EP0260275A1 - Composes optiquement actifs - Google Patents

Composes optiquement actifs

Info

Publication number
EP0260275A1
EP0260275A1 EP87901017A EP87901017A EP0260275A1 EP 0260275 A1 EP0260275 A1 EP 0260275A1 EP 87901017 A EP87901017 A EP 87901017A EP 87901017 A EP87901017 A EP 87901017A EP 0260275 A1 EP0260275 A1 EP 0260275A1
Authority
EP
European Patent Office
Prior art keywords
optically active
coo
groups
formula
active compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87901017A
Other languages
German (de)
English (en)
Inventor
Thomas Geelhaar
Andreas WÄCHTLER
Bernard Scheuble
Hans-Adolf Kurmeier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP0260275A1 publication Critical patent/EP0260275A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/188—Unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other 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
    • C09K19/08—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
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2021—Compounds containing at least one asymmetric carbon atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
    • 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
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero 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
    • C09K19/34—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
    • C09K19/34—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
    • C09K19/3452—Pyrazine
    • 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
    • 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
    • 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
    • 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
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring

Definitions

  • the invention relates to optically active compounds of the formula I.
  • a 2 , A 3 each unsubstituted or 1,4-phenylene substituted by one or and A and two F and / or Cl atoms and / or CH 3 groups and / or CN groups, which also includes one or two CH groups can be replaced by N, 1,4-cyclohexylene, wherein one or two non-adjacent CH 2 groups can also be replaced by O atoms and / or S atoms, piperidine-1,4-diyl, 1,4-bicyclo- (2,2,2) -octylene-, naphthalene -2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl groups,
  • Z 1 and Z 2 each -CO-O-, -O-CO-, -CH 2 CH 2 -, -OCH 2 -, -CH 2 O-, -C ⁇ C- or a single bond,
  • 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 base mixtures with one or more chopped 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.
  • the elongate molecules are arranged in layers, the molecules being one
  • the tilt direction changes by a small angle with respect to an axis perpendicular to the layers ate 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 will make the
  • a major disadvantage for many applications of the currently available materials with chiral-chased 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 non-zero 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 (JM 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 and high values for the spontaneous polarization and for such phases very short switching times can be produced.
  • P is the spontaneous polarization in nC / cm 2 .
  • the range of liquid-crystalline substances which are suitable for the production of ferroelectric mixtures from various application points of view is also very broadly broadened.
  • the compounds of formula I have a wide range of applications. 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 low optical anisotropy values. 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 isotropic or monotropic liquid-crystalline compounds of the formula I can also be used advantageously as components of chiral-chopped smectic phases. They are very stable chemically, thermally and against light.
  • the invention thus relates to the optically active compounds of the formula I and the use of the compounds of the formula I as components of liquid-crystalline phases.
  • the invention also relates to chiral tilted smectic liquid-crystalline phases containing at least one optically active compound of the formula I.
  • the invention further relates to such phases containing at least one compound of the formula I and 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 also have O- Atoms can be replaced and Bi a bicyclo (2,2,2) octylene group.
  • R 1 , R 5 , n, A 2 , A3, A 4 , Q, X, X ', Q', Y ', Z 1 and Z 2 have the meaning given, unless expressly stated otherwise .
  • the compounds of the formula I include, in particular, compounds of the subforms Ia and Ib (with two rings)
  • the preferred compounds of the formula Ib include those of the sub-formulas Ibl to Ib4:
  • the preferred compounds of formula Ic include those. of the sub-formulas Ic1 to Ic4:
  • the preferred compounds of the formula Id include those of the sub-formulas Idl and Id3:
  • R 1 and R 5 each independently represent alkyl.
  • a 2 , A 3 and A 4 si.nd preferably Cy or Ph.
  • Ph preferably denotes a 1,4-phenylene (Phe), 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, Pyr or Pyn.
  • the compounds according to the invention preferably no longer contain as a 1,4-phenylene group in which one or two CH groups are replaced by N.
  • Cy preferably represents a 1,4-cyclohexylene group.
  • -Ph-Ph- is particularly preferred.
  • -Ph-Ph- is preferably -Phe-Phe-, Phe-Pyr or Phe-Pyn.
  • the groups are particularly preferred
  • Z 1 and Z 2 are preferably simple formations, in the second place preferably -O-CO-, -CO-O-, -C ⁇ C- or -CH 2 CH 2 -
  • Z 1 is -CO-O, -O-CO-, -C ⁇ C- or -CH 2 CH 2 -, in particular the -CH 2 CH 2 - and the -C ⁇ C group.
  • X in the compounds of the formulas above and below is halogen, CN or CH 3 , preferably Cl or CH 3 .
  • Q alkylene with 1 to 2 carbon atoms, -O-, -O-CO- and -COO-.
  • Compounds of the formulas above and below with branched groups R 1 and R 5 may be important.
  • Branched groups of this type usually contain no more than two chain branches.
  • R 1 or R is preferably a straight-chain group or a branched group with no more than one chain branch.
  • Preferred branched radicals are isopropyl, 2-butyl
  • -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.
