CHIRAL COMPOUNDS

Abstract: This invention describes compounds of formula (I) wherein R is C1-16 alkyl or alkoxy; X is selected from F and Cl and indicates that one or more of the phenyl rings may be laterally substituted; x is selected from 0-3; A and B are independently selected from CO2, OCO, C and single bond; R1 and R2 are independently selected from H and C1-16 alkyl provided that R1 and R2 are different; n is 0 or 1 provided that if n is zero then B is single bond. These compounds may be used as dopants suitable for use in ferroelectric liquid crystal mixtures.

Description: Chiral Compm-in s. This invention relates to chiral compounds suitable for use in liquid crystal mixtures and their inclusion in liquid crystal devices. Liquid crystals can exist in various phases. In essence there are three different classes of liquid crystalline material, each possessing a characteristic molecular arrangement. These classes are nematic, cholesteric and smectic. A wide range of smectic phases exists, for example smectic A and smectic C. Some liquid crystal materials possess a nu oer of liquid crystal phases on varying the temperature, others have juεt one phase. For example, a liquid crystal material may show the following phases on being cooled from the isotropic phase:- isotropic - nematic - smectic A - smectic C - solid. If a material is described as being smectic A then it means that the material possesses a smectic A phase over a useful working temperature range. Ferroelectric smectic liquid crystal materials, which can be produced by mixing an achiral host and a chiral dopant, use the ferroelectric properties of the tilted chiral smectic C, F, G, H, I. J and K phases. The chiral smectic C phase is denoted S. * with the asterisk denoting chiralit . The S c phase is generally considered to be the most useful as it is the least viscous. Ferroelectric smectic liquid crystal materials shouiά ideally possess the following characteristics: low viscosity, controllable spontaneous polarisation (Ps) and an S e phase that persists over a broad temperature range, which should include ambient temperature and exhibits chemical and photochemical stability. Materials which possess Jrhese characteristics offer the prospect of very fast switching liquid crystal containing devices. Some applications of ferroelectric liquid cr stals are described by J.S. Patel and J. ' .v. Goodby in Opt. Er.g. , 1987. 26. 27;. In ferroelectric liquid crystal devices the molecules switch between different alignment directions depending on the polarity of an applied electric field. These devices can be arranged to exhibit bistability where the molecules tend to remain in one of two states until switched to the other switched state. Such devices are termed surface stabilised ferroelectric devices, eg as described in US 5061047 and US 4367924 and US 456305 . This bistability allows the multiplex addressing of quite large and complex devices. One common multiplex display has display elements, ie pixels, arranged in an x. y matrix format for the display of eg, alpha numeric characters. The matrix format is provided by forming the electrodes on one slide as a series of column electrodes, and the electrodes on the other slide as a series of row electrodes. The intersections between each column and row form addressable elements or pixels. Other matrix layouts are known, eg seven bar numeric displays. There are many different multiplex addressing schemes. A common feature involves the application of a voltage, called a strobe