GB2290787A - Three ring alkoxyphenyl liquid crystalline derivatives - Google Patents

Three ring alkoxyphenyl liquid crystalline derivatives Download PDF

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GB2290787A
GB2290787A GB9420920A GB9420920A GB2290787A GB 2290787 A GB2290787 A GB 2290787A GB 9420920 A GB9420920 A GB 9420920A GB 9420920 A GB9420920 A GB 9420920A GB 2290787 A GB2290787 A GB 2290787A
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formula
compounds
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liquid crystalline
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David Coates
Mark John Goulding
Shirley Ann Marden
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Merck Patent GmbH
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Merck Patent GmbH
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    • 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
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • 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
    • 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
    • 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
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • 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

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

Abstract

Compounds of formula I <IMAGE> [wherein R<1> is a C1-12 straight-chain or branched alkyl or alkenyl (in which one or more CH2 groups can also be replaced by a group selected from the group comprising -O-, -S-, -O-CO-, -S-CO-, -O-COO-, -CO-O-, -CO-S-, -CHhalogen-, and -CHCN-; two hetero atoms not being linked directly to one another) or is also F, Cl, Br or C1-5 polyfluoroalkyl (in which one CF2 group can also be replaced by -O- or -S-); R<2> is Me or Et; <IMAGE> and <IMAGE> are 1,4-phenylene or trans-1,4-cyclohexane, each optionally substituted by up to four fluorine atoms; <IMAGE> is a 1,4-phenylene optionally substituted by up to four fluorine atoms; Z<1> and Z<2> ae -CH2CH2- or a single bond; with the proviso that at least one of the rings <IMAGE> and <IMAGE> is a fluorinated 1,4-phenylene group] are new and may be used as components of liquid crystalline media.

