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EP0944570A1 - Derives de 5,7-difluoro-3,4-dihydro-2h-naphtalene-1-one pour melanges de cristaux liquides - Google Patents

Derives de 5,7-difluoro-3,4-dihydro-2h-naphtalene-1-one pour melanges de cristaux liquides

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Publication number
EP0944570A1
EP0944570A1 EP97953802A EP97953802A EP0944570A1 EP 0944570 A1 EP0944570 A1 EP 0944570A1 EP 97953802 A EP97953802 A EP 97953802A EP 97953802 A EP97953802 A EP 97953802A EP 0944570 A1 EP0944570 A1 EP 0944570A1
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Prior art keywords
replaced
diyl
atoms
different
difluoro
Prior art date
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German (de)
English (en)
Inventor
Javier Manero
Wolfgang Schmidt
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Aventis Research and Technologies GmbH and Co KG
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Aventis Research and Technologies GmbH and Co KG
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • 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
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Definitions

  • optically active inclined smectic (ferroelectric) liquid crystals have also recently been used in commercial display devices.
  • Components are either required to form compounds which form inclined or orthogonal smectic phases and are themselves optically active, or one can induce ferroelectric smectic phases by doping compounds which form such smectic phases but are not themselves optically active with optically active compounds .
  • the desired phase should be stable over the largest possible temperature range.
  • a uniform planar orientation of the liquid crystals is necessary to achieve a good contrast ratio in electro-optical components.
  • a good orientation in the S A and S * c phase can be achieved, for example, if the
  • phase sequence of the liquid crystal mixture with decreasing temperature is:
  • the optical switching time T [ ⁇ s] of ferroelectric liquid crystal systems which should be as short as possible, depends on the rotational viscosity of the system y [mPas], the spontaneous polarization P s [nC / cm 2 ] and the electric field strength E [V / m] the relationship
  • the ferroelectric display medium Since the field strength E is determined by the electrode spacing in the electro-optical component and by the voltage applied, the ferroelectric display medium must be of low viscosity and have a high spontaneous polarization so that a short switching time is achieved.
  • the basis (or matrix) used here is preferably compounds which, if possible, themselves already have the desired phase sequence IN 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 the optical activity, to compensate for pitch and to adapt the optical and dielectric anisotropy, but, for example, if possible not increasing the rotational viscosity shall be.
  • the DHF effect was described by Bl Ostrovski in Advances in Liquid Crystal Research and Applications, Oxford / Budapest 1980, 469ff. described, the PSFLCD effect is described in DE-A 39 20625 and EP-A 0 405 346.
  • a liquid crystal material with a short S c pitch is required to use these effects.
  • Naphthalene derivatives for use in liquid crystal mixtures are known for example from WO-A 92/16 500.
  • 7,8-difluoro-3,4-dihydro-2H-naphthalene-1-one derivatives are known from DE-A 19522 175.
  • the object of the present invention was therefore to provide new compounds which are suitable in liquid-crystalline mixtures for improving the property profile of these mixtures. It has now surprisingly been found that 5,7-difluoro-3,4-dihydro-2H-naphthalene-1-one derivatives of the formula (I) are particularly suitable for use in liquid-crystal mixtures.
