen nach der Erfindung so modifiziert werden, daß sie in allen bisher bekannt gewordenen Arten von Flüssigkristallanzeigeelementen verwendet werden können. The media according to the invention are produced in a conventional manner. As a rule, the components are dissolved in one another, advantageously 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 types of liquid-crystal display elements which have hitherto become known.

Derartige Zusätze sind dem Fachmann bekannt und in der Literatur ausführlich beschrieben (H. Kelker/R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). Beispielsweise können pleochroitische Farbstoffe zur Herstellung farbiger Guest-Host-Systeme oder Substanzen zur Veränderung der dielektrischen Anisotropie, der Viskosität und/oder der Orientierung der nematischen Phasen zugesetzt werden. Die folgenden Beispiele sollen die Erfindung erläutern, ohne sie zu begrenzen, mp. = Schmelzpunkt, cp. = Klärpunkt. Vor- und nachstehend bedeuten Prozentangaben Gewichtsprozent; alle Temperaturen sind in Grad Celsius angegeben. "Übliche Aufarbeitung" bedeutet: man gibt Wasser hinzu, extrahiert mit Methylenchlorid, trennt ab, trocknet die organische Phase, dampft ein und reinigt das Produkt durch Kristallisation und/oder Chromatographie. Such additives are known to the person skilled in the art and are 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, the viscosity and / or the orientation of the nematic phases can be added. The following examples are intended to illustrate the invention without limiting it, mp. = Melting point, cp. = Clearing point. Percentages above and below mean percentages by weight; all temperatures are given in degrees Celsius. "Conventional work-up" means: water is added, the mixture is extracted with methylene chloride, the mixture is separated off, the organic phase is dried, evaporated and the product is purified by crystallization and / or chromatography.

Es bedeuten ferner: It also means:

K: Kristallin-fester Zustand, S: smektische Phase (der Index kennzeichnet den Phasentyp), N: nematischer Zustand, Ch: K: crystalline solid state, S: smectic phase (the index indicates the phase type), N: nematic state, Ch:

cholesterische Phase, I: isotrope Phase. Die zwischen zwei Symbolen stehende Zahl gibt die Umwandlungstemperatur in Grad Celsius an.  cholesteric phase, I: isotropic phase. The number between two symbols indicates the transition temperature in degrees Celsius.

DAST Diethylaminoschwefeltrifluorid DAST Diethylaminosulfur trifluoride

DCC Dicyclohexylcarbodiimid  DCC dicyclohexylcarbodiimide

DDQ Dichlordicyanobenzochinon  DDQ dichlorodicyanobenzoquinone

DIBALH Diisobutylaluminiumhydrid  DIBALH diisobutyl aluminum hydride

DMSO Dimethylsulfoxid  DMSO dimethyl sulfoxide

KOT Kalium-tertiär-butanolat  KOT potassium tertiary butanolate

THF Tetrahydrofuran  THF tetrahydrofuran

pTSOH p-Toluolsulfonsäure Beispiel 1pTSOH p-toluenesulfonic acid example 1

Figure imgf000028_0002
Figure imgf000028_0002

Das gemäß Schema 1 erhaltene 1-(3,4-Difluorphenyl)-4-(p-n- propylphenyl)-cyclohexen wird in an sich bekannter Weise an Pd-C bei Raumtemperatur hydriert. Nach üblicher Aufarbeitung durch Chromatographie und Kristallisation erhält man trans-1-(3,4-Difluorphenyl)-4-(p-n-propylphenyl)-cyclohexan.  The 1- (3,4-difluorophenyl) -4- (p-n-propylphenyl) cyclohexene obtained according to Scheme 1 is hydrogenated in a manner known per se on Pd-C at room temperature. After customary working up by chromatography and crystallization, trans-1- (3,4-difluorophenyl) -4- (p-n-propylphenyl) cyclohexane is obtained.

Analog Beispiel 1 erhält man die folgenden Verbindungen der Formel (R = CnH2n+1) The following compounds of the formula (R = C n H 2n + 1 ) are obtained analogously to Example 1

Figure imgf000028_0001
Figure imgf000028_0003
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000028_0001
Figure imgf000028_0003
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001

