WO2006125511A1 - Pyran-dioxan-derivate und deren verwendung in flüssigkristallinen medien - Google Patents
Pyran-dioxan-derivate und deren verwendung in flüssigkristallinen medien Download PDFInfo
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- WO2006125511A1 WO2006125511A1 PCT/EP2006/004140 EP2006004140W WO2006125511A1 WO 2006125511 A1 WO2006125511 A1 WO 2006125511A1 EP 2006004140 W EP2006004140 W EP 2006004140W WO 2006125511 A1 WO2006125511 A1 WO 2006125511A1
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- 0 C**C(CC1)COC1C(COCc1ccccc1)COCc1ccccc1 Chemical compound C**C(CC1)COC1C(COCc1ccccc1)COCc1ccccc1 0.000 description 2
- NPJZHYOHRJFPKK-UHFFFAOYSA-N CCCC(CC1)COC1C1COC(c(cc2)cc(cc3F)c2cc3F)OC1 Chemical compound CCCC(CC1)COC1C1COC(c(cc2)cc(cc3F)c2cc3F)OC1 NPJZHYOHRJFPKK-UHFFFAOYSA-N 0.000 description 1
- DDEXEXKNWFMJMX-UHFFFAOYSA-N Cc(c(C)c1)cc(F)c1F Chemical compound Cc(c(C)c1)cc(F)c1F DDEXEXKNWFMJMX-UHFFFAOYSA-N 0.000 description 1
- QCQHUMBPYQAMGI-UHFFFAOYSA-N Fc(cc(CBr)c(CBr)c1)c1F Chemical compound Fc(cc(CBr)c(CBr)c1)c1F QCQHUMBPYQAMGI-UHFFFAOYSA-N 0.000 description 1
- YWRHTEFPOZEHST-UHFFFAOYSA-N O=Cc(cc(C1OCCO1)cc1)c1Cl Chemical compound O=Cc(cc(C1OCCO1)cc1)c1Cl YWRHTEFPOZEHST-UHFFFAOYSA-N 0.000 description 1
- CJMKRCDHULYJOT-UHFFFAOYSA-N O=Cc(cc1)cc(cc2F)c1cc2F Chemical compound O=Cc(cc1)cc(cc2F)c1cc2F CJMKRCDHULYJOT-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- 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
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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
- 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
- C09K2019/327—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems containing a spiro ring system
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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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
- C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
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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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
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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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
- C09K2019/3425—Six-membered ring with oxygen(s) in fused, bridged or spiro ring systems
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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
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
Definitions
- the invention relates to pyran dioxane derivatives and their use as component (s) in liquid-crystalline media. Moreover, the present invention relates to liquid crystal and electro-optical display elements which contain the liquid-crystalline media according to the invention.
- liquid-crystalline compounds according to the invention can be used as a liquid-crystalline compounds according to the invention.
- 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), the IPS effect plane switching) or the effect of dynamic dispersion.
- DE 102004025808 A1 discloses the synthesis of a compound consisting of 3 rings, each containing one tetrahydropyran ring and one dioxane ring.
- the substances have positive values of the dielectric anisotropy ⁇ .
- various tetrahydropyran derivatives have already been described as a liquid crystalline material and their preparation, such as.
- the compounds should simultaneously have a comparatively low viscosity and a dielectric anisotropy in the positive range.
- Liquid crystals it is advantageous to use compounds with a particularly high dielectric anisotropy ⁇ .
- a further object of the present invention was to provide liquid-crystalline or mesogenic compounds which, by themselves or in mixtures, have a high dielectric anisotropy ⁇ , a high clearing point and a low rotational viscosity Y 1 .
- the compounds of the invention should be thermally and photochemically stable.
- nematic phase As mesogens they should allow a broad nematic phase in mixtures with liquid-crystalline co-components as well as being miscible with nematic base mixtures, especially at low temperatures.
- the pyran-dioxane derivatives according to the invention are particularly suitable as components of liquid-crystalline media. With their help, it is possible to obtain stable, liquid-crystalline media, in particular suitable for TN-TFT and STN displays, but also for I PS systems or newer concepts which require particularly high dielectric anisotropies.