  • Y is preferably CH 3 , -CN or Cl, particularly preferably Cl or CR 3 .
  • R 5 is preferably straight-chain or branched alkyl having 1 to 10, in particular 1 to 7,
  • Preferred compounds of the formula I are those in which X and Y 'do not simultaneously denote methyl.
  • Preferred compounds of the formula I and Ia to Ig are those in which at least one of the radicals contained therein has one of the preferred meanings indicated.
  • optically active radicals R 1 or R -C * HX-Q
  • -X'-Q'-C * HY '-R 5 in these preferred compounds is given below:
  • R 1 -C * HX-Q may be the same or different from -X'-Q'-C * Be HY'-R 5 .
  • -X '-Q'-C * HY'-R 5 and R 1 -C * HX-Q are different and have a preferred meaning given for -X'-Q'-C * HY'-R 5 .
  • R 1 , R 5 , n, X, Y ', A 2 , A 3 , A 4 , Z 1 and Z 2 have the meaning given in claim 1.
  • -A 4 -Z 1 -A 2 - (Z 2 -A 3 ) n - is preferably a group of the following formulas 1 to 16 or its mirror image:
  • the compounds of the formula I are prepared by methods known per se, as are 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 who are known and suitable for the implementations mentioned. Use can also be made of variants which are known per se and are not mentioned here in any more detail.
  • the starting materials can also be formed in situ in such a way that they are not isolated from the reaction mixture, but instead are immediately reacted further to give the compounds of the formula I.
  • the compounds of the formula I can be prepared by reducing a compound which otherwise corresponds to the formula I but contains one or more reducible groups and / or CC bonds instead of H atoms.
  • Preferred starting materials for the reduction correspond to the formula I, but can be
  • a -CH CH group and / or instead of a -CH 2 group, a -CO group and / or instead of an H atom, a free or functional (e.g. in the form of their p-toluenesulfonate) contain modified OH group.
  • the reduction can take place, 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 such
  • 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 by the methods of Clemmensen (with zinc, amalgamated zinc or tin and hydrochloric acid, expediently in aqueous alcoholic solution or in a heterogeneous phase with water / toluene at temperatures between about 80 and 120 °) or Wolff-Kishner (with hydrazine, expedient 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 the formula I which contain alkyl groups and / or —CH 2 CH 2 bridges become.
  • Clemmensen with zinc, amalgamated zinc or tin and hydrochloric acid, expediently in aqueous alcoholic solution or in a heterogeneous phase with water / toluene at temperatures between about 80 and 120 °
  • Wolff-Kishner with hydrazine, expedient reduced in the presence of alkali such as KOH
  • arylsulfonyloxy groups with LiAlH. are reductively removed, in particular p-toluenesulfonyloxymethyl groups are reduced to methyl groups, advantageously 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!)
  • 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, e.g. 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.
  • Particularly suitable are 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 such as Dimethyl sulfoxide or sulfolane.
  • Solvents immiscible with water can at the same time advantageously be used for azeotropically distilling off the water formed during the esterification.
  • an excess of an organic base for example pyridine, quinoline or triethylamine, can also be used as a solvent for the esterification.
  • the esterification can also be carried out in the absence of a solvent, for example by simply heating the components in the presence of sodium acetate.
  • the reaction temperature is usually between -50 ° and + 250 °, preferably between -20 ° and + 80 °. At these temperatures, the esterification reactions are usually complete after 15 minutes to 48 hours.
  • reaction conditions for the esterification largely depend on the nature of the starting materials used.
  • a free carboxylic acid is usually reacted with a free alcohol or phenol in the presence of a strong acid, for example a mineral acid such as hydrochloric acid or sulfuric acid.
  • a preferred reaction mode is the reaction of an acid anhydride or, in particular, an acid chloride with an alcohol, preferably in a basic medium, the bases being in particular alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates or hydrogen carbonates such as sodium carbonate, potassium carbonate or potassium hydrogen carbonate, alkali metal acetates such as sodium - or Potassium acetate, alkaline earth metal hydroxides such as calcium hydroxide or organic bases such as triethylamine, pyridine, lutidine, collidine or quinoline are important.
  • Another preferred embodiment of the esterification is that the alcohol or the phenol is first in the
  • 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 from compounds known from the literature without difficulty using standard organic chemistry processes.
  • 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.
  • nitriles of the formula I corresponding acid amides, for example those in which a CONH 2 group is used instead of the radical X, can be dehydrated.
  • the amides can be obtained, for example, from corresponding esters or acid halides by reaction with ammonia.
  • Suitable water-releasing agents are, for example, inorganic acid chlorides such as SOCl 2 , RCl 3 , PCl 5 , POCl 3 , SO 2 Cl 2 , COCl 2 , furthermore P 2 O 5 , R 2 S 5 , AlCl 3 (for example as double compounds with NaCl), aromatic sulfonic acids and sulfonic acid halides. You can do it in the present or
  • nitriles of the formula I mentioned above corresponding acid halides, preferably the chlorides, can also be reacted with sulfamide, advantageously in an inert solvent such as tetramethylene sulfone at temperatures between about 80 ° and 150 °, preferably at 120 °. After the usual work-up, the nitriles can be isolated directly.
  • sulfamide advantageously in an inert solvent such as tetramethylene sulfone at temperatures between about 80 ° and 150 °, preferably at 120 °.
  • 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 is converted into the corresponding alkali metal alcoholate or alkali metal phenolate.