voltage to each row or line in sequence. Coincidentally with the strobe applied at each row, appropriate voltages, called data voltages, are applied to all column electrodes. The differences between the different schemes lies in the shape of the strobe and data voltage waveforms. Other addressing schemes are described in GB-2.146.473-A; GB-2.173.336-A; GB-2.173.337-A: GB-2.173.629-A; WO 89/05025; Harada et al 198 S.I.D. Paper 3.4 pp 131-13*4; Lagerwall et al 1985 I.D.R.C pp 213-221 and P Maltese et al in Proc 1988 IDRC p 90-101 Fast Addressing for Ferro Electric LC Display Panels. The material may be switched between its two states by two strobe pulses of opposite sign, in conjunction with a data waveform. Alternatively, a blankir.g pulse may be used to switch the material into one of its states. Periodically the sign of the blanking and the strobe puises may be alternated to maintain a net d.c. value. These blanking pulses are normally greater in amplitude and length of application than the strobe pulses so that the material switches irrespective of which of the two data waveforms is applied to any one intersection. Blanking pulses may be applied on a line by line basis ahead of the strobe, or the whole display may be blanked at one time, or a group of lines may be simultaneously blanked. It is well known in the field of ferroelectric liquid crystal device technology that in order to achieve the highest performance from devices, it is important to use mixtures of compounds which give materials possessing the most suitable ferroelectric smectic characteristics for particular types of device. Devices can be assessed for speed by consideration of the response time vs pulse voltage curve. This relationship may show a minimum in the switching time (t • ni.n) at a particular applied voltage (V . ) . At voltages higher or lower than Vmin the switching time is longer than t■i.n. It is well understood that devices having such a minimum in their response time vs voltage curve can be multiplex driven at high duty ratio with higher contrast than other ferroelectric liquid crystal devices. It is preferred that the said minimum in the response time vs voltage curve should occur at low applied voltage and at short pulse length respectively to allow the device to be driven using a low voltage source and fast frame address refresh rate. Typical known materials (where materials are a mixture of compounds having suitable liquid crystal characteristics) which do not allow such a minimum when included in a ferroelectric device include the commercially available materials known as SCE13 and ZLI-3654 (both supplied by Merck UK Ltd, Poole, Dorset). A device which does show such a minimum may be constructed according to PCT GB 88/01004 and utilising materials such as eg commercially available SCEδ (Merck UK Ltd.). Other examples of prior art materials are exemplified by PCT/GB/86/00040. PCT/GBβ7/Oθ44l and UK 2232416B. For all the above applications it is not usual for a single compound to exhibit all of the properties highlighted, for example ferroelectric smectic liquid crystal materials generally consist of a mixture of compounds which when mixed together induce a chiral tilted smectic phase. Chiral dopants are added to a liquid crystalline mixture in order to induce the smectic mixture to become chiral smectic and to induce a Ps in the material, or if the material already possesses a Ps then the introduction of a chiral dopant should result in a change of value for Ps. Ferroelectric liquid crystal