GB2367058A - Acetylenic biphenyl derivatives & their use as liquid crystalline components - Google Patents
Acetylenic biphenyl derivatives & their use as liquid crystalline components Download PDFInfo
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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
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
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- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
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- 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
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Abstract
Acetylene derivatives of the formula I <EMI ID=1.1 HE=33 WI=136 LX=332 LY=660 TI=CF> <PC>[in which <DL TSIZE=16> <DT>R<SP>1</SP>, R<SP>2</SP><DD>independently of one another are H, an alkyl radical (which is unsubstituted or at least monosubstituted by halogen) or CN, and in which, in addition, one or more CH<SB>2</SB> groups may each, independently of one another, be replaced by -O-, -C I C- or -CH=CH- in such a way that heteroatoms are not connected directly; <DT>L<SP>1</SP>, L<SP>2</SP>, L<SP>3</SP>, L<SP>4</SP>,<DD>independently of one another are H or F; <DT>L<SP>5</SP>, L<SP>6</SP><DD> <DT>Z<DD>is -C I C-, -CH<SB>2</SB>CH<SB>2</SB>- or a single bond; <DT>n, m, p<DD>independently of one another are 0 or 1, provided that n+m * 0] </DL> frequently have highly positive values of the optical anisotropy W n with moderate values of the dielectric anisotropy We and relatively low viscosity and can be used as components of liquid-crystalline media, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of aligned phases (DAP) or electrically controlled birefringence (ECB) or the effect of dynamic scattering.
Description
Acetylene derivatives and liquid-crystalline medium
The invention relates to acetylene derivatives of the formula I
in which R', R2 independently of one another are H, an alkyl radical having 1-12 carbon atoms which is unsubstituted or at least monosubstituted by halogen or CN and in which, in addition, one or more CH2 groups may each, independently of one another, be replaced by -O-, -C#C- or -CH=CH- in such a way that heteroatoms are not connected directly,
2 3 4 L1, L2, L3, L4, independently of one another are H or F 5 6 L5 L6 Z is-C=C-,-CH2CH2-or a single bond, n, m, p independently of one another are 0 or 1, provided that n+mO.
The invention also relates to the use of the compounds of the formula I as components of liquid-crystalline media, and to liquid-crystal and electro-optical display elements which contain the liquid-crystalline media according to the invention.
The compounds of the formula I frequently have highly positive values of the optical anisotropy An with moderate values of the dielectric anisotropy As and relatively low viscosity and can be used as components of liquid-crystalline media, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of aligned phases (DAP) or electrically controlled birefringence (ECB) or the effect of dynamic scattering.
The substances employed hitherto for this purpose all have certain disadvantages, for example inadequate stability to the action of heat, light or electric fields, or unfavourable elastic and/or dielectric properties.
The invention had the object of finding novel, stable, liquid-crystalline or mesogenic compounds of particularly high positive dielectric anisotropy and moderate to high optical anisotropy at the same time as low viscosity which are suitable as components of liquid-crystalline media, in particular for TN, TFT and
STN displays.
It has now been found that the compounds of the formula I are eminently suitable as components of liquid-crystalline media. They can be used to obtain stable liquid-crystalline media, in particular suitable for TFT or STN displays. The novel compounds are distinguished, in particular, by high thermal stability, which is advantageous for a high"holding ratio", and exhibit favourable clearing point values.
The provision of compounds of the formula I very generally considerably broadens the range of liquid-crystalline 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 range of applications. Depending on the choice of substituents, these compounds can serve as base materials of 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 compound in order, for example, to modify the dielectric and/or optical anisotropy of a dielectric of this type and/or to optimize its threshold voltage and/or its viscosity. Addition of compounds of the formula I to liquid-crystalline dielectrics allows the An values and As values of such media to be significantly affected.
The meaning of the formula I covers all isotopes of the chemical elements bound in the compounds of the formula 1. In enantiomerically pure or enriched form, the compounds of the formula I are also suitable as chiral dopants and in general for producing chiral mesophases.
In the pure state, the compounds of the formula I are colourless and form liquidcrystalline mesophases in a temperature range which is favourably located for electro-optical 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 comprising at least one compound of the formula 1, and to liquid-crystal display elements, in particular electro-optical display elements, which contain media of this type.
