EP0373186A1 - Derives de 2,3-difluorohydroquinone - Google Patents

Derives de 2,3-difluorohydroquinone

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Publication number
EP0373186A1
EP0373186A1 EP89902770A EP89902770A EP0373186A1 EP 0373186 A1 EP0373186 A1 EP 0373186A1 EP 89902770 A EP89902770 A EP 89902770A EP 89902770 A EP89902770 A EP 89902770A EP 0373186 A1 EP0373186 A1 EP 0373186A1
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EP
European Patent Office
Prior art keywords
trans
difluoro
formula
diyl
compounds
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP89902770A
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German (de)
English (en)
Inventor
Volker Reiffenrath
Joachim Krause
Andreas WÄCHTLER
Georg Weber
Thomas Geelhaar
David Coates
Ian Charles Sage
Simon Greenfield
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Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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Filing date
Publication date
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Publication of EP0373186A1 publication Critical patent/EP0373186A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
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    • 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
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2021—Compounds containing at least one asymmetric carbon atom
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    • 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
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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    • 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
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
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    • 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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
    • C09K19/3458—Uncondensed pyrimidines
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
    • C09K2019/0407—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a carbocyclic ring, e.g. dicyano-benzene, chlorofluoro-benzene or cyclohexanone

Definitions

  • the invention relates to derivatives of 2,3-difluorohydroquinone of the formula I,
  • R 1 and R 2 are each independently unsubstituted, simply by cyan or at least simply by
  • a 1 , A 2 and A 3 each independently
  • CH groups can be replaced by N, (c) residue from the group consisting of piperidine-1,4-diyl, 1,4-bicylo (2,2,2) octylene, 1,3,4-thiadiazole-2,5-diyl, naphthalene-2,6 - diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl,
  • radicals (a) and (b) can be substituted one or more times by F, Cl, CH 3 or CN,
  • Q 1 and Q 2 each independently of one another -CO- or -CH 2 -,
  • n and n each represent 0, 1 or 2
  • Cyc in the following means a 1,4-cyclohexylene group and PheF means a group of the formula
  • the compounds of the formula I can be used as components of liquid-crystalline media, in particular for displays which are based on the principle of the twisted cell, the guest-host effect, the effect of the deformation of aligned phases or the effect of dynamic scattering.
  • the compounds of the formula I are distinguished by a clearly negative anisotropy of the dielectric constant and are aligned with their molecular longitudinal axes perpendicular to the field direction in an electric field. This effect is known and is used to control the optical transparency in various liquid crystal displays, for example in liquid crystal cells of the light scattering type (dynamic scattering), of the so-called DAP type (deformation of aligned phases) or ECB type (electrically controlled birefringence) or by the guest / Host type (guest-host interaction).
  • DAP light scattering
  • ECB type electrically controlled birefringence
  • the compounds of the formula I are also suitable as components of nematic or chiral nematic liquid-crystalline media with an overall positive dielectric anisotropy.
  • the compounds of formula I are used here to increase ⁇ ⁇ .
  • the negative dielectric anisotropy of the compounds according to the invention is overcompensated here by adding dielectrically strongly positive components.
  • Media of this type are used for TN displays with a 90 ° twist or, in particular, for higher twisted TN cells, since they lead to particularly steep characteristic curves there.
  • Chiral-chopped smectic liquid-crystalline media with ferroelectric properties can be produced by adding a suitable chiral dopant to basic mixtures with one or more chopped smectic media (LA Veresnev et al., Mol. Cryst. Liq. Cryst. 89, 327 (1982 HR Brand et al., J. Physigue 44 (lett.), L-771 (1983).
  • Such media can be used as dielectrics for fast-switching displays based on the principle of SSFLC technology described by Clark and Lagerwall ( NA Clark and ST Lagerwall,
  • Liquid crystal compounds with negative dielectric anisotropy which have two or three rings linked via carboxyl groups or covalent bond and one or more side groups, such as halogen, cyano or nitro groups, are known from DE 22 40 864, DE 26 13 293, DE 28 35 662, DE 28 36 086 and EP 023 728.
