# Patent

## Title
Chiral compounds, cholesteric and ferroelectric liquid crystal compositions comprising these chiral compounds, and liquid crystal displays comprising these liquid crystal compositions

## Abstract

Chiral liquid crystal compounds of the general formula (1):




    in which at least one of R1 and R2 is a chiral substituent,
    K may be a single bond or the same as K1-5 and K1-5 denote a six-membered ring system which rings may be at least partially unsaturated, wherein the number of atoms in these rings or ring systems between the two atoms forming a part of the link to the next ring, or to one of the substituents R1 and R2, does not differ by more than one if counted in the clockwise, and in the counter-clockwise sense, starting from the same atom in each case, X1-20 denote alkyl, or alkoxy, or fluorinated alkyl, or fluorinated alkoxy groups, or atom H, or halogen atoms, mixtures comprising such chiral liquid crystal compounds, and liquid crystal displays comprising such mixtures as active ingredients.

## Background
RELATED APPLICATIONS
This application is a continuation application of U.S. patent application Ser. No. 13/119,323, filed Jun. 6, 2011, which is a national stage application (under 35 U.S.C. §371) of PCT/EP2008/062397, filed Sep. 17, 2008.


FIELD OF THE INVENTION
The present invention relates to chiral compounds, ferroelectric liquid crystal compositions and mechanical and shock-stable ferroelectric liquid crystal displays (LCDs) comprising such ferroelectric liquid crystal compositions, as well as cholesteric liquid crystal compositions and fast switching, low operating voltage and monostable or bistable cholesteric LCDs with passive matrix (static or multiplexing) or active matrix (TFT) addressing comprising such cholesteric liquid crystal compositions.
BACKGROUND OF THE INVENTION
Ferroelectric and other chiral liquid crystal compounds have been disclosed in WO 96/00710 A1, EP 0 339 414 A2, EP 0 360 042 A1, EP 0 306 195 A2, GB 2 200 912 A, U.S. Pat. No. 7,022,259, U.S. Pat. No. 5,494,605, U.S. Pat. No. 5,382,380, U.S. Pat. No. 5,250,222, U.S. Pat. No. 4,419,264, WO 89/02425 A1, EP 0 329 153 A2, U.S. Pat. No. 5,486,309 A, U.S. Pat. No. 5,358,663 A and U.S. Pat. No. 4,780,241.
However, the compounds of the prior art are not yet fully satisfactory and do not meet all of the requirements for the applications in ferroelectric and cholesteric liquid crystalline displays as mentioned supra. Especially, compounds are needed that will allow the production of shock-stable ferroelectric liquid crystal displays as well as at the same time fast switching, low operating voltage monostable or bistable chiral nematic LCDs. In the context of the present invention, it is understood that the designations “cholesteric” and “chiral nematic” are deemed equivalent.
In U.S. Pat. No. 4,419,264, a few nonchiral fluorine-containing 4,4-bis-(cyclohexyl)-biphenyl derivatives are disclosed which can be used as the components of nematic liquid crystal mixtures (examples 3 to 5). While it is mentioned that R1 or R21 can be branched (and therefore chiral), there is no information about such chiral compounds, their properties and the properties of the liquid crystal mixtures based upon them. It is clear from the description of U.S. Pat. No. 4,419,264 that these compounds cannot be used for the preparation of

    
    
        cholesteric liquid crystal mixtures with a wide temperature range of the cholesteric phase (from −30° C. up to 100° C.), good dynamic parameters (with a response time of less than 5 ms or 10 ms), low threshold and saturation voltages (less than 20 V), good sharpness of the electro-optical curve, and good mechanical, thermal and long-term stability of bistable textures, and of
        ferroelectric liquid crystal mixtures with different values of the optical anisotropy (Δn) and the spontaneous polarisation, or chiral nematic mixtures with different values of a helical pitch and an optical anisotropy (Δn), a positive or negative dielectric anisotropy (Δ∈), a needed value of the elastic constants (especially K22) and a wide temperature range of the ferroelectric or cholesteric phases.
    
    


The compounds and liquid crystal mixtures of U.S. Pat. No. 4,419,264 do not allow in combination with alignment materials to create shock-stable ferroelectric liquid crystal displays LCDs with low operating voltage and high contrast ratio, or fast switching, low operating voltage monostable or bistable chiral nematic LCDs.
And finally, the chiral compounds of U.S. Pat. No. 4,419,264 cannot be really used for the practical application. The synthetic routes to such compounds, in contrast to the compounds of present invention and the non-chiral compounds of U.S. Pat. No. 4,419,264, are multistage and the final yield of these compounds is very low. Additionally, it should be noted that the starting materials: chiral 4-alkylcyclohexanones, the Grignard reagents etc. are very difficult to prepare.
In WO 89/02425 A1, only a few chiral fluorine-containing terphenyls and nonchiral quaterphenyls are disclosed, which compounds can be used as components of ferroelectric liquid crystal mixtures (see examples 12 and 13, and 14 to 24). There is no information about chiral quaterphenyls, their properties and the properties of the liquid crystal mixtures based upon them.
In EP 0 329 153 A2 and in WO 96/00710 A1, lactic derivatives and chiral cyclohexyl derivatives are disclosed which are different from compounds of formula (1), form liquid crystal phases only in a narrow temperature range, and which have properties which do not allow to use them for the preparation of

    
    
        cholesteric liquid crystal mixtures with a wide usable temperature range of the cholesteric phase (from −30° C. up to 100° C.), good dynamic parameters (with a response time of less than 5 ms or 10 ms), low threshold and saturation voltages (less than 20 V), good sharpness of the electro-optical curve, and good mechanical, thermal and long-term stability of bistable textures, and of
        ferroelectric liquid crystal mixtures with different values of the optical anisotropy (Δn) and the spontaneous polarisation, or chiral nematic mixtures with different values of a helical pitch and an optical anisotropy (Δn), a positive or negative dielectric anisotropy (Δ∈), a needed value of the elastic constants (especially K22) and a wide temperature range of the ferroelectric or cholesteric phases.
    
    


