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WO1996030352A1 - Composes a cristaux liquides - Google Patents

Composes a cristaux liquides Download PDF

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Publication number
WO1996030352A1
WO1996030352A1 PCT/EP1996/001285 EP9601285W WO9630352A1 WO 1996030352 A1 WO1996030352 A1 WO 1996030352A1 EP 9601285 W EP9601285 W EP 9601285W WO 9630352 A1 WO9630352 A1 WO 9630352A1
Authority
WO
WIPO (PCT)
Prior art keywords
coo
oco
liquid
crystalline compounds
general formula
Prior art date
Application number
PCT/EP1996/001285
Other languages
German (de)
English (en)
Inventor
Karl Siemensmeyer
Frank Meyer
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 EP96908125A priority Critical patent/EP0815094A1/fr
Priority to JP8528909A priority patent/JPH11504001A/ja
Publication of WO1996030352A1 publication Critical patent/WO1996030352A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • 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
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
    • 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
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C07D239/62—Barbituric acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—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
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
    • C09K19/3458—Uncondensed pyrimidines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—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

  • EP-A-504 660 form stable glasses. They have a high dipole moment parallel to the longitudinal axis of the molecule and form nematic or smectic A phases. Because of the dipole moment along the longitudinal axis of the molecule, these materials orient themselves in parallel in the electric field, so that they have neither ferroelectric properties nor any helical superstructures that are present are stable in the electric field.
  • Liquid-crystalline systems which have a defined structure and in which mesogenic groups are bonded to a central unit via a spacer (e.g. DE-A-40 11 811).
  • these materials do not solidify glassy, but crystallize very easily due to their high symmetry.
  • Liquid Crystals _____________, 779 (1992) describes ferroelectric liquid crystals which are bound to a central unit via a spacer. These materials have mesogenic structures that are unstable against thermal influences as well as against weak acids or bases and against water.
  • liquid-crystalline ferroelectric materials Compounds which have a phase behavior in which the phase sequence is passed through nematic, smectic A and smectic C during cooling would be desirable for use as liquid-crystalline ferroelectric materials.
  • the materials should have high flow viscosities and, above all, be stable against weak acids and bases. What is desired is- also good miscibility with other liquid-crystalline compounds.
  • the object of the present invention is therefore to provide new, liquid-crystalline, glass-like solidifying compounds which have smectic and nematic phases, are insensitive to temperature and pH fluctuations and to water and have a high flow viscosity.
  • the invention now relates to corresponding compounds of the general formula I.
  • X is an n-valent aliphatic, aromatic or cycloaliphatic radical or an n-valent alkenyl or alkynyl radical
  • M is a mesogenic group
  • X are, for example: alkylene
  • alkylene interrupted by O, NH or NR are, for example - (CH 2 ) D -, -CH-CH 2 -. -CH 2 OCH 2 -, -CH 2 NHCH 2 - or -CH N - CH 2 -
  • n is preferably 2 or 4.
  • radicals Y in particular -OCO-, -0- and -COO- are preferred.
  • spacers All groups known for this purpose can be used as spacers;
  • the spacers are usually linked to X via ester or ether groups or a direct bond.
  • the spacers generally contain 2 to 30, preferably 2 to 12 and in particular 6 to 12 C atoms and can be interrupted in the chain, for example by O, S, NH or NCH 3 . Fluorine, chlorine, bromine, cyano, methyl or ethyl are also suitable as substituents for the spacer chain.