  • EP 084194 encompasses the compounds claimed here in a broad formula. However, no individual compounds of the formula according to the invention are mentioned there. The person skilled in the art could therefore neither easily derive synthesis possibilities for the claimed compounds from the prior art nor recognize that the compounds according to the invention predominantly have conveniently located mesophase regions and are distinguished by a large negative anisotropy of the dielectric with a simultaneously low viscosity.
  • the object of the invention was to demonstrate stable, liquid-crystalline or mesogenic compounds with a large negative anisotropy of dielectric and at the same time low viscosity.
  • the compounds of the formula I are particularly suitable as components of liquid-crystalline media.
  • they can be used to produce stable liquid-crystalline media with a wide mesophase range and comparatively low viscosity.
  • the compounds of the formula I are furthermore suitable as components of chiral-chopped smectic liquid-crystalline media.
  • the range of liquid-crystalline substances which are suitable for the production of liquid-crystalline media from various technical points of view is also broadened considerably.
  • the compounds of formula I have a wide range of uses. Depending on the selection of the substituents, these compounds can serve as base materials from which liquid-crystalline media 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 to improve 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 the To vary the pitch of such a dielectric.
  • the compounds of the formula I are also suitable as intermediates for the preparation of other substances which can be used as constituents of liquid-crystalline media.
  • 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. They are very stable chemically, thermally and against light.
  • the invention thus relates to the compounds of the formula I and to a process for their preparation, characterized in that a corresponding carboxylic acid or hydroxy compound or one of its reactive derivatives is reacted with a corresponding hydroxy compound or one of its reactive derivatives.
  • the invention furthermore relates to the use of the compounds of the formula I as components of liquid-crystalline media.
  • the invention further relates to liquid-crystalline media containing at least one compound of the formula I, and to liquid-crystal display elements that contain such media.
  • Such media have particularly advantageous elastic constants and are particularly suitable for TFT mixtures because of their low ⁇ / ⁇ ⁇ , values.
  • the invention furthermore relates to all new intermediates for the preparation of the compounds according to the invention,
  • R 1 , R 2 , A 1 , A 2 , A 3 , Z 1 , Q 1 , Q 2 , n and m have the above and below the meaning given, unless expressly stated otherwise.
  • the compounds of the formula I accordingly comprise preferred compounds having two rings of the sub-formula Ia:
  • those of the sub-formulas Ia, Ib and Ic are particularly preferred.
  • R 1 and R 2 are preferably alkyl or alkoxy. Also preferred are compounds of the formulas above and below in which one of the radicals R 1 and R 2 denotes alkenyl or oxaalkyl (for example alkoxymethyl).
  • R 1 and R 2 in the formulas above and below preferably have 2-12 C atoms, in particular 3-10 C atoms.
  • One or two CH 2 groups can also be replaced in R 1 and R 2 .
  • Preferably only one CH 2 group is replaced by -O-, or -CH CH-.
  • R 1 and R 2 are alkyl radicals, in which one ("alkoxy” or “oxaalkyl”) or two ("alkoxylakoxy” or “dioxaalkyl”) non-adjacent CH 2 groups can be replaced by O atoms, they can be straight or branched.
  • They are preferably straight-chain, have 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly preferably mean ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, furthermore methyl , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.
  • This alkenyl radical can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms.
  • it means especially vinyl, prop-1-, or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex -1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, Dec-1 -, 2-, 3-, 4-, 5-, 6-, 7-, 8 or Dec-9-enyl.
  • radicals R 1 or R 2 are simply substituted by cyan or at least by fluorine or chlorine, it is preferably ⁇ -fluoro or ⁇ -cyan alkyl with 1-12 C atoms, n-alkyl groups with 2 -12 C atoms with substitution by fluorine, chlorine or cyano on a secondary C atom or perfluoro-n-alkyl groups with 1-12 C atoms, in which one or more CF 2 groups are replaced by -O- and / or -CH 2 - can be replaced.