The compounds and liquid crystal mixtures of EP 0 329 153 A2 and WO 96/00710 A1 do not allow in combination with alignment materials to create the shock-stable ferroelectric liquid crystal displays (LCDs) of this invention with low operating voltage and high contrast ratio, or fast switching, low operating voltage monostable or bistable chiral nematic LCDs.
Similarly, in U.S. Pat. No. 5,494,605 A, U.S. Pat. No. 5,382,380 A, EP 0 360 042 A1, GB 2 200 912 A, EP 0 306 195 A2, U.S. Pat. No. 5,486,309 A, and U.S. Pat. No. 5,358,663 A, chiral terphenyls, 2,5-diphenyl-pyridines and other compounds are disclosed, which do not fall under the general formula (1).
4-Pentyl-3′′-chloro-4′′′-(2-methylbutyloxy)quaterphenyl described before forms Sm C* phase at high temperature and in a narrow temperature range and has a low spontaneous polarisation, which does not allow to use this compound for the preparation of shock-stable ferroelectric liquid crystal displays LCDs with low operating voltage, high contrast ratio and a wide temperature range of Sm C* phase.
For the reasons given above, the chiral esters of 4-decyloxy-3′′-methyl-4′′-quaterphenyl carboxylic acid as described therein cannot be used for the preparation of shock-stable ferroelectric liquid crystal displays (LCDs) with low operating voltage, high contrast ratio and a wide temperature range of Sm C* phase. These compounds do not form a Sm C* phase. And additionally, the synthetic routes to these compounds, in contrast to those leading to the compounds of present invention are multistage, and preparation and purification of the intermediate, 4-decyloxy-3′′-methyl-4′′′-quaterphenyl carboxylic acid and the final products are complicated to make.
It should be noted that the chiral compounds of WO 96/00710 A1, EP 0 339 414 A2, EP 0 360 042 A1, EP 0 306 195 A2, GB 2 200 912 A, U.S. Pat. No. 7,022,259, U.S. Pat. No. 5,494,605, U.S. Pat. No. 5,382,380, U.S. Pat. No. 5,250,222, U.S. Pat. No. 4,419,264, WO 89/02425 A1, EP 0 329 153 A2, U.S. Pat. No. 5,494,605 A, U.S. Pat. No. 5,486,309 A, U.S. Pat. No. 5,358,663 A and U.S. Pat. No. 4,780,241, opposite to the compounds of formula (I), do not have a such rigid rod shape central core of the molecules and do not form the smectic C phase in the overall temperature range of from 10° C. to 154° C. These compounds are characterised by the conformation changes of the fragments of the molecules, and the strong dependence of these changes upon the temperature, pressure etc., which do not allow to use them for the preparation of shock-stable ferroelectric or monostable or bistable chiral nematic LCDs with low operating voltage and high contrast ratio.
Low power consumption, fast response time as well as pixel bistability, when the devices have two or more stable states without field, are further desirable attributes for LCDs. Bistable chiral nematic devices such as those described in U.S. Pat. No. 6,928,271 B2, and WO 2004/104980 A2 can be driven line-by-line—once displayed—the information is stored while updating the rest of the screen, and simple matrix addressing may be employed.
However, well-known chiral compounds do not allow to obtain liquid crystal mixtures with a wide usable temperature range of the cholesteric phase (from −30° C. up to 100° C.), good dynamic parameters (with a response time of less than 5 ms or 10 ms), low threshold and saturation voltages (less than 20 V), good sharpness of the electro-optical curve, and good mechanical, thermal and long-term stability of bistable textures.
Ferroelectric liquid crystals (FLCs) are also interesting candidates for active materials in future display devices. FLCs exhibit a fast response, a wide viewing angle and bistable memory capability and have been considered for light shutter and display applications. Ferroelectric liquid crystals displays (FLCDs) are characterised by high-speed operation, in-plane switching and ultra-high resolution.
However, technical issues on the zig-zag defects, mechanical stability and DC voltage balance still hinder FLCDs from widespread applications. The zig-zag defects tend to deteriorate the electro-optic (EO) properties of the devices, while the mechanical and shock-sensitive FLC alignment and residual voltage would cause concerns for long-term stability. It is hard to fabricate defect-free FLCDs owing to the appearance of the zig-zag defect that degrades memory capability and contrast ratio of the display (S. T. Lagerwall, Ferroelectric and Antiferroelectric Liquid Crystals, Wiley-VCH, Weinheim and New York, 1999)
There are other problems with FLCDs, including high driving voltages (from 20 V to 40 V), a low cell gap (under 2 μm), no greyscale, a paucity of stable, room-temperature materials, and wide temperature range materials, and structural defects in the display cells which result from thermal and mechanical stress because of non-optimised FLC materials and alignment conditions.
SUMMARY OF THE INVENTION
The present invention overcomes the problems of the prior art by providing chiral compounds that exhibit a low temperature transition from the crystalline to smectic B, or C*, or A, or cholesteric phases, and that exhibit the liquid crystal smectic and chiral nematic (=cholesteric) phases over wide temperature ranges. These compounds have a rigid rod shape central core of the molecules and they are characterised by weak dependence conformation changes of the fragments of the molecules upon the temperature, pressure etc., which allow to use them for the preparation of shock-stable ferroelectric or monostable or bistable chiral nematic LCDs with low operating voltage and high contrast ratio.
It is another object of the invention to provide cholesteric and ferroelectric liquid crystal mixtures, forming cholesteric or smectic C* phases over broad temperature ranges and at low temperature.
A further object of the invention is to provide a fast switching, low operating voltage monostable or bistable cholesteric liquid crystal display as well as a shock-stable ferroelectric liquid crystal display, which can be operated over a wide range of temperatures and already at very low temperatures.
These objects were achieved by providing the rigid central core polyring chiral liquid crystal compounds of the general formula (1):




in which

    R1=Y—(CH2)n—(O)m—(CH2)k—(O)l—(CH2)p—, or


Y—(CH2)n—CH═CH—(CH2)p—(O)m—, or
Y—(CH2)n—CHY1—(O)m—(CH2)k—(O)l—CHY2—(CH2)p—Y3, or
Y—(CH2)n—CHY1—(O)m—(CH2)k—(O)l—(CH2)p—Y3, or
fluorinated alkyl or fluorinated alkoxy groups where the fluorinated alkyl or fluorinated alkoxy group has from 1 to 20 carbon atoms;

    R2═Y3—(CH2)n—CHY4—(O)m—(CH2)k—(O)l—CHY5—(CH2)p—Y, or


Y3—(CH2)n—(O)m—(CH2)k—(O)l—CHY5—(CH2)p—Y,
where


    Y denotes, in each occurrence, and independently of each other, one of the atoms H, F, and Cl, or one of the groups —CN, —S—CN, —O—CF3, —CF3, —CO—CH3, —CiH2i+1, —CO—O—CiH2i+1, or —O—CO—CiH2i+1;
    Y1, Y2 denote, in each occurrence, and independently of each other, one of the atoms F and Cl or one of the groups —CN, —CF3, —CjH2j+1, —O—CjH2j+1, —CO—O—CjH2j+1, —O—CO—CjH2j+1 or nonsimultaneously the atom H, or simultaneously the atom H, if R2 is a chiral substituent;
    Y3 denotes in each occurrence, and independently of each other, one of a single bond or the atom —O—,
    Y4, Y5 denote, in each occurrence, and independently of each other, one of the atoms F, Cl or one of the groups —CN, —CF3, —ChH2h+1, —O—ChH2h+1, —CO—O—ChH2h+i, —O—CO—ChH2h+1 or nonsimultaneously the atom H, or simultaneously the atom H, when R1 is a chiral substituent;
    n, p, k, j, i, h each assume values, independently for each of n, p, k, j, i, and h, from 0 to 7;
    m, l independently denote 0 or 1; and if l=m=0, then i+k+n+p is at least 6
    with the proviso that Y, Y1, Y2, Y3, Y4, Y5, h, i, j, k, l, m, n, and p are chosen such that at least one of R1 and R2 is a chiral substituent having at least one center of chirality,
    K denotes a single bond or a six-membered ring system selected from the group consisting of cyclohexane, cyclohexene, benzene, pyridine, pyrimidine, tetrazine, 1,3,2-dioxaborinane, hexahydropyridine, hexahydropyrimidine, hexahydropyridazine, hexahydropyrazine, the isomers of hexahydrotriazine, tetrahydrooxazine, cyclobutane, cyclopentane, cycloheptane, and cyclooctane rings, and from at least partially unsaturated ring compounds derived from any of these ring compounds, wherein the number of atoms in these rings or ring systems between the two atoms forming a part of the chemical bond to the next ring, or to the substituent R1 does not differ by more than one if counted in the clockwise, and if counted in the counter-clockwise sense, starting from the same atom in each case;
    where A, A1 assume value 0 or 1, and in the case when K is single bond, only one of A and A1 is 0,
    K1-5 independently of each other denote each a six-membered ring system selected from the group consisting of benzene, pyridine, pyrimidine, tetrazine, 1,3,2-dioxaborinane, hexahydropyridine, hexahydropyrimidine, hexahydropyridazine, hexahydropyrazine, the isomers of hexahydrotriazine, tetrahydrooxazine, and of the at least partially unsaturated ring compounds derived from any of these ring compounds,
    X1-20 denote, independently of each other, alkyl, or alkoxy, or fluorinated alkyl, or fluorinated alkoxy groups, or the atom H, or one of the halogen atoms, or one of the alkyl, alkoxy, fluorinated alkyl, and fluorinated alkoxy groups having, in each case independently of each other, from 1 to 20 carbon atoms,
    and wherein at least three consecutive rings of the rings from K1, K2, K3, K4 and K5 are aromatic or heteroaromatic rings selected independently from each other from the group of rings consisting of benzene, pyridine, pyrimidine, and tetrazine, consecutive rings meaning rings that are directly bonded to each other, with one atom which is a member of the one ring Kg being directly bonded to one atom which is a member of the adjacent ring Kq−1 or Kq+1, where q is an integer from 2 to 4.




DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
It has been found that those compounds which are except from formula 1 have worse performance with regard to shock-free properties (the contrast ratio of LCD cells comprising those molecules which are excepted show a strong decline in contrast ratio upon geometrical deviation).
In another preferred embodiment of this invention, one or more of the six-membered rings K and K1-5 may be replaced by a ring system selected from the group consisting of four-membered rings, which in turn are selected from the group consisting of cyclobutane, oxetane, from five-membered rings selected from the group consisting of cyclopentane, cyclopentene, pyrrolidine, imidazolidine, tetrahydrofurane, from dicyclopentane, from perhydroazulene, from seven-membered rings selected in turn from the group consisting of cycloheptane, cycloheptene, oxepane, dioxepane, azepane, diazepane, and from eight-membered rings selected in turn from the group consisting of cyclooctane, cyclooctene, and eight-membered heterocyclic rings wherein at least one carbon atom is substituted by a nitrogen or an oxygen atom, and from at least partially unsaturated ring compounds derived from any of these ring compounds mentioned hereinbefore, wherein the number of atoms in these rings or ring systems between the two atoms forming a part of the link to the next ring, or to one of the substituents R1 and R2, does not differ by more than one if counted in the clockwise, and in the counter-clockwise sense, starting from the same atom in each case. In this preferred embodiment, the substituents X are chosen in a way that the number of substituents in each ring having from 4 to 8 ring atoms is adjusted to the number of atoms in that said ring that can carry at least one substituent, and which are not bonded directly, or via a linking group, to the adjacent ring.
It is further preferred that at least one ring atom in at least one of the rings K and K1 to K5 carries a substituent (any atom or group of atoms other than a hydrogen atom).
Preferably, the six-membered rings are connected in the 1,4-position, and the compounds of formula (1) are represented by one of the formulae 1.1 to 1.7 and 1.14 to 1.17 set forth below







where the substituents X1 to X20 are as defined in the explanation of formula 1 supra.
Cholesteric, or chiral nematic liquid crystal mixtures according to the present invention contain at least two liquid crystal compounds and at least one of them is a compound of the general formula (1) supra, and optionally, one of them or more than one of them is a non-chiral or non-cholesteric liquid crystal compound.
Molecules which are not represented by formula (1) have proven in the experiments underlying the present invention to have worse performance, in combination with the said at least one non-chiral or non-cholesteric liquid crystal compounds, with regard to shock-free properties as explained supra.
Ferroelectric liquid crystalline mixtures according to the present invention contain at least two liquid crystal compounds and at least one of them is a compound of the general formula (1) supra, and optionally, one of them or more than one of them is a chiral or non-chiral smectic liquid crystal compound.
Particularly good results have been obtained for molecules of formula (1) wherein

R1=Y—(CH2)n—(O)m—(CH2)k—(O)l—(CH2)p—;

    n assumes values from 3 to 7
    K denotes a single bond
    A=1,
    K1-5 denote, independently from each other, a benzene, or pyridine, or pyrimidine ring,
    X1-20 denote, independently from each other, one of the —CH3, —C2H5, —O—CH3, —CF3, and —O—CF3 groups, or one of the atoms H, F, and Cl, or wherein

R1=Y—(CH2)n—CHY1—(O)m—(CH2)k—(O)l—CHY2—(CH2)p—Y3;

    K denotes a single bond,
    A=1, A1 assumes a value of 0 or 1;
    K1-5 denote, independently from each other, a benzene, or pyridine, or pyrimidine ring, and
    X1-20 denote —CH3, or —C2H5, or —O—CH3, or —CF3, or —O—CF3 groups, or an atom H, or F, or Cl, or wherein

R1=Y—(CH2)n—(O)m—(CH2)k—(O)l—(CH2)p—; or

Y—(CH2)n—CHY1—(O)m—(CH2)k—(O)l—CHY2—(CH2)p—Y3;

    K denotes one of benzene, pyridine, pyrimidine, cyclobutane, cyclopentane, cycloheptane, and cyclooctane rings;
    A=1, A1=0;
    K1-4 denote benzene, or pyridine, or pyrimidine ring, except the case when K1 and K3 are benzene rings;
    X1-16 denote, independently from each other, one of the groups —CH3, —C2H5, —O—CH3, —CF3, and —O—CF3, or one of the atoms H, F, and Cl, or wherein

R1=Y—(CH2)n—(O)m—(CH2)k—(O)l—(CH2)p—;

    n assumes values of from 3 to 7,
    K denotes a single bond,
    A=1, A1=0;
    K1-5 denote, independently from each other, a benzene, or pyridine, or pyrimidine ring;
    X1-16 denote, independently from each other, an atom H and not more than seven of X1-16 may be halogen atoms, or —CH3, or —CF3 groups, or wherein
    at least three, more preferably at least four, consecutive rings in formula (1) are phenylene rings which are connected in the 1- and 4-positions to the adjacent ring or bond, or wherein
    R2 is a chiral substituent, and R1 is a non-chiral linear or branched alkyl residue having from 6 to 25 carbon atoms, preferably between 7 and 24 carbon atoms, more preferred between 8 and 23 carbon atoms, still more preferred between 9 and 22 carbon atoms, and particularly preferred, between 10 and 21 carbon atoms, or wherein
    there are four or five phenylene rings each connected in the 1- and 4-positions, or wherein
    the alkyl residue R1 is directly connected with one of its carbon atoms to the outer phenylene ring in the para position, or wherein
    the outer of the consecutive rings, i.e. those rings that carry the substituents R1— or R1—K—, and R2—, respectively, do not carry substituents in the 2, 3, 5, and 6 positions, or wherein
    in a number of g consecutive rings, the rings being referred to as K, K1, K2, K3, . . . , Kg-1, for any ring Kf where f can assume values from 0 in which case Kf=K, 1 in which case Kf=K1, 2 in which case Kf=K2, etc., up to g−1 in which case Kf=Kg-1, if two rings Kf1 and Kf2 with f2>f1 bear a substituent in the 2, 3, 5, or 6 position, there is no ring Kf with f2>f>f1 which does not also bear at least one substituent in the 2, 3, 5, or 6 position, in other words, there is no unsubstituted ring between any two substituted rings, or wherein
    the at least one chiral centre in the group R2 is separated from the ring K4 or K5 by one ether bond —O— or a non-chiral alkylene group —CY6Y6—, or a non-chiral group of the formula —O—CY6Y6—, or a group of the formula —CH2—CY6Y6—, or a non-chiral group of the formula —CY6Y6—CH2—, or a non-chiral group of the formula —O—CY6Y6—CH2— where Y6 may be H, F, Cl, —CN, CF3, —CqH2q+1, —O—CqH2q+1, —CO—O—CqH2q+1, where q can be from 1 to 11.


Particularly improved results were obtained if two or more of these preferred conditions were applied in the selection of molecules.
Liquid crystal compounds according to the present invention were synthesised by the reactions of 3,6-disubstituted cyclohex-2-enones or 2,5-disubstituted cyclohexanones (V. S. Bezborodov et al., Liquid Crystals, 23, 69-75 (1997); V. S. Bezborodov et al., Liquid Crystals, 28, 1755-1760 (2001) with phosphorous pentachloride, sodium borohydride, (diethylamino)sulphur trifluoride (DAST), other chemical reagents, or by the Grignard reaction with methyl magnesium iodide and then by the transformations of the prepared intermediates in the standard ways (V. S. Bezborodov et al., Mol. Cryst. Liq. Cryst., 299, 1 (1997) accordingly to the synthetic Schemes 1 and 2, or by the cross-coupling (Suzuki) reaction (A. Suzuki, J. Organometallic Chem., 576, 147 (1999)) of the corresponding substituted bromo substituted biphenyls or terphenyls, or substituted pyridines, or pyrimidines with corresponding arylboronic acids.








Many compounds according to the present invention show better parameters for some application than compounds known in the prior art.
Liquid crystal compounds of formula (1) according to the present invention make it possible to create new ferroelectric LC mixtures with different values of the optical anisotropy (Δn) and the spontaneous polarisation, or chiral nematic mixtures with different values of a helical pitch and an optical anisotropy (Δn), a positive or negative dielectric anisotropy (Δ∈), a needed value of the elastic constants (especially K22) and a wide temperature range of the ferroelectric or cholesteric phases. These mixtures allow in combination with alignment materials to create new shock-stable ferroelectric liquid crystal displays LCDs with low operating voltage and high contrast ratio, or new mode (effect) fast switching, low operating voltage monostable or bistable chiral nematic LCDs with passive matrix (static or multiplexing) or active matrix (TFT) addressing.
Particularly good results have been obtained when at least three, more preferably at least four, consecutive rings in formula 1 are phenylene rings which are connected in the 1- and 4-positions to the adjacent ring, or bond. Particularly preferred are such compounds (quaterphenyl derivatives) which have exactly four phenylene rings connected in the 1- and 4-positions. It has been found that with four para-phenylene rings in immediate succession, i.e. adjacent to each other, the best compromise between viscosity and switching time and width of the useful temperature range is obtained. It is further preferred that one of the residues, R1, is a chiral substituent, and at the same time, the other residue, R2, is a non-chiral linear or branched, preferably linear, alkyl substituent having from 6 to 25 carbon atoms, preferably from 8 to 23 carbon atoms, and particularly preferably from 9 to 22 carbon atoms. Particularly, the alkyl residue must be directly connected to the outer phenylene ring in the para position to yield the best results. This asymmetric substitution has proved to be very promising with regard to the low influence of mechanical pressure upon the contrast ratio in a LCD cell, and also switching times.
The present invention is described in more detail by the examples 1 to 48 and the data presented in tables 1 to 9.
However, these examples do not limit the scope of the present invention. In these examples, all quantities measured in “%” are mass fractions of the substance in question, i.e. the ratio of the mass of that substance to the mass of the mixture. A concentration stated in “%” is the ratio of the mass (in g) of the solute or substance in question present in the solution or mixture, and an amount of 100 g of the solution or mixture.
Intermediate 1
6-(4-Methoxyphenyl)-3-(trans-4-heptycyclohexylphenyl)-cyclohex-2-en-1-one