  • the invention therefore relates to 5,7-difluoro-3,4-dihydro-2H-naphthalin-1-one derivatives of the formula (I)
  • Cyclopentylene can be replaced and / or b3) one or more H atoms can be replaced by F and / or Cl and / or b4) the terminal CH 3 group can be replaced by one of the following chiral groups (optically active or racemic) :
  • radicals R 1 , R 2 is hydrogen, -F, -Cl, -CF 3 , -OCF 3 or -CN;
  • R 3 , R 4 , R 5 , R 6 , R 7 are the same or different a) hydrogen b) a straight-chain or branched alkyl radical (with or without asymmetric carbon atom) with 1 to 16 carbon atoms, b1) one or more not neighboring and non-terminal CH 2 -
  • Oxirane, dioxolane, tetrahydrofuran, tetrahydropyran, butyrolactone or valerolactone system are bound;
  • a 1 , A 2 , A 3 , A 4 are identical or different 1, 4-phenylene, where one or more H atoms can be replaced by F, Cl and / or CN, pyrazine-2,5-diyl, one or two H atoms can be replaced by F, Cl and / or CN, pyridazine-3,6-diyl, it being possible for one or two H atoms to be replaced by F, Cl and / or CN, pyridine-2,5- diyl, one or more H- Atoms can be replaced by F, Cl and / or CN, pyrimidine-2,5-diyl, where one or two H atoms can be replaced by F, Cl and / or CN, 1,4-cyclohexylene, where one or two H atoms can be replaced by CN and / or CH 3 and / or F, (1, 3,4) -Thiadiazol-2,5-diyl, 1, 3-dioxan-2,5-
  • F, Cl and / or CN can be replaced, thiophene-2,4-diyl, where an H atom can be replaced by F, Cl and / or CN, thiophene-2,5-diyl, where one or two H- Atoms can be replaced by F, Cl and / or CN, naphthalene-2,6-diyl, where one or more H atoms can be replaced by F, Cl and / or CN or 1- (C r C 4 ) alkyl- 1-silacyclohexylene-1,4-diyl;
  • a, b, c, d are 0 or 1; with the proviso that the compound of formula (I) contains no more than four five or more membered ring systems.
  • the compounds of formula (I) have a wide range of uses. Depending on the selection of the substituents, they can serve as base materials from which liquid-crystalline phases 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, for example the dielectric and / or optical ones
  • the compounds of the formula (I) are particularly suitable for influencing the dielectric anisotropy ( ⁇ ) in the direction of higher negative values even in small amounts.
  • the compounds of formula (I) according to the invention are particularly suitable for use in FLC mixtures for ferroelectric switching and / or display devices which are operated in inverse mode.
  • the compounds of the formula (I) preferably contain two or more five- or more-membered ring systems.
  • R 1 , R 2 are preferably identical or different a) hydrogen, b) a straight-chain or branched alkyl radical (with or without asymmetrical carbon atom) with 1 to 18 ° C. Atoms, where b1) one or more non-adjacent and non-terminal CH 2 -
  • Groups can be replaced by -O-, -CO-O-, -O-CO-, -O-CO-O or -Si (CH 3 ) 2 - and / or b2) a CH 2 group by cyclopropane-1 , 2-diyl, 1, 4-phenylene or trans-1, 4-cyclohexylene can be replaced and / or b3) one or more H atoms can be replaced by F and / or b4) the terminal CH 3 group by a of the following chiral
  • R 1 , R 2 are particularly preferably the same or different a) hydrogen, b) a straight-chain or branched alkyl radical (with or without an asymmetric carbon atom) having 1 to 16 carbon atoms, where b1) one or two non-adjacent and non-terminal CH 2 - groups can be replaced by -O-, -CO-O-, -O-CO-, -O-CO-O- or -Si (CH 3 ) 2 - and / or b2) a CH 2 group can be replaced by 1, 4-phenylene or trans-1, 4-cyclohexylene and / or b3) one or more H atoms can be replaced by F and / or b4) the terminal CH 3 group by one of the following chiral
  • R 3 , R 4 , R 5 , R 6 , R 7 are particularly preferably the same or different a) hydrogen b) a straight-chain or branched alkyl radical (with or without asymmetric carbon atom) with 1 to 14 C atoms, where b1) a non-terminal CH 2 group can be replaced by -O- and / or c) R 4 and R 5 together also - (CH 2 ) 4 - or - (CH 2 ) 5 - if they are linked to an oxirane, dioxolane, tetrahydrofuran, tetrahydropyran, butyrolactone or valerolactone system.
  • M 1 , M 2 , M 3 , M 4 are particularly preferably identical or different -CO-O-, -O-CO-, -CH 2 -O-, -O-CH 2 - or a single bond.
