EP0370081A1 - Composes cycliques chiraux ou achiraux - Google Patents

Composes cycliques chiraux ou achiraux

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Publication number
EP0370081A1
EP0370081A1 EP89904055A EP89904055A EP0370081A1 EP 0370081 A1 EP0370081 A1 EP 0370081A1 EP 89904055 A EP89904055 A EP 89904055A EP 89904055 A EP89904055 A EP 89904055A EP 0370081 A1 EP0370081 A1 EP 0370081A1
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Prior art keywords
groups
compounds
ester
group
formula
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EP89904055A
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German (de)
English (en)
Inventor
Andreas WÄCHTLER
Klaus-Peter Stahl
Reinhard Hittich
Thomas Geelhaar
Volker Reiffenrath
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/63—Halogen-containing esters of saturated acids
    • 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
    • C09K19/34—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
    • C09K19/3444—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 one nitrogen atom, e.g. pyridine
    • 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
    • C09K19/126—Compounds containing at least one asymmetric carbon atom
    • 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
    • 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
    • C09K19/34—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
    • C09K19/3463—Pyrimidine with a carbon chain containing at least one asymmetric carbon atom, i.e. optically active pyrimidines

Definitions

  • the invention relates to chiral or achiral ring compounds of the formula I.
  • a 1 and A 2 each independently of one another 1,4-phenylene which is unsubstituted or substituted by one or two F and / or CH 3 groups and / or CN groups, in which one or two CH groups can also be replaced by N, 1,4-cyclohexylene, which is also a or two non-adjacent CH 2 groups can be replaced by O atoms and / or S atoms, 1- (4-) cyano-1,4-cyclohexylene, a piperidine-1,4-diyl, 1,4- Bicyclo (2,2,2) octylene-, 1,3,4-thiadiazole-2,5-diyl-, naphthalene-2,6-diyl-, decahydronaphthalene-2,6-diyl- or 1,2,3, 4- tetrahydronaphthalene-2,6-diyl group,
  • Z 1 in each case -CO-O-, -O-CO-, -CH 2 CH 2 -, -OCH 2 -, -CH 2 O-, -C ⁇ C- or a single bond,
  • C * is a carbon atom linked to four different substituents
  • Q 1 -O-, -O-CO-, -CO-O- or a single bond in the event that at least one of the rings A 1 and A 2 is substituted by one or two F atoms or 1,4-phenylene or A 1 unsubstituted 1,4-phenylene, in which a CH group is replaced by N, also means -O- (CH 2 ) n -, -O-CO- (CH 2 ) n - or -CO-O- (CH 2 ) n , where n is 1, 2, 3 or 4, and
  • R ° is an alkyl group other than X with 1 to 10 C atoms, or, if Q denotes a single bond, also an alkoxy or alkanoyloxy group each with 1 to 10
  • X means CH 3 when Q 1 is -O-CO- and b) Q 1 , -O-, -O-CO- or a single bond and / or R 1 -Q 1 -C * R ° CF 3 -X means and / or X means CH 3 if m is 1 or 2 , Z is -CO-O- or a single bond and the groups A 1 and A 2 are unsubstituted 1,4-phenylene.
  • the compounds of the formula I can be used as components of chiral-tapped smectic liquid-crystalline phases.
  • Chiral-chopped smectic liquid-crystalline phases with ferroelectric properties can be produced by adding a suitable chiral dopant to basic mixtures with one or more chased smectic phases (LA Beresnev et al., Mol. Cryst. Liq. Cryst. 89, 327 (1982 HR Brand et al., J. Physique 44, (lett.), L-771 (1983), such phases 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, Appl. Phys. Lett. 36, 899 (1980); USP 4,367,924) on the basis of the ferroelectric properties of the chiral-tinted phase.
  • the elongated phase is in this phase
  • the molecules having a tilt angle to the layer normal.
  • the tilt direction changes by a small angle with respect to an axis perpendicular to the layers, so that a helical structure is formed.
  • the smectic layers are arranged perpendicular to the plates of the cell.
  • the helical arrangement of the tilt directions of the molecules is suppressed by a very small distance between the plates (approx. 1-2 ⁇ m). This forces the long axes of the molecules to line up in a plane parallel to the plates of the cell, creating two excellent tilt orientations.
