WO1989003416A1 - Phases de cristaux liquides ferro-electriques - Google Patents

Phases de cristaux liquides ferro-electriques Download PDF

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WO1989003416A1
WO1989003416A1 PCT/EP1988/000862 EP8800862W WO8903416A1 WO 1989003416 A1 WO1989003416 A1 WO 1989003416A1 EP 8800862 W EP8800862 W EP 8800862W WO 8903416 A1 WO8903416 A1 WO 8903416A1
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formula
compounds
groups
propionic acid
aryl
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PCT/EP1988/000862
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Detlef Pauluth
Klaus-Peter Stahl
Andreas WÄCHTLER
Hans-Adolf Kurmeier
Thomas Geelhaar
Eike Poetsch
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MERCK Patent Gesellschaft mit beschränkter Haftung
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/26—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C07D239/28—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur 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
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—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
    • C09K19/34—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—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
    • C09K19/3469—Pyrimidine with a specific end-group other than alkyl, alkoxy or -C*-

Definitions

  • the invention relates to the use of compounds of the formula I
  • R 1 and R 2 are each independently an unsubstituted or with -CN or with at least one
  • R 2 also H, F, Cl, Br, CN or CF 3 ,
  • Z 1 and Z 2 each -CO-O-, -CO-S-, -O-CO-, -S-CO-, -CH 2 CH 2 -,
  • a 1 and A 2 each independently
  • radicals a) and b) can be substituted one or more times by halogen atoms, cyano and / or methyl groups,
  • n 0, 1 or 2
  • CH 2 groups can be replaced by -O- and / or -S-, means as components of ferroelectric liquid-crystalline phases.
  • Phe in the following means a 1,4-phenylene group, Cy a trans-1,4-cyclohexylene group, Che a 1,4-cyclohexenylene group, the double bond being both 1,2- and 2,3- and 3,4 may be pyr, a pyridine-2,5-diyl group, Pyz a pyrazine-2,5-diyl group, Pyn a pyridazine-3, 6-diyl group and Pyd a pyrimidine-2,5-diyl group, both of which are regioisomers permitted are.
  • PheX means a group of the formula where X hereinafter means chlorine, fluorine, methyl or nitrile, preferably X means chlorine or fluorine, particularly preferably fluorine.
  • 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 chopped smectic phases (LA Beresnev et al., Mol. Cryst. Lig. Cryst. 89, 327 ( 1982); HR Brand et al., J. Physigue 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 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 so that a helical structure is formed.
  • the smekti are in displays based on the principle of SSFLC technology see layers 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 chirally smectic phases is their minor chemical, thermal and photo stability.
  • Another disadvantageous property of displays based on currently available chiral-smectic mixtures is that the spontaneous polarization has values that are too small, so that the switching time behavior of the displays is adversely affected and / or the pitch and / or the tilt and / or the viscosity of the phases not the requirements of
  • the temperature range of the ferroelectric phases is usually too small and is predominantly at too high temperatures.
  • the compounds of the formula I are therefore particularly suitable as components of chiral-tipped smectic liquid-crystalline phases.
  • P is the spontaneous
  • these compounds can serve as base materials from which liquid-crystalline smectic phases are predominantly composed;
  • compounds of the formula I it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compounds, for example to improve the dielectric and / or optical anisotropy and / or the viscosity and / or the spontaneous polarization and / or the phase ranges and / or the tilt angle and / or the To vary the pitch of such a dielectric.
  • WO 86-00234 specifies a very broad general formula containing achiral heterocycles for ferroelectric mixtures, which in part comprises the compounds of the formula I claimed here. In WO 86-00234, however, no individual compounds of the formula claimed here are mentioned. The person skilled in the art could therefore neither easily derive synthesis possibilities for the claimed compounds from the prior art nor recognize that the compounds according to the invention predominantly have broad and favorably located Sc phases and are distinguished by favorable values for the rotational viscosity.
  • the invention thus relates to the use of the compounds of the formula I as components of ferroelectric liquid-crystalline phases.