A mixture of 1-(3-dimethylaminopropanoyl)-4-(trans-4-heptylcyclohexylbenzene) hydrochloride (0.167 mol), 4-methoxyphenylacetone (0.17 mol), potassium hydroxide (0.51 mol) and dioxane (250 ml) was refluxed under stirring about five to six hours and, after cooling to room temperature, was treated with a 10% aqueous solution of sulphuric acid. The product was twice extracted with ethyl acetate and after usual procedure the solution was filtered through silica gel and the solvent was removed in vacuo. The residue was recrystallised from isopropanol.
Intermediate 2
4-(trans-4-Heptylcyclohexyl)-3′-chloro-4′′-methoxyterphenyl




Phosphorous pentachloride (39.3 mmol) was added to the stirred solution of 6-(4-methoxyphenyl)-3-(trans-4-heptylcyclohexylphenyl)cyclohex-2-enone (Intermediate 1, 26.2 mmol) in 150 ml of toluene. The reaction mixture was refluxed under stirring about 5 hours and, after cooling to the room temperature, 100 ml of water were added and the mixture was stirred for one further hour. The reaction mixture was poured into water (about 300 ml) and twice extracted with methylene chloride. The organic layer was dried over magnesium sulphate and filtered through silica gel. The solvent was removed. The obtained product was used for the further transformation without any additional purification.
Intermediate 3
4-(trans-4-Heptylcyclohexyl)-3′-chloro-4′′-hydroxyterphenyl




4-(trans-4-heptylcyclohexyl)-3′-chloro-4′′-methoxyterphenyl of Intermediate 2 was mixed with 100 ml of acetic acid and 5 ml of 59% aqueous hydroiodic acid. The mixture was refluxed about twelve hours, cooled down to room temperature and poured into water. The product was twice extracted with methylene chloride. The combined organic layers were washed by diluted solution of sodium thiosulphate, water and dried over magnesium sulphate. After removing the solvent, the product was recrystallised from toluene-heptane mixture.
Intermediate 4
4-Decyl-3′′-methyl-4′′′-methoxyquaterphenyl




A solution of 6-(4-methoxyphenyl)-3-(4-decylbiphenyl)cyclohex-2-enone (33 mmol) in 80 ml of THF was treated under stirring with ethereal solution of methyl magnesium iodide prepared from 1.6 g (66 mmol) of magnesium. The reaction mixture was stirred for three hours at 35° C. and then kept overnight. After usual acidic treatment the ethereal solution of the corresponding diene was obtained. The ether was then distilled off and replaced with toluene. Air was passed through the diene solution under reflux during five hours for the oxidation to the corresponding aromatic compound. After cooling to room temperature the solution was filtered through silica gel and toluene was distilled off in vacuo. The obtained product was used for the further transformation without any additional purification.
Intermediate 5
4-Decyl-3′′-methyl-4′′′-hydroxyquaterphenyl




4-decyl-3′′-methyl-4′′′-methoxyquaterphenyl of Intermediate 4 was mixed with 100 ml of acetic acid and 5 ml of 59% aqueous hydroiodic acid. The mixture was refluxed for twelve hours, cooled down to room temperature and poured into water. The product was twice extracted with methylene chloride. The combined organic layers were washed by diluted solution of sodium thiosulphate, water and dried over magnesium sulphate. After removing the solvent, the product was recrystallised from toluene-heptane mixture.
Example 1
S-4-(trans-4-heptylcyclohexyl)-3′-chloro-4′′-(1-methylheptyloxy)terphenyl




Diisopropyl azodicarboxylate (3.76 mmol) was added during ten to fifteen minutes to the stirred mixture of 3′-chloro-4′′-hydroxy-4-(trans-4-heptylcyclohexyl)terphenyl of Intermediate 3 (3.26 mmol), R-2-octanol (3.76 mmol) and triphenylphosphine (3.76 mmol) in 20 ml of THF at a temperature between 5° C. and 10° C. The mixture was allowed to stir overnight at room temperature. THF was then distilled out in vacuo and the residue was several times washed with hexane to extract the desired product. The product was purified by flash chromatography on aluminum oxide (hexane-ethyl acetate, 50:1) followed by the crystallisation from 2-propanol. The yield was 57%.
Example 2
S-4-Decyl-3′′-methyl-4′′′-(1-methylpentyloxy)quaterphenyl




Diisopropyl azodicarboxylate (5.01 mmol) was added during ten to fifteen minutes to the stirred mixture of 4-decyl-3′′-methyl-4′′′-hydroxyquaterphenyl of Intermediate 5 (4.41 mmol), R-2-hexanol (5.01 mmol) and triphenylphosphine (5.0 mmol) in 25 ml of THF at a temperature of from 5° C. to 10° C. The mixture was allowed to stir overnight at room temperature. THF was then distilled out in vacuo and residue was several times washed with a hexane-ethyl acetate (50:1) mixture to extract the desired product. The product was purified by flash chromatography on aluminum oxide (hexane-ethyl acetate 50:1) followed by crystallisation from acetone. The yield was 63%.
Example 3
S-4-Nonyl-3′-fluoro-4′′′-(2-chloropropyloxy)quaterphenyl




This compound was synthesised by the reaction of the corresponding hydroxy quaterphenyl with R-(−)-2-chloropropanol. The yield was 55%.
The following compounds were synthesised using the similar transformation and the transformations presented on schemes 1 and 2.
Example 4
Butyl S-2-[4-octyl-2′-fluoro-3′′-trifluoromethyl-4′′′-quaterphenyloxy]-propionate




Example 5
R-4-Octyl-3′′-chloro-4′′′-(1-methylhexyloxy)quaterphenyl




Example 6
Comparative
R-4-(trans-4-Heptylcyclohexyl)-3′-Methoxy-4′′-(1-trifluoromethylheptyl-oxycarbonyl)terphenyl




Example 7
Comparative
R-4-(4-Nonyl-2-trifluoromethyllcyclohex-1-enyl)-3′-Chloro-4′′-(1-methylheptyloxy)terphenyl




Example 8
Comparative
S-2-[4-(2-Fluorohexyloxy)biphenyl-4′]-5-(trans-4-hexylcyclohexyl)-fluorocyclohex-1-ene




Example 9
S-2-[2′-Methyl-4′′-(1-methylheptyloxy)terphenyl-4]-5-heptylpyridine




Example 10
S-2-[2-fluoro-4′′-(1-methylheptyloxy)terphenyl-4]-5-octylpyrimidine




These compounds and other pyridine and pyrimidine derivatives were prepared by the cross-coupling reaction of the substituted bromo(iodo)pyridines or pyrimidines with corresponding arylboronic acids.
The transformations presented on schemes 1 and 2 and the cross-coupling reaction were used also for the synthesis of the following five ring compounds.
Example 11
S-4-Nonyl-3′,2′′-difluoro-3′′′-chloro-4′′′′-(1-methylheptyloxy)penta-phenyl




Example 12
Comparative
S-4-(trans-4-Octylcyclohexyl)-3,3′′-dichloro-4′′-(1-methylpentyloxy)-quaterphenyl




Example 13
Comparative
S-2-[4-(1-Methylheptyloxy)-3′-chloroterphenyl-4′′]-5-(trans-4-heptylcyclohexyl)-1-trifluoromethylcyclohex-1-ene




Example 14
R-2-[2-fluoro-4′′-(1-methylheptyloxy)terphenyl-4]-5-octylpyrimidine




The compounds 1.1-1.19 and the compounds presented in the tables 1 and 2 were synthesised using the similar transformations of the corresponding 3,6-disubstituted cyclohex-2-enones.