  • corresponding chlorine or bromine compounds of the formula I can also be reacted with a cyanide, advantageously with a metal cyanide such as NaCN, KCN or Cu 2 (CN) 2 , for example in the 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
  • pyridine in an inert solvent such as DMF or N-methylpyrrolidone at temperatures between 20 ° and 200 °.
  • 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 phases according to the invention contain at least one, preferably at least two, compounds of the formula I.
  • Particularly preferred are chiral tilted smectic liquid-crystalline phases, the achiral base mixture of which, in addition to compounds of the formula I, contains at least one other component with negative or small positive dielectric anisotropy.
  • These further components of the chiral base mixture can make up 1 to 50%, preferably 10 to 25%, of the base mixture.
  • Compounds of the sub-formulas Va to Vp are suitable as further components with small positive or negative dielectric anisotropy:
  • R 4 and R 5 are each preferably straight-chain alkyl
  • n is
  • R 4 and R 5 each represent straight-chain alkyl or alkoxy each having 5 to 10 C atoms.
  • the compounds of the sub-formulas 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 sub-formulas 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
  • R 4 and R 5 di.e have the preferred meaning given for Vc, Vh and Vi.
  • R 'and R''each preferably represent straight-chain
  • 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 CH group has been replaced by N.
  • R ''' is an optically active residue with an asymmetric carbon atom
  • 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.
  • liquid-crystalline phases according to the invention consist of 2 to 25, preferably 3 to 15 components, including at least one compound of the formula I.
  • the other constituents are preferably selected from the nematic or nematogenic substances, in particular the known substances, from the classes of the azoxybenzenes, benzylidene anilines, Biphenyls, terphenyls, phenyl or cyclohexyl benzoates, cyclohexane carboxylic acid phenyl or cyclohexyl esters, phenylcyclohexanes, cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalenes, 1,4-bis-cyclohexylbenzenes, 4,4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohex
  • L and E each a carbo- or heterocyclic ring system from the one of 1,4-disubstituted benzene and cyclohexane rings, 4,4'-disubstituted biphenyl, phenylcyclohexane and cyclohexylcyclohexane systems, 2,5-disubstituted pyrimidine and 1,3-dioxane rings, 2,6-disubstituted naphthalene, di- and tetrahydronaphthalene, quinazoline and tetrahydroquinazoline,
  • Y halogen preferably chlorine, or -CN
  • R 'and R' ' are different from one another, one of these radicals usually being an alkyl or alkoxy group.
  • R 'and R' ' are also common. Many such substances or mixtures thereof are commercially available. All of these substances are obtainable by methods known from the literature.
  • the phases according to the invention contain about 0.1 to 99, preferably 10 to 95%, of one or more compounds of formula I. Also preferred are liquid-crystalline phases according to the invention, containing 0.1-40, preferably 0.5-30% of one or more compounds of formula I.
  • the phases according to the invention are prepared in a conventional manner.
  • the components are dissolved in one another, expediently at elevated temperature.
  • Phases according to the invention are modified so that they can be used in all previously known types of liquid crystal display elements.
  • conductive salts preferably ethyl-dimethyl-dodecyl-ammonium-4-hexyloxybenzoate, tetrabutylammonium-tetraphenylboranate or complex salts of crown ethers (see, for example, I. Haller et al., Mol. Cryst.Liq.Cryst. Volume 24, pages 249-258 (1973)) to improve the conductivity, pleochroic dyes for producing colored guest-host systems or substances for changing the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases are added.
  • Such substances are e.g. in DE-OS 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430, 28 53 728 and 29 02 177.
  • Mp. Melting point
  • Kp. Clearing point. Percentages above and below mean percentages by weight; all temperatures are given in degrees Celsius. "Conventional work-up” means: water is added, the mixture is extracted with methylene chloride, the mixture is separated off, the organic phase is dried, evaporated and the product is purified by crystallization and / or chromatography.
  • K crystalline solid state
  • S smectic phase (the index indicates the phase type)
  • N nematic state
  • Ch cholesteric phase
  • I isotropic phase. The number between two symbols indicates the transition temperature in degrees Celsius.
  • optically active 4- (4 '- (2-octyloxy) biphenyl-4-yl) -1-cyano-1- (2-hydroxypropyl) cyclohexane available from 4- (4' - (2-octyloxy ) -biphenyl-4-yl) -cyclohexane carbonitrile by alkylation with optically active propylene oxide and lithium diisopropylamide as base
  • optically active 2-chloro-3-methylbutyric acid gives optically active 1- [4-cis- (4 '- (2-octyloxy ) -biphenyl-4-yl) -r-1-cyancyclohexyl] -2-propyl- (2-chloro-3-methylbutyrate).
  • S S-3-methyl-2-chloropentanoic acid in the presence of DCC with optically active 2- (p-hydroxyphenyl) -3- (3-methylpentyl) pyridine [can be prepared from 2- (pMethoxyphenyl) -3- (3-methylpenty1) pyridine esterified by basic ether cleavage with potassium tert-butoxide in NMP at 180 ° C.] and worked up as usual.
  • S, S 3-Methyl-2-chloropentanoic acid p-A- (3-methylpentyl) pyridin2-yl] phenyl ester is obtained.
  • a liquid-crystalline phase is produced consisting of
  • a liquid crystalline phase consisting of
  • a liquid-crystalline phase is produced consisting of
  • a liquid crystalline phase consisting of
  • a liquid crystalline phase consisting of
  • a liquid crystalline phase consisting of
  • a liquid crystalline phase consisting of
  • a liquid crystalline phase consisting of
  • a liquid crystalline phase consisting of
  • a liquid crystalline phase consisting of
  • Optically active compounds can be used as components of chirally tilted smectic liquid crystal phases.
  • Optically active compounds can be used as components of chiral-chopped smectic liquid-crystalline phases.

