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WO1993020068A1 - Derives d'oxiranne chiraux et leur utilisation comme agents dopants dans des melanges de cristaux liquides - Google Patents

Derives d'oxiranne chiraux et leur utilisation comme agents dopants dans des melanges de cristaux liquides Download PDF

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Publication number
WO1993020068A1
WO1993020068A1 PCT/EP1993/000717 EP9300717W WO9320068A1 WO 1993020068 A1 WO1993020068 A1 WO 1993020068A1 EP 9300717 W EP9300717 W EP 9300717W WO 9320068 A1 WO9320068 A1 WO 9320068A1
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Prior art keywords
diyl
alkyl radical
atoms
proviso
hydrogen
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PCT/EP1993/000717
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German (de)
English (en)
Inventor
Javier Manero
Anke Kaltbeitzel
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • C09K19/588—Heterocyclic compounds

Definitions

  • optically active smectic (ferroelectric) liquid crystal phases have also become increasingly important in recent years.
  • Clark and Lagerwall were able to show that the use of ferroelectric liquid crystal systems in very thin cells leads to optoelectric switching or display elements which have switching times that are up to a factor of 1000 faster than that of conventional TN ("twisted nematic") cells (cf. e.g. Lagerwall et al. "Ferroelectric Liquid Crystals for Displays", SID Symposium, October Meeting 1985, San Diego, Ca., USA). Because of these and other beneficial properties, e.g. the bistable switching option and the almost independent viewing angle contrast, FLC's are basically for the above-mentioned areas of application, e.g. via a matrix control, well suited.
  • connections that form inclined or orthogonal smectic phases and are themselves optically active or one can by optically doping connections that form such smectic phases but are not optically active themselves with optically active ones Compounds induce smectic phases.
  • the desired phase should be stable over the largest possible temperature range.
  • the basis (or matrix) used here is preferably compounds which, if possible, themselves already have the desired phase sequence I- * N- »S A ⁇ S c .
  • Other components of the mixture are often added to lower the melting point and broaden the S c - and usually also the N phase, to induce optical activity, to compensate for pitch and to adapt the optical and dielectric anisotropy, but, for example, do not increase the rotational viscosity if possible shall be.
  • the object of the present invention is to show chiral oxirane compounds which, at high values for their own polarization (P s ) or those induced in liquid crystal phases, have structural elements which they are also "compatible” (ie miscible) with other components in liquid crystal systems ) do.
  • the compounds according to the invention do not necessarily have to be liquid crystalline, in particular they do not necessarily have to have an S c phase.
  • a good "Compatibility" with other components of the liquid crystal mixture can, for. B. by varying the wing groups.
  • 2,2-disubstituted oxirane carboxylic acid esters on the one hand are particularly stable to racemization and, on the other hand, have a sign of spontaneous polarization that is opposite to that of HTP (Helical Twisting Power), ie the substances are excellent for pitch compensation are suitable, in particular for use in mixtures which contain oxiranes as a dopant.
  • HTP Helical Twisting Power
  • the present invention relates to chiral oxirane derivative of the general formula (I),
  • R 1 is hydrogen or a straight-chain or branched alkyl radical having 1 to 22 or 3 to 22 carbon atoms (with or without an asymmetric carbon atom), one or more -CH 2 groups also being -O-, -S- , -SO-, -CO-,
  • -CH CH-, -C ⁇ C-.A -Si (CH 3 ) 2 - or 1, 4-cyclohexylene can be replaced, with the proviso that chalcogen atoms (O, S, SO) must not be bonded directly to one another , and / or one or more H atoms of the alkyl radical can be substituted by -F, -Cl, -Br, -CN, -SCN, -OCN or -N 3 , or one of the following chiral groups:
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are independently H or a straight-chain or branched alkyl radical having 1 to 16 or 3 to 16 carbon atoms; or R 5 and R 6 together can also be - (CH 2 ) 4 - or - (CH 2 ) 5 - if they are bonded to a dioxolane system as substituents,
  • ⁇ , -Si (CH 3 ) 2 - or 1,4-cyclohexylene can be replaced, with the proviso that that oxygen atoms must not be bonded directly to one another, and the proviso that at least R 5 or R 6 must be different from hydrogen if R 9 is not methyl, and / or one or more H atoms of the alkyl radical by -F, -Cl , -Br, -CN, -SCN, -OCN or -N 3 can be substituted,