  • a 1 , A 2 , A 3 , A 4 are preferably identical or different 1, 4-phenylene, where one or two H atoms can be replaced by F and / or CN, pyridine-2,5-diyl, one or two H atoms can be replaced by F and / or CN, pyrimidine-2,5-diyl, where one or two H atoms can be replaced by F, trans-1, 4-cyclohexylene, where one or two H atoms can be replaced by CN and / or CH 3 and / or F, (1, 3,4) thiadiazole-2,5-diyl, 1, 3-dioxane-2,5-diyl, 1, 3-thiazole-2 , 4-diyl, where an H atom can be replaced by F and / or CN, 1, 3-thiazole-2,5-diyl, where an H atom can be replaced by F and / or CN or thiophene-2 , 5-diyl, where one
  • a 1 , A 2 , A 3 , A 4 are particularly preferably identical or different 1, 4-phenylene, where one or two H atoms can be replaced by F, pyridine-2,5-diyl, one H atom by F can be replaced, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, it being possible for one or two H atoms to be replaced by CN and / or CH 3 and / or F.
  • the following compounds of the formulas (Ia) to (Ii) are very particularly preferred:
  • the compounds according to the invention are prepared per se methods known from the literature, as described in standard works on organic synthesis, for example Houben-Weyl, methods of organic chemistry, Georg-Thieme-Verlag, Stuttgart.
  • the preparation takes place under reaction conditions which are known and suitable for the reactions mentioned. Use can also be made here of variants which are known per se and are not mentioned here in detail.
  • the starting materials can also be formed in situ, in such a way that they are not isolated from the reaction mixture, but instead are immediately reacted further to give the compounds of the formula (I).
  • Scheme 2 exemplifies the synthesis of compounds of formula (I) with an aryl substitution in position 6 of the naphthalene system.
  • the group R y is equal to the grouping R 1 (-A 1 -M 1 ) a (-A 2 -M 2 ) b - or a suitable, optionally protected precursor thereof, which is described in later
  • Steps can be transferred into this grouping according to methods known per se and known to the person skilled in the art.
  • the group R x is equal to the grouping (-M 3 -A 3 ) c (-M 4 -A 4 ) d -R 2 or a suitable, optionally protected precursor thereof, which in later steps according to the person skilled in the art is known per se Methods can be transferred to this grouping.
  • the preparation takes place under reaction conditions which are known and suitable for the reactions mentioned. It can also be done here by known, not here make use of the variants mentioned in more detail.
  • DE-A 26 41 724 for compounds with pyrimidine-2,5-diyl groups;
  • DE-A 40 26 223 and EP-A 03 91 203 for compounds with pyridine-2,5-diyl groups;
  • DE-A 32 31 462 for compounds with pyridazine-3,6-diyl groups;
  • EP-A 309 514 for compounds with (1, 3,4) -thiadiazole-2-5-diyl groups;
  • WO-A 92/16500 for naphthalene-2,6-diyl groups and
  • EP-A 0 630 903 for compounds with 1 -Sila-1, 4-cyclohexylene groups.
  • disubstituted pyridines disubstituted pyrazines, disubstituted pyrimidines and disubstituted pyridazines
  • disubstituted pyridines disubstituted pyrazines
  • disubstituted pyrimidines disubstituted pyridazines
  • Dioxane derivatives are expediently prepared by reacting an appropriate aldehyde (or one of its reactive derivatives) with a corresponding 1,3-diol (or one of its reactive derivatives), preferably in the presence of an inert solvent, such as benzene or toluene, and / or a catalyst, e.g. a strong acid, such as sulfuric acid, benzene or p-toluenesulfonic acid, at temperatures between about 20 ° C and about 150 ° C, preferably between 80 ° C and 120 ° C.
  • Acetals are primarily suitable as reactive derivatives of the starting materials.
  • aldehydes and 1,3-diols mentioned and their reactive derivatives are known, and in some cases they can be prepared without difficulty from standard compounds of organic chemistry from compounds known from the literature.