  • a major disadvantage for many applications of the currently available materials with chiral-chopped smectic phases is their relatively high optical anisotropy, the switching times which are not sufficiently short due to relatively high viscosity values, and that the dielectric anisotropy values are greater than zero or if negative, has little nonzero values. Negative values of the dielectric anisotropy are required if the required planar orientation is brought about by superimposing the control field with an AC holding field with a small amplitude (J.M. Geary, SID Conference, Orlando / Florida, April / May 1985, Lecture 8.3).
  • the compounds of the formula I are therefore particularly suitable as components of chiral-chopped smectic liquid-crystalline phases.
  • chemically particularly stable chiral-chopped smectic liquid-crystalline phases with favorable ferroelectric phase ranges, in particular with wide Sc * phase ranges, negative or also positive dielectric anisotropy, low optical anisotropy, favorable pitch height are lower Viscosity and for such phases high values for spontaneous polarization and very short switching times can be produced.
  • P is the spontaneous polarization in nC / cm 2 .
  • the compounds of formula I have a wide range of uses. Depending on the choice of the substituents, these compounds can serve as base materials from which liquid-crystalline phases 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 spontaneous polarization and / or the phase range and / or the tilt angle and / or the pitch and / or the Switching times of such a phase vary.
  • 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 phases.
  • the compounds of the formula I are colorless in the pure state and have favorable values of optical anisotropy. Some of the compounds of the formula I show liquid-crystalline mesophases in a temperature range which is favorably located for electro-optical use, but it is also possible to use isotropic or monotropically liquid-crystalline compounds of the formula I as components of chiral chopped smectic phases. They are very stable chemically, thermally and against light.
  • the invention thus relates to the compounds of the formula I and to the use of the compounds of the formula I as components of liquid-crystalline phases.
  • the invention also relates to chiral-chopped smectic liquid-crystalline phases containing at least one compound of the formula I having at least one carbon atom linked to four different substituents.
  • the invention further relates to such phases containing at least one compound of the formula I and to liquid-crystal display elements, in particular electro-optical display elements, which contain such phases.
  • Ph in the following means a 1,4-phenylene group in which one or two CH groups can also be replaced by N, Cy a 1,4-cyclohexylene group in which one or two non-adjacent CH 2 groups can also be replaced by O- Atoms can be replaced and Bi a bicyclo (2,2,2) octylene group.
  • the 1,4-phenylene group can be substituted by one or two F atoms and / or CH 3 and / or CN groups.
  • R 1 , m, A 1 , A 2 , Q 1 , X, R ° and Z 1 have the meaning given, unless expressly stated otherwise. Accordingly, the compounds of the formula I include, in particular, compounds of the sub-formula la (with two rings)
  • 3-fluorine or 2,3-difluorophenylene group are preferred, those in which Q is a group -O- (CH 2 ) n -, -O-CO- (CH 2 ) n - or -CO-O- (CH 2 ) n - means.
  • the preferred compounds of the formula Ia include those of the sub-formulas Ia1 to Ia4:
  • the preferred compounds of the formula Ib include those of the sub-formulas Ib1 to Ib9:
  • R ° is an alkyl group different from X and preferably having 1 to 7 C atoms are particularly preferred.
  • Q preferably denotes -O-CO- (where the carbonyl carbon atom is linked to the asymmetric C atom C *), -O-, -CO-O- (where this group is linked via the oxygen atom to the asymmetric C atom C * ) or a single bond (-).
  • R ° is an alkyl group other than X with preferably 1 to 7 C atoms, an alkoxy or an alkanoyloxy group with preferably 1 to 7 C each Atoms.
  • a 1 and A 2 are preferably Cy or Ph.
  • Ph preferably denotes a 1,4-phenylene (Phe), a 1 substituted once or twice by F, CN and / or CH 3 , 4-phenylene group (PheX) a pyrimidine-2,5-diyl- (Pyr), a pyridine-2,5-diyl- (Pyn), a pyrazine-3,6-diyl- or a pyridazine- 2,5- diyl group, particularly preferably Phe, PheX, Pyr or Pyn.
  • the compounds according to the invention preferably contain no more than one 1,4-phenylene group in which one or two CH groups are replaced by N.
  • Cy preferably represents a 1,4-cyclohexylene group.