materials are claimed in European Patent Application EP 0313 235 A2. Most liquid crystal devices incorporate a mixture of materials selected to give desired operating characteristics. The present invention provides liquid crystal materials suitable for incorporating in a wide variety of mixtures to provide the desired characteristics suitable for use in a number of devices. According to this invention there are provided compounds having a general Formula I : wherein R is C alkyl or alkoxy; X is selected from F and Cl and indicates that one or more of the phenyl rings may be laterally substituted x is selected from 0-3; A and B are independently selected from C0 2 , OCO, C^C and single bond R. and R 2 are independently selected from H and C._ l6 alkyl provided that R t and R 2 are different; n is 0 or 1 provided that if n is zero then B is single bond. Preferably X is F; Preferably A and 3 are selected from C0 2 . OCO and single bond; Preferably X is * and χ is 1 or 2; Preferably n is i. Compounds of Formula I can be included in a material, the material being a mixture of compounds. The materials of this aspect of the invention may be used in many of the known forms of liquid crystal display devices, for example chiral smectic electrooptic devices. Such a device may comprise a layer of liquid crystal material contained between two spaced cell walls bearing electrode structures and surface treated to align liquid crystal material molecules. The liquid crystal mixtures may have many applications including in ferroelectric devices. The position and structure of the chiral centre enables such materials to be used as dopants for ferroelectric mixtures, in which the magnitude of spontaneous polarisation can be adjusted to be optimal for use in different types of ferroelectric devices. The invention will now be described by way of example only with reference to the accompanying drawings of which:- Figures 1-9 illustrate synthetic schemes for the synthesis of compounds. Figure 10 illustrates a liquid crystal device in which the materials of the current invention may be included. Reagents used in the synthetic routes of Figures 1 to 9 are shown below in corresponding schemes 1 to 9* Scheme 1 (i! BuLi. THF. (ii) (MeO) '3-B. THF. (iii) 105 HC1 b H 2 0 2 , THF c C g H.-Br. K 2 C0 3 , butanone d Pd(PPh 3 )„, 2M Na.CO., DME Scheme 2 a C g H.-Br. K 2 C0,. butanone b (i) BuLi. THF. (ii) (MeO),B. THF. (iii) 10% HC. c Pd(PPh 3 ) 4 , 2M Na-CC. DME Scheme 3 a (i) BuLi. THF. (ii) (Me0},3. THF. (iii) 105 HC. b Pd(PPh.), 1 . 2M Na.CO.. DME Scheme 4 a C g H j -Br, K 2 C0-., butanone b (i) BuLi. THF. (ii) (Me0) 3 B, THF, (iii) 10% HCl c Pd(PPh 3 ) 4 , 2M Na^O... DME Scheme a Pd(PPh 3 ) ft , 2M Na 2 C0 3 , DME i) BuLi. THF. (ii) (Me0) 3 B. THF, (iii) 10% HCl Scheme 6 a (i) BuLi. THF. (ii) C0 2 (s). THF, cone HCl b DCC. DMAP, DCM Scheme 7 a (i) BuLi. THF. (ii) C0 2 (s). THF. cone HCl b DCC, DMAP. DCM Scheme 3 a (i) BuLi. THF. (ii) C0 2 (s), THF. cone HCl b DCC. DMAP, DCM Scheme 9 a (i) BuLi. THF, (ii) C0 2 (s). THF. cone HCl b DCC, DMAP. DCM EXPERIMENTAL Boronic Acid Preparations - Synthesis of compounds 2, 5, 8, 14, 16, 19, 23, 25 and 29 General Procedure:- To a stirred, cooled (-78°C) solution of die phenyl/biphenyl system in dry tetrahydrofuran, under nitrogen, was added n-butyllithium in a dropwise fashion. This mixture was maintained under these conditions for 2.5 hours or until GC revealed a complete reaction. Trimethyl-borate in dry tetrahydrofuran was added dropwise and the mixture allowed to warm