  • a 1 , A 2 , A 3 are the same or different 1,4-phenylene, it being possible for one or two H atoms to be replaced by F, Cl and / or CN, pyrazine-2,5-diyl, pyridazine-3,6 -diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, in which one or two H atoms can be replaced by CN and / or CH 3 , (1,3 , 4) -Thiadiazol-2,5-diyl, 1,3-dioxane-2,5-diyl, 1, 3-dithiane-2,5-diyl, 1, 3-thiazole-2,4-diyl, 1, 3-thiazole-2,5-diyl, th.ophen-2,4-diyl, thiophene-2,5-diyl, piperazine-1,
  • M 3 is -CH 2 -0-, -CO-O- or a single bond
  • a, b, c, d, e are zero or one, provided that the sum a + c + e is 1, 2 or 3,
  • n is the number 1 to 5.
  • chiral oxirane derivatives of the general formula (I) or (II) are used, in which the symbols and indices have the following meaning:
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are independently H or a straight-chain or branched alkyl radical having 1 to 16 or 3 to 16 carbon atoms; where R 5 and R 6 together can also be - (CH 2 ) 4 - or - (CH 2 ) 5 - if they are bonded to a dioxolane system as substituents,
  • ⁇ , -Si (CH 3 ) 2 - or 1,4-cyclohexylene can be replaced, with the proviso that oxygen atoms must not be bonded directly to one another and with the proviso that at least R 5 or R 6 must be different from hydrogen, if R 9 is not methyl, and / or one or more H atoms of the alkyl radical can be substituted by -F, -Cl, -Br, or -CN,
  • a 1 , A 2 , A 3 are the same or different 1,4-phenylene, pyrazine-2,5-diyl, pyridazine-3,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, (1,3,4) - Thiadiazole-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl or bicyclo [2.2.2] octane-1,4-diyl,
  • M 3 is -CH 2 -0-, -O-CO- or a single bond.
  • chiral oxirane derivatives of the general formulas (I) and (II) are used, in which the symbols and indices have the following meanings:
  • Cyclohexylene can be replaced, with the proviso that oxygen atoms must not be bonded directly to one another, and with the proviso that at least R 3 or R 4 must be different from hydrogen if R 2 is not methyl, and / or one or more H- Atoms of the alkyl radical can be substituted by -F,
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are independently H or a straight-chain or branched alkyl radical having 1 to 16 or 3 to 16 carbon atoms; where R 5 and R 6 together can also be - (CH 2 ) 4 - or - (CH 2 ) 5 - if they are bonded to a dioxolane system as substituents,
  • -Si (CH 3 ) 2 - or 1,4-cyclohexylene can be replaced, with the proviso that oxygen atoms must not be bonded directly to one another, and with the proviso that at least R 5 or R 6 must be different from hydrogen if R 9 is not methyl and / or one or more H atoms of the alkyl radical can be substituted by -F,
  • a 1 , A 2 , A 3 are the same or different 1, 4-phenylene, pyrazine-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2, 5-diyl, trans-1, 4-cyclohexylene, (1,3,4) thiadiazole-2,5-diyl or naphthalene-2,6-diyl,
  • M 1 , M 2 are identical or different -0-, -CO-O-, -O-CO-, -CH 2 -0-, -0-CH 2 -
  • M 3 is -CH 2 -0-, -CO-O- or a single bond.
  • Cyclohexylene can be replaced, or the chiral group:
  • R 2 is a straight-chain or branched alkyl radical having 1 to 16 or 3 to 16 carbon atoms (with or without an asymmetric carbon atom), one or more —CH 2 groups being also substituted by —O— or —Si (CH 3 ) 2 - can be replaced, with the proviso that oxygen atoms must not be bonded directly to one another and with the proviso that at least R 3 or R 4 must be different from hydrogen if R 2 is not methyl, R 3 , R 4 , R 5 , R 6 are independently H or an alkyl radical having 1 to 16 carbon atoms,
  • R 9 is hydrogen or a straight-chain or branched alkyl radical with 1 to 16 or 3 to 16 carbon atoms (with or without an asymmetric carbon atom), where one or more -CH 2 - groups by -O- or -Si ( CH 3 ) 2 can be replaced, with the proviso that oxygen atoms must not be bonded directly to one another, and with the proviso that at least R 5 or R 6 must be different from hydrogen if R 9 is not methyl
  • M c is -CH 2 -0- or -CO-O-
  • R 1 must not be bound to one of the aromatic rings via a chalcogen atom if there is a nitrogen atom in this ring in at least one ortho position to R 1 , unless the chalcogen atom is part of an ether or thioether group .
  • the compounds of the general formula (I) can be prepared by reacting the compounds of the general formula (IX) R 1 (-A 1 ) a (-M 1 ) b (-A 2 ) c (-M 2 ) d (-A 3 ) e -OH (IX)
  • Y is OH or halogen.