2 2 3 4 6 Above and below, R', R2, Z, L\ L, L3, L, L5, L6, m, n, and p are as defined above, unless expressly stated otherwise.
The following group of compounds of the sub-formulae IA to IF represents preferred embodiments of the invention:
in which R1, R2, Z, m and n are as defined above.
If R and/or R2 in the formulae above and below is an alkyl 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 is preferably ethyl, propyl, butyl, pentyl, hexyl or heptyl, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl or pentadecyl.
If f R1 and/or R2 is an alkyl radical in which one CH2 group has been replaced by - 0-, this can be straight-chain or branched. It is preferably straight-chain and has 1 to 10 carbon atoms. Preferably, the first CH2 group of this alkyl radical has been replaced by-0-, so that the radical R1 becomes alkoxy and is preferably methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy or nonyloxy.
Furthermore, one CH2 group elsewhere can also be replaced by-0-, so that the radical R and/or R2 is preferabiy 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-oxaheptyl, 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 R and/or R2 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 is in particular vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-2, -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-eny), non-1-,-2-,-3-,-4-,-5-,-6-,-7-or-8-eny !, or dec-1-,-2-,-3-,-4-, - 5-,-6-,-7-,-8-or-9-eny).
R1 and/or R2 is particularly preferably an alkenyl radical from the following group:
If R and/or R2 is an alkenyloxy radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. It is particularly preferably a radical from the following group:
If R1and/or R2is an alkyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain. Halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resultant radicals also include perfluorinated radicals. In the case of monosubstitution, the fluorine or chlorine substituent can be in any desired position, but is preferably in the o-position.
If R1 and/or R2 is an alkynyl radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Accordingly, it is in particular ethynyl, prop-1-or-2-ynyl, but-1-,-2-or-3-ynyl, pent-1-,-2-,-3-or-4 ynyl, hex-1-,-2-,-3-,-4-or-5-ynyl, hept-1-,-2-,-3-,-4-,-5-or-6-ynyl, oct-1-, -2-,-
3-,-4-,-5-,-6-or-7-ynyl, non-1-,-2-,-3-,-4-,-5-,-6-,-7-or-8-ynyl, or dec-1-,-2-,3-,-4-,-5-,-6-,-7-,-8-or-9-ynyl. Compounds of the formula I containing a branched wing group R'and/or R2 may occasionally be of importance owing to better solubility in the customary liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Smectic compounds of this type are suitable as components of ferroelectric materials.
Branched groups of this type generally contain not more than one chain branch.
Preferred branched radicals R'are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl,
3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexyloxy, 1-methylhexyloxy or 1-methylheptyloxy.
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, preference is given to those in which at least one of the radicals present therein has one of the preferred meanings indicated.
Further preferred compounds of the formula I are indicated below :
Compounds of the formula I wherein m is 0 and whose R1 group is an alkyl, oxaalkyl or alkoxy radical having 1 to 10 carbon atoms or an alkenyl radical having 2 to 10 carbon atoms.
Compounds of the formula I wherein m+n is 1.
Compounds of the formula I wherein p is 1.
Compounds of formula I in which each of the aromatic rings, independently of one another, is unsubstituted or mono-substituted by fluorine.
Compounds of the formula I in which Z is a single bond.
Compounds of formula 1, wherein at least one of the aromatic rings is monostubstituted by fluorine.
Some very particularly preferred smaller groups of compounds of the formula I are those of the sub-formulae 11 to 120 :
in which R 1 and R2 are as defined above.
Very particularly preferred compounds from this group are those of the formulae I1, I2,I7,I8 and I12.
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 Chemistry], Georg
Thieme-Verlag, Stuttgart), to be precise, under reaction conditions which are known and suitable for said reactions.
Use can be made here of variants which are known per se, but are not mentioned here in greater detail.
The starting materials can, if desired, also be formed in situ by not isolating them from the reaction mixture, but instead immediately converting them further into the compounds of the formula 1. The compounds according to the invention can be prepared, for example, as shown in the following reaction scheme:
Scheme 1
In a further process for the preparation of compounds of the formula I in which R1 and/or R2 is alkenyl, an aryl halide is reacted with an olefin in the presence of a tertiary amine and in the presence of a palladium catalyst (R. F. Heck, Acc. Chem.