  • one of the groups A 1 and A 2 is one in 1- or 4-position by CN sub means substituted 1,4-cyclohexylene group and the nitrile group is in the axial position, ie the group A 2 or A 2 has the following configuration:
  • -Ph-Ph- is particularly preferred.
  • -Ph-Ph- is preferably -Phe-Phe-, Phe-Pyr or Phe-Pyn.
  • the groups are particularly preferred
  • the groups Z each independently of one another preferably denote a single bond, in the second place preferably -O-CO-, -CO-O-, -C ⁇ C- or -CH 2 CH 2 - groups. Particular preference is given to compounds of the formulas I or of the partial formulas Ib1 to Ib9 in which one group is Z 1 -CH 2 CH 2 - and the other is -O-CO- or -CO-O-.
  • Q is -O-, -O-CO-, -CO-O- and a single bond.
  • Q 1 denotes a single bond and X is a hydrogen atom
  • the group adjacent to the asymmetric C atom C * means
  • a 2 preferably Cy.
  • Branched groups of this type usually contain no more than two chain branches.
  • R 1 is preferably a straight-chain group or a branched group with no more than one chain branch.
  • the radical R 1 can also be an optically active organic radical
  • the asymmetrical carbon atom is then preferably linked to two differently substituted carbon atoms, one hydrogen atom and one substituent selected from the group consisting of halogen (in particular F, Cl or Br), alkyl or alkoxy, each having 1 to 5 carbon atoms and CN.
  • the optically active organic radical preferably has the formula
  • Q 'alkylene with 1 to 5 C atoms, in which a CH 2 group which is not linked to X' is also replaced by -O-, -CO-, -O-CO-, -CO-O- or -CH CH- can be, or a single bond,
  • -CO-O - / - O-CO- or a single bond are particularly preferred.
  • Q ' is preferably -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or a single bond, particularly preferably a single bond.
  • CN is preferably CH 3 , -CN, F or Cl, particularly preferably CN or F.
  • R 5 is preferably straight-chain or branched alkyl having 1 to 10, in particular having 1 to 7, carbon atoms.
  • Preferred compounds of the formula I and Ia to Ic are those in which at least one of the radicals contained therein has one of the preferred meanings indicated.
  • Groups of the formulas 1, 5, 7, 9, 10, 11, 12, 13, 14, 22 and 39, in particular those of the formulas 5 and 7, are particularly preferred.
  • Some other preferred smaller group of compounds of formula I are those of sub-formulas B, C, D, E, F, G, H, J and K:
  • R 1 R °, A 1 and A 2 have the meaning given for formula I.
  • m is preferably 1 or 2.
  • - (A 1 ) m -A 2 - preferably means -
  • R 1 , R °, A 1 and n have the meaning given for formula I and Pyd a pyridine-2,5-diyl group and PheF a 2-fluoro-1,4-phenylene, a 3-fluoro-1,4 -phenylene or a 2,3-difluorophenylene group.
  • R 1 is preferably straight-chain alkyl or alkoxy having 5 to 12 carbon atoms.
  • R ° is preferably straight-chain or branched alkyl having 1 to 5 carbon atoms.
  • 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), and under reaction conditions that are known and suitable for the implementations mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail. 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.
  • the compounds of the formula I or suitable precursors for their preparation can be prepared by reducing a compound which otherwise corresponds to the formula I but contains one or more reducible groups and / or C-C bonds instead of H atoms.
  • the reduction can be carried out, for example, by catalytic hydrogenation at temperatures between about 0 ° and about 200 ° and 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.
  • 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.
  • an inert solvent for example an alcohol such as methanol, ethanol or isopropanol, an ether
  • Suitable catalysts are suitably noble metals such as Pt or Pd, which can be used in the form of oxides (for example PtO 2 , PdO), on a support (for example Pd on carbon, calcium carbonate or strontium carbonate) or in finely divided form.
  • Pt or Pd which can be used in the form of oxides (for example PtO 2 , PdO), on a support (for example Pd on carbon, calcium carbonate or strontium carbonate) or in finely divided form.
