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WO1998004544A1 - Nouveaux composes a cristaux liquides et leurs precurseurs - Google Patents

Nouveaux composes a cristaux liquides et leurs precurseurs Download PDF

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Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
independently
compounds according
compounds
ocoo
coo
Prior art date
Application number
PCT/EP1997/003986
Other languages
German (de)
English (en)
Inventor
Karl Siemensmeyer
Thies Thiemann
Masashi Tashiro
Tsuzuki HIROHISA
Mamoru Mukumoto
Volkmar Vill
Gunnar Gesekus
Shuntaro Mataka
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU41157/97A priority Critical patent/AU4115797A/en
Publication of WO1998004544A1 publication Critical patent/WO1998004544A1/fr

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Classifications

    • 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 .

Landscapes

  • 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

L'invention concerne des composés qui répondent à la formule générale (I), dans laquelle les radicaux A désignent un séparateur; r vaut 0 ou 1; les radicaux M désignent, indépendamment les uns des autres, des systèmes cycliques aliphatiques, aromatiques, hétéroaliphatiques ou hétéroaromatiques le cas échéant substitués; n et m valent indépendamment 0, 1 ou 2; X désigne O, S, COO, OCOO, CONH ou CONR; R désigne alkyle C1 à C4; les radicaux Y désignent, indépendamment les uns des autres, O, S, COO, OCO, OCOO, CONH, NHCO, CONR, NRCO ou une liaison directe; et les groupes Z désignent indépendamment les uns des autres hydrogène, cyano ou un groupe polymérisable. Ces composés peuvent être utilisés isolés ou mélangés à d'autres composés à cristaux liquides dans des éléments d'affichage ou supports de données optiques, dans des polariseurs ou dans des colorants à cristaux liquides.
PCT/EP1997/003986 1996-07-25 1997-07-23 Nouveaux composes a cristaux liquides et leurs precurseurs WO1998004544A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU41157/97A AU4115797A (en) 1996-07-25 1997-07-23 New liquid crystal compounds and their precursors

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19630068.1 1996-07-25
DE1996130068 DE19630068A1 (de) 1996-07-25 1996-07-25 Neue flüssigkristalline Verbindungen und deren Vorprodukte

Publications (1)

Publication Number Publication Date
WO1998004544A1 true WO1998004544A1 (fr) 1998-02-05

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/003986 WO1998004544A1 (fr) 1996-07-25 1997-07-23 Nouveaux composes a cristaux liquides et leurs precurseurs

Country Status (3)

Country Link
AU (1) AU4115797A (fr)
DE (1) DE19630068A1 (fr)
WO (1) WO1998004544A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6605235B1 (en) 1999-08-27 2003-08-12 Basf Aktiengesellschaft Cholesteric layered material having an improved color impression, and the production thereof
EP1357163A1 (fr) * 2002-04-24 2003-10-29 MERCK PATENT GmbH Benzodithiophènes mésogéniques réactifs
US6850310B1 (en) 1999-08-27 2005-02-01 Basf Aktiengesellschaft Cholesteric layered material having improved color stability, and the production thereof
US7592343B2 (en) 2004-09-20 2009-09-22 Xenon Pharmaceuticals Inc. Pyridazine-piperazine compounds and their use as stearoyl-CoA desaturase inhibitors
US7767677B2 (en) 2004-09-20 2010-08-03 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use 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
US7951805B2 (en) 2004-09-20 2011-05-31 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as mediators of stearoyl-CoA desaturase
US8071603B2 (en) 2004-09-20 2011-12-06 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
US8541457B2 (en) 2005-06-03 2013-09-24 Xenon Pharmaceuticals Inc. Aminothiazole derivatives as human stearoyl-CoA desaturase inhibitors
WO2016132998A1 (fr) * 2015-02-19 2016-08-25 Jnc株式会社 Composé cristallin liquide comprenant du benzothiophène, composition de cristaux liquides et élément d'affichage à cristaux liquides
WO2016199528A1 (fr) * 2015-06-08 2016-12-15 Jnc株式会社 Composé de cristaux liquides contenant du benzothiophène, composition de cristaux liquides et élément d'affichage à cristaux liquides