  • the esterification is carried out with (IX) in the presence of Bronsted or Lewis acids, if appropriate in the presence of water-binding agents or with condensation reagents such as N, N'-carbonyldiimidazole, dicyclohexyicarbodiimide, diisopropylcarbodiimide or azodicarboxylic acid ester / triphenylphosphine.
  • condensation reagents such as N, N'-carbonyldiimidazole, dicyclohexyicarbodiimide, diisopropylcarbodiimide or azodicarboxylic acid ester / triphenylphosphine.
  • the reaction with (IX) takes place in the presence of acid scavengers, in particular pyridine, triethylamine, N-methyimorpholine or basic ion exchanger.
  • the compounds (IX) are known from the literature (for example BD Demus et al., Liquid Crystals in Tables, VEB Verlag für Grundstoffindustrie, Leipzig, 1974, 1984, Vol. I + II).
  • the oxirane derivatives mentioned are suitable as components for liquid crystal mixtures.
  • the LC mixtures preferably contain 0.01 to 60% by weight, particularly preferably 0.05 to 20% by weight, in particular 0.1 to 10% by weight, of the compounds according to the invention.
  • the other constituents are preferably selected from the known compounds with nematic, cholesteric and / or smectic phases; these include, for example, Schiff bases, biphenyls, terphenyls, phenylcyclohexanes, cyclohexylbiphenyls, N, S or O-containing heterocycles, e.g.
  • liquid crystal mixtures are present as mixtures of various components, at least one of which is mesogenic, i.e. before the addition of the optically active compound (s). as a compound, in derivatized form or in a mixture with other components, shows a liquid crystal phase which can be expected to form at least one enantiotropic (clearing temperature> melting temperature) or monotropic (clearing temperature ⁇ melting temperature) mesophase formation.
  • the compounds according to the invention are particularly stable to racemization. They are particularly suitable as dopants for inclined-smectic liquid crystal phases, since they convert them into ferroelectric liquid crystal phases.
  • Liquid crystal mixtures which contain the compounds according to the invention can be used, for example, in electro-optical or completely optical components, for example as a display device, for image processing, information processing, data storage or in general in the field of non-linear optics.
  • the elements can also contain, for example, the following components: two electrodes, two carrier plates and at least one orientation layer.
  • FLC displays The structure of FLC displays is generally described in EP-B 0 032362.
  • the compounds according to the invention are mixed in concentrations of 10 mol% in each case with the non-chiral test mixtures M1 and M2 described below and the values for the spontaneous polarization (P s in nC / cm 2 , measured in M1) and the twisting force (HTP in // m "1 , measured in M2) of the mixture.
  • the P s values are determined by the method of H. Diamant et al. (Rev. Sei. Instr., 28, 30, 1957).
  • the determination of the twisting power of the cholesteric phase takes place, such as. B. P. Kassubek et al., Mol. Cryst. Liq., Vol. 8, 305 - 314, 1969, in a wedge cell with an orientation layer by measuring the dislocation lines under a polarizing microscope.
  • the non-chiral test mixtures M1 and M2 have the composition and phase sequences:
  • the table shows that the dopants (1-5) according to the invention show an increased tendency to form liquid-crystalline phases in comparison with those from Examples 6-9.
  • the substitution at the 2-position of the oxirane leads to a greater twisting force (see Examples 1 and 7).
  • the dopants according to the invention have a highly negative helical twist, which is particularly suitable for producing, together with the compounds known from EP 0 292 954 (see examples 6, 8, 9), mixtures which have an infinitely long pitch and so that it is easy to orientate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Dérivés d'oxiranne chiraux de formule générale (I), dans laquelle R?1, R2, R3, R4¿ désignent un hydrogène, un groupe alkyle ou un groupe chiral, A désigne un groupe mésogène, et M désigne un groupe d'espacement. Ces dérivés sont utilisés avantageusement dans des mélanges de cristaux liquides.
PCT/EP1993/000717 1992-04-07 1993-03-24 Derives d'oxiranne chiraux et leur utilisation comme agents dopants dans des melanges de cristaux liquides Ceased WO1993020068A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4211563.9 1992-04-07
DE19924211563 DE4211563A1 (de) 1992-04-07 1992-04-07 Chirale Oxiranderivate und ihre Verwendung als Dotierstoffe in Flüssigkristallmischungen

