WO2018015324A1 - Dérivés de difluorostilbène - Google Patents

Dérivés de difluorostilbène Download PDF

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Publication number
WO2018015324A1
WO2018015324A1 PCT/EP2017/067965 EP2017067965W WO2018015324A1 WO 2018015324 A1 WO2018015324 A1 WO 2018015324A1 EP 2017067965 W EP2017067965 W EP 2017067965W WO 2018015324 A1 WO2018015324 A1 WO 2018015324A1
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Prior art keywords
compounds
formula
independently
atoms
alkyl
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PCT/EP2017/067965
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German (de)
English (en)
Inventor
Matthias Bremer
Melanie Klasen-Memmer
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Merck Patent Gmbh
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Publication date
Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to CN201780044549.2A priority Critical patent/CN109476996A/zh
Priority to DE112017003625.9T priority patent/DE112017003625A5/de
Publication of WO2018015324A1 publication Critical patent/WO2018015324A1/fr

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    • 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
    • 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
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0459—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF=CF- chain, e.g. 1,2-difluoroethen-1,2-diyl

Definitions

  • the present invention relates to 2,3-difluoro-a, ß-difluorstilben derivatives, a process for their preparation, liquid-crystalline media containing these derivatives and electro-optical display elements containing these liquid-crystalline media.
  • the compounds have a negative dielectric anisotropy.
  • Liquid crystals have found wide application since about 30 years ago the first commercially applicable liquid crystalline compounds were found.
  • Known fields of application for conventional mixtures are, in particular, displays for timepieces and pocket calculators as well as large display panels, such as those used in railway stations, airports and sports arenas.
  • the spatial ordering of molecules in a liquid crystal causes many of its properties to be directional. Of particular importance for use in liquid crystal displays are the anisotropies in the optical, dielectric and elasto-mechanical behavior. Depending on whether the molecules are oriented with their longitudinal axes perpendicular or parallel to the two plates of a capacitor, this has a different capacity; the dielectric constant ⁇ of the liquid-crystalline medium is therefore different for the two orientations.
  • dielectrically positive Substances whose dielectric constant is greater when the molecular longitudinal axes are oriented perpendicular to the capacitor plates than in the case of a parallel arrangement are referred to as dielectrically positive. In other words, is the dielectric constant s parallel to the
  • the dielectric anisotropy ⁇ ⁇ ⁇ - ⁇ ⁇ is greater than zero.
  • the dielectric anisotropy ⁇ ⁇ ⁇ - ⁇ ⁇ is greater than zero.
  • the polarizability of the molecule and permanent dipole moments play a role.
  • the longitudinal axis of the molecules aligns to make the larger of the dielectric constants effective. The strength of the interaction with the electric field depends on the difference between the two constants.
  • the dipole moment oriented along the molecular longitudinal axis is larger than the dipole moment oriented perpendicular to the longitudinal molecular axis of the molecule.
  • An object of the present invention is to provide compounds with advantageous properties for use in liquid-crystalline media.
  • they should have a negative dielectric anisotropy, which makes them particularly suitable for use in liquid-crystalline media for VA displays. Regardless of the type of dielectric anisotropy corresponding to the type of display
  • n 0, 1 or 2, preferably 1,
  • n 0, 1 or 2, preferably 0,
  • R 1 and R 2 are independently an alkyl or alkoxy radical having 1 to 15 carbon atoms, wherein in these radicals also one or more Ch groups each independently .
  • -O-, -CO-O-, or -O-CO- can be replaced so that O atoms are not directly linked to one another, and in which also one or more H atoms can be replaced by halogen, preferably independently of one another, an unsubstituted alkyl radical or alkoxy radical having 1 to 15 carbon atoms or an alkenyl, alkenyloxy or alkynyl radical having 2 to 15 C atoms, which are each optionally mono- or polyhalogenated,
  • a 1 and A 2 are independently selected from
  • L for each occurrence independently F, Cl, CN, SCN, SF5 or straight-chain or branched, each optionally fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 or preferably 1 to 4 carbon atoms.
