WO1998004544A1 - New liquid crystal compounds and their precursors - Google Patents

New liquid crystal compounds and their precursors Download PDF

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WO1998004544A1
WO1998004544A1 PCT/EP1997/003986 EP9703986W WO9804544A1 WO 1998004544 A1 WO1998004544 A1 WO 1998004544A1 EP 9703986 W EP9703986 W EP 9703986W WO 9804544 A1 WO9804544 A1 WO 9804544A1
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independently
compounds according
compounds
ocoo
coo
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PCT/EP1997/003986
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German (de)
French (fr)
Inventor
Karl Siemensmeyer
Thies Thiemann
Masashi Tashiro
Tsuzuki HIROHISA
Mamoru Mukumoto
Volkmar Vill
Gunnar Gesekus
Shuntaro Mataka
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Basf Aktiengesellschaft
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Priority to AU41157/97A priority Critical patent/AU4115797A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C07D333/70—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur 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
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • C09K19/3497—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom the heterocyclic ring containing sulfur and nitrogen atoms

Definitions

  • liquid-crystalline phases so-called mesophases
  • mesophases can occur during heating.
  • the individual phases differ in the spatial arrangement of the molecular centers on the one hand and in the molecular arrangement with regard to the longitudinal axes on the other hand (G.W. Gray,
  • the nematic liquid-crystalline phase is characterized by the fact that only a long-distance order exists due to the parallel storage of the longitudinal axes of the molecules.
  • a so-called cholesteric phase is formed in which the longitudinal axes of the molecules form a helical superstructure that is perpendicular to them (H. Baessler, Solid State Problems XI, 1971).
  • the chiral part of the molecule can either be present in the liquid-crystalline molecule itself or be added to the nematic phase as a dopant, the cholesteric phase being induced.
  • the cholesteric phase has remarkable optical properties: a high optical rotation and a pronounced circular dichroism, which is created by selective reflection of circularly polarized light within the cholesteric layer.
  • the colors which appear different depending on the perspective, depend on the pitch of the helical superstructure, which in turn depends on the twisting power of the chiral component.
  • the pitch and thus the wavelength range of the selectively reflected light of a cholesteric layer can be varied by changing the concentration of a chiral dopant.
  • Such cholesteric systems offer interesting possibilities for practical use. By incorporating chiral molecular parts into mesogenic acrylic acid esters and orienting them in the cholesteric phase, e.g.
  • a cholesteric network can be obtained in which the chiral component can have a share of up to 50% of the material used; however, these polymers still contain significant amounts of soluble fractions (FH Kreuzer, R. Maurer, Ch. Müller-Rees, J. Stohrer, Lecture No. 7, 22nd Freiburg Working Conference on Liquid Crystals, Freiburg, 1993).
  • the application DE-OS-35 35 547 describes a method in which a mixture of cholesterol-containing monoacrylates can be processed into cholesteric layers by means of photo-crosslinking.
  • the total proportion of the chiral component in the mixture is approximately 94%.
  • a pure side chain polymer such a material is not mechanically very stable, but an increase in stability can be achieved by highly crosslinking diluents.
  • smectic networks are also known which are produced in particular by photopolymerization / photocrosslinking of smectically liquid-crystalline materials in the smectically liquid-crystalline phase.
  • the materials used for this are generally symmetrical, liquid-crystalline bisacrylates such as those used by DJ Broer and RAM Hikmet, Makromol. Chem., 190, 3201-3215 (1989). However, these materials have very high clarification temperatures of> 120 ° C., so that there is a risk of thermal polymerization.
  • piezoelectric properties can be achieved in the presence of an S c phase (RAM Hikmet, Macromolecules 23, p. 5759, 1992).
  • the object of the present invention was to produce new liquid-crystalline materials which, alone or in mixtures with other liquid crystals, have or induce broad liquid-crystalline phase ranges and high clearing temperatures.
  • the invention now relates to compounds of the general formula i
  • M independently of one another optionally substituted aliphatic, aromatic, heteroaliphatic or heteroaromatic ring systems
  • n and m independently of one another 0, 1 or 2
  • Y independently of one another 0, S, COO, OCO, OCOO, CONH, NHCO, CONR, NRCO or a direct bond and the groups
  • Z are independently hydrogen, cyano or a polymerizable group.
  • spacers A All groups known for this purpose can be used as spacers A;
  • the spacers are usually linked to M or Z via carbonate, ester or ether groups or a direct bond, ie the radicals Y preferably correspond to a direct bond, 0, S, COO or OCOO.
  • the spacers generally contain 2 to 30, preferably 2 to 12, carbon atoms and can be interrupted in the chain, for example by 0, S, NH, NR, COO, OCO, CO or OCOO. Fluorine, chlorine, bromine, cyano, hydroxy or C 1 -C 4 -alkyl can also be used as substituents for the spacer chain.
  • spacers are for example:
  • q are 1 to 3 and p are 1 to 12.