- the compounds according to the invention are both thermally and UV-stable.
- the compounds according to the invention are also distinguished by strongly positive dielectric anisotropies ⁇ , which mean that lower threshold voltages are required for use in optical switching elements.
- the quotient ⁇ / ⁇ n of the compounds according to the invention also reaches particularly high values, ie, given the same values of ⁇ , relatively small values of the optical anisotropy ⁇ n are made possible by the substances according to the invention.
- the compounds according to the invention have a high clearing point and at the same time favorable values for the rotational viscosity.
- the range of liquid-crystalline substances which are suitable for the preparation of liquid-crystalline mixtures from a variety of application-technical points of view is considerably broader.
- the pyran-dioxane derivatives of the invention 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 liquid-crystalline base materials from other classes of compounds to the compounds according to the invention 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 pyran-dioxane derivatives according to the invention are colorless in the pure state. Thermally and against light, they are stable.
- the present invention thus pyran dioxane derivatives of the general formula I.
- Heteroatoms are not directly linked to each other and unsymmetrical groups can exist in both orientations
- a 1 , A 2 are each independently, the same or different
- trans-1,4-cyclohexylene in which also one or more non-adjacent CH 2 groups can be replaced by -O- and / or -S-,
- 1,4-phenylene in which one or two CH groups can be replaced by N and in which also one or more H atoms are bonded to Br, Cl, F, CN, methyl, methoxy or a mono- or polyfluorinated methyl or methoxy group can be replaced, c) a radical from the group 1, 4-bicyclo (2,2,2) -octylene, piperidine-1,4-diyl, cyclopent-1,3-diyl, spiro [3.3] heptane-2,6-diyl,
- OCF 3 may be substituted by one or more double bonds
- Y and Y 1 are Cl, F, CN 1 is OCF 3 or CF 3 , or
- n + m is 1, 2, 3 or 4, more preferably 1, 2 or 3 and most preferably 2 or 3.
- Another object of the present invention is the use of compounds of formula I as component (s) in liquid-crystalline media.
- liquid-crystalline media having at least two liquid-crystalline components which contain at least one pyran dioxane derivative of the formula I.
- the present invention also provides liquid-crystal display elements, in particular electro-optical display elements, which contain a liquid-crystalline medium according to the invention as a dielectric.
- the meaning of the formula I includes all isotopes of the chemical elements bound in the compounds of the formula I.
- the compounds of the formula I are in principle also suitable as chiral dopants and in general for obtaining chiral mesophases.
- R 1 , R 2 , A 1 , A 2 , Z 1 , Z 2 , n and m have the meanings indicated, unless expressly stated otherwise.
- the two rings can have the same or different meanings.
- the compounds of the formula I are characterized in that n + m is greater than or equal to 2 and more particularly 2 or 3.
- -CF 2 O-, -CO-O-, -CF CF-, -CH 2 O- or -CF 2 CF 2 -.
- rings A 1 and A 2 in formula I are rings according to
- L 1 , L 2 independently, H, F, Cl, CN or CF 3 , p 0, 1 or 2, preferably 0 or 1, m + p 0, 1, or 2, preferably 0 or 1, and
- OCF 3 or CF CF 2
- the remaining variables are as defined for formula I above.
- -C ⁇ C-, -CF 2 CF 2 -, -CF CF-, -CO-O-, -O-CO-, -CF 2 O-, -OCF 2 - or a single bond, more preferably -CF 2 O-, -CF 2 CF 2 - or a single bond.
- m> 1 preferably at least one of Z 1 means a single bond.
- a 1 is 1,4-cyclohexanediyl
- a 2 is a group of the formulas
- n 0 or 1
- p 0 or 1
- m + p is 0 or 1, preferably 1.
- R 1 denotes a linear alkyl or alkoxy radical having 1 to 12 C atoms or a linear alkenyl or alkenyloxy radical having 2 to 12 C atoms.
- the very particularly preferred compounds according to the invention are accordingly 1-1 to I-4:
- X 1 and R 1 are as defined for IB, and where R 1 is preferably a linear alkyl or alkoxy radical having 1 to 10 C atoms or a linear alkenyl or alkenyloxy radical having 2 to 10 C atoms.