  • the compounds have a pronounced negative ⁇ and are therefore particularly suitable for use in liquid-crystal mixtures for VA-TFT displays.
  • Liquid-crystalline mixtures are advantageously small.
  • the further physical, physicochemical or electro-optical parameters of the compounds according to the invention are also advantageous for the use of the compounds in liquid-crystalline media.
  • the liquid-crystalline media containing these compounds have in particular a sufficient width of the nematic phase and a good low-temperature and long-term stability and sufficiently high
  • the compounds of the formula I according to the invention have suitable values of the optical anisotropy ⁇ , in particular for use in VA TFT displays.
  • the compounds according to the invention preferably have a ⁇ of greater than 0.2 and less than 0.35.
  • the compounds are relatively easy to manufacture. The balanced combination of these beneficial properties provides a significant enrichment of those available for VA blends
  • the components m and n preferably have one in the sum m + n
  • n is 0.
  • R 1 and R 2 each independently represent an alkoxy radical, alkyl radical or alkenyl radical having 1 to 7 or 2 to 7
  • R 2 in the general formula I is particularly preferably an alkoxy radical having 1 to 7 C atoms.
  • R 2 preferably represents an alkoxy or alkenyloxy group, particularly preferably an alkoxy group with 1-7 C-
  • Atoms particularly preferably with 2 to 5 C atoms and especially with 2 C atoms.
  • the sum of the number of carbon atoms in R 1 and R 2 together is preferably 4, 5, 6, 7, 8, 9 or 10, particularly preferably 6, 7, 8, 9 or 10.
  • R 2 is preferably an alkyl, alkoxy or alkenyl group, particularly preferably an alkyl group having 1-7 C atoms, particularly preferably having 2 to 5 C atoms. If R 1 and R 2 in formula I are each independently one
  • Alkyl radical these are straight-chain or branched.
  • each of these radicals is straight-chain and, unless otherwise indicated, has 1, 2, 3, 4, 5, 6 or 7 carbon atoms and is therefore preferably methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl.
  • R 1 and R 2 in formula I each independently represent an alkoxy radical, these are straight-chain or branched.
  • each of these radicals is straight-chain and, unless otherwise specified, has 1, 2, 3, 4, 5, 6 or 7 carbon atoms and is therefore preferably methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy.
  • R 1 and R 2 in formula I can each independently be an alkenyl radical having 2 to 15 C atoms which is straight-chain or branched and has at least one C-C double bond. It is preferably straight-chain and has 2 to 7 carbon atoms. It is therefore preferably vinyl, prop-1 - or prop-2-enyl, but-1 -, 2- or but-3-enyl, pent-1 -, 2-, 3- or pent-4-enyl, hexyl 1-, 2-, 3-, 4- or hex-5-enyl, hept-1, 2-, 3-, 4-, 5- or hept-6-enyl. If the two carbon atoms of the CC double bond are substituted, the alkenyl radical can be present as an E and / or Z isomer (trans / cis). In general, the respective E isomers are preferred. Among the following E isomers are preferred.
  • Alkenyl radicals are particularly preferably prop-2-enyl, 2- or but-3-enyl, and 3- or pent-4-enyl.
  • R 1 and R 2 in formula I can independently of one another also be an alkynyl radical having 2 to 15 C atoms which is straight-chain or branched and has at least one C-C triple bond. Preference is given to 1 - or 2-propynyl and 1 -, 2 - or 3-propynyl.
  • the groups A 1 and A 2 independently are preferably one
  • the group A 1 is preferably, each independently, a
  • the group L is preferably F, Cl, -CF3 or an alkyl or
  • Alkoxy group having 1, 2 or 3 carbon atoms having 1, 2 or 3 carbon atoms.
  • Halogen in the context of the present invention means fluorine, chlorine, bromine and iodine, in particular fluorine or chlorine.
  • alkyl unless otherwise defined elsewhere in this specification or in the claims, means a straight-chain or straight chain radical
  • R 1 , R 2 , A 1 and A 2 have the meanings defined for the formula I above.
  • Preferred compounds of the formulas IA, IB and IC are the
  • alkyl radical having 1 -7 C atoms.
  • Preferred compounds of the formula I or IA to IC are selected from those of the formulas: wherein "alkyl" is defined as for IA-1, IB-1, etc. Particular preference is given to compounds of the formula IB-2-1, in particular in which alkyl is an n-propyl radical.
  • radicals or substituents of the compounds according to the invention or the compounds according to the invention themselves are present as optically active or stereoisomeric radicals, substituents or compounds because they have, for example, an asymmetric center, these are also encompassed by the present invention. It is understood that the compounds of general formula I according to the invention in isomerically pure form, for example as pure enantiomers, diastereomers, E or Z isomers, trans or cis isomers, or as a mixture of several