  • the invention also relates to new compounds of the formula I '
  • R 1 and R 2 are each independently an unsubstituted or with -CN or with at least one halogen substituted alkyl or alkenyl radical with up to
  • the invention furthermore relates to a process for the preparation of the new compounds of the formula I ', characterized in that p-lithium, p-bromomagnesium or p-trialkoxytitanium (alkylthio) aryl compounds are reacted with aldehydes, ketones or nitriles , or that compounds of formula II,
  • Aryl, A 1 , A 2 , Z 1 , Z 2 , R 2 and n have the meaning given, with alkyl or alkanoyl thiolate compounds of the formula III,
  • R 1 and m have the meaning given, and M denotes a monovalent metal, or in that compound of the formula II, wherein
  • Aryl, A 1 , A 2 , Z 1 , Z 2 , R 2 and n have the meaning given, reacted with alkenes or ketenes,
  • a compound which otherwise corresponds to the formula I 'but contains one or more reducible groups and / or CC bonds instead of H atoms and / or a sulfoxide group instead of a mercapto group, with a reducing group Treated means
  • the invention further relates to ferroelectric liquid-crystalline phases containing at least one compound of the formula I and liquid-crystal display elements, in particular ferroelectric electro-optical display elements which contain such phases.
  • the phases according to the invention preferably contain at least two, in particular at least three, compounds of the formula I.
  • Particularly preferred are chiral tilted smectic liquid-crystalline phases according to the invention, the achiral base mixture of which, in addition to compounds of the formula I, contains at least one other component with a negative or small positive dielectric anisotropy.
  • These further component (s) of the achiral base mixture can make up 1 to 50%, preferably 10 to 25%, of the base mixture.
  • Compounds of the formula IV which comprise the compounds of the sub-formulas IVa to IVi are suitable as further components with small positive or negative dielectric anisotropy:
  • R 4 and R 5 are each preferably straight-chain alkyl
  • X is preferably 0.
  • a 1,4-phenylene group can also be substituted laterally by halogen or CN, particularly preferably by fluorine.
  • R 4 and R 5 each represent straight-chain alkyl or alkoxy each having 5 to 10 carbon atoms.
  • the compounds of the sub-formulas IVc, IVh and IVi 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 IVc, IVh and IVi 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 have the preferred meaning given for IVc, IVh and IVi.
  • Preferred compounds of this type correspond to the form Va, Vb and Vc:
  • R 1 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 simple formation.
  • 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 and n is 0 or 1.
  • Binuclear compounds of the formula I accordingly comprise compounds of the sub-formulas Ia to It:
  • R 1 -CO-S-Pyd-A 2 -R 2 If R 1 -S-Phe-Z 1 -A 2 -R 2 Ig R 1 -CO-S-Phe-Z 1 -A 2 -R 2 Ih
  • R 1 , R 2 , aryl, A 1 , A 2 , Z 1 , Z 2 m and n the at.
  • n 2 if R 1 is branched and aryl means unsubstituted or substituted 1,4-phenylene, and
  • aryl means pyridine-2, 5-diyl or pyrimidine-2, 5-diyl or the group linked to Z 1 1,4-phenylene, in which one or two CH groups are replaced by N.
  • Particularly preferred smaller groups of compounds are those of the formulas I "1 to I" 22
  • R 1 -S-Pyd-Phe-Phe-R 2 I "11 R 1 -S-Pyr-Phe-Phe-R 2 I” 12 R 1 -S-Pyr-Z 1 -Phe-Phe-R 2 I " 13 R 1 -S-Pyd-Z 1 -Phe-Phe-R 2 I "14 R 1 -S-Phe-Pyr-Phe-R 2 I” 15 R 1 -S-Phe-Pyd-Phe-R 2 I "16 R 1 -S-Phe-Z 1 -Pyr-Phe-R 2 I" 17 R 1 -S-Phe-Z 1 -Pyd-Phe-R 2 I "18
  • R 1 -S-Phe-Pyr-Phe-Phe-R 2 I "19 R 1 -S-Phe-Pyd-Phe-Phe-R 2 I" 20 R 1 -S-Phe-Pyr-Z 2 -Phe- Phe-R 2 I "21 R 1 -S-Phe-Pyz-Z 2 -Phe-Phe-R 2 I" 22
  • Preferred compounds of the formula I are those in which R 1 and R 2 are each straight-chain or branched
  • Alkyl or perfluoroalkyl group each having 4-13 C atoms, in which one or two CH 2 or CF 2 groups are selected by a group from -O-, -S-, -O-CO-, -CO -O-, -CH CH-, -CH-halogen and -CHCN- can be replaced, two heteroatoms not being directly linked to one another.