Description

Benzene derivatives and a liquid-crystalline medium The invention relates to benzene derivatives of formula 1,
wherein R1 is a straight-chain or branched alkyl or alkenyl with in each case up to 12 C atoms, in which one or more CH2 groups can also be replaced by a group selected from the group com prising -O-, -S-, -O-CO-, -S-CO-, -O-COO-, -CO-O-, -CO-S-, CHhalogen-, and -CHCN-, two hetero atoms not being linked directly to one another, or is also F, Cl, Br or -NCS or polyfluoroalkyl with 1-5 C atoms, in which one CF2 group can also be replaced by -O- or-S-,
are each independently 1,4-phenylene optionally substituted by up to four fluorine atoms or trans-1 ,4-cyclohexane,
is a 1,4-phenylene optionally substituted by up to four fluorine atoms, with the proviso that at least one of the rings
is a fluorinated 1,4-phenylene group. and Z1 and Z2 are each independently -CH2CH2- or a single bond.
The invention furthermore relates to the use of these compounds as components of liquid-crystalline media, and to liquid-crystal and electrooptical displays which contain the liquid-crystalline media according to the invention.
The compounds of the formula I can be used as components of liquidcrystalline media, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of aligned phases or the effect of dynamic scattering. Especially useful are the compounds of the present intention for PDLC/TFT type displays or windows.
The invention had the object of finding novel stable liquid-crystalline or mesogenic compounds which are suitable as components of liquidcrystalline media and in particular have at the same time comparatively low viscosity, a high birefringence Dn and a relatively high dielectric anisotropy.
It has now been found that compounds of formula I are eminently suitable as components of liquid-crystalline media. In particular, they allow to realize mixtures and PDLC devices with very high electrical resistivity. Using them, stable liquid-crystalline media which have a broad mesophase range, advantageous values for the optical and dielectric anisotropy and outstanding ultraviolet and temperature stability are obtained.
Liquid crystal ether compounds are known from the GB 2 134 110 A and EP 0 132 377 which contains a speculative general formula which would include the compounds of the present invention.
But the cited references refer specially to the compounds of the formulae
(F) Alkyl e C2H4{ < 9Alkyl Alkyl (F) Alkyl 1 C,H, > Alkyl (F) Alkyl whose An values are much lower than of the inventive methoxy compounds.
In view of the very wide range of areas of application of such compounds having very high An, it was, however, desirable to have further compounds available which have properties precisely customized to the particular applications.
In addition, the provision of the compounds of the formula I very generally considerable extends the range of liquid-crystailine substances which are suitable, from various applicational points of view, for the preparation of liquid-crystalline mixtures.
The compounds of the formula I have a broad field of application. Depending on the choice ob substituents, these compounds can be used as base materials from which liquid-crystalline media are predominantly composed; however, compounds of the formula I can also be added to liquid-crystalline base materials from other classes of compound, in order, for example, to influence the dielectric and/or optical anisotropy of a dielectric of this type and/or optimize its threshold voltage and/or its viscosity.
In the pure state, the compounds of the formula I are colorless and form liquid-crystalline mesophases in a very favorable temperature range for electrooptical use. They are stable chemically, thermally and to light.
The invention thus relates to the compounds of the formula I and to the use of these compounds as components of liquid-crystalline media. The invention furthermore relates to liquid-crystalline media containing at least one compound of the formula 1, and to liquid-crystal display elements, in particular electrooptical display elements, which contain media of this type.
For reasons of simplicity below, Cyc is a 1,4-cyclohexylene radical and Phe is a 1 ,4-phenylene radical optionally substituted by up to four fluorine atoms.
The compounds of the formula I accordingly include the prefered trinuclear compounds of the subformulae la to Id: R1-Phe-Z1-Phe-Z2-Phe-OCH3 la R1-Phe-Z1-Cyc-Z2-Phe-OCH3 lb R1-Cyc-Z1-Phe-Z2-Phe-OCH3 Ic R1-Cyc-Z1-Cyc-Z2-Phe-OCH3 1d Some particularly preferred smaller groups of compounds of the formula I are given below:
At least one of the radicals
present in the molecule of the formula I is
R1 is preferably alkyl, furthermore alkoxy.
are preferably Phe.
Preferred compounds of the formula I and of all the sub-formulae are those in which
are 1,4-phenylene which is monosubstituted or disubstituted by F. These are, in particular, 2fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene and 2,3-difluoro-1,4-phenylene.
Z1 and Z2 are preferably a singie bond. Preferably, only one of the groups Z1 and Z2 present in the molecule is other than a single bond.
If R1 is an alkyl radical and/or an alkoxy radical, it may be straight chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 C atoms and is accordingly preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.
Oxaalkyl is preferably straight-chain 2-oxapropyl (= methoxymethyl), 2- (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxyheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.