  • Isomers can be present in any ratio, for example as a racemate, E / Z isomer mixture or as a cis / trans isomer mixture.
  • the compounds of general formula I can be prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart) under reaction conditions, which are known and suitable for the said reactions. One can make use of known per se, not mentioned here variants.
  • the starting materials may optionally also be formed in situ, such that they are not isolated from the reaction mixture, but immediately further reacted to the compounds of general formula I.
  • radicals -R 2 in Scheme 1 instead of the radicals -R 2 in Scheme 1, general radicals of the formulas - [A 2 ] n -R 2 can also be introduced analogously to the general formula I.
  • the person skilled in the art can make appropriate variations of the syntheses presented, as well as other suitable synthetic routes to obtain compounds of formula I. According to the above-described syntheses, in one embodiment, the present invention also encompasses one or more processes for the preparation of compounds of the formula I.
  • the invention thus comprises a process for the production of
  • X is I or Br
  • a 1 , A 2 , m, n, R 1 , R 2 are as defined in formula I,
  • reaction A + B is optionally followed by further process steps which eventually lead to a compound of the formula I.
  • the reaction preferably leads directly to a compound of the formula I.
  • the inventive method allows easy and
  • Reaction mixture can in principle be carried out as a batch reaction or in a continuous reaction mode.
  • the continuous reaction includes z.
  • a stirred tank cascade As the reaction in a continuous stirred tank reactor, a stirred tank cascade, a loop or cross-flow reactor, a flow tube or in a microreactor.
  • the reaction mixtures are optionally worked up, as required, by filtration over solid phases, chromatography, separation between immiscible phases (eg extraction), adsorption on solid supports, distilling off of solvents and / or azeotropic mixtures, selective distillation, sublimation, crystallization , Cocrystallization or by nanofiltration on membranes.
  • the compounds of general formula I can be used in liquid-crystalline media.
  • the present invention therefore also provides a liquid-crystalline medium having at least two liquid-crystalline compounds containing at least one
  • the present invention also liquid-crystalline media containing in addition to one or more compounds of the formula I according to the invention as further constituents 2 to 40, preferably 4 to 30 components. With particular preference, these media contain, in addition to one or more compounds according to the invention, 7 to 25 components.
  • These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of azoxybenzenes,
  • Benzylidenanilines biphenyls, terphenyls, 1, 3-dioxanes, 2,5-tetrahydropyrans, phenyl or cyclohexyl benzoates, cyclohexanecarboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters benzoic acid, cyclohexanecarboxylic acid or cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohex
  • the 1, 4-phenylene groups in these compounds may also be mono- or polyfluorinated.
  • L and E which may be the same or different, each independently represents a bivalent radical selected from the group consisting of -Phe-, -Cyc- , -Phe-Phe, -Phe-Cyc,
  • Phe is unsubstituted or fluorine-substituted 1, 4-phenylene, Cyc trans-1, 4-cyclohexylene or 1, 4-cyclohexenylene, Pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio 1,3-dioxane-2,5-diyl, Thp tetrahydropyran-2,5-diyl and G 2- (trans-1,4-cyclohexyl) -ethyl, pyrimidine-2,5-diyl, pyridine-2,5- diyl, 1, 3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl.
  • one of L and E is Cyc or Phe.
  • E is preferably Cyc, Phe or Phe-Cyc.
  • the media according to the invention contain one or more components selected from the compounds of formulas (II), (III), (IV), (V) and (VI), wherein L and E are selected from the group Cyc and Phe and simultaneously one or more components selected from the compounds of the formulas (II), (III), (IV), (V) and (VI), wherein one of the radicals L and E is selected from the group Cyc and Phe and the other radical is selected from the Group -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-, and optionally one or more components selected from the compounds of the formulas (II), (III) , (IV), (V) and (VI), wherein the radicals L and E are selected from the group -Phe-Cyc, -Cyc
  • R 'and R "in a smaller subgroup of the compounds of formulas (II), (III), (IV), (V) and (VI) each independently represent alkyl, alkenyl, alkoxy, alkoxyalkyl (oxaalkyl), alkenyloxy or alkanoyloxy with up to 8 carbon atoms, hereinafter this smaller subgroup is called group A and the compounds are designated by the subformulae (IIa), (IIIa), (IVa), (Va) and (VIA) Most of these compounds R 'and R "are different from each other, wherein one of these radicals is usually alkyl, alkenyl, alkoxy or alkoxyalkyl (oxaalkyl).