TABLE 1







Transition temperatures of the compounds








 













Transition temperatures in ° C.























Sm

Sm






N
X
R′
Cr

C*

A

N

I





 6
Cl
CH(CH3)CH2F
•
88.7
—

•
203
•
215.7
•


 6
Cl
CH(CH3)COOCH(CH3)CH2OCH3
•
58.8
—

•
144.8
•
147.6
•


 6
Cl
CH(CH3)COOCH2CHClCH2CH(CH3)2
•
59.1
—

•

—
107.8
•


 6
Cl
CH(CH3)C5H11 R (−)
•
50.2
•
 98.8
•

—
165.2
•


 6
Cl
CH(CH3)C6H13 R (−)
•
44.7
•
 85.4
•

—
158.6
•


 6
Cl
CH(CH3)COOCH3
•
96.7
—

•

—
178.6
•


 6
Cl
CH(CH3)COOR*
•
39.2
—

•
116.3
•
139.3
•


 7
Cl
CH(CH3)C6H13 R (−)
•
42.2
•
 85.1
•

—
157.7
•


 7
Cl
CH(CH3)C6H13 S (+)
•
40.2
•
 83.4
•

—
157.6
•


 8
Cl
OCCHClCH3
•
90.0
•(**)

—
233
•
239
•


 8
F
CH(CH3)C6H13 S (+)
•
152
—



—
155.7
•


 8
CH3
CH(CH3)C6H13
•
32.1
•
105.6
•

—
142.8
•


 8
Cl
CH(CH3)COOCH3 S (+)
•
81
•
107.5
•

—
175.0
•


 8
Cl
CH(CH3)COOC2H5 S (+)
•
43
•
 95.6
•

—
149
•


 8
Cl
CH(CH3)CH2OCH3 S (+)
•
61.3
•
114.8
•
168.6
•
172.2
•


 8
Cl
CH(CH3)CH2OC3H7 S (+)
•
38.9
•
115.3
•
155.7
•
160.0
•


 8
Cl
CH(CH3)CH2OOCCHClCH3
•
43
•
 78.0
•

—
142.5
•


 8
Cl
CH(CH3)CH2OOCTHF(***)
•
40
•(**)
 78.0
—

—
143.0
•


 8
Cl
CH(CH3)CH2OPhCOOCH(CH3)C6H13
•
58.0
•(**)
 72.0
•
141.0
•
198.0
•


10
CH3
CH(CH3)C6H13 R (−)
•
48.6
•
126.8
•

—
149.8
•


10
Cl
CH(CH3)C6H13 R (−)
•
42.3
•
130.2
•

—
148.1
•





R(*) = CH(CH3)C6H13,


•(**)-Sm B,


THF(***)-tetrahydrofuran ring













TABLE 2







Transition temperatures of the compounds








 













Transition temperatures in ° C.

















n
X
R′
Cr

Sm C*
Sm A

N

I





7
Cl
CH(CH3)C6H13 R (−)
•
<20
—
•

—
135.7
•


7
CH3
CH(CH3)C6H13 R(−)
•
 28
—
•
127.3 
•
132.8
•


7
Cl
CH2CHClCH3
•
 88
—
•
175
•
203.0
•


7
Cl
CH(CH3)COOC2H5 L(−)
•
 72
—
•
134.5
•
140
•









Example 15
Comparative
Ferroelectric LC mixture A-1 of the following composition has been prepared:




Transition temperatures: Cr −6.3° C. SmC* 514° C. SmA 68.1° C. I
Example 16
Comparative
Ferroelectric LC mixture A-2 of the following composition has been prepared:




Transition temperatures: Cr 7.3° C. SmC* 67.7° C. SmA 74.2° C. I
Example 17
Comparative
Ferroelectric LC mixture B-1 of the following composition has been prepared:




Transition temperatures: Cr 5.6° C. SmC* 54.2° C. SmA 71.1° C. I
Example 18
Comparative
Ferroelectric LC mixture B-2 of the following composition has been prepared:




Transition temperatures: Cr −7.3° C. SmC* 85.0° C. SmA 109.3° C. N 114.0° C. I
Example 19
Comparative
Ferroelectric LC mixture A-3 of the following composition has been prepared:




Transition temperatures: Cr 9.5° C. SmC* 50.4° C. SmA 61.3° C. I
Example 20
Comparative
Ferroelectric LC mixture A-4 of the following composition has been prepared:




Transition temperatures: Cr 11.2° C. SmC* 61.4° C. SmA 79.1° C. I
Example 21
Comparative
Ferroelectric LC mixture B-3 of the following composition has been prepared:




Transition temperatures: Cr 8.3° C. SmC* 56.1° C. SmA 71.1° C. I
Example 22
Comparative
Ferroelectric LC mixture B-4 of the following composition has been prepared:




Transition temperatures: Cr 15.5° C. SmC* 63.1° C. SmA 94.7° C. I
Example 23
Ferroelectric LC mixture C-1 of the following composition has been prepared




Transition temperatures: Cr −23.4° C. SmC* 65.7° C. SmA 81.2° C.
Example 24
Ferroelectric LC mixture C-2 of the following composition has been prepared:




Transition temperatures: Cr −15.7° C. SmC* 89.5° C. SmA 109.5° C. 113.0° C. I
Example 25
Ferroelectric LC mixture D-1 of the following composition has been prepared:




Transition temperatures: Cr −17.1° C. SmC* 59.3° C. SmA 71.5° C. I
Example 26
Ferroelectric LC mixture D-2 of the following composition has been prepared:




Transition temperatures: Cr −9.7° C. SmC* 79.4° C. SmA 89.0° C. 100.0° C. I
The investigations of the ferroelectric mixtures containing known chiral compounds (mixtures A-1,2; B-1,2) and the chiral compounds according to the present invention (mixtures C-1,2; D-1,2) have shown that the chiral materials and mixtures comprising these, and display cells comprising such mixtures, according to the present invention, possess a wide temperature range of the SmC*-phase and a very good thermal and mechanical stability (see table 3). Prepared results have shown that the mechanical shock (in our experiments the thickness of the cells was decreased from 3.5 μm until 1.3 μm, up to 60% of its original width under the mechanical pressure) does not cause irreversible alignment destruction of FLC cells according to the present invention in comparison with the cells containing FLC mixtures (mixtures A-1,2; B-1,2) based upon known chiral compounds. We did not find any changes in alignment conditions after dozens of very serious tests. All the cells have the same alignment quality, contrast and are defect-free after mechanical pressure and mechanical shock, when the cells were dropped on a flat surface from a height of 30 cm.







TABLE 3







Dependence of the contrast ratio of the 


FLC cells from the mechanical pressure*














Operating







field
SmC* range
Geometrical




Cell gap
strength
temperatures
deviation
Contrast


Mixtures
in μm
in V/μm
in ° C.
in %
ratio


1
2
3
4
5
6















A−1
2.8
10
 −6.3 to +52.4
 0
1:50






10
1:20






20
1:10






30
1:5






40
1:3






50
1:2






60
1:2


A−2
2.7
10
 7.3 to +67.7
 0
1:32






10
1:25






20
1:12






30
1:2






40
1:2






50
1:2






60
1:2


B−1
2.9
10
 5.6 to +54.2
 0
1:64






10
1:25






20
1:10






30
1:2






40
1:2






50
1:2






60
1:2


B−2
2.8
10
 −7.3 to +85.0
 0
1:115






10
1:115






20
1:115






30
1:100






40
1:75






50
1:35






60
1:20


A−3
2.7
10
 9.5 to +50.4
 0
1:40






10
1:25






20
1:15






30
1:3






40
1:2






50
1:2






60
1:2


A−4
2.9
10
 11.2 to +61.4
 0
1:45






10
1:25






20
1:10






30
1:2






40
1:2






50
1:2






60
1:2


B−3
2.8
10
 8.3 to +56.1
 0
1:40






10
1:25






20
1:5






30
1:2






40
1:2






50
1:2






60
1:2


B−4
2.8
10
 15.5 to +63.1
 0
1:70






10
1:65






20
1:45






30
1:35






40
1:25






50
1:25






60
1:10


C−1
2.8
10
−23.4 to +65.7
 0
1:170






10
1:170






20
1:170






30
1:170






40
1:170






50
1:170






60
1:140


C−2
2.8
10
−15.7 to +89.5
 0
1:210






10
1:210






20
1:210






30
1:210






40
1:210






50
1:210






60
1:210


D−1
2.8
10
−17.1 to +59.3
 0
1:140






10
1:140






20
1:140






30
1:140






40
1:120






50
1:100






60
1:70


D−2
2.8
10
 −9.7 to +79.4
 0
1:140






10
1:140






20
1:140






30
1:140






40
1:125






50
1:110






60
1:90





*The measurements of the electrooptic parameters of the mixtures were performed at room temperature (22.5° C.)