  • -S-, -O-CO-, -CO-O-, -CH-halogen and -CHCN- are preferred in which only one CH 2 group is replaced.
  • phase according to the invention contain at least one compound of the formula I in which R 1 is n-nonyl and at least one compound of the formula I in which R 1 is n-heptyl or n-octyl. Phases according to the invention containing compounds of the formula I in which R 1 is n-heptyl, n-octyl and n-nonyl are particularly preferred.
  • the phases according to the invention preferably contain at least one compound of the formula I in which R 2 is n-hexyl, n-heptyl, n-octyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-hexylthio, n-heptylthio, octylthio, n -Hexyl, n-heptyl, n-octyl, (preferably n-hexyl, n-heptyl, n-octyl, n-heptyloxy, n-octyloxy, n-heptylthio or n-octy
  • the sum of the C atoms in the groups R 1 and R 2 of the preferred dinuclear compounds of the formula I is preferably 15 or higher, particularly preferably in the range from 15 to 20.
  • Particularly preferred individual compounds of the formula I are in the following Table II (aryl) preferably substituted or unsubstituted 1,4-phenylene):
  • phases according to the invention comprising at least one dinuclear compound of the formula I in which R 1 is n-alkyl having 7 to 10 C atoms and R 2
  • p is preferably 4 to 10, in particular 5 to 9.
  • q is preferably 1 or 2, particularly preferably 2.
  • r is 4 to 10, particularly preferably 5 to 9.
  • g can also be> 2, for example 3 to 5.
  • R 1 is n-alkyl having 7 to 10 carbon atoms and R 2 is n-alkanoyloxy or n-alkoxycarbonyl each having 5 to
  • the phases according to the invention preferably contain at least one trinuclear compound of the formula I These phases are distinguished by particularly high S C / S A conversion temperatures.
  • Trinuclear compounds of the formula I accordingly comprise compounds of the sub-formulas IA to IP:
  • R 1 and R 2 are each independently of one another preferably alkyl, alkoxy, alkanoyl, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy, each preferably having 5 to 12, in particular 6 to 10, carbon atoms. Alkyl and alkoxy are particularly preferred.
  • One of the groups R 1 and R 2 is preferably alkyl.
  • R 1 and R 2 groups with a straight-chain alkyl radical are particularly preferred.
  • a 1 and A 2 are preferably unsubstituted or substituted 1,4-phenylene, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl.
  • Substructure elements 10 to 18 are identical to Substructure elements 10 to 18:
  • PheX preferably means a 2- (or 3-) - monofluoro- or 2,3-difluoro- 1,4-phenylene group.
  • a ferroelectric liquid-crystalline phase with at least one compound of the formula I is particularly preferred, characterized in that it contains a liquid-crystalline component with negative dielectric anisotropy; in particular a phase according to the invention, characterized in that it contains at least one compound having the structural element A, B, C or D as component with negative dielectric anisotropy.
  • Such compounds of the formula I containing the structural elements A to D are preferably those of the partial forms in Iaa to Ian:
  • a Phe group can each be substituted by one or two fluorine atoms.
  • Ferroelectric liquid-crystalline phases are preferred which have at least one compound of the formula I with unbranched radicals R 1 and R 2 as the base material and additionally at least one compound of the formulas laa-las with branched, optically active wing groups R 1 or R 2 as dopants.
  • Those chirally tilted smectic phases which contain at least one compound of the formula I with straight-chain wing groups R 1 and R 2 and are doped with other chiral compounds are particularly preferred.