  • radicals M are generally not aromatic or aromatic carbocyclic or heterocyclic ring systems which are optionally substituted by fluorine, chlorine, bromine, cyano, hydroxy or nitro and which, for example, correspond to the following basic structures:
  • M are z. B. :
  • n and m are a maximum of 3 in total
  • X is 0, S, COO or OCOO
  • Z is hydrogen, vinyl, methylvinyl, chlorovinyl, NCO, OCN or
  • the rest Z- YA r - (YM) n -X corresponds in particular a Ci to C ⁇ 2 alkoxy group, optionally carrying a polymerizable group.
  • the invention further relates to the new compounds of the formula
  • T is hydrogen or Ci to -C 2 alkyl
  • T 1 are hydroxy, chlorine or bromine.
  • the units Z -YA r - (YM) n - according to the invention, in which Z, Y, A r and M have the meaning given above, are by generally known synthesis processes, as described, for example, in DE-A 39 17 196, accessible.
  • the compounds according to the invention are particularly suitable for use in electro-optical display elements, as a chiral dopant for nematic or cholesteric liquid crystals for producing color-reflecting layers or for the production of liquid-crystalline cholesteric ordered pigments.
  • the preparation is carried out analogously to Example 1. However, 1.2 ml of a 28% sodium methoxide solution in ethanol are used in the reaction.
  • the yield after working up and purification was 0.28 g, which corresponds to a yield of 97%, based on 0.25 g of 4, 5, 6, 7 -tetra-fluoro -6 -benzo- [b] -thiophene-2-carboxylic acid .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

Compounds have the general formula (I), in which the radicals A are spacers; r equals 0 or 1; the radicals M independently represent optionally substituted aliphatic, aromatic, heteroaliphatic or heteroaromatic ring systems; n and m independently equal 0, 1 or 2; X stands for O, S, COO, OCOO, CONH or CONR; R stands for C1-C4-alkyl; the radical Y independently represent O, S, COO, OCO, OCOO, CONH, NHCO, CONR, NRCO or a direct bond; and the groups Z independently represent hydrogen, cyano or a polymerisable group. These compounds are suitable for use as such or mixed with other liquid crystal compounds in optical display elements or data storage means, in polarisers or in liquid crystal dyes.

Description

Neue flüssigkristalline Verbindungen und deren Vorprodukte New liquid crystalline compounds and their precursors
Beschreibungdescription
Wie für formanisotrope Medien bekannt, können beim Erwärmen flüssigkristalline Phasen, sogenannte Mesophasen, auftreten. Die einzelnen Phasen unterscheiden sich durch die räumliche Anordnung der Molekülscnwerpunkte einerseits sowie durch die Molekülanord- nung hinsichtlich der Längsachsen andererseits (G.W. Gray,As is known for shape-anisotropic media, liquid-crystalline phases, so-called mesophases, can occur during heating. The individual phases differ in the spatial arrangement of the molecular centers on the one hand and in the molecular arrangement with regard to the longitudinal axes on the other hand (G.W. Gray,
P.A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974). Die nematisch flüssigkristalline Phase zeichnet sich dadurch aus, daß lediglich eine Orientierungsfern- Ordnung durch Parallellagerung der Moleküllängsachsen existiert. Unter der Voraussetzung, daß die die nematische Phase aufbauenden Moleküle chiral sind, entsteht eine sogenannte cholesterische Phase, bei der die Längsacnsen der Moleküle eine zu ihnen senkrechte, helixartige ύberstruktur ausbilden (H. Baessler, Fest- korperprobleme XI, 1971) . Der chirale Molekulteil kann sowohl im flüssigkristallinen Molekül selbst vorhanden sein als auch als Dotierstoff zur nematischen Phase gegeben werden, wobei die cholesterische Phase induziert wird. Dieses Phänomen wurde zuerst an Cholesterolderivaten untersucht (z.B. H. Baessler, M.M. Labes, J. Chem. Phys., 5 , 631 (1970); H. Baessler, T.M. Laronge, M.M. Labes, J. Chem. Phys., 51 799 (1969); H. Finkelmann,P.A. Winsor, Liquid Crystals and Plastic Crystals, Ellis Horwood Limited, Chichester 1974). The nematic liquid-crystalline phase is characterized by the fact that only a long-distance order exists due to the parallel storage of the longitudinal axes of the molecules. Provided that the molecules that make up the nematic phase are chiral, a so-called cholesteric phase is formed in which the longitudinal axes of the molecules form a helical superstructure that is perpendicular to them (H. Baessler, Solid State Problems XI, 1971). The chiral part of the molecule can either be present in the liquid-crystalline molecule itself or be added to the nematic phase as a dopant, the cholesteric phase being induced. This phenomenon was first investigated on cholesterol derivatives (e.g. H. Baessler, MM Labes, J. Chem. Phys., 5, 631 (1970); H. Baessler, TM Laronge, MM Labes, J. Chem. Phys., 51 799 ( 1969); H. Finkelmann,
H. Stegemeyer, Z. Naturforschg. 28a, 799 (1973); H. Stegemeyer, K.J. Mainusch, Naturwiss., üi 599 (1971), H. Finkelmann, H. Stegemeyer, Ber. Bunsenges. Phys. Chem. IS., 869 (1974)).H. Stegemeyer, Z. Naturforschg. 28a, 799 (1973); H. Stegemeyer, K.J. Mainusch, Naturwiss., Üi 599 (1971), H. Finkelmann, H. Stegemeyer, Ber. Bunsenges. Phys. Chem. IS., 869 (1974)).