Example 27
Ferroelectric LC mixture C-2.2 of the following composition has been prepared:




Transition temperatures: Cr −15.3° C. SmC* 69.2° C. SmA 90.1° C. I
The investigations of the electro-optical and dynamic parameters of the FLC mixtures based upon the invented (C-2.2) and known (A-2) compounds have shown that the new ferroelectric LCDs are characterised by a lower operating voltage, fast response time (ton−toff), high contrast ratio—more than 300:1 and have a wide temperature range of the ferroelectric LC phase (Table 4).







TABLE 4







Physical parameters of FLC mixtures*















SmC* range



Operating





temperature
Ps


field strength
ton
toff


Mixture
in ° C.
in nC/cm2
Tilt angle
Birefringence
in V/μm
in μs
in μs

















A-2
 7.3 to +67.7
12.3
21.7
0.24
2
290
615







4
190
310







6
148
205







8
93
136







10
47
108


C-2.2
−15.3 to +69.2
24.5
28.3
0.27
2
180
320







4
78
150







6
53
102







8
35
74







10
22
48





*The measurements of the electrooptic parameters of the mixtures were performed at room temperature (22.5° C.)






These types of displays have many advantages over other display technologies and can be widely used in future.
Electro-optical studies were performed in the glass cells supplied with ITO electrodes (with the resistivity 150 Ω/cm2) and SiO2 insulating layers 170 nm thick. Commercial aligning layers (nylon 6, or AL-1254, or PL-3001) were spinned and parallelly or unidirectionally rubbed. The thickness of the cells (from 1.5 μm up to 30 μm) was measured in each case interferometrically. During the electro-optical measurements the temperature of the cells was controlled with an accuracy ±0.3° C. and the gradients across the sample did not exceed 1° C. Response time (ton and toff) was measured when the transmission was changed from 10% to 90% correspondingly.
The new cholesteric (or chiral nematic) mixtures according to the invention were prepared by blending of the compounds of formula (1) with the different nematic liquid crystal compounds.
The new cholesteric materials have a temperature range of the chiral nematic phase from −30° C. up to +100° C., and the helical pitch is from 10 nm up to 300 μm.
The new mode (effect) monostable or bistable chiral nematic LCDs according to the present invention were made with parallel, antiparallel or twisted rubbing directions on two alignment layers of the cells. Commercial polyamides, nylons and other polymer materials were used as alignment layers. The cells with different gaps (from 1.5 μm up to 20 μm) were filled with the chiral nematic materials of the present invention. The corresponding driving wave forms were used to switch and to get monostable or bistable states. The detailed parameters of the chiral nematic cells are listed in the next examples and tables 5 to 9.
Example 28
Comparative
Nematic mixture M-1 of the following composition has been prepared:




Example 29
Comparative
Nematic mixture M-3 of the following composition has been prepared:




Example 30
Comparative
A cholesteric mixture M-1.1 of the following composition has been prepared:




Example 31
A cholesteric mixture M-1.2 of the following composition has been prepared:




Example 32
Comparative
A cholesteric mixture M-2.1 of the following composition has been prepared:




Example 33
A cholesteric mixture M-2.2 of the following composition has been prepared:




Example 34
Comparative
A cholesteric mixture M-3.1 of the following composition has been prepared:




Example 35
A cholesteric mixture M-3.2 of the following composition has been prepared:




The investigations of the nematic (mixtures M-1, commercial mixture “MLC-6657-100” as obtained from Merck, M-3) and cholesteric mixtures containing known chiral compounds (mixtures M-1.1; M-2.1, M-3.1) and the chiral compounds according to the present invention (mixtures M1.2, M-2.2, M-3.2) have shown that the compositions according to the present invention are characterised by very fast response time ton and toff of less than 1.0 ms (see table 5), in comparison with the cholesteric materials (mixtures M-1.1; M-2.1, M-3.1) based upon known chiral compounds. The fastest response time ton and toff of these materials is only about 20 ms.







TABLE 5







Response time (ton and toff) of nematic and chiral nematic mixtures*









Mixture




















MLC-6657-








M-1
M-1.1
M-1.2
100
M-2.1
M-2.2
M-3
M-3.1
M-3.2




















Cell gap
4.07
4.06
4.08
4.1
4.11
4.1
4.05
4.09
4.1


d/μm


ton/ms
12.3
13.2
1.3
3.4
4.6
0.35
3.8
4.7
0.16


toff/ms
25.6
28.4
4.2
13.6
17.3
7
12.2
14.8
0.8





*The measurements of the electrooptic parameters of the mixtures were performed at room temperature (22.5° C.)






Example 36
Comparative
A cholesteric mixture M-1.3 of the following composition has been prepared:




Example 37
A cholesteric mixture M-1.4 of the following composition has been prepared:




Example 38
Comparative
A cholesteric mixture M-2.3 of the following composition has been prepared:




Example 39
A cholesteric mixture M-2.4 of the following composition has been prepared:




Example 40
Comparative
A cholesteric mixture M-3.3 of the following composition has been prepared:




Example 41
A cholesteric mixture M-3.4 of the following composition has been prepared:




The investigations of the cholesteric mixtures containing known chiral compounds (mixtures M-1.3; M-2.3, M-3.3) and the chiral compounds according to the present invention (mixtures M1.4, M-2.4, M-3.4) have shown that the compositions according to the present invention are characterised by very good sharpness of the electro-optical curve and, at the same time, fast response time (ton+toff) (see table 6) in comparison with the cholesteric materials (mixtures M-1.1; M-2.1, M-3.1) based upon known chiral compounds and the known chiral nematic materials for STN displays.
These types of materials have advantages over other material and can be widely used in the production of LCDs with multiplex driving scheme having, for example, duty ratio 1:64.







TABLE 6







Sharpness and the response time (ton and toff) of the chiral nematic


mixtures*









Mixture














M-1.3
M-1.4 
M-2.3
M-2.4 
M-3.3
M-3.4

















Cell gap
5.12
5.08
5.11
5.1
5.09
5.1


d/μm


ton/ms
101
35
89
32
82
17


toff/ms
148
43
122
38
105
22


Vth/V
1.94
1.87
2.17
2.10
1.8
1.65


Vst/V
2.24
2.1
2.49
2.34
2.04
1.8


Sharpness
0.154
0.124
0.147
0.114
0.133
0.091





*The measurements of the electrooptic parameters of the mixtures were performed at room temperature (22.5° C.)






Example 42
Comparative
A cholesteric mixture M-2.5 of the following composition has been prepared:




Example 43
A cholesteric mixture M-2.6 of the following composition has been prepared:




Example 44
Comparative
A cholesteric mixture M-3.5 of the following composition has been prepared:




Example 45
Chiral nematic mixture M-3.6 of the following composition has been prepared:




The investigations of the nematic (mixtures MLC-6657-100, M-3) and the chiral nematic mixtures containing known chiral compounds (mixtures M-2.5, M-3.5) and the chiral compounds according to the present invention (mixtures M-2.6, M-3.6) have shown that the invented compositions are characterised by excellent bistability (stable image memory during long period) and, at the same time, very fast response time ton and toff (see table 7) in comparison with the cholesteric materials (mixtures M-2.5, M-3.5) based upon known chiral compounds.
These types of materials have advantages over other material and can be widely used in future. Once displayed, the information is memorised for a long time, ranging from seconds up to years, depending on the application needs. This intrinsic memory is the main advantage of the bistable devices. It enables to lower the power consumption; especially, when the application does not require a frequent update. For some mobile applications, e-book for instance, the energy saving can be a decisive improvement, increasing the battery lifetime by orders of magnitude.
The additional investigations of the nematic (mixture M-3) and the cholesteric mixtures containing the chiral compounds according to the present invention (mixtures M-3.6) have shown (see table 8), that the response time ton and toff of the compositions according to the present invention are not depending so strongly upon the thickness of the cell in comparison with the nematic materials (mixture M-3).