Res. 12 (1979) 146). Examples of suitable aryl halides are chlorides, bromides and iodides, in particular bromides and iodides. The tertiary amines necessary for the success of the coupling reaction, such as, for example, triethylamine, are also suitable as solvent. Examples of suitable palladium catalysts are its salts, in particular Pd (tut) acetate, wirh organophosphorus (lil) compounds, such as, for example, triarylphosphines. This process can be carried out in the presence or absence of an inert solvent at temperatures between about 0 C and 150oC, preferably between 20 C and 100oC ; suitable solvents are, for example, nitriles, such as acetonitrile, or hydrocarbons, such as benzene or toluene. The aryl halides and olefins employed as starting materials are frequently commercially available and can be prepared by processes known from the literature, for example by halogenation of corresponding parent compounds or by elimination reactions on corresponding alcohols or halides.
Ethers of the formula I are obtainable by etherification of corresponding hydroxyl compounds, preferably corresponding phenols, the hydroxyl compound advantageously first being converted into a corresponding metal derivative, for example into the corresponding alkali metal alkoxide or alkali metal phenoxide, by treatment with NaH, NaNH2, NaOH, KOH, Na2CO3 or K2CO3. This metal derivative can then be reacted with the appropriate alkyl halide, alkyl sulfonate or dialkyl sulfate, advantageously in an inert solvent, such as, for example, acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide, or alternatively with an excess of aqueous or aqueous-alcoholic NaOH or KOH, at temperatures between about 20'C and 100*C.
In order to prepare the laterally substituted fluorine or chlorine compounds of the formula 1, corresponding aniline derivatives can be reacted with sodium nitrite and either with tetrafluoroboric acid (in order to introduce an F atom) or with copper (l) chloride (in order to introduce a chlorine atom), to give the diazonium salts, which are then decomposed thermally at temperatures of 100-140 The organometallic compounds are prepared, for example, by metal-halogen exchange (for example in accordance with Org. React. 6, 339-366 (1951) ) between the corresponding halogen compound and an organolithium compound, such as, preferably, tert-butyllithium or lithium naphthalenide, or by reaction with magnesium turnings.
The linking of an aliphatic group R1 to an aromatic ring is preferably carried out by
Friedel-Crafts alkylation or acylation by reacting the corresponding aromatic compounds with Lewis acid catalysis. Examples of suitable Lewis acids are Suc14, ZnC12 and in particular AICb and Tic4.
In addition, the compounds of the formula I can be prepared by reducing a compound which contains one or more reducible groups and/or C-C bonds in place of H atoms, but otherwise conforms to the formula 1.
Suitable reducible groups are preferably carbonyl groups, in particular keto groups, furthermore, for example, free or esterified hydroxyl groups or aromatically bonded halogen atoms. Preferred starting materials for the reduction are compounds which conform to the formula 1, but contain a-CH=CH-group in place of a-CH2CH2-group and/or contain a-CO-group in place of a-CH2-group and/or contain a free or functionally derived (for example in the form of its p-toluenesulfonate) OH group in place of an H atom.
The reduction can be carried out, for example, by catalytic hydrogenation at temperatures between about 00 and about 2000 and at pressures between about 1 and 200 bar in an inert solvent, for example an alcohol, such as methanol, ethanol or isopropanol, an ether, such as tetrahydrofuran (THF) or dioxane, an ester, such as ethyl acetate, a carboxylic acid, such as acetic acid, or a hydrocarbon, such as cyclohexane. Suitable catalysts are advantageously noble metals, such as Pt or Pd, which may be employed in the form of oxides (for example PtO2 or PdO), on a support (for example Pd on carbon, calcium carbonate or strontium carbonate) or in finely divided form.
Ketones can also be reduced by the methods of Clemmensen (using zinc, zinc amalgam or tin and hydrochloric acid, advantageously in aqueous-alcoholic solution or in the heterogeneous phase with water/toluene at temperatures between about 80 and 120 C) or Wolff-Kishner (using hydrazine, advantageously in the presence of alkali, such as KOH or NaOH, in a high-boiling solvent, such as diethylene glycol or triethylene glycol, at temperatures between about 100 and 2000C) to give the corresponding compounds of the formula I which contain alkyl groups and/or CH2CH2-bridges.