  • Ketones can also be prepared using the Clemmensen methods (with zinc, amalgamated zinc or tin and hydrochloric acid, expediently in an aqueous-alcoholic solution or in a heterogeneous phase with water / toluene at temperatures between about 80 and 120 °) or Wolff-Kishner (with hydrazine, expediently reduced 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 200 °) to the corresponding compounds of formula I which contain alkyl groups and / or -CH 2 CH 2 bridges .
  • Clemmensen methods with zinc, amalgamated zinc or tin and hydrochloric acid, expediently in an aqueous-alcoholic solution or in a heterogeneous phase with water / toluene at temperatures between about 80 and 120 °
  • Wolff-Kishner with hydrazine, expediently reduced in the presence of alkal
  • arylsulfonyloxy groups can be removed reductively with LiAlH 4 , in particular p-toluenesulfonyloxymethyl groups can be reduced to methyl groups, expediently in an inert solvent such as diethyl ether or THF at temperatures between about 0 and 100 °. Double bonds can be hydrogenated (even in the presence of CN groups!) With NaBH 4 or tributyltin hydride in methanol; for example, the corresponding cyclohexane derivatives are formed from 1-cyanocyclohexene derivatives.
  • Esters of the formula I can also be obtained 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, in particular, the acid halides, especially the chlorides and bromides, and also the anhydrides, for example also mixed anhydrides, azides or esters, in particular alkyl esters with 1 to 4 carbon 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 sulfoxides are particularly suitable 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.
  • an excess of an organic base e.g. Pyridine, quinoline or triethylamine can be used as a solvent for the esterification.
  • the esterification can also be carried out in the absence of a solvent, e.g. 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 with a free alcohol or phenol is usually 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, 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.
  • alkali metal hydroxides such as sodium or potassium hydroxide
  • alkali metal carbonates or hydrogen carbonates such as sodium 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.
  • a further preferred embodiment of the esterification consists in first converting the alcohol or the phenol into the sodium or potassium alcoholate or phenolate, for example by treatment with ethanolic sodium or potassium hydroxide solution, isolating it and together with sodium bicarbonate or potassium carbonate with stirring suspended in acetone or diethyl ether and this suspension mixed with a solution of the acid chloride or anhydride in diethyl ether, acetone or DMF, advantageously at temperatures between about -25 ° and + 20 °.
  • Dioxane derivatives or dithiane derivatives of the formula I are expediently prepared by reacting an appropriate aldehyde (or one of its reactive derivatives) with a corresponding 1,3-diol or a corresponding 1,3-dithiol (or one of its reactive derivatives), preferably in the presence an inert solvent such as benzene or toluene and / or a catalyst, for example a strong acid such as sulfuric acid, benzene or p-toluenesulfonic acid, at temperatures between 20 ° and about 150 °, preferably between 80 ° and 120 °.
  • Acetals are primarily suitable as reactive derivatives of the starting materials.
  • aldehydes and 1,3-diols or 1,3-dithiols mentioned and their reactive derivatives are known, and all of them can be prepared without difficulty from standard compounds of organic chemistry from compounds known from the literature.
  • the aldehydes can be obtained by oxidation of corresponding alcohols or by reduction of corresponding carboxylic acids or their derivatives, the diols by reduction of corresponding diesters and the dithiols by reaction of corresponding dihalides with NaSH.
  • Ethers of the formula I can be obtained by etherification of corresponding hydroxyl compounds, preferably corresponding phenols, the hydroxyl compound advantageously first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3 or K 2 CO 3 corresponding alkali metal alcoholate or alkali metal phenolate is converted.
  • optically active carboxylic acids can be prepared from the corresponding benzyl esters by hydrogenolytic cleavage.
  • benzyl esters are obtained by reacting the alcohols or phenols of the formula
  • corresponding chlorine or bromine compounds of the formula I or suitable precursors can also be reacted with a cyanide, advantageously with a metal cyanide such as NaCN, KCN or Cu 2 (CN) 2 , for example in Presence of pyridine in an inert solvent such as DMF or N-methylpyrrolidone at temperatures between 20 ° and 200 °.
  • a cyanide advantageously with a metal cyanide such as NaCN, KCN or Cu 2 (CN) 2
  • a metal cyanide such as NaCN, KCN or Cu 2 (CN) 2
  • optically active compounds of the formula I are obtained by using appropriate optically active starting materials and / or by separating the optical antipodes by means of chromatography using known methods.