Claims

Patentansprüche 1. Phenylcyclohexane der Formel I,
Figure imgf000075_0005
1. Phenylcyclohexanes of the formula I,
Figure imgf000075_0005
 I
Figure imgf000075_0001
worin I
Figure imgf000075_0001
wherein Q OderQ Or
Figure imgf000075_0002
Figure imgf000075_0002
Figure imgf000075_0004
Figure imgf000075_0003
Figure imgf000075_0004
Figure imgf000075_0003
 R Alkyl, Alkoxy, Oxaalkyl, Alkenyl oder Haloalkyl  R is alkyl, alkoxy, oxaalkyl, alkenyl or haloalkyl mit jeweils bis zu 12 C-Atomen, r 0 oder 1,  each with up to 12 carbon atoms, r 0 or 1, X F, Cl, CF3, CHF2, OCF3 oder OCHF2, und L1, L2, Y und XF, Cl, CF 3 , CHF 2 , OCF 3 or OCHF 2 , and L 1 , L 2 , Y and Z jeweils unabhängig voneinander H oder F bedeuten, mit der Maßgabe, daß im Falle Y = Z = H und  Z each independently of one another denote H or F, with the proviso that in the case Y = Z = H and gleichzeitig r = o und Q = X CF3, CHF2,simultaneously r = o and Q = X CF 3 , CHF 2 ,
Figure imgf000075_0006
Figure imgf000075_0006
 OCF3 oder OCHF2 und/ oder L1 und/oder L2 F bedeutet . OCF 3 or OCHF 2 and / or L 1 and / or L 2 F means. 2. Phenylcyclohexane nach Anspruch 1, gekennzeichnet durch die Formel la. 2. phenylcyclohexanes according to claim 1, characterized by the formula la.
Figure imgf000076_0001
worin n 1 bis 7 und L1, L2, X, Y und Z die angegebene Bedeutung haben.
Figure imgf000076_0001
wherein n 1 to 7 and L 1 , L 2 , X, Y and Z have the meaning given. Phenylcyclohexane nach Anspruch 1, gekennzeichnet durch die Formel Ib, Phenylcyclohexanes according to Claim 1, characterized by the formula Ib,
Figure imgf000076_0002
worin n 1 bis 7, X, L1 und L2 die angegebene Bedeutung haben.
Figure imgf000076_0002
wherein n 1 to 7, X, L 1 and L 2 have the meaning given. 4. Phenylcyclohexane nach Anspruch 1, gekennzeichnet durch die Formel Ic, 4. phenylcyclohexanes according to claim 1, characterized by the formula Ic,
Figure imgf000076_0003
worin n 1 bis 7 und X, Y, Z, L1 und L2 die angegebene Bedeutung haben.
Figure imgf000076_0003
wherein n 1 to 7 and X, Y, Z, L 1 and L 2 have the meaning given. 5. Phenylcyclohexane nach Anspruch 1, gekennzeichnet durch die Formel Id, 5. phenylcyclohexanes according to claim 1, characterized by the formula Id,
Figure imgf000077_0001
worin n 1 bis 7 und X, Y, Z, L1 und L2 die angegebene Bedeutung haben .
Figure imgf000077_0001
wherein n 1 to 7 and X, Y, Z, L 1 and L 2 have the meaning given. 6. Phenylcyclohexane nach Anspruch 1, gekennzeichnet durch die Formel le, 6. phenylcyclohexanes according to claim 1, characterized by the formula le,
Figure imgf000077_0002
worin n 1 bis 7 und X, Y, Z, L1 und L2 die eingegebene Bedeutung haben.
Figure imgf000077_0002
where n 1 to 7 and X, Y, Z, L 1 and L 2 have the meaning entered. 7. Phenylcyclohexane nach Anspruch 1, gekennzeichnet durch die Formel If, 7. phenylcyclohexanes according to claim 1, characterized by the formula If,
Figure imgf000077_0003
worin n 1 bis 7 und X, Y, Z, L1 und L2 die eingegebene
Figure imgf000077_0003
where n 1 to 7 and X, Y, Z, L 1 and L 2 the input Bedeutung haben. Have meaning. 8. Verwendung der Phenylcyclohexane der Formel I nach Anspruch 1 als Komponenten flüssigkristalliner Medien für elektrooptische Anzeigen. 8. Use of the phenylcyclohexanes of the formula I according to claim 1 as components of liquid-crystalline media for electro-optical displays. 9. Flüssigkristallines Medium für elektrooptische Anzeigen mit mindestens zwei flüssigkristallinen Komponenten, dadruch gekennzeichnet, daß mindestens eine Komponente ein Phenylcyclohexan der Formel I nach Anspruch 1 ist. 9. Liquid-crystalline medium for electro-optical displays with at least two liquid-crystalline components, characterized in that at least one component is a phenylcyclohexane of the formula I according to claim 1. 10. Elektrooptische Anzeige auf der Basis einer Flüssigkristallzelle, dadurch gekennzeichnet, daß die Flüssigkristallzelle eine Medium nach Anspruch 7 enthält. 10. Electro-optical display based on a liquid crystal cell, characterized in that the liquid crystal cell contains a medium according to claim 7.
PCT/EP1991/000662 1990-04-30 1991-04-08 Phenyl cyclohexanes and liquid cristal medium Ceased WO1991017134A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497176A3 (en) * 1991-02-01 1993-01-13 F. Hoffmann-La Roche Ag Four rings compounds and liquid crystal mixtures containing them
EP0785179A4 (en) * 1994-09-22 1998-02-25 Chisso Corp Chlorobenzene derivative and liquid-crystal composition containing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3139130A1 (en) * 1980-10-09 1982-05-06 Chisso Corp., Osaka LIQUID CRYSTALLINE HALOGENBENEOL DERIVATIVES
EP0272580A2 (en) * 1986-12-24 1988-06-29 Wojskowa Akademia Techniczna im. Jaroslawa Dabrowskiego Liquidcrystalline cyclohexylbenzene derivatives their manufacturing and novel nematic admixtures containing same
DE3734116A1 (en) * 1987-10-09 1989-04-20 Merck Patent Gmbh Liquid crystals having an alternating structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3139130A1 (en) * 1980-10-09 1982-05-06 Chisso Corp., Osaka LIQUID CRYSTALLINE HALOGENBENEOL DERIVATIVES
EP0272580A2 (en) * 1986-12-24 1988-06-29 Wojskowa Akademia Techniczna im. Jaroslawa Dabrowskiego Liquidcrystalline cyclohexylbenzene derivatives their manufacturing and novel nematic admixtures containing same
DE3734116A1 (en) * 1987-10-09 1989-04-20 Merck Patent Gmbh Liquid crystals having an alternating structure

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497176A3 (en) * 1991-02-01 1993-01-13 F. Hoffmann-La Roche Ag Four rings compounds and liquid crystal mixtures containing them
EP0785179A4 (en) * 1994-09-22 1998-02-25 Chisso Corp Chlorobenzene derivative and liquid-crystal composition containing the same
US5858275A (en) * 1994-09-22 1999-01-12 Chisso Corporation Chlorobenzene derivative and liquid crystal composition containing the same

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EP0479972A1 (en) 1992-04-15

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