  • a phase according to the invention is furthermore particularly preferred, characterized in that it contains at least one compound of the formula VI,
  • R 4 and R 5 are each alkyl with 1-15 C atoms, in which also one or two non-adjacent CH 2 groups by -O-, -CO-, -O-CO-, -CO-O- and / or
  • a 1 and A 2 each represent 1,4-phenylene or trans-1,4-cyclohexylene, one of the groups A 1 and A 2 optionally also 4,4'-biphenylyl or trans, trans-4,4'-bicyclohexyl .
  • ferroelectric phases according to the invention containing at least one compound of the formula VII
  • R 1 and R 2 each independently of one another are a straight-chain alkyl group having 1 to 15 C atoms, in which one or more non-adjacent CH 2 groups are also replaced by -O-, -S-, -CO-, CHCH 3 -O-, - CHCH 3 -, -CH-halogen-, CHCN-,
  • 1,4-cyclohexylene which is unsubstituted or substituted one or more times by halogen atoms, CH 3 and / or nitrile groups, in which also one or two non-adjacent CH 2 groups by -O- and / or -S- and / or a Grouping by can be replaced
  • (Ph) means one the radicals A ° also 2, 6-naphthylene (Na) or tetrahydro-2,6-naphthylene (4H-Na), optionally substituted by halogen or CN, Zo, Z 1 each independently of one another -CO-O-, -O- CO- and Z 2 -CH 2 O-, OCH 2 -, -CH 2 CH 2 -, -CHCNCH 2 -, -CH 2 -CHCN- or a single bond, and
  • R 1 and R 2 at least one CH 2 group is replaced by -CHCN-.
  • the compounds of formula VII can have straight-chain or branched wing groups R 1 and / or R 2 .
  • Compounds with branched wing groups can be used in the form of the racemate or as optically active compounds.
  • Achiral base mixtures of compounds of the formula VII and, if appropriate, further achiral components can be doped with chiral compounds of the formula I or additionally with other chiral compounds in order to obtain chirally tilted smectic phases.
  • Particularly preferred smaller groups of compounds are those of the formulas VIII to VII18:
  • Another particularly preferred smaller group of compounds are those of the formulas VII19 to VII22: R 1 -A ° -Cy- (CH 2 ) r -CHCN-C s H 2s + 1 VI119
  • r represents 0, 1, 2 or 3 (r + s) is 1 to 14.
  • phases of the invention can also compounds of the formula
  • 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 'or I ".
  • Alcohols, phenols, thiols or thiophenols can be obtained.
  • Suitable reactive derivatives of the carboxylic acids mentioned are, in particular, the acid halides, especially the chlorides and bromides, furthermore the anhydrides, azides or esters, in particular alkyl esters with 1-4 C atoms in the alkyl group.
  • Suitable reactive derivatives of the alcohols or phenols, thiols or thiophenols mentioned are, in particular, the corresponding metal alcoholates, phenolates, thiolates or thiophenolates, preferably an alkali metal such as Na or K.
  • the esterification is advantageously carried out in the presence of an inert solvent.
  • an inert solvent such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, amides such as DMF, hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride or tetrachlorethylene and sulfoxides such as dimethyl sulfoxide or sulfanol are particularly suitable.
  • Solvents which are immiscible with water can at the same time advantageously be used for azeotropically distilling off the water formed during the esterification become.
  • an excess of an organic base for example pyridine, quinoline or triethylamine, can also be used as a solvent for the esterification, the addition of catalytic amounts of 4-dimethylaminopyridine having a particularly favorable effect.
  • 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, phenol, thioalcohol or thiophenol 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 or thiol, preferably in a basic medium, the bases being in particular alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates or hydrogen carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, alkali metal acetates such as sodium or potassium acetate, alkaline earth metal hydroxides such as calcium hydroxide or organic bases such as triethylamine, pyridine, lutidine, collidine or quinoline are important.