Die cholesterische Phase hat bemerKenswerte optische Eigenschaften: eine hohe optische Rotation sowie einen ausgeprägten Zirkulardichroismus, der durch Selektivreflexion von zirkulär polarisiertem Licht innerhalb der cholesterischen Schicht entsteht. Die je nach Blickwinkel unterschiedlich erscheinenden Farben sind abhängig von der Ganghohe der helixartigen ύberstruktur, die ihrerseits vom Verdrillungsvermogen der chiralen Komponente abhängt. Dabei kann insbesondere durch Änderung der Konzentration eines chiralen Dotierstoffes die Ganghöhe und damit der Wellenlängenbereich des selektiv reflektierten Lichtes einer cholesterischen Schicht variiert werden. Solche cholesterischen Systeme bieten für eine praktische Anwendung interessante Möglichkeiten. So kann durch Einbau chiraler Molekulteile in mesogene Acryisäureester und Orientierung in der cholesterischen Phase, z.B. nach der Photovernetzung, ein stabiles, farbiges Netzwerk hergestellt werden, dessen Konzentration an chiraler Komponente dann aber nicht mehr verändert werden kann (G. Galli, M. Laus, A. Angelon, Makromol. Chemie, 121, 289 (1986)). Durch Zumischen von nichtvernetzbaren chiralen Verbindungen zu ne ati- schen Acrylsäureestern kann durch Photovernetzung ein farbiges Polymer hergestellt werden, welches noch hohe Anteile löslicher Komponenten enthält (I. Heyndricks, D.J. Broer, Mol. Cryst. Liq. Cryst. 203. 113 (1991)). Weiterhin kann durch statistische Hydro- silylierung von Gemischen aus Cholesterolderivaten und acrylat- haltigen Mesogenen mit definierten zyklischen Siloxanen und anschließende Photopolymerisation ein cholesterisches Netzwerk gewonnen werden, bei dem die chirale Komponente einen Anteil von bis zu 50 % an dem eingesetzten Material haben kann; diese Polymerisate enthalten jedoch noch deutliche Mengen löslicher Anteile (F.H. Kreuzer, R. Maurer, Ch. Müller-Rees, J. Stohrer, Vortrag Nr. 7, 22. Freiburger Arbeitstagung Flüssigkristalle, Freiburg, 1993) .The cholesteric phase has remarkable optical properties: a high optical rotation and a pronounced circular dichroism, which is created by selective reflection of circularly polarized light within the cholesteric layer. The colors, which appear different depending on the perspective, depend on the pitch of the helical superstructure, which in turn depends on the twisting power of the chiral component. In particular, the pitch and thus the wavelength range of the selectively reflected light of a cholesteric layer can be varied by changing the concentration of a chiral dopant. Such cholesteric systems offer interesting possibilities for practical use. By incorporating chiral molecular parts into mesogenic acrylic acid esters and orienting them in the cholesteric phase, e.g. after photocrosslinking, a stable, colored network can be produced, but the concentration of chiral components can then no longer be changed (G. Galli, M. Laus, A. Angelon, Makromol. Chemie, 121, 289 (1986)). By Mixing non-crosslinkable chiral compounds to neic acrylic acid esters can be achieved by photocrosslinking a colored polymer that still contains high proportions of soluble components (I. Heyndricks, DJ Broer, Mol. Cryst. Liq. Cryst. 203, 113 (1991)) . Furthermore, by statistical hydrosilylation of mixtures of cholesterol derivatives and acrylate-containing mesogens with defined cyclic siloxanes and subsequent photopolymerization, a cholesteric network can be obtained in which the chiral component can have a share of up to 50% of the material used; however, these polymers still contain significant amounts of soluble fractions (FH Kreuzer, R. Maurer, Ch. Müller-Rees, J. Stohrer, Lecture No. 7, 22nd Freiburg Working Conference on Liquid Crystals, Freiburg, 1993).
In der Anmeldung DE-OS-35 35 547 wird ein Verfahren beschrieben, bei dem eine Mischung cholesterolhaltiger Monoacrylate über eine Photovernetzung zu cholesterischen Schichten verarbeitet werden kann. Allerdings beträgt der Gesamtanteil der chiralen Komponente in der Mischung ca. 94 %. Als reines Seitenkettenpolymer ist ein solches Material zwar mechanisch nicht sehr stabil, eine Erhöhung der Stabilität kann aber durch hochvernetzende Verdünnungsmittel erreicht werden.The application DE-OS-35 35 547 describes a method in which a mixture of cholesterol-containing monoacrylates can be processed into cholesteric layers by means of photo-crosslinking. However, the total proportion of the chiral component in the mixture is approximately 94%. As a pure side chain polymer, such a material is not mechanically very stable, but an increase in stability can be achieved by highly crosslinking diluents.