Furthermore, reductions using complex hydrides are possible. For example, arylsulfonyloxy groups can be removed reductively using LiAIH4, in particular p-toluenesulfonyloxymethyl groups can be reduced to methyl groups, advantageously in an inert solvent, such as diethyl ether or THF, at temperatures between about 0 and 1000C. Double bonds can be hydrogenated using NaBH4 or tributyltin hydride in methanol.
The starting materials are either known or can be prepared analogously to known compounds.
The liquid-crystalline media according to the invention preferably comprise from 2 to 40 components, in particular from 4 to 30 components, as further constituents besides one or more compounds according to the invention. These media very particularly preferably comprise from 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 or of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes, 1, 4-bis-cyclohexylbenzenes, 4,4'-biscyclohexylbiphenyls, phenyl-or cyclohexylpyrimidines, phenyl-or cyclohexylpyridines, phenyl-or cyclohexyldioxanes, phenyl-or cyclohexyl-1, 3 dithianes, 1, 2-diphenylethanes, 1, 2-dicyclohexylethanes, 1-phenyl-2cyclohexylethanes, 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 1,4phenylen 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-C=C-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 fluorine-substituted 1, 4-phenylen, Cyc is trans-1, 4-cyclohexylen or 1, 4-cyclohexylene, Pyr is pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, Dio is 1,3-dioxane-2, 5-diyl and G is 2- (trans1, 4-cyclohexyl) 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 comprise 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 consisting of 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 consisting of Cyc, Phe and Pyr and the other radical is selected from the group consisting of-Phe-Phe-, -Phe-Cyc-,-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 consisting of-Phe Cyc-, -Cyc-Cyc-,-G-Phe-and-G-Cyc-.
In a smaller sub-group of the compounds of the formulae 1,2, 3,4 and 5, R' and R" are each, independently of one another, alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. This smaller sub-group is called group
A below, and the compounds are denoted by the sub-formulae 1 a, 2a, 3a, 4a and 5a. In most of these compounds, R'and R"are different from one another, one of these radicals usually being alkyl, alkenyl, alkoxy or alkoxyalkyl.
In another smaller sub-group of the compounds of the formulae 1,2, 3,4 and 5, which is called group B, R"is-F,-Cl,-NCS or- (O), CH3- (k+!) FkCII, where i is 0 or 1, and k and I are 1,2 or 3; the compounds in which R"has this meaning are denoted by the sub-formulae 1 b, 2b, 3b, 4b and 5b. Particular preference is given to those compounds of the sub-formulae 1b, 2b, 3b, 4b and 5b in which R"is-F,-Cl,-NCS,
- CF3.-OCHF2or-OCF3. In the compounds of the sub-formulae 1 b, 2b, 3b, 4b and 5b, R'is as defined for the compounds of the sub-formulae 1a-5a and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
In a further smaller sub-group of the compounds of the formulae 1,2, 3,4 and 5, R" is-CN; this sub-group is called group C below, and the compounds of this sub-group are correspondingly described by sub-formulae 1c, 2c, 3c, 4c and 5c. In the compounds of the sub-formulae 1 c, 2c, 3c, 4c and 5c, R'is as defined for the compounds of the sub-formulae 1a-5a and is preferably alkyl, alkoxy or alkenyl.
In addition to the preferred compounds of groups A, B and C, other compounds of the formulae 1,2, 3,4 and 5 having other variants of the proposed substituents are also customary. All these substances can be obtained by methods which are known from the literature or analogously thereto.
Besides compounds of the formula I according to the invention, the media according to the invention preferably comprise one or more compounds selected from group A and/or group B and/or group C. The proportions by weight of the compounds from these groups in the media according to the invention are preferably:
Group A: 0 to 90%, preferably 20 to 90%, in particular 30 to 90%
Group B: 0 to 80%, preferably 10 to 80%, in particular 10 to 65%
Group C: 0 to 80%, preferably 5 to 80%, in particular 5 to 50%, the sum of the proportions by weight of the group A and/or B and/or C compounds present in the particular media according to the invention preferably being 5%-90% and in particular from 10% to 90%.