  • alkali metal hydroxides such as sodium or potassium hydroxide
  • alkali metal carbonates or hydrogen carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate
  • alkali metal acetates such as sodium or potassium acetate
  • alkaline earth metal hydroxides such as calcium hydroxide or organic bases such as triethylamine, pyridine, lutidine, collidine
  • esterification consists in first converting the alcohol, the phenol, the thiol or the thiophenol into the sodium or potassium alcoholate, phenolate, thiolate or thiophenolate, for example by treatment with etha nolische sodium or potassium hydroxide solution, this isolated and reacted with an acid anhydride or in particular acid chloride.
  • alkyl halide, sulfonate or dialkyl sulfonate advantageously in an inert solvent such as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide or an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between 20 ° and 100 °.
  • -Alkyl means, in which one or more CH 2 groups by
  • N + 2 , Cl, Br or J means can be obtained with thio alcoholates.
  • Copper (I) 'alkyl mercaptides produced, for example, by R. Adams, A. Ferretti, J. Am. Chem. Soc, 811 4927 (1959)
  • organic, basic solvents such as, for example, pyridine and quinoline, with compounds of the formula II implemented.
  • sodium mercaptides are best reacted with aryl iodides in polar aprotic solvents such as DMF, dimethyl sulfoxide or in liquid ammonia with simultaneous exposure.
  • reaction of alkali metal mercaptides with aryldiazonium compounds is further preferred.
  • a further preferred possibility of representation of the thioethers of the formula I 'or I "is the addition of the mercaptans of the formula II (X SH) to alkenes.
  • the reaction conditions here have to be based on the type of the olefin. While in the case of olefins with activated double bonds, catalytic amounts increase Base are required (e.g. Brason, Org. React. 5, 79 (1949)), strong acids or radical formers are usually required for non-activated double bonds (e.g. Griesbaum, Angew. Chem., 82, 276 (1970)).
  • the thioalcohols and thiophenols frequently required as starting compounds can be obtained by reducing the sulfonyl halides with LiAlH 4 , by reductive cleavage of the disulfides with zinc and dilute acid or by reacting Grignard compounds with elemental sulfur. Furthermore, the methods described for the preparation of sulfides are also suitable for the preparation of the mercaptans if sodium sulfide is used instead of alkyl mercaptides.
  • Corresponding acid amides can be dehydrated to produce nitriles of the formula I 'or I "(in which R 2 denotes CN).
  • the amides can be obtained, for example, from corresponding esters or acid halides by reaction with ammonia.
  • suitable water-releasing agents are inorganic acid chlorides such as
  • Work 150 come as solvents e.g. Bases such as pyridine or triethylamine, aromatic hydrocarbons such as benzene, toluene or xylene or amides such as DMF into consideration.
  • Bases such as pyridine or triethylamine, aromatic hydrocarbons such as benzene, toluene or xylene or amides such as DMF into consideration.
  • Formula I 'or I " corresponding acid halides, preferably the chlorides, can also be reacted with sulfamide, advantageously in an inert solvent such as tetramethyl sulfone at temperatures between about 80 ° and 150 °, preferably at 120 °. After customary working up, the nitriles can be used directly isolate.
  • R 2 is CN and / or aryl and / or A 1 and / or A 2 is substituted by at least one CN group) can also be corresponding chlorine or bromine compounds
  • Formula I are 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 metal cyanide such as NaCN, KCN or Cu 2 (CN) 2
  • Diazonium salts are implemented, which are then thermally decomposed at temperatures of 100 ° -140 °.
  • connection of an aromatic nucleus with a non-aromatic nucleus or two non-aromatic nuclei is preferably obtained by condensation of a lithium, (trialkoxy) titanium or halogen magnesium organyl with a ketone or an aldehyde or nitrile, if an aliphatic group Z should be.
  • the organometallic compounds are made, for example, by metal-halogen exchange (e.g. according to Org.
  • the linking of two aromatic rings or an aliphatic group Z with an aromatic ring is preferably carried out by Friedel-Crafts alkylation or acylation in that the corresponding halogenver bonds with the corresponding aromatic compound under Lewis acid catalysis.
