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WO2019034588A1 - Composés cristallins liquides - Google Patents

Composés cristallins liquides Download PDF

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Publication number
WO2019034588A1
WO2019034588A1 PCT/EP2018/071891 EP2018071891W WO2019034588A1 WO 2019034588 A1 WO2019034588 A1 WO 2019034588A1 EP 2018071891 W EP2018071891 W EP 2018071891W WO 2019034588 A1 WO2019034588 A1 WO 2019034588A1
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WO
WIPO (PCT)
Prior art keywords
atoms
compounds
formula
mmol
alkenyl
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2018/071891
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German (de)
English (en)
Inventor
Constanze Brocke
Lars Lietzau
Katharina LINKE
Achim Goetz
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Merck Patent GmbH
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Merck Patent GmbH
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Priority to DE112018004157.3T priority Critical patent/DE112018004157A5/de
Priority to CN201880052122.1A priority patent/CN110997871B/zh
Publication of WO2019034588A1 publication Critical patent/WO2019034588A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention relates to compounds of the formula I, wherein the alkyl / alkenyl radicals R 1 and R 2 are as defined below, a process for their preparation, liquid-crystalline media containing at least one compound of formula I and their use as component (s) in liquid-crystalline media. Moreover, the present invention relates to liquid crystal and electro-optical
  • nematic liquid crystals have hitherto found the widest application in flat display devices. They were particularly used in passive TN or STN matrix displays or systems with a TFT active matrix.
  • liquid-crystalline compounds according to the invention can be used as component (s) of liquid-crystalline media, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of upright phases DAP or ECB (electrically controlled birefringence), based on the IPS effect (in-plane switching) or the effect of dynamic dispersion.
  • Cydohexene ring and a total of three rings is known in the art.
  • Cydohexenring As a liquid crystalline or mesogenic material and its preparation described, such.
  • One of the compounds proposed therein has a cylohexene ring besides a biphenyl unit and as
  • End groups pentyl and methyl.
  • the compounds should simultaneously have a comparatively low viscosity, as well as a high optical
  • the invention was thus an object of new stable
  • the compounds of the invention should be thermally and photochemically stable under the conditions prevailing in the fields of application. As mesogens they should have a broad
  • liquid-crystalline media can be obtained for displays that require particularly high optical anisotropies, in particular for IPS and FFS displays, but also for TN or STN displays.
  • the compounds of the invention are sufficiently stable and colorless. In particular, they are characterized by neutral to slightly positive dielectric anisotropy ⁇ . They are well soluble for compounds with comparable properties.
  • the compounds according to the invention have a comparatively very high clearing point and at the same time low values for the rotational viscosity.
  • the compounds have relatively low melting points.
  • the invention thus relates to compounds of the formula I, in which an alkyl or alkenyl radical having 1 to 15 or 2 to 15 C atoms, wherein in these radicals also one or more CH 2 groups each independently of one another by -C ⁇ C-,
  • -CF 2 O-, -OCF 2 -, / ⁇ , ->" ⁇ ⁇ ⁇ > ⁇ _S - > -CO-O-, or -O-CO- can be replaced so that O / S atoms are not directly linked to one another, and in which also one or more H atoms can be replaced by halogen, or H .
  • alkyl or alkenyl radical having 1 to 15 or 2 to 15 C atoms, where in these radicals also one or more CH 2 groups are each independently of one another by -C 1 -C-,
  • -O-, -S-, -CO-O-, or -O-CO- can be replaced so that O / S atoms are not directly linked to each other, and in which also one or more H atoms are replaced by halogen can, or H, preferably a halogenated or unsubstituted alkenyl radical having 2 to 15 carbon atoms, wherein in these radicals also one or more CH 2 groups each independently