Neben oben beschriebenen nematischen und cholesterischen Netzwerken sind auch smektische Netzwerke bekannt, welche insbesondere durch Photopolymerisation/Photovernetzung von smektisch flüssigkristallinen Materialien in der smektisch flüssigkristallinen Phase hergestellt werden. Die hierfür verwendeten Materialien sind in der Regel symmetrische, flüssigkristalline Bisacrylate, wie sie z.B. D.J. Broer und R.A.M. Hikmet, Makromol. Chem., 190, 3201-3215 (1989) beschrieben haben. Diese Materialien weisen aber sehr hohe Klärtemperaturen von > 120°C auf, so daß die Gefahr einer thermischen Polymerisation gegeben ist. Durch Zumischen chiraler Materialien können beim Vorliegen einer Sc-Phase piezoelektrische Eigenschaften erzielt werden (R.A.M. Hikmet, Macromolecules 23., S. 5759, 1992).In addition to the nematic and cholesteric networks described above, smectic networks are also known which are produced in particular by photopolymerization / photocrosslinking of smectically liquid-crystalline materials in the smectically liquid-crystalline phase. The materials used for this are generally symmetrical, liquid-crystalline bisacrylates such as those used by DJ Broer and RAM Hikmet, Makromol. Chem., 190, 3201-3215 (1989). However, these materials have very high clarification temperatures of> 120 ° C., so that there is a risk of thermal polymerization. By adding chiral materials, piezoelectric properties can be achieved in the presence of an S c phase (RAM Hikmet, Macromolecules 23, p. 5759, 1992).
Aufgabe der vorliegenden Erfindung war die Herstellung neuer flüssigkristalliner Materialien, die allein oder in Mischungen mit anderen Flüssigkristallen breite flüssigkristalline Phasenbereiche und hohe Klärtemperaturen aufweisen oder induzieren. Die Erfindung betrifft nun Verbindungen der allgemeinen Formel iThe object of the present invention was to produce new liquid-crystalline materials which, alone or in mixtures with other liquid crystals, have or induce broad liquid-crystalline phase ranges and high clearing temperatures. The invention now relates to compounds of the general formula i
Figure imgf000005_0001
Figure imgf000005_0001
in der die Restein which the leftovers
A Spacer,A spacer,
r 0 oder 1, die Rester 0 or 1, the residues
M unabhängig voneinander gegebenenfalls substituierte aliphatische, aromatische, heteroaliphatische oder heteroaromatische Ringsysteme,M independently of one another optionally substituted aliphatic, aromatic, heteroaliphatic or heteroaromatic ring systems,
n und m unabhängig voneinander 0, 1 oder 2,n and m independently of one another 0, 1 or 2,
X 0, S, COO, OCOO, CONH oder CONR,X 0, S, COO, OCOO, CONH or CONR,
R Ci- bis C -Alkyl, die ResteR Ci to C alkyl, the radicals
Y unabhängig voneinander 0, S, COO, OCO, OCOO, CONH, NHCO, CONR, NRCO oder eine direkte Bindung und die GruppenY independently of one another 0, S, COO, OCO, OCOO, CONH, NHCO, CONR, NRCO or a direct bond and the groups
Z unabhängig voneinander Wasserstoff, Cyan oder eine poly- merisierbare Gruppe sind.Z are independently hydrogen, cyano or a polymerizable group.
Als Spacer A können alle für diesen Zweck bekannten Gruppen verwendet werden; üblicherweise sind die Spacer über Carbonat-, Ester- oder Ethergruppen oder eine direkte Bindung mit M oder Z verknüpft, d.h. die Reste Y entsprechen vorzugsweise einer direkten Bindung, 0, S, COO oder OCOO. Die Spacer enthalten in der Regel 2 bis 30, vorzugsweise 2 bis 12 C-Atome und können in der Kette z.B. durch 0, S, NH, NR, COO, OCO, CO oder OCOO unterbrochen sein. Als Substituenten für die Spacerkette kommen dabei noch Fluor, Chlor, Brom, Cyan, Hydroxy oder Ci- bis C4-Alkyl in Betracht.All groups known for this purpose can be used as spacers A; The spacers are usually linked to M or Z via carbonate, ester or ether groups or a direct bond, ie the radicals Y preferably correspond to a direct bond, 0, S, COO or OCOO. The spacers generally contain 2 to 30, preferably 2 to 12, carbon atoms and can be interrupted in the chain, for example by 0, S, NH, NR, COO, OCO, CO or OCOO. Fluorine, chlorine, bromine, cyano, hydroxy or C 1 -C 4 -alkyl can also be used as substituents for the spacer chain.
Repräsentative Spacer sind beispielsweise:Representative spacers are for example:
(CH2)p, (CH2CH20)qCH2CH2, CH2CH2SCH2CH2 , CH2CH2NHCH2CH2 , CH3 CH3 CH3 CH3 CI(CH 2 ) p , (CH 2 CH 2 0) q CH 2 CH 2 , CH 2 CH 2 SCH 2 CH 2 , CH 2 CH 2 NHCH 2 CH 2 , CH 3 CH 3 CH 3 CH 3 CI
CH2CH2N CH2CH2 (CH2CHO) qCH2CH ' (CH2 ) 6CH oder CH2CH2CH 'CH 2 CH 2 N CH 2 CH 2 (CH 2 CHO) q CH 2 CH '(CH 2 ) 6 CH or CH 2 CH 2 CH'
wobeiin which
q 1 bis 3 und p 1 bis 12 sind.q are 1 to 3 and p are 1 to 12.