TABLE 7







Bistability and the response time (ton and toff) of the nematic and


cholesteric mixtures*









Mixture














MLC-








6657-



100
M-2.5
M-2.6
M-3
M-3.5
M-3.6

















Cell gap d/
4.2
4.17
4.18
4.18
4.19
4.19


μm


ton/ms
3.6
17
0.42
3.9
14
0.28


toff/ms
13.8
35
6.9
11.7
26
2.9


Bistability**
no
Poor
excellent
no
poor
excellent





*The measurements of the electrooptic parameters of the mixtures were performed at room temperature (22.5° C.)


**Rating of bistability: poor—image memory during one minute or less, excellent—stable image memory during long period (more than two weeks)













TABLE 8







Dependence of the response time (ton and toff)


of the nematic and chiral nematic mixtures from the cell gap*









Mixture










M-3
M-3.6





















Cell gap d/μm
3.5
4.2
5.2
6.2
7.2
3.5
4.2
5.2
6.2
7.2


ton/ms
2.9
3.9
5.8
8.4
11.2
0.26
0.28
0.33
0.41
0.52


toff/ms
9.3
11.7
16.8
24.8
32.7
2.7
2.9
3.2
3.8
4.6





*The measurements of the electrooptic parameters of the mixtures were performed at room temperature (22.5° C.)






Example 46
Comparative
A cholesteric mixture M-1.5 of the following composition has been prepared:




Example 47
Comparative
A cholesteric mixture M-1.6 of the following composition has been prepared:




Example 48
A cholesteric mixture M-1.7 of the following composition has been prepared:




The investigations of the cholesteric mixtures (mixtures M-1.5, M-1.6, M 1.7, see table 9) have shown that the selective reflection cells containing the chiral compositions according to the present invention (mixture M-1.7) have lower operating voltage in comparison with the cells containing the materials based upon the known chiral compounds (mixtures M-1.5, M-1.6)







TABLE 9







Threshold voltage of the chiral nematic cells*












Mixture
M-1.5
M-1.6
M-1.7
















Cell gap d/μm
5.2
5.2
5.2



Vth/ V
48
25
1.7



reflection
580
540
540



wavelength in nm










*The measurements of the electrooptic parameters of the mixtures were performed at room temperature (22.5° C.)






Liquid crystal compounds of formula (1) according to the present invention make it possible to create chiral nematic mixtures with different values of a helical pitch and an optical anisotropy (Δn), a positive or negative dielectric anisotropy (Δ∈), a needed value of the elastic constants (especially K22) and a wide temperature range of the chiral nematic phase. The mixtures allow in combination with alignment materials to create the new mode (effect) fast switching, low operating voltage monostable or bistable cholesteric LCDs with passive matrix (static or multiplexing) or active matrix (TFT) addressing.
These types of displays, especially due to the fast switching, low operating voltage and bistability, have many advantages over other display technologies and can be widely used in future. The intrinsic memory is the main advantage of the bistable devices. It enables to the low power consumption, especially when the application does not require a frequent update. For some mobile application the energy saving can be a decisive improvement, increasing the battery lifetime by orders of magnitude.
It should be noted that the additional investigations of the chiral compounds presented in WO 96/00710 A1, EP 0 339 414 A2, EP 0 360 042 A1, EP 0 306 195 A2, GB 2 200 912 A, U.S. Pat. No. 7,022,259, U.S. Pat. No. 5,494,605, U.S. Pat. No. 5,382,380, U.S. Pat. No. 5,250,222, U.S. Pat. No. 4,419,264, WO 89/02425 A1, EP 0 329 153 A2, U.S. Pat. No. 5,486,309 A, U.S. Pat. No. 5,358,663 A and U.S. Pat. No. 4,780,241 have shown that these compounds, in contrast to the compounds of formula (I), do not have a rigid rod shape central core of the molecules and do not form the smectic C phase in the overall temperature range of from 10° C. to 154° C. Investigations have shown that these compounds cannot be used for the preparation of

    
    
        cholesteric liquid crystal mixtures with a wide temperature range of the cholesteric phase (from −30° C. up to 100° C.), good dynamic parameters (with a response time of less than 5 ms or 10 ms), low threshold and saturation voltages (less than 20 V), good sharpness of the electro-optical curve, and good mechanical, thermal and long-term stability of bistable textures, and of
        ferroelectric liquid crystal mixtures with different values of the optical anisotropy (Δn) and the spontaneous polarisation, or chiral nematic mixtures with different values of a helical pitch and an optical anisotropy (Δn), a positive or negative dielectric anisotropy (Δ∈), a needed value of the elastic constants (especially K22) and a wide temperature range of the ferroelectric or cholesteric phases.
    
    


The compounds and liquid crystal mixtures of WO 96/00710 A1, EP 0 339 414 A2, EP 0 360 042 A1, EP 0 306 195 A2, GB 2 200 912 A, U.S. Pat. No. 7,022,259, U.S. Pat. No. 5,494,605, U.S. Pat. No. 5,382,380, U.S. Pat. No. 5,250,222, U.S. Pat. No. 4,419,264, WO 89/02425 A1, EP 0 329 153 A2, U.S. Pat. No. 5,486,309 A, U.S. Pat. No. 5,358,663 A and U.S. Pat. No. 4,780,241 do not allow in combination with alignment materials to create the shock-stable ferroelectric liquid crystal displays LCDs with low operating voltage and high contrast ratio, or fast switching, low operating voltage monostable or bistable chiral nematic LCDs.

## Claims

1. A chiral liquid crystal compound of the general formula (1):



in which
R1=Y—(CH2)n—(O)m—(CH2)k—(O)l—(CH2)p—, or
Y—(CH2)n—CH═CH—(CH2)p—(O)m—, or
Y—(CH2)n—CHYl—(O)m—(CH2)k—(O)l—CHY2—(CH2)p—Y3, or
Y—(CH2)n—CHY1—(O)m—(CH2)k—(O)l—(CH2)p—Y3, or
fluorinated alkyl or fluorinated alkoxy groups where the fluorinated alkyl or fluorinated alkoxy group has from 1 to 20 carbon atoms;

R2=Y3—(CH2)n—CHY4—(O)m—(CH2)k—(O)l—CHY5—(CH2)p—Y, or
Y3—(CH2)n—(O)m—(CH2)k—(O)l—CHY5—(CH2)p—Y,

where
R2 is a chiral substituent, and R1 is a non-chiral linear or branched alkyl residue having from 6 to 25 carbon atoms, and where
Y denotes, in each occurrence, and independently of each other, one of the atoms H, F, and Cl, or one of the groups —CN, —S—CN, —O—CF3, —CF3, —CO—CH3, —CiH2i+1, —O—CiCH2i+1, —CO—O—CiCH2i+1, or —O—CO—CiH2i+1;
Y1 and Y2 denote, in each occurrence, and independently of each other, one of the atoms F and Cl or one of the groups —CN, —CF3, —CjH2j+1, —CO—O—CjH2j+1, —O—CO—CjH2j+1 or nonsimultaneously the atom H, or simultaneously the atom H;
Y3 denotes in each occurrence, and independently of each other, one of a single bond or the atom —O—,
Y4 and Y5 denote, in each occurrence, and independently of each other, one of the atoms F, Cl or one of the groups —CN, —CF3, —ChH2h+1, —O—ChH2h+1, —CO—O—ChH2h+1, —O—CO—ChH2h+1 or nonsimultaneously the atom H;
n, p, k, j, i, h each assume values, independently for each of n, p, k, j, i, and h, from 0 to 7;
m and l independently denote 0 or 1; and if l=m=0, then i+k+n+p is at least 6
with the proviso that Y, Y1, Y2, Y3, Y4, Y5, h, i, j, k, l, m, n, and p are chosen such that R2 is a chiral substituent having at least one center of chirality,
K denotes a single bond or a six-membered ring system selected from the group consisting of cyclohexane, cyclohexene, benzene, pyridine, pyrimidine, tetrazine, 1,3,2-dioxaborinane, hexahydropyridine, hexahydropyrimidine, hexahydropyridazine, hexahydropyrazine, the isomers of hexahydrotriazine, tetrahydrooxazine, cyclobutane, cyclopentane, cycloheptane, and cyclooctane rings, and from at least partially unsaturated ring compounds derived from any of these ring compounds, wherein the number of atoms in these rings or ring systems between the two atoms forming a part of the chemical bond to the next ring, or to the substituent R1 does not differ by more than one if counted in the clockwise, and if counted in the counter-clockwise sense, starting from the same atom in each case;
where A and A1 assume value 0 or 1, and in the case when K is single bond, only one of A and A1 is 0,
K1-5 independently of each other denote each a six-membered ring system selected from the group consisting of benzene, pyridine, pyrimidine, tetrazine, 1,3,2-dioxaborinane, hexahydropyridine, hexahydropyrimidine, hexahydropyridazine, hexahydropyrazine, the isomers of hexahydrotriazine, tetrahydrooxazine, and of the at least partially unsaturated ring compounds derived from any of these ring compounds,
X1-20 denote, independently of each other, alkyl, or alkoxy, or fluorinated alkyl, or fluorinated alkoxy groups, or the atom H, or one of the halogen atoms, or one of the alkyl, alkoxy, fluorinated alkyl, and fluorinated alkoxy groups having, in each case independently of each other, from 1 to 20 carbon atoms,
wherein the outer of the consecutive rings, (the rings that carry the substituents R1 and R2, respectively), do not carry substituents in the 2, 3, 5, and 6 positions
and wherein at least three consecutive rings of the rings from K1, K2, K3, K4 and K5 are aromatic or heteroaromatic rings selected independently from each other from the group of rings consisting of benzene, pyridine, pyrimidine, and tetrazine, consecutive rings meaning rings that are directly bonded to each other, with one atom which is a member of the one ring being directly bonded to one atom which is a member of the next ring.