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19913349A1 (de) 1999-03-24 2000-09-28 Clariant Gmbh Benzothiophene und ihre Verwendung in flüssigkristallinen Mischungen
EP1214306A1 (fr) * 1999-09-21 2002-06-19 Qinetiq Limited Composes cristaux liquides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364923A2 (fr) * 1988-10-17 1990-04-25 Canon Kabushiki Kaisha Composé mésomorphe, compositions de cristaux liquides le contenant et son utilisation dans un dispositif à cristaux liquides
DE4342280A1 (de) * 1993-12-11 1995-06-14 Basf Ag Polymerisierbare chirale Verbindungen und deren Verwendung
EP0667385A1 (fr) * 1990-01-22 1995-08-16 Canon Kabushiki Kaisha Composé mésomorphe, composition liquido-cristallique le contenant, dispositif liquido-cristallique utilisant cette composition et appareil indicateur
WO1996030352A1 (fr) * 1995-03-24 1996-10-03 Basf Aktiengesellschaft Composes a cristaux liquides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0364923A2 (fr) * 1988-10-17 1990-04-25 Canon Kabushiki Kaisha Composé mésomorphe, compositions de cristaux liquides le contenant et son utilisation dans un dispositif à cristaux liquides
EP0667385A1 (fr) * 1990-01-22 1995-08-16 Canon Kabushiki Kaisha Composé mésomorphe, composition liquido-cristallique le contenant, dispositif liquido-cristallique utilisant cette composition et appareil indicateur
DE4342280A1 (de) * 1993-12-11 1995-06-14 Basf Ag Polymerisierbare chirale Verbindungen und deren Verwendung
WO1996030352A1 (fr) * 1995-03-24 1996-10-03 Basf Aktiengesellschaft Composes a cristaux liquides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 120, no. 23, 6 June 1994, Columbus, Ohio, US; abstract no. 298395, SHIRLEY I M: "Oxidation and halogenation of methyl 4,5,6,7-tetrafluorobenzo[b]thi ophene-2-carboxylate" XP002047420 *
J. FLUORINE CHEM. (JFLCAR,00221139);94; VOL.66 (1); PP.51-7, ICI CHEM. AND POLYMERS LTD.;RUNCORN/CHESIRE; WA7 4QD; UK (GB) *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6605235B1 (en) 1999-08-27 2003-08-12 Basf Aktiengesellschaft Cholesteric layered material having an improved color impression, and the production thereof
US6850310B1 (en) 1999-08-27 2005-02-01 Basf Aktiengesellschaft Cholesteric layered material having improved color stability, and the production thereof
EP1357163A1 (fr) * 2002-04-24 2003-10-29 MERCK PATENT GmbH Benzodithiophènes mésogéniques réactifs
US7951805B2 (en) 2004-09-20 2011-05-31 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as mediators of stearoyl-CoA desaturase
US8071603B2 (en) 2004-09-20 2011-12-06 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use 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
US7592343B2 (en) 2004-09-20 2009-09-22 Xenon Pharmaceuticals Inc. Pyridazine-piperazine compounds and their use as stearoyl-CoA desaturase inhibitors
US8026360B2 (en) 2004-09-20 2011-09-27 Xenon Pharmaceuticals Inc. Substituted pyridazines as stearoyl-CoA desaturase inhibitors
US7767677B2 (en) 2004-09-20 2010-08-03 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
US8541457B2 (en) 2005-06-03 2013-09-24 Xenon Pharmaceuticals Inc. Aminothiazole derivatives as human stearoyl-CoA desaturase inhibitors
WO2016132998A1 (fr) * 2015-02-19 2016-08-25 Jnc株式会社 Composé cristallin liquide comprenant du benzothiophène, composition de cristaux liquides et élément d'affichage à cristaux liquides
JPWO2016132998A1 (ja) * 2015-02-19 2017-09-14 Jnc株式会社 ベンゾチオフェンを有する液晶性化合物、液晶組成物および液晶表示素子
US10308871B2 (en) 2015-02-19 2019-06-04 Jnc Corporation Liquid crystal compound having benzothiophene, liquid crystal composition and liquid crystal display device
WO2016199528A1 (fr) * 2015-06-08 2016-12-15 Jnc株式会社 Composé de cristaux liquides contenant du benzothiophène, composition de cristaux liquides et élément d'affichage à cristaux liquides
US10563126B2 (en) 2015-06-08 2020-02-18 Jnc Corporation Liquid crystal compound having benzothiophene, liquid crystal composition and liquid crystal display device

Also Published As

Publication number Publication date
AU4115797A (en) 1998-02-20
DE19630068A1 (de) 1998-01-29

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