Die Reste M sind in der Regel nicht aromatisch oder aromatisch carbocyclische oder heterocyclische, gegebenenfalls durch Fluor, Chlor, Brom, Cyan, Hydroxy oder Nitro substituierte Ringsysteme, die z.B. folgenden Grundstrukturen entsprechen:The radicals M are generally not aromatic or aromatic carbocyclic or heterocyclic ring systems which are optionally substituted by fluorine, chlorine, bromine, cyano, hydroxy or nitro and which, for example, correspond to the following basic structures:
Figure imgf000006_0001
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000007_0001
Besonders bevorzugt sind als Gruppen (M-Y)n z.B:Particularly preferred as groups (MY) n are :
Figure imgf000007_0002
Figure imgf000007_0002
Figure imgf000008_0001
Figure imgf000008_0001
Besonders bevorzugt für M sind z . B . :Particularly preferred for M are z. B. :
Figure imgf000008_0002
Von besonderer Bedeutung sind weiterhin Verbindungen, bei denen n und m in der Summe maximal 3 sind, X 0, S, COO oder OCOO ist und Z Wasserstoff, Vinyl, Methylvinyl, Chlorvinyl, NCO, OCN oder
Figure imgf000008_0002
Also of particular importance are compounds in which n and m are a maximum of 3 in total, X is 0, S, COO or OCOO and Z is hydrogen, vinyl, methylvinyl, chlorovinyl, NCO, OCN or
—CH CH2 bedeutet.—CH CH 2 means.
Der Rest Z- Y-Ar- (Y-M)n-X entspricht insbesondere auch einer Ci- bis Cχ2-Alkoxygruppe, die gegebenenfalls eine polymerisierbare Gruppe trägt. Die Erfindung betrifft weiterhin die neuen Verbindungen der FormelThe rest Z- YA r - (YM) n -X corresponds in particular a Ci to Cχ 2 alkoxy group, optionally carrying a polymerizable group. The invention further relates to the new compounds of the formula
Figure imgf000009_0001
Figure imgf000009_0001
in derin the
T Wasserstoff oder Ci- bis Cι2-Alkyl undT is hydrogen or Ci to -C 2 alkyl and
T1 Hydroxy, Chlor oder Brom sind.T 1 are hydroxy, chlorine or bromine.
Die erfindungsgemäßen Einheiten Z -Y-Ar- (Y-M)n- , in denen Z, Y, Ar und M die oben angegebene Bedeutung haben, sind durch allgemein bekannte Syntheseverfahren, wie sie beispielsweise in der DE-A 39 17 196 beschrieben sind, zugänglich.The units Z -YA r - (YM) n - according to the invention, in which Z, Y, A r and M have the meaning given above, are by generally known synthesis processes, as described, for example, in DE-A 39 17 196, accessible.
Die erfindungsgemäßen Verbindungen eignen sich insbesondere zur Verwendung in elektro -optischen Anzeigeelementen, als chiraler Dotierstoff für nematische oder cholesterische Flüssigkristalle zur Erzeugung farbig reflektierender Schichten oder zur Herstellung von flüssigkristallin cholesterisch geordneten Pigmenten.The compounds according to the invention are particularly suitable for use in electro-optical display elements, as a chiral dopant for nematic or cholesteric liquid crystals for producing color-reflecting layers or for the production of liquid-crystalline cholesteric ordered pigments.
Beispiel 1example 1
Herstellung von 4 , 5 , 7 -Trifluoro -6 -methoxybenzo- fb] - thio- phen - 2 -carbonsäurePreparation of 4, 5, 7 -trifluoro -6 -methoxybenzo- fb] - thiophene - 2-carboxylic acid
Eine Mischung von 0,5 g (2 m ol) 4 , 5, 6 , 7 -Tetrafluoro- benzo- [b] - hiophen- 2 -carbonsäure, 0,96 ml 28 %ige Natrium- methanolatlösung in Methanol und 5 ml Dimethylformamid (DMF) werden 25 h unter Rückfluß erhitzt. Nach dem Abkühlen wird Wasser zum Reaktionsgemisch gegeben und mit konzentrierter Salzsäure sauer gestellt.A mixture of 0.5 g (2 mol) of 4, 5, 6, 7-tetrafluorobenzo- [b] - hiophene-2-carboxylic acid, 0.96 ml of 28% sodium methanolate solution in methanol and 5 ml of dimethylformamide (DMF) are heated under reflux for 25 h. After cooling, water is added to the reaction mixture and acidified with concentrated hydrochloric acid.