Landscapes

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

Abstract

Des composés optiquement actifs peuvent être utilisés comme constituants de phases cristallines liquides smectiques à inclinaison chirale.
EP87901017A 1986-02-17 1987-01-31 Composes optiquement actifs Withdrawn EP0260275A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3604905 1986-02-17
DE3604905 1986-02-17
DE3630771 1986-09-10
DE3630771 1986-09-10

Publications (1)

Publication Number Publication Date
EP0260275A1 true EP0260275A1 (fr) 1988-03-23

Family

ID=25841022

Family Applications (2)

Application Number Title Priority Date Filing Date
EP87901017A Withdrawn EP0260275A1 (fr) 1986-02-17 1987-01-31 Composes optiquement actifs
EP87901018A Expired - Lifetime EP0257048B1 (fr) 1986-02-17 1987-01-31 Composes optiquement actifs

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP87901018A Expired - Lifetime EP0257048B1 (fr) 1986-02-17 1987-01-31 Composes optiquement actifs

Country Status (6)

Country Link
US (1) US5064569A (fr)
EP (2) EP0260275A1 (fr)
KR (2) KR880700795A (fr)
AT (1) ATE110368T1 (fr)
DE (1) DE3750419D1 (fr)
WO (2) WO1987005017A2 (fr)