to room temperature overnight with the cooling bath in place. At room temperature, 10% hydrochloric acid was added and the mixture stirred for 1 hour. The product was then extracted into diethyl edier (x2), washed with water, and dried (MgSO4). After filϋ-ation the product was obtained by removing the solvent in vacito. Compound 2 Quantities : Compound 1 15.02 g, 0.132 mol n-Butyllithium, 10 M in hexanes 15.00 ml, 0.150 mol Trimethyl borate 23.07 g, 0.221 mol Tetrahydrofuran 180 ml Yield - 20.19 g (97%) of an off-white waxy solid Compound 5 Quantities : Compound 4 2.52 g, 0.010 mol n-Butyllithium, 10 M in hexanes 1.50 ml, 0.015 mol Trimethyl borate 2.10 g, 0.010 mol Tetrahydrofuran 90 ml Yield - 2.43 g (85%) of an pale brown waxy solid Compound 8 Quantities : Compound 7 2.76 g, 0.007 moi n-Butyllithium, 1.6 M in hexanes 5.63 ml. 0.009 moi Trimethyl borate 1.46 g, 0.014 mol Tetrahvdrofuran 100 ml Yield - 2.29 g (90%) of an off-white waxy solid Compound 14 Quantities : Compound 13 5.00 g, 0.016 moi n-Butyllithium. 1.6 M in hexanes 12.5 ml. 0.020 mol Trimethyl borate 3.13 g, 0.030 mol Tetrahydrofuran 150 ml Yield - 6.79 g ( 112%) of white waxv solid Compound 16 Quantities : Compound 12 20.00 g, 0007 mol n-Butyllithium. 10 M in hexanes 10.0 ml. 0.010 mol Trimethyl borate 14.60 g, 0.014 mol Tetrahydrofuran 200 ml Yield - 15.74 g (90%) of an off-white waxy solid Compound 19 Quantities : Compound 18 2.49 g. 0.007 mol n-Butyllithium, 2.5 M in hexanes 3.20 ml. 0.008 mol Trimethyl borate 1.50 g, 0.014 mol Tetrahydrofuran 1 0 ml Yield - 1.91 g (83%) of an off-white waxy solid Compound 23 Quantities : Compound 22 10.01 g, 0.033 mol n-Butyllithium, 2.5 M in hexanes 15.00 ml, 0.038 mol Trimethyl borate 6.86 g, 0.066 mol Tetrahydrofuran 200 ml Yield - 7.10 g (79%) a brown waxy solid Compound 25 Quantities : Compound 24 3.46 g, 0.0091 mol n-Butyllithium. 2.5 M in hexanes 4.4 ml, 0.0110 mol Trimethyl borate 1.89 g, 0.0182 mol Tetrahydrofuran 100 ml Yield - 2.94 g (93%) a brown waxy solid Compound 29 Quantities : Compound 28 4.18 g, 0.011 mol n-Butyllithium. 2.5 M in hexanes 5.2 ml, 0.013 mol Trimethyl borate 2.70 g, 0.026 mol Tetrahydrofuran 120 ml Yield - 3.67 g (96%) a white waxy solid Conversion of Boronic Acid to Hydroxy Group - Synthesis of compound 3 General Procedure:- Hydrogen Peroxide was added dropwise to a stirred, refluxing solution of boronic acid in tetrahyrofuran. The mixture was refluxed overnight and allowed to cool before being poured into water. The product was extracted into dichloromethane (x2), dried (MgSO4), filtered and obtained after removal of die solvent in vacuo. Compond 3 Quantities : Compound 2 23.0 lg, 0.15 mol Hydrogen peroxide 150 ml. 40 vol Tetrahydrofuran 150 ml Yield - 18.20 g (93%) of an orange oil. Alkylation Reactions - Synthesis of compounds 4, 12 and 22 General Procedure:- 1-Bromooctane in butanone was added dropwise to a stirred mixture of the hvdroxvphenyi system and potassium carbonate in butanone. The mixture was refluxed until GC revealed a complete reaction and then the mixture was allowed to cool. When cool the potassium carbonate was filtered off and the solvent removed in vacuo. The crude product was distilled to yield a pure product. Comouπd 4 Quantities : Compound 3 1.75 g, 0.013 mol 1-Bromooctane 3.86 g, 0.020 mol Potassium carbonate 5.38 g, 0.039 mol Butanone 65 ml Yield - 3.10 g (927c) of colourless oil Comound 12 Quantities : Compound 12 23.70 g, 0.137 mol 1-Bromooctane 53.08 g, 0.275 mol Potassium carbonate 49.06 g, 0.481 mol Butanone 160 