  • Suitable Lewis acids are, for example, SnCl 4 , ZnCl 2 and especially A1C1 3 and TiCl 4 .
  • 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 C — C bonds instead of H atoms.
  • Possible reducible groups are preferably carbonyl groups, in particular keto groups, furthermore, for example, free or esterified hydroxyl groups or aromatically bonded halogen 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.
  • 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 or aluminum oxide) or in finely divided form.
  • Ketones can also be prepared using 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, expediently 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 give the corresponding compounds of the formula I 'or I'', the alkyl groups and / or -CH 2 CH 2 - Contain bridges, be reduced.
  • 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 hydrazin
  • Sulfoxides and sulfones can preferably be reduced with complex hydrides.
  • the thioethers of the formula I 'or I can also be obtained from them by heating with elemental sulfur.
  • arylsulfonyloxy groups can be removed reductively with LiAlH 4 , in particular p-toluenesulfonyloxymethyl groups can be reduced to methyl groups, advantageously in an inert solvent. Double bonds can be hydrogenated with tributyltin hydride.
  • Suitable solvents are preferably ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, amides such as dimethylformamide, hexamethylphosphoric triamide, hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, tetrachlorethylene, sulfoxides such as dimethyl sulfoxide, sulfolane, alcohols such as methanol, ethanol, isopropanol and other organic solvents such as acetonitrile and nitromethane.
  • ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, amides such as dimethylformamide, hexamethylphosphoric triamide
  • hydrocarbons such as
  • the reaction temperatures are between -20 and + 100 °, preferably between 0 and 50 °. At these temperatures, the reactions are usually complete after 30 minutes to 24 hours.
  • the phases according to the invention are produced in a conventional manner.
  • the components are dissolved in one another, expediently at elevated temperature.
  • 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.
  • Percentages above and below mean percentages by weight; all temperatures are given in degrees Celsius.
  • Custom work-up means optionally adding water, extraction with methylene chloride, ether or toluene, separating the phases, drying the organic phase, evaporating the organic phase, purifying the residue by distillation and / or crystallization and / or chromatography.
  • Pentyl 4-pentylthiobiphenyl-4'-carboxylate 4-hexylthiobiphenyl-4'-carboxylate 4-heptylthiobiphenyl-4'-carboxylate 4-octylthiobiphenyl-4'-carboxylate pentyl 4-nonylthiobiphenyl-4'-carboxylate 4'-carboxylate
  • a mixture of 13.2 g of dicyclohexycarbodiimide and 13 ml is added to a mixture of 21.9 g of 4-octylthiobiphenyl-4'-carboxylic acid (prepared according to Example 2), 12.4 g of heptylphenol, 1 g of 4-dimethylaminopyridine and 150 ml of toluene Given toluene.
  • the mixture is mixed with 0.2 g of oxalic acid and stirred for a further 30 minutes.
  • 4- (4-octylthiobiphenyl-4'-carbonyloxy) -heptylbenzene is obtained.
  • Hydrogen sulfide is passed into an aqueous solution of 4-octylthiobiphenyl-4'-dia-zonium chloride, prepared from 4-bromo-4'-nitrobiphenyl by reaction with copper (I) octyl mercaptide (analogously to Example 5), reduction and subsequent diazotization and heated to 60 ° C. After the usual work-up, 4-octyltiobiphenyl-4'-thiol is obtained.
  • optically active compounds are obtained analogously with the 4-alkyloxybiphenyl-4'-thiol:
  • optically active propionic acid esters are obtained analogously by reacting 4- (2-alkylthio- (S) -pyrimidin-5-yl) -benzoic acid with (S) -lactic acid esters:
  • optically active connections are made analogously:
  • optically active (R) -2-benzoyloxypropionitriles are obtained analogously with the (R) -2-benzoyloxypropionic acid benzyl esters prepared in Example 16 as starting compounds:

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  • Organic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Liquid Crystal Substances (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

On utilise des composés ayant la formule (I): R1-(CO)m-S-aryle-Z1-(A1-Z2)n-A2-R2 dans laquelle R1, R2, aryle, Z1, Z2, A1, A2, m et n ont la signification décrite dans la première revendication, comme composants de phases de cristaux liquides ferro-électriques. L'invention concerne également les composés ayant la formule (I) et leur procédé de production.