If R1 is an alkyl radical in which one CH2 group has been replaced by -CH=CH-, it may be straight-chain or branched. It is preferably straight- chain and has 2 to 10 C atoms. It is accordingly particularly vinyl, prop-1- or-2-enyl, but-1-, -2- or-3-enyl, pent-1-, -2-, -3- or-4-enyl, hex-1-, -2-, -3-, -4- or-5-enyl, hept-1-, -2-, -3-, -4-, -5- or-6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7- enyl1 non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, or dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or-9-enyl.
If R1 is an alkyl radical in which one CH2 group has been replaced by-O- and one has been replaced by-CO-, these are preferably adjacent. These thus contain an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-.
These are preferably straight-chain and have 2 to 6 C atoms.
They are accordingly particularly acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxywarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl and 4-(methoxycarbonyl)butyl.
If R1 is an alkyl radical in which one CH2 group has been replaced by unsubstituted or substituted -CH=CH- and adjacent CH2 group has been replaced by CO or CO-O or O-CO-, it may be straight or branched. It is preferably straight-chain and has 4 to 13 C atoms. It is accordingly particularly acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl. 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 1 0-acryloyloxydecyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyloxyoctyl or 9-methacryloyloxynonyl.
Compounds of the formula I which contain wing groups R1 which are suitable for polymerization reactions are suitable for the preparation of liquid-crystalline polymers.
Compounds of the formula I containing branched wing groups may occasionally be of importance due to better solubility in the customary liquid-crystalline base materials, but in particular as chiral dopes if they are optically active. Smectic compounds of this type are suitable as components of ferroelectric materials.
Compounds of the formula I having SA phases are suitable, for example, for thermally addressed displays.
Branched groups of this type generally contain not more than one chain branch. Preferred branched radicals R1 and R2 are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propyl- pentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy or 1 -methylheptoxy.
If R1 is an alkyl radical in which two or more CH2 groups have been replaced by -O- and/or-CO-O-, it may be straight-chain or branched. It is preferably branched and has 3 to 12 C atoms. It is accordingly particularly biscarboxymethyl, 2,2-biscarboxyethyl, 3,3-biscarboxypropyl, 4,4-biscarboxybutyl, 5,5-biscarboxypentyl, 6,6-biscarboxyhexyl, 7,7-biscarboxyheptyl, 8,8-biscarboxyoctyl, 9,9-biscarboxynonyl, 10,10-biscarboxydecyl, bis (methoxycarbonyl)methyl, 2,2-bis(methoxycarbonyl)ethyl, 3,3-bis-(methoxycarbonyl)propyl, 4,4-bis(methoxycarbonyl)butyi, 5,5-bis-(methoxycarbonyl)pentyl, 6,6-bis(methoxycarbonyl)hexyl, 7,7-bis(methoxycarbonyl)- heptyl, 8, 8-bis(methoxycarbonyl )octyl, bis(ethoxycarbonyl)methyl, 2,2-bis (ethoxycarbonyl)ethyl, 3,3-bis(ethoxycarbonyl)propyl, 4,4-bis-(ethoxycarbonyl)butyl or 5,5-bis(ethoxycarbonyl)hexyl.
Compounds of the formula I which contain wing groups R1 which are suitable for polycondensations are suitable for the preparation of liquidcrystalline polycondensates.
The formula I covers the racemates of these compounds and the optical antipodes, and mixtures thereof.
Of these compounds of the formula I and the sub-formulae, those are preferred in which at least one of the radicals present therein has one of the preferred meanings indicated.
In the compounds of the formula 1, these stereo-isomers in which the rings Cyc are trans-1,4-disubstituted are preferred.
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, Methoden der Organischen Chemie [Methods of Organic Chemistryl, Georg-Thieme-Verlag, Stuttgart, Vol. IX, pp. 867 ff.), to be precise under reaction conditions which are known and suitable for the reactions mentioned. Use can aiso be made here of variants which are known per se, but are not described in greater detail here.
The compounds according to the invention can be prepared in accordance with the following reaction schemes: Scheme 1
F XBr R'-COCI t AICI3. CH2CL2 O F R'-C +} 8r Triethylsilane Trifluoroacetic acid RT v RT F R'- Br H3eB(OH)2 Pd(PPh,, DME Na2COs, aT, N2 F -OCH, (o) R' = Alkyl Scheme 2
p-Toluene Sulphonyl LiAIH4 A Chloride R'- CH,OH Chlorae THF, RT, N2 CH2CI2, A, Pyridine RLCH,O-SO-- R'-$4-CH2CN OH Butanol R'-,CO,H SOCK, R'-H,COCI CH2CI2, 0 C, DMF Friedel Crafts Acylation > 2-OCH, 2- or 3-Fluoroanisole, 0 C t CH2C12 AICISX 0 C F HUANG MINLON R'- /7 t R' -(0)-OH Hydr ine Hydrate Diethylene Glycol, A, N2 F Trifluoromethane Sulfonic Anhydride RCH,CH2 (O)-OSO,CF, Pyridine, CH2CI2, 0 C F 17 (HO)2B O eOCHs R'-t-CH,CH- ( 0 )I O rOCH, 1,2-Dimethoxy Ethane, Na2CO3 (aq) F Pd(PPh3)4. A, N2 Scheme 3
Scheme 4
F Friedel-Crafts- O F H Acylation gI 7 < Br ( < Br R'-C < Br R'COCI, CH2CI2 Triethylsilane F Reduction F R'--Br Trifluoroacetic acid room temperature Magnesium THF. B(oCHs) A A, N2 F RL' \B(OH), (o) F )= 1 ,2-Dimethoxyethane SOCH, Na2CO3 (aeq.) Pd (PPh3)4 fl ' 4N2 F F R'+OCH3 Scheme 5
X R'-COCI CH,CI,, AICI, v CH2C12, AlCIs O F R'-C Triethylsilane Trifluoroacetic acid F R D CIOCCH, 0 )- OCH, CH,CI,, AICI, v CH2CI2, AICI3 F O R'-i CHS " -C-CHOr OCH, Triethylsilane l Trifluoroacetic acid F R'- CH2CH2H} SOCH, Scheme 6