  • -CEC-, -CF 2 O-, -OCF 2 -, / ⁇ , ->" ⁇ ⁇ ⁇ > -O-, -S-, -CO-O-, or -O-CO- can be replaced so that O / S atoms are not directly linked to each other, and in which also one or more H atoms are replaced by halogen in which R 1 and R 2 are not simultaneously an alkyl chain having 1 to 15 C atoms, and wherein R 1 and R 2 preferably comprise at least one halogenated or unsubstituted alkenyl radical, in which radical also one or more CH 2 - Each independently of one another by -C ⁇ C-, -CF 2 O-, -OCF 2 -, ⁇ , - ⁇ > -,
  • ⁇ C ⁇ ⁇ 0 ⁇ ⁇ 'S-' -CO-O-, or -O-CO- so be replaced may be that O / S atoms are not directly linked to each other, and in which also one or more H atoms may be replaced by halogen.
  • the invention further relates to the use of the compounds of the formula I in liquid-crystalline media.
  • liquid-crystalline media having at least two liquid-crystalline components which comprise at least one compound of the formula I,
  • R 1 is an alkyl or alkenyl radical having 1 to 15 or 2 to 15 C
  • -CF 2 O-, -OCF 2 -, / ⁇ , ->" ⁇ ⁇ ⁇ > ⁇ - ° ' ⁇ -CO-O-, or -O-CO- can be replaced so that O / S atoms are not directly linked to each other, and in which also one or more H atoms may be replaced by halogen, or H,
  • alkyl or alkenyl radical having 1 to 15 or 2 to 15 C atoms, where in these radicals also one or more CH 2 groups are each independently of one another by -C 1 -C-,
  • -CF 2 O-, -OCF 2 -, / ⁇ , ->" ⁇ ⁇ ⁇ > ⁇ - ° ' ⁇ -CO-O-, or -O-CO- can be replaced so that O / S atoms are not directly linked to each other, and in which also one or more H atoms may be replaced by halogen, or H.
  • Preferred liquid-crystalline media according to the invention comprise at least one compound of the formula I according to the preferred Embodiments of the compounds as indicated above and below.
  • the compounds of the formula I have a wide range of applications. Depending on the choice of substituents, these compounds may serve as base materials from which liquid crystalline media are predominantly composed; However, it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compounds in order, for example, to influence the dielectric and / or optical anisotropy of such a dielectric and / or to optimize its threshold voltage and / or its viscosity.
  • the compounds of the formula I are colorless in the pure state and form liquid-crystalline mesophases in their own or in mixtures in a temperature range which is favorably located for electrooptical use. With the compounds according to the invention, broad nematic phase ranges can be achieved. In liquid-crystalline mixtures, the substances according to the invention significantly increase the optical anisotropy and / or lead to an improvement in the low-temperature storage stability compared to comparable mixtures with a high dielectric content
  • the radical R 1 of the formula I and its sub-formulas preferably denotes alkyl or alkenyl having up to 8 carbon atoms.
  • R 1 particularly preferably represents an unbranched alkenyl radical having 2 to 8 C atoms, in particular unbranched alkenyl having 2 to 7 C atoms.
  • the radical R 2 of the formula I is preferably alkyl or alkenyl having up to 8 carbon atoms.
  • R 2 particularly preferably means one
  • R 1 and R 2 are alkenyl radical and the other is an alkyl radical.
  • R 1 is more preferably an alkenyl radical having up to 8 carbon atoms and R 2 is an alkyl radical having up to 8 carbon atoms, or R 1 is an alkyl radical having up to 8 carbon atoms and R 2 is an alkenyl radical having up to 8 carbon atoms
  • Wing groups R 1 and R 2 may occasionally for reasons of better solubility in the usual liquid crystal inen base materials of
  • the group R 1 is preferably straight-chain.
  • alkenyl chains are preferably E-configured.
  • Particularly preferred compounds of formula I are the compounds of formulas 1-1 to I-6: alkenyl alkenyl
  • alkenyl 1.5 wherein alkenyl is independently an alkenyl radical having 2-8 C atoms or one of the meanings given above.
  • the formulas 1-1, I-2, I-5 and I-6 are preferred, in particular the compounds of the formulas 1-1 and I-5.
  • the invention therefore also has a process for the preparation of