  • the aldehydes can be obtained by oxidation of corresponding alcohols or by reduction of nitriles or corresponding carboxylic acids or their derivatives
  • the diols can be obtained by reducing corresponding diesters.
  • Compounds in which an aromatic ring is substituted by at least one F atom can also be obtained from the corresponding diazonium salts by exchanging the diazonium group for a fluorine atom, for example by the methods of Balz and Schiemann.
  • Suitable reactive derivatives of the carboxylic acids mentioned are in particular the acid halides, especially the chlorides and bromides, and also the anhydrides, e.g. also mixed anhydrides, azides or esters, in particular alkyl esters with 1-4 C atoms in the alkyl group.
  • Suitable reactive derivatives of the alcohols or phenols mentioned are in particular the corresponding metal alcoholates or phenolates, preferably an alkali metal, such as sodium or potassium.
  • the esterification is advantageously carried out in the presence of an inert solvent.
  • ethers such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones such as acetone, butanone or cyclohexanone, amides such as DMF or phosphoric acid hexamethylthamide, hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride are particularly suitable , Dichloromethane or tetrachlorethylene and sulfoxides such as dimethyl sulfoxide or sulfolane.
  • Ethers of the formula (I) can be obtained by etherification of corresponding hydroxyl compounds, preferably corresponding phenols, the hydroxyl compound advantageously first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3 or K 2 CO 3 is converted into the corresponding alkali metal alcoholate or alkali metal phenolate.
  • alkyl halide alkyl sulfonate or dialkyl sulfate
  • an inert solvent such as acetone, 1, 2-dimethoxyethane, DMF or dimethyl sulfoxide
  • aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° and 100 ° C.
  • EP-B 0 355 008 for connections with silicon-containing side chains
  • EP-B 0 292 954 for optically active connections with oxirane ester unit
  • EP-B 0 263 437 for optically active connections with oxirane ether unit
  • EP-B 0 361 272 for optically active connections with dioxolane ester unit
  • EP-B 0 351 746 for optically active compounds with a dioxolane ether unit
  • the compounds of formula (I) according to the invention are preferably suitable for use in smectic and nematic liquid crystal mixtures, in the case of nematic mixtures preferably for "active matrix displays” (AM-LCD) (see, for example, C. Prince, Seminar Lecture Notes, Volume I, p. M-3/3-M-22 , SID International Symposium 1997, BB Bahadur, Liquid Crystal Applications and Uses, Vol 1, p. 410, World Scientific Publishing, 1990, E. Lüder, Recent Progress of AM LCD's, Proceedings of the 15 * International Displays Research Conference, 1995, p.
  • AM-LCD active matrix displays
  • IPS-LCD in-plane-switching displays
  • smectic liquid crystal mixtures preferably for chiral inclined smectic (ferroelectric or antiferroelectric) displays, for ECB displays (Electrically Controlled Birefringence) and for electroclines Displays.
  • the invention also relates to the use of compounds of the formula (I) in liquid-crystal mixtures, preferably smectic and nematic, particularly preferably ferroelectric.
  • liquid-crystal mixtures preferably smectic and nematic, particularly preferably ferroelectric.
  • ferroelectric liquid crystal mixtures which are operated in inverse mode is particularly preferred.
  • the invention furthermore relates to liquid-crystal mixtures, preferably smectic and nematic, particularly preferably ferroelectric and antiferroelectric, in particular ferroelectric, comprising one or more compounds of the formula (I).
  • the smectic or nematic liquid crystal mixtures according to the invention are preferably suitable for use in electro-optical displays, in the case of nematic mixtures particularly for "active matrix displays” and “in-plane switching displays” (IPS-LCD), in the case of smectic liquid crystal mixtures for ECB -Displays (Electrically Controlled Birefringence), for electroclinic displays and chiral inclined smectic (ferroelectric or antiferroelectric) displays.