F l4}Br 1,2-Dimethoxy- BuLi ethane (HO),B -OCH, Br-oCH, Na,CO, (HO)2B < } THF, , N2 Pd(PPh3)4 s B(oCH3)3 F Br+(+OCH3 n-BuLi, THF l B(OCH3)3 F (HO2)B+}OCHS 1 ,2-Dimethoxy- F ethane 1 Á Na2CO3 R Pd(PPh3)4 t F F R' R'+OCH3 The liquid-crystalline media according to the invention preferably contain 2 to 40, in particular 4 to 30, components as further constituents besides one or more compounds according to the invention. These media very particularly preferably contain 7 to 25 components besides 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 azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid and of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexenes, cyclohexylcyclohexylcyclohexenes, 1,4-biscyclohexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl or cyclohexyldioxanes, phenyl- or cyclohexyl-1 ,3-dithianes, 1 ,2-diphenylethanes, 1,2- dicyclohexylethanes, 1-phenyl-2-cyclohexylethanes, 1-cyclohexyl-2-(4- phenylcyclohexyl)ethanes, 1-cyclohexyl-2-biphenylylethanes, 1-phenyl-2- cyclohexylphenylethanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene groups in these compounds may also be fluorinated.
The most important compounds suitable as further constituents of media according to the invention can be characterized by the formulae 1, 2, 3, 4 and 5: R'-L-E-R" 1 R'-L-COO-E-R" 2 R'-L-OOC-E-R" 3 R'-L-CH2CH2-E-R" 4 R'-L-CEC-E-R" 5 In the formulae 1, 2, 3, 4 and 5, L and E, which may be identical or different, are, in each case independently of one another, a bivalent radical from the group formed by -Phe-, -Cyc-, -Phe-Phe, -Phe-Cyc-, -Cyc Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- and their mirror images, where Phe is unsubstituted or fluorinesubstituted 1,4-phenylene, Cyc is trans1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr is pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio is 1,3-dioxane-2,5-diyl and G is 2-(trans-1,4-cyclo- hexyl)ethyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.
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 formulae 1, 2, 3, 4 and 5 in which L and E are selected from the group comprising Cyc, Phe and Pyr and simultaneously one or more components selected from the compounds of the formulae 1, 2, 3, 4 and 5 in which one of the radicals L and E is selected from the group comprising Cyc, Phe and Pyr and the other radical is selected from the group comprising -Phe Phe-, -PheCyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulae 1, 2, 3, 4 and 5 in which the radicals L and E are selected from the group comprising -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-.
In the compounds of the sub-formulae 1a, 2a, 3a, 4a and 5a, R' and R" are, in each case independently of one another, 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, one of these radicals usually being alkyl or alkenyl. In the compounds of the sub-formulae 1b, 2b, 3b, 4b and 5b, R" is -CN, -CF3, F, Cl or -NCS; in this case, R has the meaning given for the compounds of the sub-formulae 1a to 5a and is preferably aikyl or alkenyl.
However, other variants of the proposed substituents in the compounds of the formulae 1, 2, 3, 4 and 5 are common. Many @ such substances or alter- natively mixtures thereof are commercially available. All these substances can be obtained by methods which are known from the literature or analogously thereto.
Besides components from the group comprising the compound 1 a, 2a, 3a, 4a and 5a (Group 1), the media according to the invention also preferably contain components from the comprising the compounds 1 b, 2b, 3b, 4b and 5b (Group 2), whose proportions are preferably as follows: --Ir 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 adding up to 100 %.
The media according to the invention preferably contain 1 to 40 %, in particular preferably 5 to 30 %, of compounds according to the invention.
Further preferred media are those which contain 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 prepared in a manner which is customary per se. In general, the components are dissolved in one another, expediently at elevated temperature. By means of suitable additives, the liquid-crystalline phases can be modified in accordance with the invention in a manner such that they can be used in all types of liquidcrystal display elements which have hitherto been disclosed. Additives of this type are known to those skilled in the art and are described in detail in the literature (H. Kelker/R. Hatz, Handbood of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic dyes can be added for the production of colored guest-host systems, or substances can be added to modify the dielectric anisotropy, the viscosity and/or the orientation of the nematic phases.
In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by acronyms, the transformation into chemical formulae taking place in accordance with Tables A and B below. All the radicals CnH2n+1 and CmH2m+, are straight-chain alkyl radicals containing n or m carbon atoms respectively. The coding in Table B needs no explanation. In Table A, only the acronym for the parent structure is given.In individual cases, the acronym for the parent structure is followed, separated by a dash, by a code for the substituents R1, R2, L and L2
Code for R1, R1 R2 L1 L2 L3 R2, L1, L2 nm CnH2n+1 CmH2m+1 H H H nOm CnH2n+1 OCmH2m+1 H H H nO.m OCnH2n+1 CmH2m+1 H H H n CnH2n+1 CN H H H n N.F CnH2n+1 CN H F H nF CnH2n+1 F H H H nOF OCnH2n+1 F H H H nCI CnH2n+1 Cl H H H n F.F CnH2n+1 F H F H nOmFF CnH2n+1 OCmH2m+1 F F H nmF CnH2n+1 CmH2m+1 F H H nCF3 CnH2n+1 CF3 H H H nOCF3 CnH2n+, OCF3 H H H nOCF2 CnH2n+1 OCHF2 H H H nS CnH2n+1 NCS H H H rVsN C1H2r+1-CH=CH-CsH2s- CN H H H rEsN CrH2r+1-O-CsH2s- CN H H H nNF CnH2n+1 CN F H H nAm CnH2n+1 COOCmH2m+1 H H H Table A:
PYP PYRP
BCH CBC
CCH CCP
CP CPTP
CEPTP
D ECCP
CECP EPCH
HP ME
PCH PDX
PTP BECH
EBCH CPC Table B::
T15 K3n
M3n BCH-n.Fm
Inm
CBC-nmF
CCPC-nm
CH-nm
OS-nm CHE
ECBC-nm
ECCH-nm CCH-n1 EM
T-nFm ECCH-nm
CCH-n1 EM FET-nCI
T-nFN CCP-nF.F.F.