  • the invention relates to compounds of the formula I which comprise a process step in which an arylmetal compound of the formula II wherein R 2 is as defined for formula I, and
  • M means Li, MgBr or MgCl
  • R 1 is as defined for formula I, is reacted, and in a further reaction step comprising an elimination of the OH function formed in the preceding reaction step to a compound of formula I:
  • reaction methods and reagents used are in principle known from the literature. Further reaction conditions may be the
  • 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 work-up of the reaction mixtures is optionally carried out, as required, by filtration over solid phases, chromatography, separation between immiscible phases (eg extraction), adsorption on solid supports, distilling off solvents and / or azeotropic mixtures, selective distillation, sublimation, crystallization, cocrystallization or by nanofiltration on membranes.
  • the invention also liquid-crystalline media containing one or more of the compounds of formula I as defined above, preferably the compounds of the invention and their
  • the liquid-crystalline media contain at least two components. They are preferably obtained by mixing the components, for. As mesogenic or liquid crystalline compounds, mixed together.
  • the invention therefore also relates to a liquid-crystalline medium containing at least two mesogenic
  • liquid-crystalline media according to the invention contain
  • Compounds as further constituents 2 to 40 more preferably 4 to 30 components.
  • these media contain, in addition to one or more compounds according to the invention 7 to 25 components.
  • These other ingredients are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of azoxybenzenes,
  • Cyclohexylbenzoe phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic, Cyclohexylphenylester of benzoic acid, cyclohexanecarboxylic or Cyclohexylcyclohexancarbonklare, Phenylcyclohexane, Cyclohexylbiphenyls, Phenylcyclohexylcyclohexane, Cyclohexylcyclohexane, Cyclohexylcyclohexylcyclohexane, 1, 4-bis-cyclo-hexylbenzenes, 4,4'-bis-cyclohexylbiphenyls , Phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyl-dioxanes, phen
  • L and E which may be identical or different, each independently of one another represent a bivalent radical from the structural elements -Phe-, -Cyc-, -Phe- Phe, -Phe-Cyc, -Cyc-Cyc, -Pyr, -Dio, -Py, -G-Phe, -G-Cyc and their mirror images formed group, wherein Phe is unsubstituted or by fluorine substituted 1,4-phenylene, Cyc trans-1,4-cyclohexylene, Pyr Pyhmidine-2,5-diyl or Pyridine-2,5-diyl, Dio 1, 3-dioxane-2,5-diyl, Py
  • one of L and E is Cyc, Phe or Pyr.
  • E is preferably Cyc, Phe or Phe-Cyc.
  • the media according to the invention preferably comprise one or more components selected from the compounds of the formulas 1, 2, 3, 4 and 5, in which L and E are selected from the group Cyc, Phe and Pyr and simultaneously one or more components selected from the compounds of the Formulas 1, 2, 3, 4 and 5, wherein one of the radicals L and E is selected from the group Cyc, Phe, Py and Pyr 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 formulas 1, 2, 3, 4 and 5, wherein the radicals L and E are selected from the group -Phe-Cyc, -Cyc-Cyc, -G-Phe and -G-Cyc-.
  • R 'and / or R each independently represent alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 C atoms, -F, -Cl, -CN, -NCS or - (O) iCH 3 -kF k , where i is 0 or 1 and k is 1, 2 or 3.
  • R 'and R "in a smaller subgroup of the compounds of the formulas 1, 2, 3, 4 and 5 are each independently alkyl, alkenyl, alkoxy, alkoxyalkyl, Alkenyloxy or alkanoyloxy with up to 8 C atoms. In the following, this smaller subgroup will be called Group A and the compounds will be described with the subformulae 1a, 2a, 3a, 4a and 5a
  • R 'and R "are different from each other one of these radicals is usually alkyl, alkenyl, alkoxy or alkoxyalkyl.
  • R " is -F, -Cl, -NCS or - (O) I 3-k F k, where i is 0 or 1 and k is 1, 2 or 3.
  • R "has this meaning are designated by the subformulae 1 b, 2b, 3b, 4b and 5b, particular preference is given to those compounds of the subformulae 1 b, 2b, 3b, 4b and 5b in which R" denotes -F, Has -Cl, -NCS, -CF 3 , -OCHF 2 or -OCF 3 .