Der ausgefallene Feststoff wird in 100 ml Dichlormethan aufgenommen und über MgS04 getrocknet. Nach dem Abfiltrieren wird die Lösung im Vacuum eingeengt und der Rückstand mit einem Überschuß von Diazomethan, gelöst in Ether, versetzt. Die Lösung wird eingeengt und der Rückstand säulenchromatografisch gereinigt (Kieselgel 60, Hexan: Dichlormethan = 1:1). Man erhält 0,55 g des Methylesters der oben genannten Säure (99 % d. Th. ) . Der Methylester wird anschließend mit NaOH in Ethanol hydrolysiert . Die Säure wird durch Ansäuern mit konz . HC1 ausgefällt und durch Sublimation gereinigt.The precipitated solid is taken up in 100 ml dichloromethane and dried over MgSO 4 . After filtering off, the solution is concentrated in vacuo and the residue is treated with an excess of diazomethane, dissolved in ether. The solution is concentrated and the residue is purified by column chromatography (silica gel 60, hexane: dichloromethane = 1: 1). 0.55 g of the methyl ester of the abovementioned acid (99% of theory) is obtained. The methyl ester is then hydrolyzed with NaOH in ethanol. The Acid is acidified with conc. HC1 precipitated and cleaned by sublimation.
Beispiel 2Example 2
Herstellung von 4 , 5, 7 -Trifluoro-6 -ethoxybenzo- [b] - thio- phen - 2 -carbonsäurePreparation of 4, 5, 7 -trifluoro-6-ethoxybenzo- [b] - thiophene - 2-carboxylic acid
Die Herstellung erfolgt analog Beispiel 1. Es werden jedoch 1,2 ml einer 28 %igen Natriummethanolatlosung in Ethanol bei der Reaktion eingesetzt.The preparation is carried out analogously to Example 1. However, 1.2 ml of a 28% sodium methoxide solution in ethanol are used in the reaction.
Die Ausbeute nach Aufarbeitung und Reinigung betrug 0,28 g, was 97 % Ausbeute, bezogen auf 0,25 g eingesetzte 4 , 5 , 6 , 7 -Tetra - fluoro -6 -benzo- [b] -thiophene- 2 -carbonsäure entspricht.The yield after working up and purification was 0.28 g, which corresponds to a yield of 97%, based on 0.25 g of 4, 5, 6, 7 -tetra-fluoro -6 -benzo- [b] -thiophene-2-carboxylic acid .
Beispiel 3Example 3
Herstellung von 4 , 5 , 7 -Trifluoro- 6 -butoxybenzo- [b] -thio- phen - 2 -carbonsäurePreparation of 4, 5, 7 -trifluoro- 6 -butoxybenzo- [b] -thiophene - 2-carboxylic acid
Eine Mischung von 4 , 5, 6, 7 -Tetraf luorobenzo- [b] - thiophen-2 -carbon- säure (0,50 g; 2 mmol), Natriumhydroxid (0,56 g; 10 mmol) und Butanol (12 ml) wird 25 h unter Ruckfluß erhitzt. Die Aufaroei- tung der Reaktionsmischung erfolgt analog Beispiel 1.A mixture of 4, 5, 6, 7-tetrafluorobenzo- [b] - thiophene-2-carboxylic acid (0.50 g; 2 mmol), sodium hydroxide (0.56 g; 10 mmol) and butanol (12 ml ) is heated under reflux for 25 h. The reaction mixture is prepared analogously to Example 1.
Ausbeute: 0,30 g = 77 % d. Th. Phasenverhal en: K 120 N 141,8 IYield: 0.30 g = 77% of theory. Th. Phase behavior: K 120 N 141.8 I
Beispiel 4Example 4
Herstellung von 4 , 5, 7 -Trifluoro-6 -butoxybenzo- [b] -thio- phen- 2 -carbonsaure- (4 -cyanphenyl) -esterPreparation of 4, 5, 7 -trifluoro-6-butoxybenzo- [b] -thio-phen- 2 -carboxylic acid- (4 -cyanphenyl) -ester
3,04 g (0,01 mol) , 5 , 7 -Tetrafluor- 6 -butoxybenzo- [bj - thio- phen- 2 -carbonsäure und 1,19 g (0,01 mol) 4-Cyanphenol werden in 50 ml Methylenchlorid gelost. Zu dieser Losung werden bei 0°C 5,15 g (0,025 mol) Dicyclohexylcarbodiimid und 0,305 g (0,0025 mol) Dimethylaminopyridin gelöst m Methylenchlorid gege- ben. Die Reaktionsmischung rührt 14 h bei Raumtemperatur. Zur3.04 g (0.01 mol), 5, 7-tetrafluoro-6-butoxybenzo- [bj - thiophene-2-carboxylic acid and 1.19 g (0.01 mol) 4-cyanophenol are dissolved in 50 ml methylene chloride solved. 5.15 g (0.025 mol) of dicyclohexylcarbodiimide and 0.305 g (0.0025 mol) of dimethylaminopyridine dissolved in methylene chloride are added to this solution at 0 ° C. The reaction mixture is stirred at room temperature for 14 h. to