  • Solubility in the usual liquid-crystalline base materials can be important, but especially as chiral dopants if they are optically active.
  • Branched groups of this type usually contain no more than one chain branch. Preferred branched
  • Formula I includes both the racemates of these compounds and the optical antipodes and mixtures thereof.
  • a 1 , A 2 and A 3 each independently of one another preferably mean trans-1,4-cyclohexylene, 1,4-phenylene, 2-or 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4- phenylene,
  • a 1 , A 2 and A 3 are trans-1,4-cyclohexylene and 1,4-phenylene.
  • n and n are each preferably 0 or 1.
  • Z is preferably -CH 2 CH 2 - or a single bond.
  • a 2 radical (b) [ie for example 1,4-phenylene]
  • Q 1 is preferably -CO-.
  • Preferred compounds of the formulas I and Ia to If are those in which at least one of the radicals contained therein has one of the preferred meanings indicated.
  • R 3 and R 4 are each independently alkyl
  • m is 0 or 1
  • Z is -CH 2 -CH 2 - or a single bond
  • a 1 and A 2 are each trans-1,4-cyclohexylene.
  • the compounds of the formula I are 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), namely under Reaction conditions which are known and suitable for the reactions mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail. 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.
  • 1,2-difluorobenzene or 1-substituted 2,3-difluorobenzene is optionally added in an inert solvent such as diethyl ether, tetrahydrofuran, dirthoxyethane, tert-butyl methyl ether or dioxane, hydrocarbons such as hexane, heptane, cyclohexane, benzene or toluene or mixtures of these solvents
  • a complexing agent such as tetramethylethylene diamine (TMEDA) or hexamethylphosphoric triamide with phenyllithium, lithium tetramethylpiperidine, n-, sec- or tert-butyllithium at temperatures from -100 ° C to +50 ° C, preferably -78 ° C to 0 ° C.
  • the lithium-2,3-difluorophenyl compounds are reacted at -100 ° C. to 0 ° C., preferably at -50 ° C., with the corresponding electrophiles.
  • Suitable electrophiles are aldehydes, ketones, nitriles, epoxies, carboxylic acid derivatives such as esters, anhydrides or halides, halogen formate or carbon dioxide.
  • the lithium 2,3-difluorophenyl compounds are transmetallated and with transition metal catalysis coupled.
  • Zinc cf. DE OS 36 32 410) or titanium-2,3-difluorophenyl compounds (cf. DE OS 37 36 489) are particularly suitable for this.
  • the compounds of the formula I can be prepared by esterifying corresponding carboxylic acids (or their reactive derivatives) with alcohols or phenols (or their reactive derivatives).
  • Suitable reactive derivatives of the carboxylic acids mentioned are especially the acid halides, especially the chlorides and bromides, and also the anhydrides, e.g. B. also mixed anhydrides, azides or esters, especially alkyl esters with 1-4 C atoms in the alkyl group.
  • Suitable reactive derivatives of the alcohols or phenols mentioned are in particular the corresponding metal alcoholates or phenolates, preferably an alkali metal such as Na or K.
  • the esterification is advantageously carried out in the presence of an inert solvent.
  • Ethers such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones such as acetone, butanone or cyclohexanone, amides such as DMF or phosphoric acid hexamethyltriamide, hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride or tetrachlorethylene and are particularly suitable Sulfoxides such as dimethyl sulfoxide or sulfolane.
  • Water-immiscible solvents can at the same time advantageously be used for azeotropically distilling off the water formed during the esterification. Occasionally an excess of an organic base, e.g. Pyridine, quinoline or triethylamine can be used as a solvent for the esterification.