- R 1 is preferably F or OCF 3 .
- R 1 preferably denotes a linear alkyl or alkoxy radical having 1 to 7 C atoms or a linear alkenyl or alkenyloxy radical having 2 to 7 C atoms in which a -CH 2 group is replaced by -O - can be replaced so that two adjacent groups are not replaced by -O-.
- R 1 particularly preferably denotes a linear alkyl radical or alkoxy radical having 1 to 7 C atoms or a linear alkenyl radical having 2 to 7 C atoms.
- R 1 or R 2 in the formulas above and below denotes an alkyl radical, this may be straight-chain or branched. It is particularly preferably straight-chain, has 1, 2, 3, 4, 5, 6 or 7 C atoms and accordingly denotes methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl, furthermore octyl, nonyl, decyl, undecyl, dodecyl , Tridecyl, tetradecyl or
- R 1 or R 2 is an alkyl radical in which one CH 2 group has been replaced by --O--, this may be straight-chain or branched. It is preferably straight-chain and has 1 to 10 C atoms. Particularly preferably, the first Ch ⁇ group of this alkyl radical is replaced by -O-, so that the radical R 1 is alkoxy and methoxy, ethoxy,
- R 1 or R 2 is an alkyl radical in which a CH 2 group by
- -CH CH-
- CH- CH-
- It may be straight-chain or branched. It is preferably straight-chain and has 2 to 10 C atoms. It therefore means vinyl, prop-1 or prop-2-enyl, but-1, 2- or but-3-enyl, pent-1, 2-, 3- or pent-4-enyl, hex-1 -, 2-, 3-, A- or hex-5-enyl, hept-1, 2-, 3-, A-, 5- or hept-6-enyl, OcM-, 2-, 3-, A -, 5-, 6- or
- Oct-7-enyl non-1-, 2-, 3-, A-, 5-, 6-, 7- or non-8-enyl, Dec-1, 2-, 3-, A-, 5 -, 6-, 7-, 8- or dec-9-enyl.
- Preferred alkenyl groups are C 2 -C 7 -I E-alkenyl, C 4 -C 7 -EE-alkenyl, C 5 -C 7 -alkenyl, C 6 -C 7 -5-alkenyl, and C 7 -6- Alkenyl, more preferably C 2 -C 7 -I E-alkenyl, C 4 -C 7 3E-alkenyl and C 5 -C 7 -4-alkenyl.
- alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z -Hexenyl,
- R 1 or R 2 is an alkyl radical in which one CH 2 group has been replaced by -O- and one by -CO-, these are preferably adjacent. Thus, they include an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. These are particularly preferably straight-chain and have 2 to 6 C atoms.
- R 1 or R 2 is a monosubstituted by CN or CF 3 alkyl or alkenyl radical, this radical is preferably straight-chain and the substitution by CN or CF 3 in ⁇ -position.
- R 1 or R 2 is an alkyl or alkenyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain.
- Halogen is preferably F or Cl. In the case of multiple substitution, halogen is preferably F.
- the resulting radicals also include perfluorinated radicals. For single substitution, the fluoro or chloro substituent may be in any position, but preferably in the ⁇ position.
- Branched groups of this type preferably contain no more than one chain branch.
- the formula I and the sub-formulas IA, IB and IC include, if they are chiral compounds, usually the racemates of these compounds, but also both optically pure components per se, as well as enriched mixtures of these components.
- the compounds of the formula I are 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.
- the dioxane ring in the compounds is usually prepared by condensation from an aldehyde with a 2-substituted 1,3-diol.
- the tetrahydropyran ring which either on the diol or on the
- Aldehyde group is prepared by one of the numerous known methods for the synthesis of 2,5-disubstituted tetrahydropyrans.
- tetrahydropyran-2-aldehydes there are several synthetic routes: By reduction of a corresponding carboxylic acid derivative, by mild oxidation of a corresponding Alcohol (carbinol) or by catalytic hydroformylation of a suitable Dihydropyrans.
- the starting materials for the above process are either known or can be prepared in analogy to known compounds.
- the starting materials can also be formed in situ, such that they are not isolated from the reaction mixture, but immediately further reacted to the compounds of formula I.