  • the esterification can be carried out by one of the methods mentioned above. However, the DCC method given in the examples is preferably used.
  • optically active 2-trifluoromethylcarboxylic acids are obtained from the optically active dialkylated malonic half-esters according to US Pat. No. 4,187,381 by reaction with sulfur tetrafluoride and subsequent saponification of the ester.
  • optically active dialkylated 2-cyanocarboxylic acids produced according to DE-OS 36 38 026
  • sulfur tetrafluoride reducing the cyano group with e.g. Diisobutylaluminum hydride and subsequent oxidation give optically active 2-trifluoromethyl carboxylic acids.
  • optically active or dialkylated malonic half-esters can e.g. according to F. Bjorkling et al., Tetrahedron Letters by enzymatic cleavage of the corresponding malonic diesters, e.g. with pork liver esterase.
  • racemic malon half esters it is also possible to separate the racemic malon half esters by resolving racemates using optically active bases.
  • Ephedrine, quinine, threobase and dehydroabietylamine may be mentioned as preferred bases here.
  • a preferred embodiment of this racemate resolution is, after the desired diastereomer has been separated off, to convert the remaining one into the racemate by means of an intramolecular transesterification and to subject it to racemate resolution again. (see DE-OS 35 41 450).
  • Esters of the formula I in which Q 1 -CO-O- or R ° denotes an alkanoyloxy group can easily be obtained from the corresponding optically active 1-trifluoromethylalkan-1-ols by esterification with mesogenic carboxylic acids, for example of the formula R -
  • the esterification can be carried out by one of the methods mentioned above. However, the DCC method given in the examples is preferred.
  • the optically active 1-trifluoromethylalkan-1-ols can be obtained by reducing the corresponding trifluoromethylalkyl ketones with optically active reducing agents or enzymatically with dehydrogenases.
  • Optically active 1-trifluoroalkan-1-ols can also be obtained by enzymatic cleavage of the racemic 2-acetyloxy-1,1,1-trifuoralkanes with lipases according to J.T. Lin, T. Yamazaki, T. Kitazume J. Org. Chem., 52 3211-3217 (1987).
  • the trifluoromethyl ketones required as starting materials can e.g. according to E.T. McBee, O.R. Pierce, D.O. Meyer, J. Am. Chem. Soc, 77, 917 (1955) can be obtained by reacting lithium organylene or Grignard reagents with trifluoroacetic acid or its derivatives.
  • racemic 1-trifluoromethylalkan-1-ols can e.g. according to T. Kitazume et al., J. of Fluorine Chemistry, 24, 419 (1984) can also be obtained by reacting lithium organylene with trifluoroacetaldehyde.
  • the phases according to the invention contain at least one, preferably at least two compounds of the formula I.
  • Particular preference is given to chiral tutated smectic liquid-crystalline phases whose achiral base mixture contains, in addition to compounds of the formula I, at least one other component with a negative or small positive dielectric anisotropy.
  • the chirality is preferably partly or completely based on chiral compounds of the formula I.
  • These phases preferably contain one or two chiral compounds of the formula I.
  • achiral compounds of the formula I (for example in the form of a racemate) can also be used, in which case the Chirality of the phase is caused by other optically active compounds. If chiral
  • Q 1 and Q 2 each represent 1,4-phenylene, trans-1,4-cyclohexylene, 4,4'-biphenylyl, 4- (trans-4-cyclohexyl) phenyl, trans, trans-4,4'-bicyclohexyl or one of the groups Q 1 and Q 2 also a single bond.
  • Q 3 and Q 4 each represent 1,4-phenylene, 4,4'-biphenylyl or trans-1,4-cyclohexylene.
  • One of the groups Q 3 and Q 4 can also mean 1,4-phenylene, in which at least one
  • R '' ' is an optically active residue with an asymmetric carbon atom
  • the structure has preferably the formula
  • R 4 and R 5 are each preferably straight-chain or branched alkyl, alkoxy, alkanoyloxy or alkoxycarbonyl, each having 3 to 12 carbon atoms.
  • n is 0 or 1.
  • R 4 and R 5 each represent straight-chain alkyl or alkoxy each having 5 to 10 carbon atoms.
  • the compounds of the partial form in Vc, Vh and Vi are suitable as additives for lowering the melting point and are normally added to the base mixtures in an amount of not more than 5%, preferably 1 to 3%.