Families Citing this family (76)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5167857A (en) * 1984-09-20 1992-12-01 Canon Kabushiki Kaisha Lactic acid derivative, liquid crystal composition containing same and liquid crystal device
EP0263843B1 (fr) * 1986-02-21 1992-12-02 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Composes et melanges pour cristaux liquides, et dispositifs les contenant
CA1341038C (fr) * 1986-03-10 2000-06-27 Masanao Kamei Derive du fluoroalcane
JPH0739393B2 (ja) * 1986-03-26 1995-05-01 チッソ株式会社 ２−（４′−アルコキシフエニル）−５−アルキルピリジン
DE3768691D1 (de) * 1986-04-22 1991-04-25 Hoffmann La Roche Fluessigkristalline pyridinderivate.
DE3788243D1 (de) * 1986-05-22 1994-01-05 Hoffmann La Roche Flüssigkristalline Derivate von Phenylbenzoat.
US5082589A (en) * 1986-05-22 1992-01-21 Hoffmann-La Roche Inc. Liquid crystalline esters
ES2019077B3 (es) * 1986-05-30 1991-06-01 Hoechst Ag Esteres enantiomorfos de acidos carboxilicos alfa-sustituidos y compuestos hidroxilicos mesogenos y su empleo como material de dotacion en fases de cristal liquido.
GB8621689D0 (en) * 1986-09-09 1986-10-15 Ici Plc Liquid crystal material
US4882084A (en) * 1986-11-07 1989-11-21 Chisso Corporation Optically active substituted biphenyl compounds
EP0267758A3 (fr) * 1986-11-10 1989-10-18 Chisso Corporation Esters alpha-substitués de l'acide propionique
EP0268198B1 (fr) * 1986-11-20 1993-09-01 F. Hoffmann-La Roche Ag Cristaux liquides ferroélectriques
EP0269963B1 (fr) * 1986-11-28 1995-02-22 F. Hoffmann-La Roche Ag Cristaux liquides ferroélectriques
JP2538578B2 (ja) * 1987-02-02 1996-09-25 チッソ株式会社 ２−置換アルキルエ−テル類および液晶組成物
DD257638A1 (de) * 1987-02-19 1988-06-22 Univ Halle Wittenberg Ferroelektrische fluessigkristalle
US4973426A (en) * 1987-03-04 1990-11-27 Chisso Corporation Optically active compound having a plurality of asymmetric carbon atoms
US5274168A (en) * 1987-03-23 1993-12-28 Sumitomo Chemical Company, Limited Optically active benzene derivatives, process for producing the same and liquid-crystalline substances containing said derivatives as active ingredient and optical switching elements
US5002693A (en) * 1987-03-23 1991-03-26 Sumitomo Chemical Company, Limited Novel optically active benzene derivatives, process for producing the same and liquid-crystalline substances containing said derivatives as active ingredient and optical switching elements
DE3709549A1 (de) * 1987-03-24 1988-10-06 Hoechst Ag Verwendung von 5-phenyl-pyrimidinderivaten als komponenten in smektischen fluessigkristallmischungen
DE3709618A1 (de) * 1987-03-24 1988-10-06 Hoechst Ag Neue fluessigkristalline 5-phenylpyrimidin-derivate mit s(pfeil abwaerts)c(pfeil abwaerts)-oder s(pfeil abwaerts)c(pfeil abwaerts) -phase und verfahren zu ihrer herstellung
JPH0629259B2 (ja) * 1987-03-31 1994-04-20 キヤノン株式会社 液晶性化合物およびそれを含む液晶組成物
US4904410A (en) * 1987-03-31 1990-02-27 Canon Kabushiki Kaisha Mesomorphic compound and liquid crystal composition containing same
EP0289270B1 (fr) * 1987-04-27 1994-12-14 Chisso Corporation Dérivés optiquement actifs de la biphénylyl-2 pyrimidine et compositions de cristaux liquides les contenant
JPH0832659B2 (ja) * 1987-06-10 1996-03-29 住友化学工業株式会社 光学活性なエーテル誘導体、その製造法、これを有効成分とする液晶材料およびこれを用いてなる光スイッチング素子
US5250222A (en) * 1987-08-25 1993-10-05 Hoffmann-La Roche Inc. Optically active compounds used for liquid crystalline mixtures
JPS6463571A (en) * 1987-09-03 1989-03-09 Chisso Corp Optically active-2,5-diphenylpyridines
EP0307880B1 (fr) * 1987-09-19 1994-01-12 Hoechst Aktiengesellschaft Mélanges liquides cristallins ferro-électriques
GB8724458D0 (en) * 1987-10-19 1987-11-25 Secr Defence Lateral cyano terphenyls
DE3850842T2 (de) * 1987-10-20 1995-01-19 Chisso Corp 2,5-Diphenylpyrimidin-Verbindungen und sie enthaltende flüssigkristalline Zusammensetzungen.
JPH01106870A (ja) * 1987-10-20 1989-04-24 Chisso Corp ２，５−ジフェニルピリミジン誘導体、液晶組成物および電気光学素子
JP2566807B2 (ja) * 1987-11-11 1996-12-25 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
JP2610467B2 (ja) * 1987-11-12 1997-05-14 キヤノン株式会社 液晶性化合物、それを含有する液晶組成物およびそれを使用した液晶素子
EP0329153B1 (fr) * 1988-02-18 1992-10-21 Dainippon Ink And Chemicals, Inc. Dérivé d'acide lactique et composition liquide cristalline le contenant
US5130048A (en) * 1988-03-04 1992-07-14 Displaytech, Inc. Ferroelectric liquid crystal compositions containing chiral haloalkoxy tails units
US5051506A (en) * 1988-03-04 1991-09-24 Displaytech, Inc. Ferroelectric liquid crystal compounds containing chiral haloalkyoxy tail units and compositions containing them