2. The chiral liquid crystal compound of claim 1, wherein:


R1=Y—(CH2)n—(O)m—(CH2)k—(O)l—(CH2)p—;

n assumes values from 3 to 7
K denotes a single bond,
A=1,
K1-5 denote, independently from each other, a benzene, or pyridine, or pyrimidine ring
X1-20 denote, independently from each other, one of the —CH3, —C2H5, —O—CH3, —CF3, or —O—CF3 groups, or one of the atoms H, F, or Cl.

3. The chiral liquid crystal compound of claim 1, wherein


R1=Y—(CH2)n—CHY1—(O)m—(CH2)k—(O)l—CHY2—(CH2)p—Y3;

where
K denotes a single bond,
A=1, A1 assumes a value of 0 or 1;
K1-5 denote, independently from each other, a benzene, or pyridine, or pyrimidine ring, and
X1-20 denote —CH3, or —C2H5, or —O—CH3, or —CF3, or —O—CF3 groups, or an atom H, or F, or Cl.

4. The chiral liquid crystal compound of claim 1, wherein


R1=Y—(CH2)n—(O)m—(CH2)k—(O)l—(CH2)p—; or



Y—(CH2)n—CHY1—(O)m—(CH2)k—(O)l—CHY2—(CH2)p—Y3;

where
K denotes one of benzene, pyridine, pyrimidine, cyclobutane, cyclopentane, cycloheptane, and cyclooctane rings;
where A=1, A1=0;
K1-4 denote benzene, or pyridine, or pyrimidine ring, except the case when K1 and K3 are benzene rings;
X1-16 denote, independently from each other, one of the groups —CH3, —C2H5, —O—CH3, —CF3, or —O—CF3, or one of the atoms H, F, or Cl.

5. The chiral liquid crystal compound of claim 1, wherein


R1=Y—(CH2)n—(O)m—(CH2)k—(O)l—(CH2)p—;

where
n assumes values of from 3 to 7
K denotes a single bond
A=1, A1=0;
K1-5 denote, independently from each other, a benzene, or pyridine, or pyrimidine ring;
X1-16 denote, independently from each other, an atom H and not more than seven of X1-16 may be halogen atoms, or —CH3, or —CF3 groups.

6. The chiral liquid crystal compound of claim 1, wherein at least three consecutive rings in formula 1 are phenylene rings which are connected in the 1- and 4-positions to the adjacent ring or bond.

7. The chiral liquid crystal compound of claim 1, wherein at least four consecutive rings in formula 1 are phenylene rings which are connected in the 1- and 4-positions to the adjacent ring or bond.

8. The chiral liquid crystal compound of claim 6, which have four or five phenylene rings each connected in the 1- and 4-positions.

9. The chiral liquid crystal compound of claim 6, wherein the alkyl residue R1 is directly connected with one of its carbon atoms to the outer phenylene ring in the para position.

10. The chiral liquid crystal compound of claim 6, wherein in a number of g consecutive rings, the rings being referred to as K, K1, K2, K3, . . . , Kg-1, for any ring Kf where f can assume values from 0 in which case Kf=K, 1 in which case Kf=K1, 2 in which case Kf=K2, etc., up to g−1 in which case Kf=Kg-1, if two rings Kf1 and Kf2 with f2>f1 bear a substituent in the 2, 3, 5, or 6 position, there is no ring Kf with f2>f>f1 which does not also bear at least one substituent in the 2, 3, 5, or 6 position.

11. The chiral liquid crystal compound of claim 6 wherein the at least one chiral centre in the group R2 is separated from the ring K4 or K5 by one ether bond —O— or a non-chiral alkylene group —CY6Y6—, or a non-chiral group of the formula —O—CY6Y6—, or a group of the formula —CH2—CY6Y6—, or a non-chiral group of the formula —CY6Y6—CH2—, or a non-chiral group of the formula —O—CY6Y6—CH2— where Y6 may be H, F, Cl, —CN, CF3, —CqH2q+1, —O—CqH2q+1, —CO—O—CqH2q+1, where q can be from 1 to 11.

12. A liquid crystal mixture containing at least two compounds, comprising a mass fraction of from 0.5% up to 99.5% of at least one or more dielectric organic compounds and a mass fraction of from 99.5% to 0.5% of the chiral liquid crystal compound according to claim 1.

13. A liquid crystal mixture containing at least two compounds, having ferroelectric properties, and comprising as dielectric organic compound, a mass fraction of from 5% to 90% of at least one non-chiral or chiral smectic compound, and a mass fraction of from 10% to 95% of at least one chiral liquid crystal compound according to claim 1.

14. A liquid crystal mixture containing at least two compounds and comprising as dielectric organic compound, a mass fraction of from 30% to 70% of at least one non-chiral or chiral smectic compound, and a mass fraction of from 70% to 30% of at least one chiral liquid crystal compound according to claim 1.

15. A liquid crystal mixture containing at least two compounds, having chiral nematic properties, and comprising as dielectric organic compound, a mass fraction of from 50% to 99.5% of at least one compound which is neither chiral nor chiral nematic, and a mass fraction of from 0.5% to 50% of at least one chiral liquid crystal compound according to claim 1.

16. The liquid crystal mixture of claim 15, wherein the mass fraction of the at least one compound which is neither chiral nor chiral nematic is from 70% to 99.5%, and the at least one compound which is neither chiral nor chiral nematic has a positive dielectric anisotropy, and wherein the mass fraction of the at least one chiral liquid crystal compound is from 30% to 0.5%.

17. The liquid crystal mixture of claim 16, wherein the mass fraction of the at least one compound which is neither chiral nor chiral nematic is from 70% to 99.5%, and the at least one compound which is neither chiral nor chiral nematic has a negative dielectric anisotropy, and wherein the mass fraction of the at least one chiral liquid crystal compound is from 30% to 0.5%.

18. The liquid crystal mixture of claim 12, containing at least three compounds, wherein the mass fraction of the at least one chiral liquid crystal compound according is from 0.5% to 50%, and wherein at least two dielectric organic compounds are present, wherein the sum of the mass fractions of such compounds is from 50% to 99.5%, and at least one of such compounds is neither chiral nor chiral nematic, and at least one of such compounds is a smectic compound.

19. A liquid crystal display with passive matrix (static or multiplexing) addressing containing the liquid crystal mixture according to claim 1.

20. A liquid crystal display with active matrix (TFT) addressing containing the liquid crystal mixture according to claim 12.

21. A ferroelectric liquid crystal display with passive matrix (static or multiplexing) addressing containing the liquid crystal mixture according to claim 13.

22. A ferroelectric liquid crystal display with active matrix (TFT) addressing containing the liquid crystal mixture according to claim 13.

23. A bistable ferroelectric liquid crystal display containing the liquid crystal mixture according to claim 13.

24. A cholesteric liquid crystal display with passive matrix (static or multiplexing) addressing containing the liquid crystal mixture according to claim 15.

25. A cholesteric liquid crystal display with active matrix (TFT) addressing, containing the liquid crystal mixture according to claim 15.

26. A bistable cholesteric liquid crystal display containing the liquid crystal mixture according to claim 15.

27. A selective reflection cholesteric liquid crystal display containing the liquid crystal mixture according to claim 15.