  • an organic base e.g. Pyridine, quinoline or triethylamine
  • Esterification can also take place in the absence of a solvent, for example by simply heating the components in the presence of sodium acetate.
  • the reaction temperature is usually between -50 ° and +250 °, preferably between -20 ° and +80 °. At these temperatures, the esterification reactions are usually complete after 15 minutes to 48 hours.
  • reaction conditions for the esterification largely depend on the nature of the starting materials used.
  • a free carboxylic acid is usually reacted with a free alcohol or phenol in the presence of a strong acid, for example a mineral acid such as hydrochloric acid or sulfuric acid.
  • a preferred reaction mode is the reaction of an acid anhydride or, in particular, an acid chloride with an alcohol, preferably in a basic medium, the bases being in particular alkali metal hydroxides such as sodium or potassium hydroxide,
  • Alkali metal carbonates or hydrogen carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, alkali metal acetates such as sodium or potassium acetate, alkaline earth metal hydroxides such as calcium hydroxide or organic bases such as triethylamine, pyridine, lutidine, collidine or quinoline are important.
  • Another preferred embodiment of the esterification consists in first converting the alcohol or the phenol into the sodium or potassium alcoholate or phenolate, e.g.
  • the methyl ethers of the formula I can be prepared by known etherifications, for example by adding a compound of the formula R- 1 - (A 1 -Z 1 ) m -A 2 -Q 1 -O-PheF 2 -Z A or R 2 - ( A 3 ) n - Q 2 -O-PheF 2 -Z A , wherein Z A is OH or OMe, SH or SMe, where Me is an equivalent of a metal cation and Hal is a halogen atom, preferably chlorine or bromine (reactive derivative of the phenols), with a compound of Formula R 2 - (A 3 ) n -Z B or R 1 - (A 1 -Z 1 ) m -A 2 -Z B , in which Z B
  • -CH 2 -OH or -CH 2 -Hal means reacting in the presence of a base.
  • the radicals R 1 , R 2 , A 1 , A 2 , A 3 , Z 1 , m, n, Q 1 and Q 2 have the meanings given in formula I.
  • the reaction conditions for these ether syntheses are the usual ones for such reactions; polar, aprotic solvents are used as solvents, for example dimethyl sulfoxide, N, N-dimethylformamide or N-methylpyrrolidone; Alkali salts of weak acids, for example sodium acetate, potassium carbonate or sodium carbonate, are preferably used as bases.
  • the reactions can be carried out at temperatures between 0 ° C and the boiling point of the lowest boiling component of the reaction mixture; it has proven particularly advantageous to use temperatures between 60 and 120 ° C.
  • the starting materials are for
  • An important new intermediate for the synthesis of compounds according to the invention is 2,3-difluorohydroquinone.
  • This new compound which is also the subject of the invention, can be oxidized by known 2,3-difluorophenol in a manner known per se, e.g. can be obtained by oxidation with potassium peroxodisulfate in alkaline, aqueous solution.
  • the liquid-crystalline media according to the invention preferably contain 2 to 40, in particular 4 to 30, components as further constituents. Ent is particularly preferred these media hold 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 azoxybenzenes, benzylidene anilines, biphenyls, terphenyls, phenyl- or cyclohexylbenzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters Cyclohexylbenzoic acid, phenyl- or cyclohexyl ester of cyclohexylcyclohexane carboxylic acid, cyclohexylphenyl ester of benzoic acid, cyclohe
  • one of the radicals L and E is 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 selected from the compounds of 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 '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 has the at the compounds of the partial form in la to 5a and is preferably alkyl or alkenyl.
  • 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 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, expediently at elevated temperature.
  • the liquid-crystalline phases according to the invention can be modified so that they are used in all types of Liquid crystal display elements can be used.
  • 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).
  • 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.
  • K crystalline solid state
  • S smectic phase (the index indicates the phase type)
  • N nematic state
  • Ch cholesteric phase
  • I isotropic phase. The number between two symbols indicates the transition temperature in degrees Celsius.