- the liquid-crystalline media according to the invention preferably contain, in addition to one or more compounds according to the invention, as further constituents 2 to 40, particularly preferably 4 to 30 components.
- these media contain, in addition to one or more compounds according to the invention 7 to 25 components.
- nematic or nematogenic (monotropic or isotropic) substances are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters Cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid or of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexy
- 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, -Cyc-Cyc, -Pyr, -Dio, -Py, -G-Phe and -G-Cyc- and their mirror images formed group, wherein Phe is unsubstituted or substituted by fluorine 1, 4-phenylene , Cyc trans-1,4-cyclohexylene or 1,4-cyclohexenylene, pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, dioio-1,3-dioxane-2,5-diyl, Py tetrahydropyran-2 , 5-diyl and G 2- (trans-1,4-cyclohexyl) -ethyl.
- 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
- radicals L and E are 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
- R 'and / or R are each independently of one another alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 C atoms, -F, -Cl, -CN, -NCS, - (O) 1 CH 3 ( K + I) FkCIi, where i is 0 or 1, k and I are independently, the same or different, 0, 1, 2 or 3, but with the proviso that the sum (k + I) is 1, 2 or 3 ,
- R 1 and R each independently represent alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 C atoms in a smaller subgroup of the compounds of the formulas 1, 2, 3, 4 and 5 Subgroup group A and the compounds are denoted by sub-formulas 1a, 2a, 3a, 4a and 5a In most of these compounds, R 1 and R "are different from one another, one of these radicals being usually alkyl, alkenyl, alkoxy or alkoxyalkyl.
- R " is -F, -Cl, -NCS or - (O) 1 CH3 - (k + i ) F k Cl
- the compounds in which R "has this meaning have, are denoted by the sub-formulas 1b, 2b, 3b, 4b and 5b.
- R has the meaning -F, -Cl, -NCS, -CF 3 , -OCHF 2 or -OCF 3 .
- R 1 has the meanings given for the compounds of sub-formulas 1a to 5a and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
- R 1 has the same as that of the
- the media according to the invention preferably comprise one or more compounds which are selected from the groups A, B and / or C.
- the mass fractions of the compounds from these groups in the media according to the invention are preferably:
- Group A 0 to 90%, preferably 20 to 90%, particularly preferably 30 to 90%;
- Group B 0 to 80%, preferably 10 to 80%, particularly preferably 10 to 65%;
- Group C 0 to 80%, preferably 5 to 80%, particularly preferably 5 to 50%;
- 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 5 to 30%, of the compounds according to the invention. Preference is furthermore given to media containing more than 40%, particularly preferably 45 to 90%, of compounds according to the invention.
- the media preferably contain three, four or five 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 is dissolved in the components making up the main component, preferably at elevated temperature.
- solutions of the components in an organic solvent e.g. in acetone, chloroform or methanol, and to remove the solvent again after thorough mixing, for example by distillation.
- 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%, of pleochroic dyes and / or chiral dopants may be added.
- the individual compounds added are used in concentrations of from 0.01 to 6%, preferably from 0.1 to 3%. However, the 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.
- K crystalline phase
- N nematic phase
- I isotropic phase
- Sm smectic phase.
- the numbers between the abbreviations for the phases correspond to the transition temperatures for the pure substance.
- the first transition temperature starting from the crystalline phase (K) corresponds to the melting point.
- measured values are determined at a temperature of 20 ° C.
- ⁇ , ⁇ n and ⁇ i 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 100% content.
- a compound analogous to Example La with double bond in the terminal side chain can be prepared via the homoallylic alcohol D, which is prepared according to J.N. Zonjee et al., Tetrahedron 1989, 45, 7553-7567.
- the compound D is reacted analogously to Example 1.a successively with 5 to Bromopyran, then with DBU in toluene and subsequent hydrogenation (after elimination of all protecting groups, see reaction 8 -> 9) to compound E.
- the aldehyde 15 is then reacted with 2-ethyl-1, 3-propanediol to dioxane 16.
- 2-ethyl-1, 3-propanediol to dioxane 16.
