WO1991017134A1 - Phenylcyclohexanes et milieu de cristaux liquides - Google Patents

Phenylcyclohexanes et milieu de cristaux liquides 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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WO
WIPO (PCT)
Prior art keywords
formula
compounds
cyclohexyl
phenylcyclohexanes
liquid
Prior art date
Application number
PCT/EP1991/000662
Other languages
German (de)
English (en)
Inventor
Volker Reiffenrath
Reinhard Hittich
Ulrich Finkenzeller
Original Assignee
MERCK Patent Gesellschaft mit beschränkter Haftung
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by MERCK Patent Gesellschaft mit beschränkter Haftung filed Critical MERCK Patent Gesellschaft mit beschränkter Haftung
Publication of WO1991017134A1 publication Critical patent/WO1991017134A1/fr

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Classifications

    • 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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  • Chemical & Material Sciences (AREA)
  • 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

L'invention concerne des phénylcyclohexanes de formule (I) où Q désigne (a), (b) ou (c), R désigne alkyle, alcoxy, oxaalkyle, alcényle ou haloalkyle avec chacun jusqu'à 12 atomes de C, r désigne 0 ou 1, X désigne F, Cl, CF3, CHF2 OCF3 ou OCHF2 et L1, L2, Y et Z désignent chacun indépendamment H ou F, à la condition que, lorsque Y = Z = H et que simultanément r = o et Q = (a), X désigne CF¿3?, CHF2, OCF3 ou OCHF2 et/ou L?1¿ et/ou L2 désignent F.
PCT/EP1991/000662 1990-04-30 1991-04-08 Phenylcyclohexanes et milieu de cristaux liquides WO1991017134A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4013854.2 1990-04-30
DE4013854 1990-04-30

Publications (1)

Publication Number Publication Date
WO1991017134A1 true WO1991017134A1 (fr) 1991-11-14

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Application Number Title Priority Date Filing Date
PCT/EP1991/000662 WO1991017134A1 (fr) 1990-04-30 1991-04-08 Phenylcyclohexanes et milieu de cristaux liquides

Country Status (3)

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EP (1) EP0479972A1 (fr)
JP (1) JPH04507104A (fr)
WO (1) WO1991017134A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497176A2 (fr) * 1991-02-01 1992-08-05 F. Hoffmann-La Roche Ag Composés à quatre cycles et mélanges de cristaux liquides les contenant
EP0785179A1 (fr) * 1994-09-22 1997-07-23 Chisso Corporation Derive de chlorobenzene et composition de cristaux liquides contenant ce derive

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3139130A1 (de) * 1980-10-09 1982-05-06 Chisso Corp., Osaka Fluessigkristalline halogenbenzolderivate
EP0272580A2 (fr) * 1986-12-24 1988-06-29 Wojskowa Akademia Techniczna im. Jaroslawa Dabrowskiego Dérivés de cyclohexylbenzène liquides cristallins, leur préparation et nouveaux mélanges nématiques les contenants
DE3734116A1 (de) * 1987-10-09 1989-04-20 Merck Patent Gmbh Fluessigkristalle mit alternierender struktur

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3139130A1 (de) * 1980-10-09 1982-05-06 Chisso Corp., Osaka Fluessigkristalline halogenbenzolderivate
EP0272580A2 (fr) * 1986-12-24 1988-06-29 Wojskowa Akademia Techniczna im. Jaroslawa Dabrowskiego Dérivés de cyclohexylbenzène liquides cristallins, leur préparation et nouveaux mélanges nématiques les contenants
DE3734116A1 (de) * 1987-10-09 1989-04-20 Merck Patent Gmbh Fluessigkristalle mit alternierender struktur

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497176A2 (fr) * 1991-02-01 1992-08-05 F. Hoffmann-La Roche Ag Composés à quatre cycles et mélanges de cristaux liquides les contenant
EP0497176A3 (en) * 1991-02-01 1993-01-13 F. Hoffmann-La Roche Ag Four rings compounds and liquid crystal mixtures containing them
EP0785179A1 (fr) * 1994-09-22 1997-07-23 Chisso Corporation Derive de chlorobenzene et composition de cristaux liquides contenant ce derive
EP0785179A4 (fr) * 1994-09-22 1998-02-25 Chisso Corp Derive de chlorobenzene et composition de cristaux liquides contenant ce derive
US5858275A (en) * 1994-09-22 1999-01-12 Chisso Corporation Chlorobenzene derivative and liquid crystal composition containing the same

Also Published As

Publication number Publication date
JPH04507104A (ja) 1992-12-10
EP0479972A1 (fr) 1992-04-15

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