US5167855A (en) * 1988-03-04 1992-12-01 University Research Corporation Ferroelectric liquid crystal compositions chiral haloalkoxy tail units
US5422037A (en) * 1988-03-04 1995-06-06 Displaytech, Inc. Ferroelectric liquid crystal compounds containing halogenated cores and chiral haloalkoxy tail units
USRE34726E (en) * 1988-03-04 1994-09-13 Displaytech, Inc. Ferroelectric liquid crystal compositions containing chiral haloalkoxy tail units
US5180520A (en) * 1988-03-04 1993-01-19 University Research Corporation Ferroelectric liquid crystal compositions containing halogenated cores and chiral halogenated cores and chiral haloalkoxy tail units
US5585036A (en) * 1988-03-04 1996-12-17 Displaytech, Inc. Liquid crystal compounds containing chiral 2-halo-2-methyl ether and ester tails
DE3807863A1 (de) * 1988-03-10 1989-09-21 Merck Patent Gmbh 2,3-difluorbenzolderivate
JP2554122B2 (ja) * 1988-03-25 1996-11-13 旭電化工業株式会社 光学活性化合物
US5242619A (en) * 1988-04-27 1993-09-07 Hoffmann-La Roche Inc. Liquid crystalline mixtures having a chiral tilted smectic phase
US5486310A (en) * 1988-04-27 1996-01-23 Hoffmann-La Roche Inc. Liquid crystalline mixtures having a chiral tilted smectic phase
US5244597A (en) * 1988-05-26 1993-09-14 Hoffmann-La Roche Inc. Liquid crystalline mixtures having a chiral tilted smectic phase
EP0343487B1 (fr) * 1988-05-26 1993-01-20 F. Hoffmann-La Roche Ag Esters de cyclohexyle d'acides alpha fluoro carboxyliques
JPH04234841A (ja) * 1988-07-08 1992-08-24 Mitsubishi Rayon Co Ltd 光学活性化合物及び液晶組成物
KR900701959A (ko) * 1988-08-31 1990-12-05 호이만, 쉬틀러 열색 혼합물
JP2655333B2 (ja) * 1988-09-01 1997-09-17 関東化学 株式会社 新規なｐ‐ターフエニル誘導体並びに液晶組成物
JP2728702B2 (ja) * 1988-11-28 1998-03-18 チッソ株式会社 強誘電性液晶組成物とその液晶表示素子
DE3939982A1 (de) * 1988-12-22 1990-07-05 Merck Patent Gmbh 2,5-disubstituierter heterocyclus und fluessigkristalline phase
EP0385692B1 (fr) * 1989-02-27 1993-10-06 Sanyo Chemical Industries Ltd. Composés optiquement actifs
JP2893798B2 (ja) * 1989-04-25 1999-05-24 住友化学工業株式会社 光学活性なビフェニル誘導体、その製造法、それを有効成分とする液晶組成物およびそれを用いてなる液晶素子
DE3923324A1 (de) * 1989-05-11 1990-11-22 Merck Patent Gmbh Chirale oder achirale ringverbindungen
DE3915698A1 (de) * 1989-05-13 1990-11-15 Merck Patent Gmbh Optisch aktive verbindungen und fluessigkristalline phase
US5393459A (en) * 1989-05-11 1995-02-28 Merck Patent Gesellschaft Mit Beschrankter Haftung Optically active compounds, and a liquid-crystalline phase
JP2768365B2 (ja) * 1989-06-24 1998-06-25 富士通株式会社 液晶組成物
US5327273A (en) * 1989-06-29 1994-07-05 Hoffmann-La Roche Inc. Bistable ferroelectric liquid crystal display cell
US5141669A (en) * 1989-06-30 1992-08-25 Polaroid Corporation Liquid crystal compounds having chiral ester head groups
US5235443A (en) * 1989-07-10 1993-08-10 Hoffmann-La Roche Inc. Polarizer device
DE4002609A1 (de) * 1989-09-07 1991-03-21 Merck Patent Gmbh Difluorbenzonitrile und fluessigkristallines medium
JP2890759B2 (ja) * 1989-09-08 1999-05-17 住友化学工業株式会社 光学活性なナフタレン誘導体、その製造法、それを有効成分とする液晶組成物およびこれを用いてなる液晶素子
DE4001965A1 (de) * 1990-01-24 1991-07-25 Hoechst Ag Ester von 3-halogen- bzw. 3-cyano-substituierten 2-methylalkancarbonsaeuren und ihre verwendung als dotierstoffe in fluessigkristallinen mischungen
EP0449049B1 (fr) * 1990-03-27 1994-12-28 F. Hoffmann-La Roche Ag Esters de l'acide naphtaline-dicarboxylique
JP2830361B2 (ja) * 1990-04-28 1998-12-02 ソニー株式会社 光学活性化合物及びこれを用いた強誘電性液晶組成物
US5380460A (en) * 1991-09-20 1995-01-10 Displaytech, Inc. Ferroelectric liquid crystal compounds containing chiral haloalkoxy tail units and compositions containing them
JP3078573B2 (ja) * 1990-11-16 2000-08-21 株式会社半導体エネルギー研究所 液晶電気光学装置
US5178791A (en) * 1991-03-11 1993-01-12 Displaytech, Inc. Halogenated diphenyldiacetylene liquid crystals
JPH0682743A (ja) * 1992-09-04 1994-03-25 Sony Corp 強誘電性液晶組成物
US5417885A (en) * 1993-08-03 1995-05-23 Showa Shell Sekiyu Kabushiki Kaisha Antiferroelectric liquid crystal compound
US5626792A (en) * 1994-09-06 1997-05-06 Displaytech, Inc. High birefringence liquid crystal compounds
GB9506308D0 (en) * 1995-03-28 1995-05-17 Secr Defence Chiral compounds
US6413448B1 (en) 1999-04-26 2002-07-02 Displaytech, Inc. Cyclohexyl- and cyclohexenyl-substituted liquid crystals with low birefringence
US7195719B1 (en) 2001-01-03 2007-03-27 Displaytech, Inc. High polarization ferroelectric liquid crystal compositions
US6838128B1 (en) 2002-02-05 2005-01-04 Displaytech, Inc. High polarization dopants for ferroelectric liquid crystal compositions
US10550327B2 (en) 2012-11-21 2020-02-04 Merck Patent Gmbh Polymerisable compounds and the use thereof in liquid-crystal displays