The media according to the invention preferably comprise from 1 to 40%, particularly preferably from 5 to 30%, of the compounds according to the invention. Further preferred media are those which comprise more than 40%, in particular from 45 to 90%, of compounds according to the invention. The media preferably comprise 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, advantageously at elevated temperature. By means of suitable additives, the liquid-crystalline phases can be modified in accordance with the invention in such a manner that they can be used in all types of liquid-crystal display elements which have been disclosed hitherto. Additives of this type are known to those 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 can be added for the production of coloured guest-host systems, or substances can be added to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases.
The examples below are intended to illustrate the invention without representing a limitation. Above and below, percentages are percent by weight. All temperatures are given in degrees Celsius. m. p. denotes melting point, cl. p. = clearing point, Tg = glass transition temperature. Furthermore, C = crystalline state, N = nematic phase, Sm = smectic phase and I = isotropic phase. The numbers between these symbols indicate the conversion temperatures. An denotes the optical anisotropy (589 nm, 200C) and As the dielectric anisotropy (1 kHz, 20 C). The An and As values of the compounds according to the invention were obtained by extrapolation from liquidcrystalline mixtures consisting of 10% of the particular compound according to the invention and 90% of the commercially available liquid crystal ZLI 4792 (Merck,
Darmstadt).
The viscosity (mm2/sec) was determined at 20oC.
"Conventional work-up"means that water is added if necessary, the mixture is extracted with methylene chloride, diethyl ether or toluene, the phases are separated, the organic phase is dried and evaporated, and the product is purified by distillation under reduced pressure or crystallization and/or chromatography.
The following abbreviations are used:
THF tetrahydrofuran
KOtBu potassium tert-butoxide
RT room temperature
MTB ether methyl tert-butyl ether
Example 1
A mixture of 2. 0 g of 4"-Bromo-2', 2"-difluoro-4-pentyl-[1, 1' ; 4', terphenyl 1, 5. 0 g of pentyne, 0. 020 g of bis (triphenylphosphine)-palladium ( !))-chloride, 0. 054 g of copper (l) iodide and 50 ml of triethylamine was stirred overnight at 40 OC (reflux of pentyne). The mixture was allowed to cool and was subsequently subjected to conventional work-up, giving 2', 2"-Difluoro-4-pentyl-4"-pent-1-ynyl- [1, 1', 4', 1"]terphenyI2 (K67 N 124 I, ## = 1. 9, An = 0.3138).
The following examples can be prepared analogously :
Examples 2-24
R3-0-Z R4 (2) n-propyl F 1-propynyl zu (3) n-propyl-0--1-pentynyl (4) n-pentyl 4 propynyl F (5) 1-propynyl-1-propynyl - 0- (6) 1-pentynyl-1-pentynyl - 0- (7) n-propyl -CH2CH2-1-propynyl (8) n-pentyl -CH2CH2-1-propynyl --D (9) 1-propynyl -CH2CH2-1-propynyl -D (10) 1-pentynyl ',-C*C-1-pentynyl (11) n-propyl-0--1-propynyl (12) n-propyl 1-pentynyl (K 73 N 131 I, Ag = 2. 3, An = 0. 3192) (13) n-pentyl-0--1-propynyl
(14) 1-propynyl-0--1-propynyl (15) 1-pentynyl-0--1-pentynyl (16) n-propyl-CH2CH2-1-propynyl (17) n-pentyl-CH2CH2-1-propynyl (18) 1-propynyl-0--CH2CH2-1-propynyl (19) 1-pentynyl-C=-C-1-pentynyl (20) n-propyl--1-propynyl (21) n-propyl--1-pentynyl (22) n-pentyl--1-propynyl (23) 1-propynyl--1-propynyl (24) 1-pentynyl--1-pentynyl Examples 25-46