  • R 4 and R 5 in the compounds of the partial form in Vc, Vh and Vi are preferably straight-chain alkyl having 2 to 7, preferably 3 to 5, carbon atoms.
  • Another class of compounds suitable for lowering the melting point in the phases according to the invention is that of the formula wherein R 4 and R 5 have the preferred meaning given for Vc, Vh and Vi. with the preferred meanings mentioned above.
  • Particularly preferred components with negative dielectric anisotropy are the compounds with the structural element M or N described in WO 86-00529. Those of the formula VId are particularly preferred
  • alkyl is a straight-chain or branched alkyl group with preferably 3 to 10 carbon atoms and R 'has the meaning given above.
  • compounds according to formula VId in which one or both single bonds linking the rings are replaced by a group selected from -CH 2 CH 2 -, -O-CO- or -CO-O-.
  • Particularly preferred compounds of the formula VIc are those of the formula VIc ':
  • A is 1,4-phenylene or trans-1,4-cyclohexylene, Z ° CH or N and n is 0 or 1.
  • the compounds of formula I are also suitable as components of nematic liquid crystalline phases, e.g. to avoid reverse twist.
  • these liquid-crystalline media according to the invention preferably contain 2 to 40, in particular 4 to 30, components as further constituents.
  • These media very particularly preferably contain, in addition to one or more of the invention
  • Components 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 of cyclohexylbenzoic acid, cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl of
  • Benzylphenyl ether, tolanes and substituted cinnamic acids can also be fluorinated.
  • R'-LC CER "5
  • L and E which may be the same or different, each independently represent a bivalent radical from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe- Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -G-Phe- and -G-Cyc- as well as their mirror images formed group, whereby Phe unsubstituted or fluorine substituted 1,4-phenylene, Cyc trans- 1,4-cyclohexylene or 1,4-cyclohexenylene, pyr pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, dio 1,3-dioxane-2,5-diyl and G 2- (trans-1, 4-Cyclohexyl) ethyl, pyrimidine-2,5-diyl, pyridine
  • One of the radicals L and E is preferably Cyc, Phe or Pyr.
  • E is preferably Cyc, Phe or Phe-Cyc.
  • the media according to the invention preferably contain one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which L and E are selected from the group Cyc, Phe and Pyr and at the same time one or more components 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-C
  • 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 each other different, one of these radicals is usually alkyl or alkenyl.
  • R In the Compounds of the sub-formulas Ib, 2b, 3b, 4b and 5b mean R "-CN, -CF 3 , F, Cl or -NCS; R has the meaning given for the compounds of the sub-formulas 1a to 5a and is preferably alkyl or alkenyl.
  • R has the meaning given for the compounds of the sub-formulas 1a 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 which 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 Ib, 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. As a rule, 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 can be used in all types of liquid-crystal display elements which have hitherto become known.
  • 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,
  • pleochroic dyes can be added to produce colored guest-host systems or substances to change the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases.
  • 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.
  • optically active 2-methyl-2-trifluoromethyloctanoic acid prepared from the optically active 2-methoxy-2-hexylmalonic acid monomethyl ester with sulfur tetrafluoride and subsequent saponification with
  • optically active connections are made analogously:
  • 4-Ethyloxy-2 ', 3'-difluorobiphenyl-4'-ylcarboxylic acid (1-trifluoromethyloctyl) ester Analogously, 4-alkyl-2 ', 3'-difluorobiphenyl4'-ylcarboxylic acids (prepared from 4-alkyl-2', 3'-difluorobiphenylene by ortho-lithiation with n-butyllithium and
  • optically active 1- (2- (trans-4-nonylcyclohexyl) ethyl) -4- (4- (2-methyl-2-trifluoromethyloctanoyloxy) benzoyloxy) benzene is obtained.
  • optically active connections are made analogously:
  • optically active 4-octyloxy-2 ', 3'-difluorobiphenyl-4'-ylcarboxylic acid (3-trifluoromethylnonyl) ester is obtained.