  • 2,3-difluoro-4-ethoxyphenol can be prepared from 2,3-difluorophenol by alkylation with diethyl sulfate / potassium carbonate in dimethylformamide, lithiation at -70 to -80 °, reaction with N-methylpiperidine and oxidation of the aldehyde according to Baeyer -Villiger with performic acid
  • 0.1 mol pyridine were dissolved in 100 ml toluene.
  • 0.1 mol of trans-4-pentylcyclohexane carboxylic acid is added dropwise at 80 ° Chloride and stir for 3 hours.
  • the precipitated pyridine hydrochloride is filtered off with suction, the toluene is distilled off and the (2,3-difluoro-4-ethoxyphenyl) trans-4-pentylcyclohexanoate which remains is purified by crystallization from ethanol, mp 48 °, K. 62.5 °.
  • Example 2 Analogously to Example 1, the same phenol is obtained by reaction with 4- (trans-4-propylcyclohexyl) cyclohexane carboxylic acid chloride (2,3-difluoro-4-ethoxyphenyl) trans- 4- (trans-4-propylcyclohexyl) cyclohexanoate, K 88 ° S A 100 ° N 223 ° I.
  • 0.1 mol of 2,3-difluoro-4-benzyloxyphenol are esterified with 0.1 mol of pyridine and 0.1 mol of 4-ethoxybenzoyl chloride in toluene, the resulting ester is isolated and then the benzyl ether is hydrogenolytically cleaved with palladium-carbon as a catalyst.
  • a liquid crystalline phase consisting of
  • a liquid crystalline phase consisting of
  • a nematic liquid crystalline phase consisting of
  • Example D is characterized by good multiplex properties.
  • a liquid crystalline phase consisting of
  • a liquid crystalline phase consisting of

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Abstract

Des dérivés de 2,3-difluorohydroquinone ont la formule (I), dans laquelle R1 et R2 représentent indépendamment l'un de l'autre un alkyle ayant entre 1 et 15 atomes C ou un alkényle ayant entre 3 et 15 atomes C, non substitué ou monosubstitué par du cyanogène ou au moins monosubstitué par du fluor ou du chlore, un groupe CH2 pouvant également être substitué dans ces résidus par -O-, -CO-, -CO-O-, -O-CO-, ou -O-CO-O-; A1, A2 et A3 représentent indépendamment les uns des autres: (a) trans-1,4-cyclohexylène, dans lequel un ou deux groupes CH2 non adjacents peuvent également être substitués par -O- et/ou -S-; (b) 1,4-phénylène, dans lequel un ou deux groupes CH peuvent également être substitués par N; (c) un résidu du groupe composé de pipéridin- 1,4-diyle, 1,4-bicyclo(2,2,2)octylène, 1,3,4-thiadiazol-2,5-diyle, naphtalin-2,6-diyl, décahydronaphtalin-2,6-diyle et 1,2,3,4-tétrahydronaphtalin-2,6-diyle, les résidus (a) et (b) pouvant être substitués une ou plusieurs fois par F, Cl, CH3 ou CN; Z1 représente -CO-O-, -O-CO, -CH2-CH2-, -OCH2-, -CH2O-, -C=C- ou ne liaison simple, Q1 et Q2 représentent indépendamment l'un de l'autre -CO- ou -CH2-; m et n sont égaux à 0, 1 ou 2, et (m + n) est égal à 0, 1 ou 2. Ces dérivés sont utiles comme composants de phases de cristaux liquides.