- 44.5 g (110 mmol) of the aldehyde 15 and 11, 2 g of the diol are dissolved in 250 ml of toluene, 400 mg of p-toluenesulfonic acid monohydrate and heated to complete conversion of the aldehyde (DC) to the water at reflux , The cooled batch is washed three times with sat.
- Washed sodium bicarbonate solution concentrated and passed through silica gel (toluene / heptane 7: 3, toluene, toluene / ethyl acetate 95: 5).
- the product-containing fractions are concentrated and the residue recrystallized at -2O 0 C from ethanol.
- R 12 , A 11 , A 21 , Z 21 , A 22 and X 11 in particular according to Table 2 mean:
- a solution of 25 g (176 mmol) of the aromatic 20 in 250 ml of carbon tetrachloride is mixed with 78 g (440 mmol) of N-bromosuccinimide and 1 g of azobisisobutyronitrile and warmed carefully until the reaction has started.
- the batch is heated to boiling for 30 minutes. After cooling, the solid is separated and washed with carbon tetrachloride. The filtrate is concentrated and the residue is purified on silica gel.
- a suspension of 34.5 g (250 mmol) of potassium carbonate in 350 ml of ethyl methyl ketone is mixed with 16.0 g (100 mol) of diethyl malonate and 30 g (100 mmol) of dibromide 21 and heated to boiling until the end of the reaction (TLC). , The solid is separated. The filtrate is concentrated and the residue is purified on silica gel.
- the naphthalene derivative 38 is prepared analogously to Example 5.
- a suspension of 3.0 g (80 mmol) of lithium aluminum hydride in 50 ml of THF is treated with a solution of 28.2 g (100 mol) of the acid 43 in 100 ml of THF and heated to boiling for 2 h.
- the cooled mixture is carefully hydrolyzed with a THF / water mixture and then treated with a 80 0 C warm solution of 22.9 g of sodium carbonate decahydrate in 20 ml of water. After stirring for 30 minutes, the solid is separated off. The organic phase is dried and concentrated. The residue is reacted further without further purification.
- pyridinium chlorochromate PCC
- Celite® JTBaker
- dichloromethane a solution of the residue in 75 ml of dichloromethane is added to the suspension.
- the batch is stirred overnight at RT.
- the Celite® is separated and washed with dichloromethane.
- the organic phase is concentrated and the residue obtained is passed through silica gel.
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Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06753478A EP1891059B1 (de) | 2005-05-25 | 2006-05-03 | Pyran-dioxan-derivate und deren verwendung in flüssigkristallinen medien |
KR1020077030211A KR101309905B1 (ko) | 2005-05-25 | 2006-05-03 | 피란/다이옥세인 유도체 및 액정 매질 내에서의 그의 용도 |
JP2008512716A JP5028413B2 (ja) | 2005-05-25 | 2006-05-03 | ピラン−ジオキサン誘導体類、および液晶媒体中におけるそれの使用 |
US11/915,243 US7674507B2 (en) | 2005-05-25 | 2006-05-03 | Pyran-dioxane derivatives, and the use thereof in liquid-crystalline media |
CN2006800179744A CN101180294B (zh) | 2005-05-25 | 2006-05-03 | 吡喃-二*烷衍生物及其在液晶介质中的用途 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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EP05011324 | 2005-05-25 | ||
EP05011324.0 | 2005-05-25 | ||
EP05017654 | 2005-08-12 | ||
EP05017654.4 | 2005-08-12 |
Publications (1)
Publication Number | Publication Date |
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WO2006125511A1 true WO2006125511A1 (de) | 2006-11-30 |