BCH-nF.F.F The examples below are intended to illustrate the invention without representing a limitation. Above and below, percentages are percent by weight. Temperatures are given in degrees Celsius. Mp. denotes melting point, Bp. = clear point. Furthermore, C = crystalline stage, N = nematic phase, S = smectic phase and I = isotropic phase. The data between these symbols represent the transition temperatures. on denotes optical anisotropy (589 nm, 20 C), and the viscosity (mm2/sec) was determined at 20 C.
"Customary work-up" means that water is added if necessary, the mixture is extracted with methylene chloride, diethyl ether or toluene, the organic phase is separated off, dried and evaporated, the product is purified by distillation under reduced pressure or crystallization andlor chromatography. The following abbreviation are used: DAST Diethylaminosulfur trifluoride DCC Dicyclohexylcarbodiimide DDQ Dichlorodicyanobenzoquinone DIBALH Diisobutylaluminum hydride KOT Potassium tertiary-butoxide THF Tetrahydrofuran pTSOH p-Toluenesulfonic acid TMEDA Tetramethylethylenediamine Example 1
Step 1.1 4-Methoxyphenylboronic acid 4-Bromoanisole (0.08 mol) was dissolved in THF (100 ml) and cooled to 70 C under an N2 atmosphere. 1.6 M n-BuLi solution in hexane (0.085 mol) was first added dropwise, then trimethoxyborate (0.09 mol) was added dropwise keeping the temperature at -70 C. The reaction mixture was allowed to warm up to room temperature. 2 M HCI (aq) solution and diethylether were added.The reaction mixture was stirred and separated. The organic phase was washed with water, dried (Na2SO4) and the solvent was removed under reduced pressure.
Step 1.2 4-(trans-4-(n-Propyl)cyclohexylethyl)-2-fluoro-4'-methoxybiphenyl 4-(trans-4-(n-Propyl)cyclohexylethyl)-2-fluorophenyltrifluromethanesulphonate (0.027 moles), 4-methoxyphenylboronic acid (0.03168 moles), 2 M Na2CO3 (aq) solution (20 ml), DME (50 ml) and tetrakistriphenylphosphine palladium(0) (0.1 9) were refluxed under N2 for 18 hrs. The reaction mixture was cooled to room temperature and water and dichloromethane were added. The reaction mixture was stirred and separated. The organic extract was washed with water, dried (Na2SO4) and the solvent was removed under reduced pressure.The crude product was flash column chromatographed over silica gel, eluting with petroleum spirit (b.p. 4060 C). The columned materials was recrystallized from propane-2-ol and dried in a vacuum oven at 40 C for 48 hours.K 60 N 143 I; An = + 0.178; ## = 1 The following commpounds are prepared analogously:
K 96 N 175 I; an = +0.195; ## = +1 .5 Example 2
Step 2.1
A solution of 0.05 mol 4-n-propyl-1-brombenzene in ethanol is added dropwise to a stirred mixture of 40 ml 0.05 mol 3-fluorophenyl boronic acid and 1 g tetrakis(triphenylphosphine)palladium(0) in 100 ml benzene and 50 ml 2 M Na2CO3 at room temperature under dry N2. The stirred mixture is heated under reflux until gic analysis confirmed absence of starting materials. The product is extracted with ether and dried (MgSO4).The solvent is removed and residue is purified by column chromatography and crystallization.
Step 2.2
A solution of n-butyllithium (10.0 M in hexene) is added dropwise to a stirred cooled solution (-78 C) of 0.5 mol 4'-n-propyl-3-fluorophenyl in 100 ml dry THF under dry N2. The stirred mixture is maintained under these conditions for 2.5 h and then a cooled solution of tri-isopropylborate in dry THF is allowed to warm to room temperature overnight and then stirred for 1 h at room temperature with 10 % HCI. The product is extracted and combined etheral extracts are washed with water and dried. The solution is removed in vacuo.
Step 2.3
5.0 g of 4-propyl-2'-fluoro-4'-biphenyl boronic acid, 3.5 9 of 4bromoanisole, 30 ml of 1,2-dimethoxyethane, 20 ml of 2 M aqueous sodium carbonate solution and 0.2 g of tetrakistriphenylphosphine palladium(0) were refluxed for 24 hrs under N2.
The crude product was extracted out of the mixture with dichloromethane and purified by column chromatography and recrystallization. K 85 N 185 I; An = +2.96; ## = 2.0 The following compounds are prepared analogously:
K 72 N 177 I; #n = +0.278; ## = 2.0 K 88 N 145 1; #n = +0.270; ## = -0.5 K 84 N 138 1; #n = +0.256; ## = -0.9 K 68 N 147 1; #n = +0.269; ## = +2.6
K 39 N 134 1; #n = +0.249; ## = +2.1 Example 3
Step 3.1
4-Methoxy phenyl boronic acid (29 9), 4-bromo-2-fluoroiodobenzene (52 9), 1,2-dimethoxyethane (300 ml), 2M Na2CO3 (aq.) (200 ml) and tetrakistriphenylphosphine palladium(0) (0.5 g) were heated under reflux for 24 hours. The crude product was purified by recrystallization and column chromatography.
Step 3.2
4'-Methoxy-2-fluoro-4-bromo-biphenyl (25 9), n-Butyllithium (1.6 M hexane solution) (55 ml) and THF were combined slowly at -70 C under N2.
Trimethyl borate (11 ml) was then added and the mixture was stirred. The crude product was isolated after hydrolysis with hydrochloric acid.
Step 3.3
4'-Methoxy-2-fluoro-4-biphenyl boronic acid (4.0 g), 4-n-propyl-2-fluorophenyl-triflate (4.86 g), 1,2-dimethoxyethane (30 ml), 2M Na2CO3 (aq.) (20 ml) and tetrakistriphenylphosphine palladium(0) (0.2 g) were heated and refluxed. The crude product was purified by recrystallisation and column chromatography. K 77 N 153.2 I; An = +0.272; ## = +0.9 The following compounds of the formula
are prepared analogously: R1 R2 C2H5 CH3 n-C4Hg CH3 n-C5H11 CH3 K 63 N 138 I; an = 0.250; ## = +1.6 n-C6H13 CH3 F CH3 Cl CH3 F C2H5 Cl C2H5 NCS CH3 NCS C2H5 C2F5 CH3 OCH2CF3 C2H5 Mixture A
15.7% 8.1% 21.2% 12.5% 8.7% 13.8% 10.0% 10.0% Clearing point ( C): 98.9 ## [1 kHz, 20 C]: 5.05 #n [589 nm, 20 C]: 0.224 @20 [cSt]: 65