Aufarbeitung wird der abgeschiedene Feststoff abfiltriert und die Reaktionsmischung bis zur Trockne eingeengt. Das rohe Reaktions- produkt wird anschließend in Toluol aufgenommen und säulenchroma- tografisch (Kieselgel 60, Toluol/Ethanol= 9:1) gereinigt. Ausbeute: 3,48 g = 86 % d. Th. Phasenverhalten: K 125,5 (N) IWorking up, the separated solid is filtered off and the reaction mixture is evaporated to dryness. The crude reaction product is then taken up in toluene and purified by column chromatography (silica gel 60, toluene / ethanol = 9: 1). Yield: 3.48 g = 86% of theory. Th. Phase behavior: K 125.5 (N) I
Beispiel 5Example 5
Herstellung von 4 , 5, 7 -Trifluoro-6 -butoxybenzo- [b] - thio- phen-2 -carbonsäure- [ -2 - (4 -octoxyphenyDpyranyl - (5) ] -esterPreparation of 4, 5, 7 -trifluoro-6-butoxybenzo- [b] - thiophene-2-carboxylic acid- [-2 - (4 -octoxyphenyDpyranyl - (5)] ester
3,04 g (0,01 mol) 4 , 5 , 7 -Tetrafluor- 6 -butoxybenzo- [b] - hio- phen- 2 -carbonsäure und 3,06 g (0,01 mol) 244 -0ctoxyphenyl-)-5 - hydroxypyran werden in 50 ml Methylenchlorid gelöst. Zu dieser Lösung werden bei 0°C 5,15 g (0,025 mol) Dicyclohexylcarbodiimid und 0,305 g (0,0025 mol) Dimethylaminopyridin gelöst in Methylenchlorid gegeben. Die Reaktionsmischung rührt 14 h bei Raumtempe- ratur. Zur Aufarbeitung wird der abgeschiedene Feststoff abfiltriert und die Reaktionsmischung bis zur Trockne eingeengt. Das rohe Reaktionsprodukt wird anschließend in Toluol aufgenommen und säulenchromatograf isch (Kieselgei 60, Toluol/Ethanol= 9:1) gereinigt.3.04 g (0.01 mol) 4, 5, 7-tetrafluoro-6-butoxybenzo- [b] - hiophen-2-carboxylic acid and 3.06 g (0.01 mol) 244 -0ctoxyphenyl -) - 5-hydroxypyran are dissolved in 50 ml of methylene chloride. 5.15 g (0.025 mol) of dicyclohexylcarbodiimide and 0.305 g (0.0025 mol) of dimethylaminopyridine dissolved in methylene chloride are added to this solution at 0.degree. The reaction mixture is stirred for 14 h at room temperature. For working up, the separated solid is filtered off and the reaction mixture is evaporated to dryness. The crude reaction product is then taken up in toluene and purified by column chromatography (Kieselgei 60, toluene / ethanol = 9: 1).
Ausbeute: 4,38 g = 74 % d. Th. Phasenverhalten: K 80 Sa 126 CH 136 BP 138 IYield: 4.38 g = 74% of theory. Th. Phase behavior: K 80 Sa 126 CH 136 BP 138 I
Analog Beispiel 4 und 5 können die folgenden Verbindungen herge- stellt werden:The following compounds can be produced analogously to Examples 4 and 5:
Beispiel 6Example 6
Figure imgf000011_0001
Figure imgf000011_0001
Beispiel 7Example 7
Figure imgf000011_0002
Beispiel 8
Figure imgf000011_0002
Example 8
Figure imgf000012_0001
Figure imgf000012_0001
Beispiel 9Example 9
Figure imgf000012_0002
Figure imgf000012_0002
Beispiel 10Example 10
Figure imgf000012_0003
Figure imgf000012_0003
Beispiel 11Example 11
Figure imgf000012_0004
Figure imgf000012_0004
Beispiel 12Example 12
Figure imgf000012_0005
Beispiel 13
Figure imgf000012_0005
Example 13
Figure imgf000013_0001
Figure imgf000013_0001

Claims

Patentansprüche claims
1. Verbindungen der allgemeinen Formel1. Compounds of the general formula
FF
Figure imgf000014_0001
Figure imgf000014_0001
in der die Restein which the leftovers
A Spacer,A spacer,
r 0 oder 1, die Rester 0 or 1, the residues
M unabhängig voneinander gegebenenfalls substituierte aliphatische, aromatische, heteroaliphatische oder heteroaromatische Ringsysteme,M independently of one another optionally substituted aliphatic, aromatic, heteroaliphatic or heteroaromatic ring systems,
n und m unabhängig voneinander 0, 1 oder 2,n and m independently of one another 0, 1 or 2,
X 0, S, COO, OCOO, CONH oder CONR,X 0, S, COO, OCOO, CONH or CONR,
R Ci- bis C4-Alkyl, die ResteR Ci to C 4 alkyl, the radicals
Y unabhängig voneinander 0, S, COO, OCO, OCOO, CONH, NHCO, CONR, NRCO oder eine direkte Bindung und dieY independently of one another 0, S, COO, OCO, OCOO, CONH, NHCO, CONR, NRCO or a direct bond and the
Gruppengroups
Z unabhängig voneinander Wasserstoff, Cyan oder eine polymerisierbare Gruppe sind.Z are independently hydrogen, cyan or a polymerizable group.