ml Yield - 35.51 g (91%) of colourless oil Comound 22 Quantities : compound 21 19.98 g, 0.104 mol 1-Bromooctane 24.03 g, 0.124 mol Potassium carbonate 28.99 g, 0.210 mol Butanone 150 ml Yield - 24.33 g (80%) of colourless oil Palladium-Catalysed Cross-coupling Reactions - Synthesis of Compounds 7, 10, 13;' 15, 18, 20, 24, 26, 28 and 30 General Procedure:- To a stirred solution of the bromo- or iodo-phenyl system in 1,2-dimethoxyethane under nitrogen was sequentially added 2M aqueous sodium carbonate, tetrakis (triphenylphosphine)palladium (0) in dimethoxyethane, and the boronic acid in dimethoxyethane. The mixture was heated overnight at 80-100°C overnight or until GC revealed a complete reaction. The product was extracted into diethyl ether (x2) and the washed with brine before being dried (MgSO4). The solution was filtered and the product was obtained by removing the solvent in vacuo. Compound 7 Quantities : Compound 5 4.55 g, 0.0180 mol 4-Bromo- 1 -iodobenzene (6) 4.25 g, 0.0150 mol Palladium catalyst 0.58 g, 0.0005 mol 2M Sodium Carbonate 100 ml Dimethoxymethane 100 ml Yield 2.76 g (48%) of white powder after column chromatography with silica gel using 5% dichloromethane in petroleum ether (40-60°C) as a solvent, and recrystallisarion from ethanol. Compound 10a (R=H, Quantities : Compound 8 0.70 g, 0.0019 mol 2-Methyl-2-(4-brornophenyl)octanenitrile (9) 4.25 g, 0.0016 mol Palladium catalyst 0.46 g, 0.0004 mol 2M Sodium Carbonate 80 ml Dimethoxymethane 80 ml Yield 0.51 g (62%) of white powder after column chromatography with silica gel using 10% dichloromethane in petroleum ether (40-60°C) as a solvent, and recrvstallisation from ethanol. Compound 13 Quantities : Compound 2 9.10 g, 0.063 mol Compound 12 15.31 g, 0.053 mol Palladium catalyst 1.44 g, 0.0012 mol 2M Sodium Carbonate 200 ml Dimethoxymethane 200 ml Yield 13.72 g (81 ) of off-white powder after column chromatography with silica gel using petroleum ether (40-60°C) as a solvent, and recrvstallisation from ethanol. Compound 15a (R=H, R ! =Et) Quantities : Compound 13 0.77 g. 0.0021 mol 2-(4-bromophenynbutyronitrile (9) 0.34 g, 0.0015 mol Palladium catalyst 0.60 g, 0.0005 mol 2M Sodium Carbonate 60 ml Dimethoxymethane 60 ml Yield 0.37 g (36%) of white powder after column chromatography with silica gel using 10% dichloromethane in petroleum ether (40-60°C) as a solvent, and recrystallisarion from ethanol. Compound 15b (R=Me, R-^Et) Quantities : compound 13 0.81 g, 0.0024 mol 2-Methyl-2-(4-bromophenyl)butyronitrile (9) 0.38 g, 0.0016 mol Palladium catalyst 0.70 g, 0.0006 mol 2M Sodium Carbonate 60 ml Dimethoxymethane 60 ml Yield 0.36 g (34%) of white powder after column chromatography with silica gel using 10% dichloromethane in petroleum ether (40-60°C) as a solvent, and recrvstallisation from ethanol. Compound 18 Quantities : Compound 16 5.00 g, 0.020 mol 4-Bromo-l-iodobenzene (17) 4.60 g, 0.015 mol Palladium catalyst 0.34 g, 0.0003 mol 2M Sodium Carbonate 130 ml Dimethoxymethane 130 ml Yield 2.53 g (48%) of white crystals after column chromatography with silica gel using 10% dichloromethane in petroleum ether (40-60°C) as a solvent, and recrvstallisation from ethanol. Compound 20a R=H, R-^Et) Quantities : Compound 19 2.00 g, 0.0055 mol 2-(4-bromophenyl)butyronitrile (9) 0.83 g, 0.0037 mol Palladium catalyst 0.57 g, 0.0005 mol 2M Sodium Carbonate 80 ml Dimethoxymethane 80 ml Yield 0.73 g (41%) of white powder after column chromatography with silica gel using 10% ethyl acetate in petroleum ether (40-60°C) as a solvent, and