  • E denotes
  • R 'and R “have the meanings for the compounds of the sub-formulas (IIa) to ( Via) and are preferably alkyl, alkenyl, alkoxy or alkoxyalkyl (oxaalkyl).
  • R ' has the meaning given for the compounds of sub-formulas (IIa) to (Via) and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl (oxaalkyl).
  • R ' has the meaning given for the compounds of sub-formulas (IIa) to (Via) and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl (oxaalkyl).
  • other compounds of the formulas (II), (III), (IV), (V) and (VI) with other variants of the substituents provided are also customary. All these substances are available by literature methods or by analogy.
  • the media according to the invention preferably contain one or more compounds from groups A, B and / or C.
  • the mass fractions of the compounds from these groups on the media according to the invention are as follows:
  • 0 to 90% preferably 20 to 90%, especially 30 to 90%.
  • 0 to 80% preferably 5 to 80%, especially 5 to 50%.
  • the media according to the invention preferably contain 1 to 40%, more preferably 5 to 30%, of the compounds of the formula I according to the invention.
  • the media preferably comprise one, two, three, four or five compounds of the formula I according to the invention.
  • the preparation of the media according to the invention is carried out in a conventional manner.
  • the components are dissolved in each other, preferably at elevated temperature.
  • the liquid-crystalline phases of the present invention can be modified so that they can be used in all types of liquid-crystal display elements known hitherto.
  • Such additives are known to the person skilled in the art and are described in detail in the literature (H. Kelker / R. Hussi, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980).
  • pleochroic dyes can be used to prepare colored guest-host systems or agents for modifying the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases are added.
  • the compounds of the formula I are particularly suitable for use in VA TFT displays.
  • the present invention therefore also provides electro-optical display elements comprising a liquid-crystalline medium according to the invention.
  • the display element is preferably a VA TFT display element (VA: vertical alignment, TFT: thin film transistor).
  • K crystalline phase
  • N nematic phase
  • Sm smectic phase
  • I Isotropic phase. The numbers between these symbols represent the transition temperatures of the substance in question.
  • dielectric anisotropy ⁇ is determined at 20 ° C and 1 kHz.
  • the optical anisotropy ⁇ is determined at 20 ° C and a wavelength of 589.3 nm.
  • Rotational viscosity ( ⁇ ) of the compounds of the invention are obtained by linear extrapolation of liquid crystalline mixtures containing from 5 to 10% of the respective compound of the invention and 90-95% from the commercially available liquid crystal mixture ZLI-2857 (for As, Klp.) Or ZLI-4792 (for An, ⁇ ) exist (mixtures Fa. Merck KGaA, Darmstadt).
  • the starting materials can be obtained according to generally available literature or commercially available.
  • the olefin (31 g, from step 1) is dissolved in 120 ml of THF, 70 ml of pentane and 70 ml of diethyl ether and cooled to -100 ° C. 59 ml of 1 .6M n-butyllithium in n-hexane are added dropwise and the mixture is stirred for an additional hour. There are added dropwise 1 1 ml of trimethyl borate dissolved in 60 ml of THF, 30 ml of pentane and 30 ml of diethyl ether. After stirring for one hour is warmed up and worked up as usual. 14 g of boronic acid are obtained.
  • the radicals R 1 2 are straight-chain, that is, unbranched, unless otherwise indicated.
  • the substance data are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des dérivés de 2,3-difluoro-α,β-difluorostilbène de formule (I), dans laquelle R1, R2, A1, A2, m et n sont tels que définis dans la revendication 1, leur préparation, leur utilisation comme composants dans des milieux à cristaux liquides, ainsi que des éléments d'affichage électro-optiques qui contiennent les milieux à cristaux liquides selon l'invention. Ces composés présentent une anisotropie diélectrique négative.
PCT/EP2017/067965 2016-07-20 2017-07-17 Dérivés de difluorostilbène WO2018015324A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201780044549.2A CN109476996A (zh) 2016-07-20 2017-07-17 二氟茋衍生物
DE112017003625.9T DE112017003625A5 (de) 2016-07-20 2017-07-17 Difluorstilben-Derivate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16180334 2016-07-20
EP16180334.1 2016-07-20