  • R ' has the meanings given for the compounds of the subformulae 1a to 5a and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
  • R ' has the meanings given for the compounds of the subformulae 1a to 5a and is preferably alkyl, alkoxy or alkenyl.
  • the media according to the invention preferably comprise one or more compounds which are selected from groups A, B and / or C.
  • the mass fractions of the compounds from these groups in the media according to the invention are preferably:
  • the sum of the mass fractions of the compounds of the groups A, B and / or C contained in the respective inventive media is preferably 5 to 90% and particularly preferably 10 to 90%.
  • the media according to the invention preferably contain 1 to 40%, particularly preferably 3 to 30%, of the compounds according to the invention.
  • the preparation of the liquid-crystal mixtures according to the invention is carried out in a conventional manner.
  • the desired amount of the components used in lesser amount in the main constituent components is dissolved, preferably at elevated
  • premixes e.g. Homologous mixtures or using so-called “multi-bottle” systems produce.
  • the dielectrics may also contain further additives known to the person skilled in the art and described in the literature. For example, 0 to 15%, preferably 0 to 10%, pleochroic dyes, chiral
  • Dopants, stabilizers or nanoparticles can be added.
  • the individual added compounds are used in concentrations of 0.01 to 6%, preferably from 0.1 to 3%.
  • concentration data of the other constituents of the liquid-crystal mixtures ie the liquid-crystalline or mesogenic compounds are given, without taking into account the concentration of these additives.
  • the liquid-crystal mixtures according to the invention enable a significant expansion of the available parameter space.
  • the invention also electro-optical displays (in particular TFT displays with two plane-parallel support plates, which form a cell with a border, integrated non-linear elements for switching individual pixels on the carrier plates and one in the Cell-containing nematic liquid-crystal mixture having positive dielectric anisotropy and high resistivity) containing such media and the use of these media for electro-optical purposes.
  • electro-optical displays in particular TFT displays with two plane-parallel support plates, which form a cell with a border, integrated non-linear elements for switching individual pixels on the carrier plates and one in the Cell-containing nematic liquid-crystal mixture having positive dielectric anisotropy and high resistivity
  • alkyl embraces unbranched and branched alkyl groups having 1-15 carbon atoms, in particular the unbranched groups methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and n-heptyl. Groups of 2-5 carbon atoms are generally preferred.
  • alkenyl includes unbranched and branched alkenyl groups having up to 15 carbon atoms, especially the unbranched groups. Particularly preferred alkenyl groups are C 2 -C 7 -1E-alkenyl, C 4 -C 7 3E-alkenyl, C 5 -C 7 -alkenyl, C 6 -C 7 -5-alkenyl and C 7 -6- Alkenyl, in particular C 2 -C 7 -1 E-alkenyl, C 4 -C 7 3E-alkenyl and C 5 -C 7 -4-alkenyl. Examples of preferred alkenyl groups are vinyl, 1 E-propenyl,
  • Carbon atoms are generally preferred.
  • halogenated alkyl preferably includes mono- or polyfluorinated and / or chlorinated radicals. Perhalogenated radicals are included. Particularly preferred are fluorinated alkyl radicals,
  • the total amount of compounds of the formula I in the mixtures according to the invention is not critical.
  • the mixtures may therefore contain one or more other components to optimize various properties.
  • the structure of the matrix display of polarizers, electrode base plates and electrodes with surface treatment according to the invention corresponds to the usual construction for such displays. It is the Concept of the usual construction here broadly and includes all modifications and modifications of the matrix display, in particular matrix display elements based on poly-Si TFT. However, a significant difference of the displays of the invention on the basis of the usual twisted nematic cell is the choice of the liquid crystal parameters of the liquid crystal layer.