  • spacers are for example:
  • the known mesogenic groups can in turn be used as residues M.
  • Aromatic or heteroaromatic groups containing radicals are particularly suitable.
  • the mesogenic residues correspond in particular to the formula III
  • R is preferably 1 or 2.
  • Y 1 is preferably -COO-, -OCO- or a direct bond.
  • the radicals T are generally aromatic carbocyclic or heterocyclic ring systems optionally substituted by fluorine, chlorine, bromine, cyano, hydroxyl or nitro, which e.g. correspond to the following basic structures:
  • mesogenic groups M are e.g.
  • Side chains B are, for example, C - to C 3 o-alkyl or alkenyl, preferably C - to Cn-alkyl or alkenyl, the radicals being linear or branched, one or more times by -0-, -OCO-, -CO- O, -CH— CH - / -NH- or -N (CH 3 ) - interrupted and by
  • Phenyl, fluorine, chlorine, bromine, cyan or hydroxy may be substituted.
  • B is particularly preferably a C 3 - to C 11 -alkyl group which is bonded via -O-, -COO- or -OCO- and which can be interrupted one or more times by oxygen and is preferably unbranched.
  • Individual radicals B are, for example, -C 2 H 5 , -C 3 H, -C Hg, -C 5 H 11 , -C 6 H 13 , -C 7 H 15 , -C ⁇ H 17 , -C9H19, -C10H21, -C11H23. - 12H25-
  • side chains B are chiral C 3 -Cn-alkyl groups bonded via -0-, -COO- or -OCO- which are also substituted by fluorine, chlorine, bromine, cyano or hydroxyl or by
  • -O-, -COO-, -OCO- or -CH— CH— can be interrupted, in consideration.
  • Chiral side chains B are e.g. B.: Cl CH C 6 Hi 3 'CH 2 - - CH - - C 2 H 5
  • R 1 is a Ci to Ci 2 alkylres, which can be chiral or achiral and R 2 is a radical R 1 , fluorine or chlorine.
  • Preferred radicals R 1 are, for example:
  • p 1 to 12.
  • the compounds of the formula I are liquid-crystalline and, depending on the structure, can form smectic, nematic or cholesteric phases. They are suitable for all purposes in which liquid-crystalline compounds are usually used.
  • the compounds according to the invention occupy an intermediate position between low-molecular and polymeric liquid-crystalline compounds.
  • they can be produced reproducibly, have largely uniform structures and nevertheless have viscosities like the polymers.
  • mixtures of compounds of the formula I these mixtures in situ, i.e. can be produced in the synthesis, or by mechanical mixing.
  • the compounds according to the invention can be used alone, in a mixture with one another or together with other liquid crystals in arrangements for the optical display of information. They are particularly suitable for use in displays and for the production of light-reflecting layers. Examples
  • Liquid-crystalline phases marked in this way are chiral Z Central unit, consists of the residues X and Y S unspecified smectic phase
  • phase transition temperatures were recorded polarization microscopically. The temperature was checked in a Mettler microscope heating table FP80 / 82. The spontaneous polarization was determined according to the method of Miyasato et al. Jpn. J. Appl. Phys. 22, L230 (1986).
  • Examples 2 to 14 were prepared analogously to Example 1. If mixtures are specified in the table for the grouping (-AYMYB), corresponding molar mixtures of the compounds HO-AYMYB were used in the synthesis, statistical mixtures of the compounds I resulting.
  • 0.53 g (0.0005 mol) of the acid chloride are dispersed in 50 ml of absolute toluene and heated to 40 ° C.
  • a solution of 0.44 g (0.0011 mol) of 2-heptyl-5- [4- (8-hydroxyoxoxy) phenyl-1,3,4,4-thiadiazole in 50 ml of toluene and 30 ml is added to this solution Dropped pyridine.
  • the reaction is followed by thin layer chromatography. After the reaction has ended, the mixture is precipitated in water and the reaction mixture is purified by column chromatography (silica gel 60, toluene / ethyl acetate: 4: 1).
  • Phase behavior S a 87 I (no crystallization up to room temperature).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Abstract