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1603076A (en) * 1977-04-05 1981-11-18 Secr Defence Esters of (+)-4-(2'-methylbutyl)phenol and their use as liquid crystal materials
US4273929A (en) * 1979-02-05 1981-06-16 Hoffmann-La Roche Inc. Heterocyclic compounds
JPS5846040A (ja) * 1981-09-11 1983-03-17 Chisso Corp 光学活性液晶添加物
US4613209A (en) * 1982-03-23 1986-09-23 At&T Bell Laboratories Smectic liquid crystals
EP0110299B2 (fr) * 1982-11-26 1993-06-09 Hitachi, Ltd. Composés cristaux liquides smectiques et compositions de cristaux liquides
EP0115693B1 (fr) * 1983-01-06 1987-08-26 Chisso Corporation Composés cristaux liquides et mélanges de ceux-ci
US4613609A (en) * 1983-07-12 1986-09-23 Schering A. G. Antiarrhythmic imidazoliums
EP0133489B1 (fr) * 1983-08-04 1988-01-20 MERCK PATENT GmbH Composés nématiques
JPS6054341A (ja) * 1983-09-05 1985-03-28 Chisso Corp 液晶性炭酸エステル類
DE3333677A1 (de) * 1983-09-17 1985-04-04 Merck Patent Gmbh, 6100 Darmstadt Fluessigkristall-phase
JPS6090290A (ja) * 1983-10-05 1985-05-21 Chisso Corp カイラルスメクチツク液晶組成物
JPS60218358A (ja) * 1984-04-13 1985-11-01 Ajinomoto Co Inc 液晶
EP0163229A3 (fr) * 1984-05-23 1988-08-17 Hitachi, Ltd. Composition liquide cristalline ferro-électrique
US4725688A (en) * 1984-06-07 1988-02-16 Seiko Instruments Inc. Liquid crystal compound
JPS6143A (ja) * 1984-06-11 1986-01-06 Chisso Corp 強誘電性液晶化合物及び液晶組成物
EP0168043B1 (fr) * 1984-07-11 1990-11-07 MERCK PATENT GmbH Phase liquide cristalline
DE3577843D1 (de) * 1984-09-10 1990-06-28 Ajinomoto Kk Biphenyldiesterverbindungen und fluessigkristallkompositionen die diese enthalten.
GB2170214A (en) * 1985-01-26 1986-07-30 Stc Plc Ferroelectric smectic liquid crystal mixture
EP0191600B1 (fr) * 1985-02-08 1991-12-27 Ajinomoto Co., Inc. Composés esters à base de polyphényles et compositions de polyphényles les contenant
US5076962A (en) * 1985-03-12 1991-12-31 Chisso Corporation Ferroelectric chiral smectic liquid crystal composition
DE3515373A1 (de) * 1985-04-27 1986-11-06 Merck Patent Gmbh, 6100 Darmstadt Stickstoffhaltige heterocyclen
DE3515374C2 (de) * 1985-04-27 1998-02-26 Hoechst Ag Chirale getilte smektische flüssigkristalline Phasen und deren Verwendung in elektrooptischen Anzeigeelementen
DE3667052D1 (en) * 1985-07-01 1989-12-28 Ajinomoto Kk Biphenyl carbonic acid ester compounds and liquid crystal composition containing the same
GB8520715D0 (en) * 1985-08-19 1985-09-25 Secr Defence Secondary alcohol derivatives
DD240386B1 (de) * 1985-08-26 1989-01-18 Univ Halle Wittenberg Verfahren zur herstellung von verzweigten acyclischen alpha-chlorcarbonsaeuren
DD240385A1 (de) * 1985-08-26 1986-10-29 Univ Halle Wittenberg Anwendung ferroelektrischer fluessigkristalle
US4886620A (en) * 1985-09-18 1989-12-12 Merck Patent Gesellschaft Mit Beschrankter Haftung Smectic liquid-crystalline phases
DE3534777A1 (de) * 1985-09-30 1987-04-02 Hoechst Ag Fluessigkristall-phase mit eine temperaturkompensation bewirkenden dotierstoffen
US4754051A (en) * 1985-09-30 1988-06-28 Dainippon Ink And Chemicals, Inc. Optically active tolan derivative
EP0225195B1 (fr) * 1985-12-04 1993-11-24 Ajinomoto Co., Inc. Composés à base de phénylpyrimidines et compositions de cristaux liquides les contenant
JPS62181238A (ja) * 1986-02-05 1987-08-08 Dainippon Ink & Chem Inc 液晶性化合物
DE3604898A1 (de) * 1986-02-17 1987-08-20 Hoechst Ag Chirale umsetzungsprodukte aus mesogenen molekuelbausteinen und bifunktionell reaktionsfaehigen weinsaeurederivaten und ihre verwendung als dotierstoff in fluessigkristall-phasen
US4688427A (en) * 1986-04-11 1987-08-25 United Technologies Corporation Dynamic balance tester
DE3718174A1 (de) * 1987-05-29 1988-12-15 Hoechst Ag Verwendung von optisch aktiven oxiran-2-carbonsaeureestern als dotierstoffe in fluessigkristallmischungen, diese enthaltende fluessigkristallmischungen und neue optisch aktive oxiran-2-carbonsaeureester
US4959173A (en) * 1987-09-29 1990-09-25 Adeka Argus Chemical Co., Ltd. Optically active ester compound
DE3827603A1 (de) * 1988-08-13 1990-03-15 Hoechst Ag Chirale smektische fluessigkristalle und diese enthaltende glasartige materialien zur darstellung und speicherung von information