recrystallisarion from ethanol. Compound 20b (R= e, R-^Et) Quantities : Compound 19 2.00 g, 0.0055 mol 2-Methyl-2-(4-bromophenyl)butyronitrile (9) 0.88 g, 0.0037 mol Palladium catalyst 0.57 g, 0.0005 mol 2M Sodium Carbonate 80 ml Dimethoxymethane 80 ml Yield 0.93 g (54%) of white powder after column chromatography with silica gel using 20% dichloromethane in petroleum ether (40-60°C) as a solvent, and recrvstallisation from ethanol. Compound 24 Quantities : Compound 23 8.31 g, 0.031 mol 4-Bromo-l-iodobenzeπe (6) 7.33 g, 0.026 mol Palladium catalyst 1.10 g, 0.001 mol 2M Sodium Carbonate 80 ml Dimethoxymethane 80 ml Yield 4.78 g (50%) of white solid after column chromatography with silica gel using petroleum ether (40-60°C) as a solvent, and recrvstallisation from ethanol. Compound 26 (R=H, Rl=Et) Quantities : Compound 25 1.00 g, 0.0029 mol 2-(4-bromophenyl)butyronitrile (9) 0.51 g, 0.0023 mol Palladium catalyst 0.11 g, 0.0001 mol 2M Sodium Carbonate 60 ml Dimethoxymethane 60 ml Yield 0.67 g (66%) of white powder after column chromatography with silica gel using 20% ethyl acetate in petroleum ether (40-60°C) as a solvent, and recrvstallisation from ethanol. Compound 28 Quantities : Compound 16 3.50 g, 0.014 mol 4-Bromo- 1 -iodobenzene (27) 3.44 g, 0.011 mol Palladium catalyst 0.42 g, 0.0004 mol 2M Sodium Carbonate 60 ml Dimethoxymethane 60 ml Yield 2.51 g (60%) of white crystals after column chromatography with silica gel using 20% dichloromethane in petroleum ether (40-60°C) as a solvent, and recrystallisarion from ethanol. Compound 30a (R=H, R^Et) Quantities : Compound 29 1.00 g, 0.0029 mol 2-(4-bromophenyl)butyronitrile (9) 0.50 g, 0.0022 mol Palladium catalyst 0.13 g, 0.0001 mol 2M Sodium Carbonate 100 ml Dimethoxymethane 100 ml Yield 0.45 g (46%) of white powder after column chromatography with silica gel using 20% ethyl acetate in petroleum ether (40-60°C) as a solvent, and recrvstallisation from ethanol. Compound 30b (R=Me, R*=Et) Quantities : Compound 29 1.01 g, 0.0029 mol 2-Methyl-2-(4-bromophenyl)butyronitrile (9) 0.53 g, 0.0023 mol Palladium catalyst 0.13 g, 0.0001 mol 2M Sodium Carbonate 100 ml Dimethoxymethane 100 ml Yield 0.45 g (44%) of white powder after column chromatography with silica gel using 5% dichloromethane in petroleum ether (40-60°C) as a solvent, and recrystallisarion from ethanol. Compound 30c (R=Me, R**=C6Hi3) Quantities : Compound 29 1.01 g, 0.0029 mol 2-Methyl-2-(4-bromophenyl)butyronitπle (9) 0.67 g, 0.0022 mol Palladium catalyst 0.16 g, 0.0001 mol 2M Sodium Carbonate 60 ml Dimethoxymethane 60 ml Yield 0.52 g (44%) of white powder after column chromatography with silica gel using 1:2:7 methanol/dichloromethane/petroleum ether (40-60°C) as a solvent, and recrystallisaαon from ethanol Formation of Carboxylic Acids - Synthesis of Compounds 31, 34. 36 and 38 General Procedure:- n-Butyllithium was added dropwise to a stirred, cooled (-78°C) mixture of the biphenyl system in dry tetrahydrofuran under nitrogen The mixture was maintained under these conditions for 2.5 hours or until GC revealed a complete reaction. The mixture was added to a slurry of solid carbon dioxide in dry tetrahdrofuran and allowed to warm to room temperature overnight When at room temperatue the mixture was acidified (cone. HCl) and the product extracted into diethyl ether (x2). The product was obtained after filtration and removal of the solvent in vacuo. Compound 31 Quantities : Compound 7 2.30 g, 0.0058 mol n-Butyllithium, 1 6 M in hexanes 4.38 ml. 0.0070 mol Tetrahydrofuran 