  • the liquid crystal mixtures according to the invention generally contain 2 to 35, preferably 2 to 25, particularly preferably 2 to 20 components.
  • They generally contain 0.01 to 80% by weight, preferably 0.1 to 60% by weight, particularly preferably 0.1 to 30% by weight, of one or more, preferably 1 to 10, particularly preferably 1 to 5, very particularly preferably 1 to 3, of the compounds of the formula (I) according to the invention.
  • liquid crystal mixtures which contain compounds of the formula (I) according to the invention are preferably selected from the known compounds with smectic and / or nematic and / or cholesteric phases. These include e.g. B .:
  • Silicon compounds as described for example in EP-A 0 355 008, mesogenic compounds with only one side chain, as described for example in EP-A 0541 081, hydroquinone derivatives, as described for example in EP-A 0 603 786,
  • Phenylbenzoates as described, for example, by P. Keller, Ferroelectrics 1984, 58, 3 and J.W. Goodby et al., Liquid Crystals and Ordered Fluids, Vol. 4, New York 1984, and
  • Suitable chiral, non-racemic dopants are: optically active phenyl benzoates, as described, for example, by P. Keller, Ferroelectrics 1984, 58, 3 and JW Goodby et al., Liquid Crystals and Ordered Fluids, Vol. 4, New York 1984, - Optically active oxirane ethers, such as, for example, in EP-A 0 263 437 and WO-A
  • optically active oxirane esters as described, for example, in EP-A 0 292 954, optically active dioxolane ethers, as described for example in EP-A 0 351 746, optically active dioxolan esters, as described for example in EP-A 0 361 272, optically active tetrahydrofuran-2-carboxylic acid esters, as described for example in EP-A 0 355 561, and optically active 2-fluoroalkyl ethers, as described for example in EP-A 0 237 007, EP-A 0 428 720 and US-5,051, 506.
  • Preferred further components of FLC mixtures which are used in inverse mode are: phenanthrene derivatives of the formula (II),
  • X 1 , X 2 are identical or different, independently of one another, CH, CF or N; Y is F, CF 3 or R;
  • R, R ', identical or different, independently of one another have the same meanings as R 1 , R 2 in formula (I);
  • A, M, identical or different, independently of one another have the same meanings as in formula (I) and
  • a, b, c, d are identical or different, independently of one another 0 or 1, with the proviso that the compounds are not more than may contain four ring systems and, with the exception of formula (II), must contain at least two ring systems.
  • the mixtures in turn can be used in electro-optical or completely optical elements, e.g. B. display elements, switching elements, light modulators, elements for image processing and / or signal processing or generally in the field of non-linear optics.
  • mixtures for field treatment i.e. H. suitable for operation in quasi-bookshelf geometry (QBG) (see, for example, H. Rieger et al., SID 91 Digest (Anaheim) 1991, 396).
  • QBG quasi-bookshelf geometry
  • the ferroelectric liquid crystal mixtures according to the invention are particularly suitable for operation in the so-called inverse or ⁇ V / min mode (see, for example: JC Jones, MJ Towler, JR Hughes, Displays 1993, 14, No. 2, 86-93; M. Koden, Ferroelectrics 1996, 179, 121-129).
  • Liquid-crystalline mixtures which contain compounds of the general formula (I) are particularly suitable for use in electro-optical switching and Suitable display devices. These displays are usually constructed in such a way that a liquid crystal layer is enclosed on both sides by layers which, starting from the LC layer, are usually at least one orientation layer, electrodes and a boundary plate (eg made of glass). They can also use spacers, adhesive frames, polarizers and thin ones for color displays
  • Other possible components are antireflection, passivation, compensation and barrier layers as well as electrically non-linear elements, such as thin-film transistors (TFT) and metal-insulator-metal (MIM) elements.
  • TFT thin-film transistors
  • MIM metal-insulator-metal
  • the invention therefore furthermore relates to a switching and / or display device, preferably a smectic or nematic, in particular a ferroelectric, comprising a liquid-crystal mixture which contains one or more compounds of the formula (I).