Also Published As

Publication number Publication date
DE3750419D1 (de) 1994-09-29
WO1987005017A3 (fr) 1988-01-14
KR880700795A (ko) 1988-04-12
WO1987005017A2 (fr) 1987-08-27
EP0257048A1 (fr) 1988-03-02
WO1987005018A3 (fr) 1988-03-24
EP0257048B1 (fr) 1994-08-24
US5064569A (en) 1991-11-12
KR880700796A (ko) 1988-04-12
WO1987005018A2 (fr) 1987-08-27
ATE110368T1 (de) 1994-09-15

Similar Documents

Publication Publication Date Title
EP0260275A1 (fr) Composes optiquement actifs
EP0264435B1 (fr) Phases smectiques de cristaux liquides
EP0154840B1 (fr) Composés de cristaux liquides
EP0216880B1 (fr) Derives de cyclohexane
EP0308438B1 (fr) Phase liquide cristalline contenant des tolanes
EP0471813B1 (fr) 2',3-difluorbiphenyles 4,4'-disubstitues et milieu cristallin liquide
DE3510432A1 (de) Cyclohexanderivate
DE3342631A1 (de) Thienothiophenderivate
WO1987001717A2 (fr) Phases smectiques a cristaux liquides
EP0357739A1 (fr) Derives chiraux du 1,2-difluorobenzene
WO1987004158A2 (fr) Composes heterocycliques utilises comme composants de phases de cristaux liquides
WO1991000897A1 (fr) Composes cycliques chiraux ou achiraux
EP0257049B1 (fr) Composes chiraux
EP0154849A2 (fr) Dérivés de cyclohexane
WO1994012455A1 (fr) Derives de cyclobutane-benzol
EP0439089A1 (fr) Terphényles halogénés et milieu à base de métaux cristallins
EP0290570B1 (fr) Composes cycliques chiraux ou achiraux
EP0184068A1 (fr) Nitriles d'acides carboxyliques
DE3706766A1 (de) Smektische fluessigkristalline phasen
DE3812191A1 (de) Chirale oder achirale ringverbindungen
DE3711306A1 (de) Tolanderivate und verwendung von carbonitrilen in fluessigkristallinen phasen fuer anzeigeelemente basierend auf dem ecb-effekt
WO1987005316A1 (fr) Phases de cristaux liquides nematiques
DE69028985T2 (de) Halophenyl-substituierte heterozyklische derivate
WO1991002780A1 (fr) Heterocycles 2,5-disubstitues et milieu mesomorphe
DE3922416A1 (de) Chirale oder achirale ringverbindungen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE FR GB LI

D17D Deferred search report published (deleted)
17P Request for examination filed

Effective date: 19880518

17Q First examination report despatched

Effective date: 19900713

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19920204

RIN1 Information on inventor provided before grant (corrected)

Inventor name: GEELHAAR, THOMAS

Inventor name: KURMEIER, HANS-ADOLF

Inventor name: WAECHTLER, ANDREAS

Inventor name: SCHEUBLE, BERNARD