Claims (9)

  1. Claims A A compound of the formula I
    wherein R1 is a straight-chain or branched alkyl or alkenyl with in each case up to 12 C atoms, in which one or more CH2 groups can also be replaced by a group selected from the group comprising -O-, -S-, -O-CO-, -S-CO-, -O COO-, -CO-O-, -CO-S-, -CHhalogen-, and -CHCN-, two hetero atoms not being linked directly to one another, or is also F, Cl, Br or -NCS or polyfluoroalkyl with 1-5 C atoms, in which one CF2 group can also be replaced by -O- or-S-,
    are each independently 1,4-phenylene optionally substituted by up to four fluorine atoms or trans-1,4- cyclohexane,
    is a 1,4-phenylene optionally substituted by up to four fluorine atoms, with the proviso that at least one of the rings
    is a fluorinated 1,4-phenyl ene group.
    Z1 and Z2 are each independently -CH2CH2- or a single bond,
  2. 2. A compound of the formula I1
    in which R1 has the meaning given in claim 1.
  3. 3. A Compound of the formula 12
    in which R1 has the meaning given in claim 1.
  4. 4. A compound of the formula I3
    in which R1 has the meaning given in claim 1.
  5. 5- A compound of the formula I4
    in which R1 has the meaning given in claim 1.
  6. 6.
    in which R1 has the meaning given in claim 1.
  7. 7. Liquid crystalline medium comprising at least two liquid crystalline components characterized in that it contains at least one compound of the formula 1.
  8. 8. Liquid crystalline display element characterized in that it contains a liquid crystalline medium according to claim 7.
  9. 9. Electrooptical display element characterized in that it contains a liquid crystalline phase according to claim 7 as the dielectric.
GB9420920A 1994-06-30 1994-10-17 Benzene derivatives and a liquid-crystalline medium Expired - Lifetime GB2290787B (en)