L'invention concerne des composés à cristaux liquides de la formule générale (I) X(-Y-A-Y-M-Y-B)n dans laquelle X désigne un reste aliphatique, aromatique ou cycloaliphatique n-valent ou un reste alcényle ou alkinyle n-valent, n vaut 2, 4 ou 5, les symboles Y, indépendamment les uns des autres, désignent une liaison directe, -COO-, -OCO-, -O-, -CONH-, ou -CON(R)- où R = alkyle C1 à C4, A désigne un segment espaceur, M désigne un groupe mésogène et B désigne une chaîne latérale. Ces composés s'utilisent tout particulièrement pour l'affichage de données.
PCT/EP1996/001285 1995-03-24 1996-03-22 Composes a cristaux liquides WO1996030352A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP96908125A EP0815094A1 (fr) 1995-03-24 1996-03-22 Composes a cristaux liquides
JP8528909A JPH11504001A (ja) 1995-03-24 1996-03-22 液晶化合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/EP1995/001113 WO1996030351A1 (fr) 1995-03-24 1995-03-24 Composes de cristaux liquides
ATPCT/EP95/01113 1995-03-24

Publications (1)

Publication Number Publication Date
WO1996030352A1 true WO1996030352A1 (fr) 1996-10-03

Family

ID=8165982

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/EP1995/001113 WO1996030351A1 (fr) 1995-03-24 1995-03-24 Composes de cristaux liquides
PCT/EP1996/001285 WO1996030352A1 (fr) 1995-03-24 1996-03-22 Composes a cristaux liquides

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/001113 WO1996030351A1 (fr) 1995-03-24 1995-03-24 Composes de cristaux liquides

Country Status (5)

Country Link
EP (1) EP0815094A1 (fr)
JP (1) JPH11504001A (fr)
KR (1) KR19980703220A (fr)
CN (1) CN1179153A (fr)
WO (2) WO1996030351A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998004544A1 (fr) * 1996-07-25 1998-02-05 Basf Aktiengesellschaft Nouveaux composes a cristaux liquides et leurs precurseurs

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112079862A (zh) * 2020-10-29 2020-12-15 江苏创拓新材料有限公司 一种碳酸脂类液晶中间体及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3608764A1 (de) * 1985-03-22 1986-10-02 Merck Patent Gmbh, 6100 Darmstadt Carbocyclische verbindungen
EP0504660A2 (fr) * 1991-03-16 1992-09-23 BASF Aktiengesellschaft Composés cristaux liquides
EP0583605A1 (fr) * 1992-07-22 1994-02-23 BASF Aktiengesellschaft Composés oligomères liquides cristallins définis avec des phases liquides installines smectiques
WO1995008604A1 (fr) * 1993-09-25 1995-03-30 Basf Aktiengesellschaft Composes de cristaux liquides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3608764A1 (de) * 1985-03-22 1986-10-02 Merck Patent Gmbh, 6100 Darmstadt Carbocyclische verbindungen
EP0504660A2 (fr) * 1991-03-16 1992-09-23 BASF Aktiengesellschaft Composés cristaux liquides
EP0583605A1 (fr) * 1992-07-22 1994-02-23 BASF Aktiengesellschaft Composés oligomères liquides cristallins définis avec des phases liquides installines smectiques
WO1995008604A1 (fr) * 1993-09-25 1995-03-30 Basf Aktiengesellschaft Composes de cristaux liquides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIQUID CRYSTALS, Bd.11, Nr.5, 1992 Seiten 779-784 G. S. ATTARD et al. 'liquid-crystalline cyclic trimers derived from benzene-1,3,5-tricarboxylic acid' *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998004544A1 (fr) * 1996-07-25 1998-02-05 Basf Aktiengesellschaft Nouveaux composes a cristaux liquides et leurs precurseurs

Also Published As

Publication number Publication date
WO1996030351A1 (fr) 1996-10-03
EP0815094A1 (fr) 1998-01-07
CN1179153A (zh) 1998-04-15
KR19980703220A (ko) 1998-10-15
JPH11504001A (ja) 1999-04-06

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