R3 {+ Z R4 (25) n-propyl \-1-propynyl F (26) n-propyl \,-1-pentynyl (27) n-pentyl \-1-propynyl F (28) 1-propynyl)-1-pentynyl F (29) n-propyl -CH2CH2-1-propynyl
(30) n-pentyl \-CH2CH2-1-propynyl (31) 1-propynyl ! --D (32) 1-pentynyl F-C=C-1-pentynyl - 0 (33) n-propyl-0--1-propynyl (34) n-propyl-0--1-pentynyl (35) n-pentyl-0--1-propynyl (36) 1-propynyl-0--1-propynyl (37) 1-pentynyl-0--1-pentynyl (38) n-propyl-AA-.-CH2CH2-1-propynyl (39) n-pentyl-CH2CH2-1-propynyl (40) 1-propynyl-CH2CH2-1-propynyl (41) 1-pentynyl-0--C=C-1-pentynyl (42) n-propyl--1-propynyl (43) n-propyl--1-pentynyl (44) n-pentyl--1-propynyl (45) 1-propynyl--1-propynyl (46) 1-pentynyl--1-pentynyl
Examples 47-69
R3-0-Z R4 (47) n-propyl F 1-propynyl - 0- (48) n-propyl \-1-pentynyl - 0- (49) n-pentyl \-1-propynyl - 0- (50) 1-propyny ! \-1-propynyt - 0- (51) 1-pentynyl F 1-pentynyl - 0- (52) n-propyl F-CH2CH2-1-propynyl - \. ) (53) n-pentyl F-CH2CH2-1-propynyl - 0 (54) 1-propynyl F-CH2CH2-1-propynyl - zu (55) 1-pentynyl 1-pentynyl - 0 (56) n-propyl 1-propynyl (57) n-propyl-0--1-pentynyl (58) n-pentyl-0--1-propynyl (59) 1-propynyl-0--1-propynyl (60) 1-pentynyl-0--1-pentynyl
(61) n-propyl-Y\--CH2CH2-1-propynyl (62) n-pentyl-0--CH2CH2-1-propynyl (63) 1-propynyl-0--CH2CH2-1-propynyl (64) 1-pentynyl-o\-C=C-1-pentynyl (65) n-propyl--1-propynyl (66) n-propyl--1-pentynyl (67) n-pentyl--1-propynyl (68) 1-propynyl--1-propynyl (69) 1-pentynyl--1-pentynyl
Claims (13)
1. An acetylene derivative of the formula I :
in which R1, R2 independently of one another are H, an alkyl radical having 1-12 carbon atoms which is unsubstituted or at least monosubstituted by halogen or CN and in which, in addition, one or more CH2 groups may each, independently of one another, be replaced by-0-,-CC or-CH=CH-in such a way that heteroatoms are not
connected directly, 2 3 L1, L2, L3, independently of one another are H or F L4, L5 L6 Z is-C=C-or a single bond, n, m, p independently of one another are 0 or 1, provided that n + m # 0.
2. An acetylene derivative ester as claimed in claim 1, wherein m is 0 and R1 is an alkyl, oxaalkyl or alkoxy radical having 1 to 10 carbon atoms or an alkenyl radical having 2 to 10 carbon atoms.
3. An acetylene derivative as claimed in claim 1 or claim 2, wherein m + n is 1.
4. An acetylene derivative as claimed in any of claims 1 to 3, wherein pis 1.
5. An acetylene derivative as claimed in any of claims 1 to 3, wherein each of the aromatic rings independently of one another, is unsubstituted or mono-substituted by fluorine.
6. An acetylene derivative as claimed in any of the preceding claims, wherein at least one of the aromatic rings is mono-substituted by fluorine.
7. An acetylene derivative as claimed in any of the preceding claims, in which Z is a single bond.
8. An acetylene derivative of the formulae IA to IF:
1 2 in which R, R2, Z m and n are as defined in claim 1.
9. An acetylene derivative substantially as hereinbefore described in the foregoing examples.
10. Use of a compound of the formula I as claimed in any of claims 1 to 9 as components of liquid-crystalline media.
11. A liquid-crystalline medium having at least two liquid-crystalline components, wherein it comprises at least one compound of the formula 1.