  • the dielectric anisotropy ⁇ of the individual substances is determined at 20 ° C and 1 kHz. To this end, 5-10% by weight of the substance to be investigated is dissolved in the dielectrically positive mixture ZLI-4792 (Merck KGaA) and the measured value extrapolated to a concentration of 100%.
  • the optical anisotropy ⁇ is at 20 ° C and a
  • Wavelength of 589.3 nm determines the rotational viscosity at 20 ° C, both also by linear extrapolation.
  • the plural form of a term means both the singular form and the plural form, and vice versa.
  • LiDBB lithium di-tert-butylbiphenyl
  • the present invention is not affected by the following
  • Step 1 1 - (4-Bromophenyl) -4-propylcyclohexanol 5
  • Step 1 .2 1 -Brom-4- (4-propyl-cyclohex-1-enyl) -benzene
  • Step 1 .3 4'-Eth 1-4- (4-propylcyclohex-1-enyl) -biphenyl
  • Compound 6 shows the following phase behavior:
  • Tetrakis (triphenylphoshin) palladium (0) (12 g, 10 mmol) and then heated to boiling. Under reflux, a solution of p-toluene boronic acid 7 (47 g, 346 mmol) in ethanol (100 mL) is added rapidly. The reaction mixture is heated at reflux overnight and after cooling with dist. Water and toluene are added. The aqueous phase is extracted with toluene. The combined organic
  • Compound 17 shows the following phase behavior:
  • Step 3.1 4-prop- (1E) -enyl-cyclohexanone
  • Reaction mixture is warmed to 0 ° C and with dist. Water and MTB ether diluted. After phase separation, the organic phase is washed with dist. Water and sat. Sodium chloride solution washed and over
  • Step 3.2 1- (4'-methyl-biphenyl-4-yl) -4-prop- (1E) -enyl) -cyclohexanol
  • Step 3.3 4'-Methyl-4 - [(4-prop- (1E) -enyl) -cyclohex-1-enyl] -biphenyl
  • the crude product is purified by crystallization (1st isopropanol / acetone, 2nd heptane / activated carbon) to give 4'-methyl-4 - [(4-prop- (1E) -enyl) -cyclohex-1-enyl] -biphenyl 21 as a colorless shimmering
  • Compound 21 shows the following phase behavior:
  • Step 4.1 [4- (2-methoxyvinyl) cyclohexyloxymethyl] benzene
  • Methoxymethyltriphenylphosphonium chloride (69.0 g, 200 mmol) are initially charged in THF (450 mL) and potassium tert-butoxide (25.6 g, 228 mmol) is added in portions at RT. The reaction mixture is stirred for 18 h and then diluted with heptane, with dist. Water and sat. Washed sodium chloride solution and dried over sodium sulfate. The crude product is purified by silica gel chromatography (heptane / MTB ether 9: 1) to give [4- (2-methoxyvinyl) -cyclohexyloxymethyl] -benzene 22 as a light yellow oil.
  • Step 4.2 4-benzyloxy-cyclohexyl) -acetaldehyde
  • a mixture of DBB (38.0 g, 141 mmol) and lithium granules (1 .0 g, 144 mmol) in THF (200 mL) is stirred under argon for 4 h.
  • the LiDBB solution prepared in the first step is added dropwise at -75 ° C.
  • reaction mixture is stirred for 1 h, warmed to 0 ° C and treated with ice water cooling with bicarbonate solution and MTB ether.
  • the aqueous phase is separated and extracted with MTB ether.
  • the combined organic phases are washed with sodium chloride solution, dried over sodium sulfate, filtered and concentrated in vacuo.
  • the residue is purified by silica gel chromatography
  • Step 4.8 4-But-3-enyl-1 - (4'-methyl-biphenyl-4-yl) -cyclohexanol
  • Compound 30 shows the following phase behavior:
  • Step 5.2 4-Pent- (3E) -enyl-cyclohexanol
  • a mixture of DBB (84 g, 312 mmol) and lithium granules (2.2 g, 312 mmol) in THF (400 mL) is stirred under argon for 4 h.
  • the LiDBB solution prepared in the first step is added dropwise at -75 ° C.
  • reaction mixture is stirred for 1 h, warmed to 0 ° C and treated with ice water cooling with bicarbonate solution and MTB ether.
  • the aqueous phase is separated and extracted with MTB ether.
  • the combined organic phases are washed with sodium chloride solution, dried over sodium sulfate, filtered and concentrated in vacuo.
  • the residue is purified by silica gel chromatography
  • Step 5.4 1- (4'-Methyl-biphenyl-4-yl) -4-pent- (3E) -enyl-cyclohexanol
  • the crude product is purified by crystallization (1st isopropanol / acetone, 2nd heptane) to give 4'-methyl-4 - [(4-pent- (3E) -enyl) -cyclohex-1-enyl] -biphenyl 35 as colorless shimmering crystals.
  • Compound 35 shows the following phase behavior:

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

Abstract

L'invention concerne des composés de formule (I) dans laquelle les restes alkyle/alkényle R1 et R2 ont les significations mentionnées dans la revendication 1, un procédé pour leur préparation, des milieux cristallins liquides contenant au moins un composé de formule (I) ainsi que des affichages électro-optiques contenant un tel milieu cristallin liquide.
PCT/EP2018/071891 2017-08-14 2018-08-13 Composés cristallins liquides Ceased WO2019034588A1 (fr)

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DE112018004157.3T DE112018004157A5 (de) 2017-08-14 2018-08-13 Flüssigkristalline verbindungen
CN201880052122.1A CN110997871B (zh) 2017-08-14 2018-08-13 液晶化合物

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DE102017007672.3A DE102017007672A1 (de) 2017-08-14 2017-08-14 Flüssigkristalline Verbindungen
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022023400A1 (fr) 2020-07-31 2022-02-03 Merck Patent Gmbh Milieu cristallin liquide, dispositif d'affichage à cristaux liquides comprenant celui-ci et composés
EP4306614A1 (fr) * 2022-07-15 2024-01-17 Merck Patent GmbH Milieu à base de cristaux liquides

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4211666A (en) * 1977-11-21 1980-07-08 Chisso Corporation Liquid crystal compounds
US4940822A (en) 1988-11-04 1990-07-10 Warner-Lambert Company Substituted benzenemethanol compounds, intermediates thereof, and preparation thereof
DE4326020A1 (de) * 1993-08-03 1995-02-09 Merck Patent Gmbh Biphenylcyclohexen-Derivate und flüssigkristallines Medium
EP0728829A2 (fr) * 1995-02-23 1996-08-28 Chisso Corporation Dérivé d'alkényle cyclohexène liquide cristallin, composition liquide cristalline et élément d'affichage à cristaux liquides
US5560863A (en) * 1993-08-06 1996-10-01 Merck Patent Gesellschaft Mit Beschrankter Haftung 2-Fluorocyclohexene derivatives
EP3127991A1 (fr) * 2015-08-05 2017-02-08 Merck Patent GmbH Milieu cristallin liquide
CN107674687A (zh) * 2016-08-02 2018-02-09 石家庄诚志永华显示材料有限公司 液晶组合物及液晶显示元件或液晶显示器

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE502007004625D1 (de) * 2006-09-13 2010-09-16 Merck Patent Gmbh Fluorphenyl-Verbindungen für flüssigkristalline Mischungen
JP2014516366A (ja) * 2011-03-29 2014-07-10 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 液晶媒体
WO2016208411A1 (fr) * 2015-06-24 2016-12-29 Dic株式会社 Composition de cristaux liquides nématiques et élément d'affichage à cristaux liquides la contenant
EP3112440B1 (fr) * 2015-07-02 2019-07-24 Merck Patent GmbH Milieu cristallin liquide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4211666A (en) * 1977-11-21 1980-07-08 Chisso Corporation Liquid crystal compounds
US4940822A (en) 1988-11-04 1990-07-10 Warner-Lambert Company Substituted benzenemethanol compounds, intermediates thereof, and preparation thereof
DE4326020A1 (de) * 1993-08-03 1995-02-09 Merck Patent Gmbh Biphenylcyclohexen-Derivate und flüssigkristallines Medium
US5560863A (en) * 1993-08-06 1996-10-01 Merck Patent Gesellschaft Mit Beschrankter Haftung 2-Fluorocyclohexene derivatives
EP0728829A2 (fr) * 1995-02-23 1996-08-28 Chisso Corporation Dérivé d'alkényle cyclohexène liquide cristallin, composition liquide cristalline et élément d'affichage à cristaux liquides
EP3127991A1 (fr) * 2015-08-05 2017-02-08 Merck Patent GmbH Milieu cristallin liquide
CN107674687A (zh) * 2016-08-02 2018-02-09 石家庄诚志永华显示材料有限公司 液晶组合物及液晶显示元件或液晶显示器

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Broschüre", 1998, MERCK KGAA, article "Merck Liquid Crystals - Licristal® - Physical Properties of Liquid Crystals - Description of the Measurements Methods"
V.S. BEZBORODOV, DRUCKSCHRIFT LIQUID CRYSTALS, vol. 23, 1997, pages 69 - 75

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022023400A1 (fr) 2020-07-31 2022-02-03 Merck Patent Gmbh Milieu cristallin liquide, dispositif d'affichage à cristaux liquides comprenant celui-ci et composés
EP4306614A1 (fr) * 2022-07-15 2024-01-17 Merck Patent GmbH Milieu à base de cristaux liquides

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TWI785092B (zh) 2022-12-01
DE112018004157A5 (de) 2020-04-23

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