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WO2018015324A1 true WO2018015324A1 (fr) 2018-01-25

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DE (1) DE112017003625A5 (fr)
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0341037A (ja) 1989-04-18 1991-02-21 Seimi Chem Kk トランス―ジハロゲノスチルベン誘導体化合物を含有する液晶組成物
US5380461A (en) 1990-04-13 1995-01-10 Seimi Chemical Co., Ltd. Trans-dihalogenostilbene compounds and liquid crystal electro-optical devices using them
JPH07133241A (ja) 1993-11-09 1995-05-23 Asahi Glass Co Ltd ジフルオロスチルベン誘導体化合物およびそれを含有する液晶組成物
EP1932896A1 (fr) * 2006-12-11 2008-06-18 MERCK PATENT GmbH Dérivés de stilbène, mélanges à base de cristaux liquides et affichages électro-optiques
DE102011008687A1 (de) * 2010-02-11 2011-08-11 Merck Patent GmbH, 64293 Flüssigkristallanzeige und Flüssigkristallines Medium

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE519829T1 (de) * 2005-06-13 2011-08-15 Merck Patent Gmbh Flüssigkristallines medium enthaltend 1,2- difluorethenverbindungen, sowie flüssigkristallanzeige
DE502007004625D1 (de) * 2006-09-13 2010-09-16 Merck Patent Gmbh Fluorphenyl-Verbindungen für flüssigkristalline Mischungen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0341037A (ja) 1989-04-18 1991-02-21 Seimi Chem Kk トランス―ジハロゲノスチルベン誘導体化合物を含有する液晶組成物
US5380461A (en) 1990-04-13 1995-01-10 Seimi Chemical Co., Ltd. Trans-dihalogenostilbene compounds and liquid crystal electro-optical devices using them
JPH07133241A (ja) 1993-11-09 1995-05-23 Asahi Glass Co Ltd ジフルオロスチルベン誘導体化合物およびそれを含有する液晶組成物
EP1932896A1 (fr) * 2006-12-11 2008-06-18 MERCK PATENT GmbH Dérivés de stilbène, mélanges à base de cristaux liquides et affichages électro-optiques
DE102011008687A1 (de) * 2010-02-11 2011-08-11 Merck Patent GmbH, 64293 Flüssigkristallanzeige und Flüssigkristallines Medium

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BROSCHÜRE, MERCK LIQUID CRYSTALS - LICRISTAL® - PHYSICAL PROPERTIES OF LIQUID CRYSTALS - DESCRIPTION OF THE MEASUREMENTS METHODS, 1998
GOODBY J W ET AL: "Trans-1,2-Difluorosilbenes: Promising Materials for High Dielectric Biaxiality Ferroelectric Mixtures", MOLECULAR CRYSTALS AND LIQUID CRYST, GORDON AND BREACH, LONDON, GB, vol. 364, 1 January 2001 (2001-01-01), pages 889 - 898, XP008089178, ISSN: 0026-8941 *
H. KELKER; R. HATZ: "Handbook of Liquid Crystals", 1980, VERLAG CHEMIE

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CN109476996A (zh) 2019-03-15

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