12. A liquid-crystal display element, wherein it contains a liquidcrystalline medium as claimed in claim 11.
13. An electro-optical display element, wherein it contains, as dielectric, a liquid-crystalline medium as claimed in claim 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00114151 | 2000-07-12 |
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| GB0115694D0 GB0115694D0 (en) | 2001-08-22 |
| GB2367058A true GB2367058A (en) | 2002-03-27 |
| GB2367058B GB2367058B (en) | 2004-07-14 |
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| GB0115694A Expired - Fee Related GB2367058B (en) | 2000-07-12 | 2001-06-27 | Acetylene derivatives and liquid-crystalline medium |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1346995A1 (en) * | 2002-03-15 | 2003-09-24 | MERCK PATENT GmbH | Process for the preparation of ring compounds |
| WO2005007775A1 (en) * | 2003-07-11 | 2005-01-27 | Merck Patent Gmbh | Liquid-crystal medium containing monofluoroterphenyl compounds |
| CN107109221A (en) * | 2014-12-19 | 2017-08-29 | 默克专利股份有限公司 | Double mesomorphic compounds and mesogenic media |
| CN107636114A (en) * | 2015-07-02 | 2018-01-26 | Dic株式会社 | Liquid-crystal composition and use its liquid crystal display cells |
| CN113604227A (en) * | 2021-08-06 | 2021-11-05 | 南昌虚拟现实研究院股份有限公司 | Liquid crystal medium, preparation method thereof and liquid crystal lens |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113773226B (en) * | 2021-08-06 | 2023-12-08 | 南昌虚拟现实研究院股份有限公司 | Process for producing cyanopropyne derivative, liquid crystal medium and liquid crystal lens |
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| EP0377516A2 (en) * | 1989-01-06 | 1990-07-11 | Chisso Corporation | Liquid crystal compounds having high optical anisotropy |
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| EP2332944A3 (en) * | 2002-03-15 | 2011-11-16 | Merck Patent GmbH | Process for the preparation of ring compounds |
| US7786332B2 (en) | 2002-03-15 | 2010-08-31 | Merck Patent Gmbh | Process for the preparation of ring compounds |
| US7183447B2 (en) | 2002-03-15 | 2007-02-27 | Merck Patent Gmbh | Process for the preparation of ring compounds |
| US8350100B2 (en) | 2002-03-15 | 2013-01-08 | Merck Patent Gmbh | Process for the preparation of ring compounds |
| EP1346995A1 (en) * | 2002-03-15 | 2003-09-24 | MERCK PATENT GmbH | Process for the preparation of ring compounds |
| EP2103589A1 (en) * | 2002-03-15 | 2009-09-23 | Merck Patent GmbH | Polypenylenes as liquid crystals |
| US8124817B2 (en) | 2002-03-15 | 2012-02-28 | Merck Patent Gmbh | Process for the preparation of ring compounds |
| US7842845B2 (en) | 2002-03-15 | 2010-11-30 | Merck Gmbh | Process for the preparation of ring compounds |
| US7411100B2 (en) | 2002-03-15 | 2008-08-12 | Merck Gmbh | Process for the preparation of ring compounds |
| WO2005007775A1 (en) * | 2003-07-11 | 2005-01-27 | Merck Patent Gmbh | Liquid-crystal medium containing monofluoroterphenyl compounds |
| US7390538B2 (en) | 2003-07-11 | 2008-06-24 | Merck Patent Gmbh | Liquid-crystal medium containing monofluoroterphenyl compounds |
| CN107109221A (en) * | 2014-12-19 | 2017-08-29 | 默克专利股份有限公司 | Double mesomorphic compounds and mesogenic media |
| JP2018501248A (en) * | 2014-12-19 | 2018-01-18 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Bimesogenic compounds and mesogenic media |
| CN107109221B (en) * | 2014-12-19 | 2021-03-12 | 默克专利股份有限公司 | Bimesogenic compounds and mesogenic media |
| CN107636114A (en) * | 2015-07-02 | 2018-01-26 | Dic株式会社 | Liquid-crystal composition and use its liquid crystal display cells |
| CN113604227A (en) * | 2021-08-06 | 2021-11-05 | 南昌虚拟现实研究院股份有限公司 | Liquid crystal medium, preparation method thereof and liquid crystal lens |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0115694D0 (en) | 2001-08-22 |
| GB2367058B (en) | 2004-07-14 |
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