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6133485A (en) * 1998-04-15 2000-10-17 Synphar Laboratories, Inc. Asymmetric synthesis of 2-(2,4-difluorophenyl)-1-heterocycl-1-yl butan-2,3-diols
JP2011144159A (ja) * 2009-12-17 2011-07-28 Jnc Corp オキシラニル基を有する重合性液晶化合物、重合性液晶組成物および重合体

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0292954A2 (fr) * 1987-05-29 1988-11-30 Hoechst Aktiengesellschaft Utilisation d'esters d'acides oxirane-2-carboxyliques optiquement actifs comme dopants de mélanges liquides cristallins, mélanges liquides cristallins les contenant et esters d'acides oxirane-2-carboxyliques
EP0475444A1 (fr) * 1990-09-14 1992-03-18 Hoechst Aktiengesellschaft Utilisation de derivés de fluoro-4-pyrimidines comme composants de mélanges ferroélectriques de cristaux liquides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0292954A2 (fr) * 1987-05-29 1988-11-30 Hoechst Aktiengesellschaft Utilisation d'esters d'acides oxirane-2-carboxyliques optiquement actifs comme dopants de mélanges liquides cristallins, mélanges liquides cristallins les contenant et esters d'acides oxirane-2-carboxyliques
EP0475444A1 (fr) * 1990-09-14 1992-03-18 Hoechst Aktiengesellschaft Utilisation de derivés de fluoro-4-pyrimidines comme composants de mélanges ferroélectriques de cristaux liquides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6133485A (en) * 1998-04-15 2000-10-17 Synphar Laboratories, Inc. Asymmetric synthesis of 2-(2,4-difluorophenyl)-1-heterocycl-1-yl butan-2,3-diols
JP2011144159A (ja) * 2009-12-17 2011-07-28 Jnc Corp オキシラニル基を有する重合性液晶化合物、重合性液晶組成物および重合体

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