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PCT/EP2006/004140 WO2006125511A1 (de) | 2005-05-25 | 2006-05-03 | Pyran-dioxan-derivate und deren verwendung in flüssigkristallinen medien |
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US (1) | US7674507B2 (de) |
EP (1) | EP1891059B1 (de) |
JP (1) | JP5028413B2 (de) |
KR (1) | KR101309905B1 (de) |
CN (1) | CN101180294B (de) |
TW (1) | TWI391475B (de) |
WO (1) | WO2006125511A1 (de) |
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JP2008163316A (ja) * | 2006-11-27 | 2008-07-17 | Merck Patent Gmbh | 液晶媒体および液晶ディスプレイ |
WO2008092491A1 (de) * | 2007-01-31 | 2008-08-07 | Merck Patent Gmbh | Chromanverbindungen zur verwendung als komponenten in flüssigkristallinen medien z.b. in elektrooptischen anzeigeelementen |
WO2008105286A1 (ja) | 2007-02-28 | 2008-09-04 | Chisso Corporation | Cf2o結合基を有する5環液晶化合物、液晶組成物および液晶表示素子 |
WO2009150963A1 (ja) | 2008-06-09 | 2009-12-17 | チッソ株式会社 | シクロヘキサン環を有する5環液晶化合物、液晶組成物および液晶表示素子 |
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JP2010526771A (ja) * | 2007-04-24 | 2010-08-05 | 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 | 液晶混合物のためのピリジン化合物 |
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WO2020064173A1 (en) | 2018-09-25 | 2020-04-02 | Antabio Sas | Indane derivatives for use in the treatment of bacterial infection |
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WO2021191240A1 (en) | 2020-03-24 | 2021-09-30 | Antabio Sas | Combination therapy |
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WO2006125530A1 (de) * | 2005-05-25 | 2006-11-30 | Merck Patent Gmbh | Tetrahydropyranderivate mit mehreren sauerstoffhaltigen ringen und verfahren zu ihrer herstellung |
EP2757139A4 (de) * | 2011-09-14 | 2015-06-17 | Jnc Corp | Verbindung, flüssigkristallzusammensetzung und flüssigkristallanzeigeelement |
JP6299020B2 (ja) * | 2012-10-23 | 2018-03-28 | Jnc株式会社 | 液晶化合物、液晶媒体および光素子 |
WO2015029876A1 (ja) | 2013-08-30 | 2015-03-05 | Dic株式会社 | ネマチック液晶組成物 |
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JP6435923B2 (ja) * | 2014-03-07 | 2018-12-12 | Jnc株式会社 | ジヒドロピラン化合物、液晶組成物および液晶表示素子 |
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KR20160052898A (ko) | 2014-10-29 | 2016-05-13 | 삼성디스플레이 주식회사 | 액정 조성물 및 이를 포함하는 액정 표시 장치 |
JP6630789B2 (ja) * | 2018-07-25 | 2020-01-15 | 富士フイルム株式会社 | サラシノールの製造に有用な化合物およびそれらの製造法、サラシノールの製造法、ジオール基の保護方法および脱保護方法、並びにジオール基の保護剤 |
CN115057847B (zh) * | 2022-07-26 | 2024-01-26 | 山东百启生物医药有限公司 | 一种4,6-二氯-5-(1,3-二氧戊环-2-基)-2-甲基嘧啶的制备方法 |
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2006
- 2006-05-03 CN CN2006800179744A patent/CN101180294B/zh active Active
- 2006-05-03 EP EP06753478A patent/EP1891059B1/de active Active
- 2006-05-03 KR KR1020077030211A patent/KR101309905B1/ko active IP Right Grant
- 2006-05-03 WO PCT/EP2006/004140 patent/WO2006125511A1/de not_active Application Discontinuation
- 2006-05-03 JP JP2008512716A patent/JP5028413B2/ja not_active Expired - Fee Related
- 2006-05-03 US US11/915,243 patent/US7674507B2/en active Active
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Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2008034511A1 (de) * | 2006-09-21 | 2008-03-27 | Merck Patent Gmbh | Indanverbindungen zur verwendung als komponenten flüssigkristalliner medien |