2. Verbindungen gemäß Anspruch 1, bei denen die Spacer A unabhängig voneinander gegebenenfalls durch Ci - bis C -Alkyl, Fluor, Chlor, Brom, Cyan oder Hydroxy substituiertes und gegebenenfalls ein- oder mehrfach durch 0, S, NH, NR, COO, OCO, OCOO oder CO unterbrochenes C2- bis C3rj-Alkylen oder -Alkenylen sind. 2. Compounds according to claim 1, in which the spacers A independently of one another are optionally substituted by C 1 -C 4 -alkyl, fluorine, chlorine, bromine, cyano or hydroxyl and are optionally substituted one or more times by 0, S, NH, NR, COO, OCO, OCOO or CO are interrupted C 2 - to C 3 rj-alkylene or alkenylene.
3 . Verbindungen gemäß Anspruch 1 , bei denen die Spacer A unabhängig voneinander den Formeln3rd Compounds according to Claim 1, in which the spacers A independently of one another have the formulas
( CH2 ) p , (CH2CH20) qCH2CH2 , CH2CH2SCH2CH2 , CH2CH2NHCH2CH2 ,(CH 2 ) p , (CH 2 CH 2 0) q CH 2 CH 2 , CH 2 CH 2 SCH 2 CH 2 , CH 2 CH 2 NHCH 2 CH 2 ,
CH2CH2N CH2CH2 , (CH2CHO) q CH2CH , (CH2 ) 6CH oderCH 2 CH 2 N CH 2 CH 2 , (CH 2 CHO) q CH 2 CH, (CH 2 ) 6 CH or
CH3 CH3 CH3 CH3 CH 3 CH 3 CH 3 CH 3
CH2CH2CHCH 2 CH 2 CH
II.
CICI
entsprechen, wobeicorrespond with
p 1 bis 12 undp 1 to 12 and
q 1 bis 3 sind.q are 1 to 3.
4. Verbindungen gemäß Anspruch 1, bei denen die Reste M den For' mein4. Compounds according to claim 1, in which the radicals M the form 'my
Figure imgf000015_0001
Figure imgf000015_0001
N—N oder — (/ \ — entsprechen. SN — N or - (/ \ -. S
5. Verbindungen gemäß Anspruch 1, bei denen5. Compounds according to claim 1, in which
n und m in der Summe maximal 3 sind.n and m are a maximum of 3 in total.
6. Verbindungen gemäß Anspruch 1, bei denen6. Compounds according to claim 1, in which
X 0, S, COO oder OCOO ist.X is 0, S, COO or OCOO.
7. Verbindungen gemäß Anspruch 1, bei denen7. Compounds according to claim 1, in which
Y unabhängig voneinander für 0, S, COO, OCO, OCOO oder eine direkte Bindung steht. Y independently of one another represents 0, S, COO, OCO, OCOO or a direct bond.
8. Verbindungen gemäß Anspruch 1, bei denen die Reste8. Compounds according to claim 1, in which the radicals
Z unabhängig voneinander Wasserstoff, Vinyl, Methylvinyl, Chlorvinyl, NCO, OCN oder — CH — CH sind.Z are independently hydrogen, vinyl, methyl vinyl , chlorovinyl, NCO, OCN or - CH - CH.
\ /\ /
00
9. Verbindungen gemäß Anspruch 1, bei denen der Rest Z-Y-Ar- (Y-M)n-X- eine Ci- bis C12-Alkoxygruppe ist, die gegebenenfalls eine polymerisierbare Gruppe trägt.9. Compounds according to claim 1, in which the radical r ZYA - (YM) n -X- is a Ci to C 12 alkoxy group optionally having a polymerizable group.
10. Verbindungen der Formel10. Compounds of the formula
Figure imgf000016_0001
Figure imgf000016_0001
in derin the
T Wasserstoff oder Ci- bis C12-Alkyl undT is hydrogen or Ci to C 12 alkyl and
T1 Hydroxy, Chlor oder Brom sind.T 1 are hydroxy, chlorine or bromine.
11. Verwendung der Verbindungen gemäß Anspruch 1 als solche oder im Gemisch mit anderen flussigkristallinen Verbindungen in optischen Anzeigeelementen oder Datenspeichern, in Polarisa- toren oder in flüssigkristallinen Farbmitteln. 11. Use of the compounds according to claim 1 as such or in a mixture with other liquid-crystalline compounds in optical display elements or data memories, in polarizers or in liquid-crystalline colorants.
PCT/EP1997/003986 1996-07-25 1997-07-23 New liquid crystal compounds and their precursors WO1998004544A1 (en)

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US6850310B1 (en) 1999-08-27 2005-02-01 Basf Aktiengesellschaft Cholesteric layered material having improved color stability, and the production thereof
EP1357163A1 (en) * 2002-04-24 2003-10-29 MERCK PATENT GmbH Reactive mesogenic benzodithiophenes
US8026360B2 (en) 2004-09-20 2011-09-27 Xenon Pharmaceuticals Inc. Substituted pyridazines as stearoyl-CoA desaturase inhibitors
US7777036B2 (en) 2004-09-20 2010-08-17 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as therapeutic agents
US7829712B2 (en) 2004-09-20 2010-11-09 Xenon Pharmaceuticals Inc. Pyridazine derivatives for inhibiting human stearoyl-CoA-desaturase
US7919496B2 (en) 2004-09-20 2011-04-05 Xenon Pharmaceuticals Inc. Heterocyclic derivatives for the treatment of diseases mediated by stearoyl-CoA desaturase enzymes
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