  • a switching and / or display device preferably a smectic or nematic, in particular a ferroelectric, comprising a liquid-crystal mixture which contains one or more compounds of the formula (I).
  • active matrix displays and “in-plane switching displays” (IPS-LCD) are preferred.
  • IPS-LCD in-plane switching displays
  • ECB displays Electroically Controlled Birefringence
  • electroclinic displays electroclinic displays
  • chiral inclined smectic (ferroelectric or antiferroelectric) displays are preferred.
  • Such devices can be used, for example, as computer displays or in chip cards.
  • a ferroelectric switching and / or display device is preferably operated in normal or inverse mode.
  • Display devices can be operated in two different ways, the so-called normal (normal mode) or the so-called inverse (inverse mode also ⁇ V, min) mode).
  • normal normal
  • inverse inverse mode also ⁇ V, min
  • the switching characteristics of an FLC device can generally be represented by a diagram in which the driver voltage (V) is plotted horizontally and the width of the drive pulses (T, time) is plotted vertically (see, for example, Jones, Fig. 4, 8, 10 and 11).
  • a switching curve is determined experimentally and divides the V, ⁇ area into a switching and a non-switching area.
  • the pulse width usually shortens when the voltage is increased. This behavior characterizes the so-called normal mode (see e.g. Jones, Fig. 4).
  • the V ⁇ curve has a minimum (at the voltage V, mir ⁇ , as seen, for example, in Jones in Figures 8, 10 and 11. This minimum is due to the superposition of dielectric and ferroelectric twist.
  • FLC devices are operated in inverse mode if the sum of the row and column drive voltages in the working temperature range are higher than the minimum on the V ⁇ curve, ie V (Zei! E) + V (Spa! Tej > V (min ) .
  • German patent application 196 52 246.3 the priority of which is claimed by the present application, and the summary of the present application are hereby expressly referred to; by quotation they are considered part of the present application.
  • the invention is further illustrated by the following examples, without wishing to restrict it thereby.

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Abstract

Des dérivés de 5,7-difluoro-3,4-dihydro-2H-naphtalène-1-one de formule (I): R<1>(-A<1>-M<1>)a(-A<2>-M<2>)b-B(-M<3>-A<3>)c(-M<4>-A<4>)d-R<2> dans laquelle B représente la formule (ii) et R<1>(-A<1>-M<1>)a(-A<2>-M<2>) et (-M<3>-A<3>)(-M<4>-A<4>)R<2> désignent des restes mésogènes, sont utilisés comme composants de mélanges de cristaux liquides, notamment ferroélectriques.
EP97953802A 1996-12-16 1997-12-12 Derives de 5,7-difluoro-3,4-dihydro-2h-naphtalene-1-one pour melanges de cristaux liquides Withdrawn EP0944570A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19652246 1996-12-16
DE1996152246 DE19652246A1 (de) 1996-12-16 1996-12-16 5,7-Difluor-3,4-dihydro-2H-naphthalin-1-on-Derivate und ihre Verwendung in flüssigkristallinen Mischungen
PCT/EP1997/006996 WO1998027045A1 (fr) 1996-12-16 1997-12-12 Derives de 5,7-difluoro-3,4-dihydro-2h-naphtalene-1-one pour melanges de cristaux liquides

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EP0944570A1 true EP0944570A1 (fr) 1999-09-29

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BR0309551A (pt) 2002-04-26 2005-02-09 Upjohn Co Derivados substituìdos de pirazina

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DE19522175A1 (de) * 1994-06-20 1995-12-21 Hoechst Ag 7,8-Difluor-3,4-dihydro-2H-naphthalin-1-on-Derivate und ihre Verwendung in flüssigkristallinen Mischungen
DE19517051A1 (de) * 1995-05-10 1996-11-14 Hoechst Ag 1-Fluor-6,7-dihydro-5H-isochinolin-8-on-Derivate und ihre Verwendung in flüssigkristallinen Mischungen

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