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EP1054001A1 (en) * 1999-05-19 2000-11-22 MERCK PATENT GmbH Isothiocyanate tolanes and liquid crystal mixtures containing them
US6569505B2 (en) * 2000-02-14 2003-05-27 MERCK Patent Gesellschaft mit beschränkter Haftung Liquid crystal compounds, liquid crystal medium and liquid crystal display
EP1352943A1 (en) * 2002-04-12 2003-10-15 MERCK PATENT GmbH Liquid crystalline medium and electrooptical display containing it
US9951089B2 (en) 2010-02-03 2018-04-24 Infinity Pharmaceuticals, Inc. Methods of treating a fatty acid amide hydrolase-mediated condition
CN113265261A (en) * 2021-05-27 2021-08-17 苏州汉朗光电有限公司 Liquid crystal composition and liquid crystal display

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JO3598B1 (en) 2006-10-10 2020-07-05 Infinity Discovery Inc Boronic acids and esters as inhibitors of fatty acid amide hydrolase

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EP1352943A1 (en) * 2002-04-12 2003-10-15 MERCK PATENT GmbH Liquid crystalline medium and electrooptical display containing it
EP1798273A2 (en) * 2002-04-12 2007-06-20 Merck Patent GmbH Liquid crystalline medium and electrooptical display containing it
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EP1840186A3 (en) * 2002-04-12 2008-03-12 MERCK PATENT GmbH Liquid crystalline medium and electrooptical display containing it
EP2251397A3 (en) * 2002-04-12 2011-05-25 Merck Patent GmbH Liquid crystalline medium and electrooptical display containing it
US9951089B2 (en) 2010-02-03 2018-04-24 Infinity Pharmaceuticals, Inc. Methods of treating a fatty acid amide hydrolase-mediated condition
CN113265261A (en) * 2021-05-27 2021-08-17 苏州汉朗光电有限公司 Liquid crystal composition and liquid crystal display

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