PCT/EP1988/000862 1987-10-07 1988-09-24 Phases de cristaux liquides ferro-electriques WO1989003416A1 (fr)

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DEP3733818.8 1987-10-07
DE19873733818 DE3733818A1 (de) 1987-10-07 1987-10-07 Ferroelektrische fluessigkristalline phasen

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990008756A1 (fr) * 1989-01-27 1990-08-09 MERCK Patent Gesellschaft mit beschränkter Haftung Biphenylylethanes
EP0410142A2 (fr) * 1989-06-23 1991-01-30 Mitsubishi Petrochemical Co., Ltd. Composés cristaux liquides optiquement actifs
WO1991019695A2 (fr) * 1990-06-11 1991-12-26 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Composes a base de thiol a cristaux liquides
GB2253395A (en) * 1990-06-11 1992-09-09 Secr Defence Liquid crystal thiol compounds
WO2001096314A1 (fr) * 2000-06-13 2001-12-20 Basf Aktiengesellschaft 2-(cyanoamino)pyrimidines 5-phenyl-substituees a action fongicide

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH089565B2 (ja) * 1989-07-20 1996-01-31 三洋化成工業株式会社 液晶化合物
US5128061A (en) * 1990-08-14 1992-07-07 Optical Shields, Inc. Phenyl-pyrimidine liquid crystal materials
JP4654474B2 (ja) * 1999-10-13 2011-03-23 チッソ株式会社 分岐メチル基を有する液晶性化合物、液晶組成物及び液晶表示素子

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3434335A1 (de) * 1984-09-19 1986-03-27 Merck Patent Gmbh, 6100 Darmstadt Fluessigkristalline phase
EP0184012A1 (fr) * 1984-11-16 1986-06-11 Bayer Ag Compositions liquides cristallines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3434335A1 (de) * 1984-09-19 1986-03-27 Merck Patent Gmbh, 6100 Darmstadt Fluessigkristalline phase
EP0184012A1 (fr) * 1984-11-16 1986-06-11 Bayer Ag Compositions liquides cristallines

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990008756A1 (fr) * 1989-01-27 1990-08-09 MERCK Patent Gesellschaft mit beschränkter Haftung Biphenylylethanes
US5093026A (en) * 1989-01-27 1992-03-03 Merck Patent Gesellschaft Mit Beschrankter Haftung Biphenylylethanes
EP0410142A2 (fr) * 1989-06-23 1991-01-30 Mitsubishi Petrochemical Co., Ltd. Composés cristaux liquides optiquement actifs
EP0410142A3 (en) * 1989-06-23 1992-02-19 Mitsubishi Petrochemical Co., Ltd. Optically active liquid crystal compounds
US5118442A (en) * 1989-06-23 1992-06-02 Mitsubishi Petrochemical Co., Ltd. Optically active compound
WO1991019695A2 (fr) * 1990-06-11 1991-12-26 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Composes a base de thiol a cristaux liquides
WO1991019695A3 (fr) * 1990-06-11 1992-06-25 Secr Defence Brit Composes a base de thiol a cristaux liquides
GB2253395A (en) * 1990-06-11 1992-09-09 Secr Defence Liquid crystal thiol compounds
GB2253395B (en) * 1990-06-11 1994-03-02 Secr Defence Liquid crystal thiol compounds
WO2001096314A1 (fr) * 2000-06-13 2001-12-20 Basf Aktiengesellschaft 2-(cyanoamino)pyrimidines 5-phenyl-substituees a action fongicide
US6943252B2 (en) 2000-06-13 2005-09-13 Basf Aktiengesellschaft Fungicidal 5-phenyl substituted 2-(cyanoamino) pyrimidines
US7230104B2 (en) 2000-06-13 2007-06-12 Basf Aktiengesellschaft Fungicidal 5-phenyl substituted 2-(cyanoamino) pyrimidines

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