EP89902770A 1988-03-10 1989-02-27 Derives de 2,3-difluorohydroquinone Pending EP0373186A1 (fr)

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DE3807801 1988-03-10
DE3807801A DE3807801A1 (de) 1988-03-10 1988-03-10 Derivate des 2,3-difluorhydrochinons

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JP2977410B2 (ja) * 1993-04-26 1999-11-15 シャープ株式会社 強誘電性液晶組成物およびこれを用いた素子
DE19803112A1 (de) 1997-03-14 1998-09-17 Merck Patent Gmbh Elektrooptische Flüssigkristallanzeige
DE10150198A1 (de) * 2001-10-12 2003-04-24 Merck Patent Gmbh Flüssigkristallines Medium
JP2004339483A (ja) * 2003-03-14 2004-12-02 Merck Patent Gmbh 液晶媒質
EP1591512A1 (fr) * 2004-04-26 2005-11-02 AZ Electronic Materials (Germany) GmbH Mélange liquide cristallin chiral smectique
TWI378139B (en) 2005-01-27 2012-12-01 Dainippon Ink & Chemicals A difluorobenzene derivative and a nematic liquid crystal composition using the same
WO2006098366A1 (fr) 2005-03-17 2006-09-21 Dainippon Ink And Chemicals, Inc. Derive de difluorobenzene et composition de cristaux liquides nematiques l’utilisant
JP5056118B2 (ja) * 2006-03-31 2012-10-24 Ｄｉｃ株式会社 ジフルオロベンゼン誘導体の製造方法
CN102344434B (zh) * 2006-03-31 2013-09-25 大日本油墨化学工业株式会社 二氟苯衍生物的制备方法
DE102007045759B4 (de) 2006-09-29 2019-03-28 Dainippon Ink And Chemicals, Inc. Difluorbenzol-Derivat und Herstellungsverfahren dafür
JP5240494B2 (ja) * 2006-09-29 2013-07-17 Ｄｉｃ株式会社 ジフルオロベンゼン誘導体及びその製造方法
CN103183591B (zh) * 2007-01-31 2016-01-20 Dic株式会社 4′-二烷氧基甲基双环己烷-4-基甲醇及其制造方法
CN101980996B (zh) * 2008-04-09 2013-06-26 Jnc株式会社 含有侧向氟的3环液晶性化合物、液晶组成物及液晶显示元件
KR101617482B1 (ko) 2008-09-17 2016-05-02 제이엔씨 석유 화학 주식회사 액정 조성물 및 액정 표시 소자
CN101838264B (zh) * 2009-03-16 2014-12-03 住友化学株式会社 化合物、光学膜和光学膜的制造方法
JP5545514B2 (ja) * 2009-03-23 2014-07-09 Ｄｉｃ株式会社 液晶材料の精製方法
KR101677764B1 (ko) * 2009-04-21 2016-11-18 스미또모 가가꾸 가부시끼가이샤 화합물
TWI468381B (zh) 2009-08-18 2015-01-11 Jnc Corp 十氫化萘化合物、含有此化合物的液晶組成物及含有此液晶組成物的液晶顯示元件
TWI488946B (zh) 2009-08-24 2015-06-21 Jnc Corp 液晶組成物及液晶顯示元件
TWI482843B (zh) 2009-08-25 2015-05-01 Jnc Corp 液晶組成物及液晶顯示元件
TWI437080B (zh) 2009-08-26 2014-05-11 Jnc Corp 液晶組成物及液晶顯示元件
TWI518171B (zh) 2010-06-03 2016-01-21 捷恩智股份有限公司 液晶組成物及液晶顯示元件
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JP6476691B2 (ja) 2014-09-26 2019-03-06 Jnc株式会社 液晶組成物および液晶表示素子
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DE3807801A1 (de) 1989-09-21
EP0332007B1 (fr) 1992-11-25
EP0332007A1 (fr) 1989-09-13
JP2567288B2 (ja) 1996-12-25
CN1040024A (zh) 1990-02-28
KR920010640B1 (ko) 1992-12-12
ATE82744T1 (de) 1992-12-15
WO1989008637A1 (fr) 1989-09-21
AU3188889A (en) 1989-10-05
DE58902788D1 (de) 1993-01-07
JPH02503568A (ja) 1990-10-25
KR900700431A (ko) 1990-08-13

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