EP2248872A2 (de) | 2006-10-04 | 2010-11-10 | Merck Patent GmbH | Flüssigkristallines Medium |
US7790247B2 (en) * | 2006-10-04 | 2010-09-07 | Merck Patent Gmbh | Liquid-crystalline medium |
US7691455B2 (en) | 2006-11-27 | 2010-04-06 | Merck Patent Gmbh | Liquid crystalline medium and liquid crystal display |
JP2008163316A (ja) * | 2006-11-27 | 2008-07-17 | Merck Patent Gmbh | 液晶媒体および液晶ディスプレイ |
WO2008092491A1 (de) * | 2007-01-31 | 2008-08-07 | Merck Patent Gmbh | Chromanverbindungen zur verwendung als komponenten in flüssigkristallinen medien z.b. in elektrooptischen anzeigeelementen |
US7955664B2 (en) | 2007-01-31 | 2011-06-07 | Merck Patent Gesellschaft | Chroman compounds |
KR101437711B1 (ko) | 2007-01-31 | 2014-09-03 | 메르크 파텐트 게엠베하 | 전기광학적 디스플레이 부재와 같은 액정 매질에서 성분으로서 사용되는 크로만 화합물 |
WO2008105286A1 (ja) | 2007-02-28 | 2008-09-04 | Chisso Corporation | Cf2o結合基を有する5環液晶化合物、液晶組成物および液晶表示素子 |
JP2010526771A (ja) * | 2007-04-24 | 2010-08-05 | 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 | 液晶混合物のためのピリジン化合物 |
WO2009150963A1 (ja) | 2008-06-09 | 2009-12-17 | チッソ株式会社 | シクロヘキサン環を有する5環液晶化合物、液晶組成物および液晶表示素子 |
US8003175B2 (en) | 2008-06-24 | 2011-08-23 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
US8110256B2 (en) | 2008-06-25 | 2012-02-07 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
WO2010047260A1 (ja) | 2008-10-21 | 2010-04-29 | チッソ株式会社 | 含窒素複素環を有する5環液晶化合物、液晶組成物および液晶表示素子 |
CN102186821A (zh) * | 2008-10-21 | 2011-09-14 | Jnc株式会社 | 有含氮杂环的5环液晶化合物、液晶组成物及液晶显示元件 |
KR20110070988A (ko) | 2008-10-21 | 2011-06-27 | 제이엔씨 주식회사 | 함질소 복소고리를 갖는 5 고리 액정 화합물, 액정 조성물 및 액정 표시 소자 |
EP2522679A4 (de) * | 2010-01-05 | 2014-03-05 | Nat Inst For Materials Science | Phenylboronsäuremonomer und phenylboronsäurepolymer |
EP2671866A1 (de) | 2012-06-04 | 2013-12-11 | Saltigo GmbH | Verfahren zur Herstellung von Styrolderivaten |
CN110003161A (zh) * | 2014-03-20 | 2019-07-12 | 富士胶片株式会社 | 二醇基的保护方法、二醇基的保护剂及脱保护方法 |
CN110003161B (zh) * | 2014-03-20 | 2022-01-04 | 富士胶片株式会社 | 二醇基的保护方法、二醇基的保护剂及脱保护方法 |
EP3628666A1 (de) | 2018-09-25 | 2020-04-01 | Antabio SAS | Indan derivate zur verwendung in der behandlung von bakterieller entzundungen |
EP3628672A1 (de) | 2018-09-25 | 2020-04-01 | Antabio SAS | Indan derivate zur verwendung in der behandlung von bakterieller entzündung |
WO2020064173A1 (en) | 2018-09-25 | 2020-04-02 | Antabio Sas | Indane derivatives for use in the treatment of bacterial infection |
WO2020064174A1 (en) | 2018-09-25 | 2020-04-02 | Antabio Sas | Indane derivatives for use in the treatment of bacterial infection |
WO2020064175A1 (en) | 2018-09-25 | 2020-04-02 | Antabio Sas | Indane derivatives for use in the treatment of bacterial infection |
WO2021191240A1 (en) | 2020-03-24 | 2021-09-30 | Antabio Sas | Combination therapy |
Also Published As
Publication number | Publication date |
---|---|
TWI391475B (zh) | 2013-04-01 |
JP5028413B2 (ja) | 2012-09-19 |
CN101180294B (zh) | 2011-05-11 |
EP1891059B1 (de) | 2012-12-05 |
TW200706644A (en) | 2007-02-16 |
US7674507B2 (en) | 2010-03-09 |
KR101309905B1 (ko) | 2013-09-17 |
KR20080016672A (ko) | 2008-02-21 |
EP1891059A1 (de) | 2008-02-27 |
JP2008545666A (ja) | 2008-12-18 |
CN101180294A (zh) | 2008-05-14 |
US20080193682A1 (en) | 2008-08-14 |
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