  • optically active connections are made analogously:
  • a liquid crystalline mixture consisting of the following components:

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

Abstract

Des composés cycliques chiraux ou achiraux ont la formule R1-(A1-Z1)m-A2-Q1-C*R°CF3-X, dans laquelle R1 représente alkyle ou perfluoralkyle pouvant être interrompu par O- et/ou -CO- et/ou -CO-O- et/ou -CH=CH- et/ou -CH halogène et/ou -CHCN- et/ou -O-CO-CH halogène et/ou -CO-O-CHCN, F, Cl, Br, CN ou -Q1-C*R°CF3-X; A1 et A2 représentent 1,4-phénylène non substitué ou substitué par un ou deux F et/ou CH3 et/ou CN, où un ou deux groupes CH peuvent également être substitués par N; 1,4-cyclohexylène, où un ou deux groupes CH2 non adjacents peuvent également être substitués par O et/ou S; 1-(4-)cyano-1,4-cyclohexylène, pipéridin-1,4-diyle, 1,4-bicyclo(2,2,2)-octylène, 1,3,4-thyadiazol-2,5-diyle, naphtalin-2,6-diyle, décahydronaphtalin-2,6-diyle ou 1,2,3,4-tétrahydronaphtalin-2,6-diyle; Z1 représente -CO-O-, -O-CO, -CH2CH2-, -OCH2-, -CH2O-, -C=C- ou une liaison simple; X représente H ou CH3; C* est un atome de carbone lié à quatre substituants différents, m est égal à 1, 2 ou 3; Q1 représente -O-, -O-CO-, -CO-O- ou une liaison simple lorsqu'au moins un des composés cycliques A1 et A2 représente 1,4-phénylène substitué par un ou deux atomes F ou A1 représente 1,4-phénylène non substitué, où un groupe CH est substitué par N, ou -O-(CH2)n-, -O-CO-(CH2)n- ou -CO-O-(CH2)n, où n est égal à 1, 2, 3 ou 4; R° représente alkyle différent de X ou, lorsque Q est une liaison simple, alkoxy ou alkanoyloxy. Ces composés peuvent être utilisés comme constituants de phases de cristaux liquides smectiques à inclinaison chirale.
EP89904055A 1988-04-13 1989-04-01 Composes cycliques chiraux ou achiraux Withdrawn EP0370081A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3812191 1988-04-13
DE3812191A DE3812191A1 (de) 1988-04-13 1988-04-13 Chirale oder achirale ringverbindungen

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EP0370081A1 true EP0370081A1 (fr) 1990-05-30

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EP (1) EP0370081A1 (fr)
JP (1) JP2843629B2 (fr)
KR (1) KR900700429A (fr)
DD (1) DD283832A5 (fr)
DE (1) DE3812191A1 (fr)
WO (1) WO1989009764A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0745420B2 (ja) * 1987-07-24 1995-05-17 キヤノン株式会社 光学活性物質、その製造方法およびそれを含む液晶組成物
DE69003709T2 (de) * 1989-02-27 1994-03-10 Sanyo Chemical Ind Ltd Optisch aktive Verbindungen.
JPH03221588A (ja) * 1990-01-26 1991-09-30 Showa Shell Sekiyu Kk 液晶組成物用配合剤およびそれらを含む液晶組成物
JPH0488080A (ja) * 1990-07-30 1992-03-19 Sharp Corp 強誘電性液晶組成物及び液晶素子

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Publication number Priority date Publication date Assignee Title
EP0294852B1 (fr) * 1987-06-12 1995-12-06 Canon Kabushiki Kaisha Dispositif à cristal liquide ferro-électrique
JPH0745420B2 (ja) * 1987-07-24 1995-05-17 キヤノン株式会社 光学活性物質、その製造方法およびそれを含む液晶組成物
JP2510664B2 (ja) * 1988-03-25 1996-06-26 キヤノン株式会社 液晶性化合物及びそれを含む液晶組成物、液晶素子
DE3867949D1 (de) * 1987-07-28 1992-03-05 Canon Kk Optisch aktive verbindung und sie enthaltende fluessigkristalline zusammensetzung.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8909764A1 *

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KR900700429A (ko) 1990-08-13
JP2843629B2 (ja) 1999-01-06
WO1989009764A1 (fr) 1989-10-19
DD283832A5 (de) 1990-10-24
DE3812191A1 (de) 1989-10-26
JPH02503803A (ja) 1990-11-08

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