100 ml Solid carbon dioxide Yield - 1.84 g (87%) of white crystals ompound 34 Quantities : Compound 13 2.42 g, 0.0061mol n-Butyllithium, 1.6 M in hexanes 4.56 ml, 0.0073 mol Tetrahydrofuran 100 ml Solid carbon dioxide Yield - 2.08 g (94%) of white crystals Compound 36 Quantities : Compound 24 3.78 g, 0.0097mol n-Butyllithium, 1.6 M in hexanes 4.56 ml, 0.012 mol Tetrahydrofuran 100 ml Solid carbon dioxide Yield - 2.89 g (84%) of white crystals Compound 38 Quantities : Compound 28 1.89 g, 0.0048mol n-Butyllithium, 1.6 M in hexanes 3.50 ml, 0.0056 mol Tetrahydrofuran 80 ml Solid carbon dioxide Yie.d - 1.03 g (60%) of white crystals Esterification Reactions - Synthesis of Compounds 33, 35, 37 and 39 General Procedure.-4-Dimethvlaminopvridine in dichloromethane and N,N'- dicyclohexylcarbodimide in dichloromethane were added sequentially to a stirred mixture of the carboxylic acid and the 2,4-hydroxyphenyl-butyronitrilein dichloromethane at room temperature. These conditions were maintained until TLC revealed a complete reaction, the mixture was then filtered, washed with 5% potassium hydroxide and the product extracted into diethyl ether (x2). The mixture was dried (MgSO4) and the product obtained by removal of die solvent in vacuo. Compound 33 Quantities : Compound 31 0.99 g, 0.027 mol 4-Hydroxyphenylbutyronitrile (32) 0.40 g, 0.025 mol N,N'-dicycIohexylcarbodimide 0.96 g, 00047 mol 4-Dimethylaminopyridine 0.20 g, 0.0016 mol Dichloromethane 100ml Yield 0.65 g (52%) of white powder after purification by column chromatography through silica gel in dichloromethane and recrystallisation from ethanol Compound 35 Quantities : Compound 34 1.03 g, .0029 mol (-)-4-Hydroxyphenylbutyronitrile (32) 0.41 g, 0.026mol N,N'-dicyclohexylcarbodimide 0.61 g, 00050 mol 4-Dimethylaminopyridine 0.35 g, 0.0017 mol Dichloromethane 100ml Yield 0.72 g (60%) of white powder after purification by column chromatography through silica gel in dichloromethane and recrystallisation from ethanol Compound 37 Quantities : Compound 36 0.75 g, .0022 mol 4-Hydroxyphenylbutyronitrile (32) 0.32 g, 0.0204mol N,N'-dicyclohexylcarbodimide 0.54 g, 00026 mol 4-Dimethylaminopyridine 0.108 g, 0.0089 mol Dichloromethane 150ml Yield 0.54 g (55%) of white powder after purification by column chromatography through silica gel in dichloromethane and recrystallisation from ethanol Compound 39 Quantities : Compound 38 0.75 g, .0022 mol (+)-4-Hydroxyphenylbutyronitrile (32) 0.32 g, 0.0204mol N,N'-dicyclohexylcarbodimide 0.54 g, 00026 mol 4-Dimethy la i nopyridi ne 0.108 g, 0.0089 mol Dichloromethane 150ml Yield 0.48 ^ (50%) of white powder after purification by column chromatography through silica gel in dichloromethane and recrystallisation from ethanol Compounds of formula I may be mi.xed with a wide range of hosts, for e.xample smectic hosts to form a useful liquid crystal composition. Such compositions can have a range of Ps values. Compounds of formula I may be mixed with one or more of the types of hosts VIII - XIII. These different types of hosts may be mixed together to which the compound of general formula I may also be added. Typical hosts include: The compounds described in PCT/GB86/000-0. eg of formula VIII where R. and R_ are independently C, -C ? aiky± or alkoxy. The fluoro-terphenyls described in EPA 84304894.3 and GBA 8725928. eg of formula IX where R χ and R, are independently C 3 -C 12 alkyl or alkoxy, x is 1 and F may be on any of the available substitution positions on the phenyl ring specified. The difluoro-πerphenyls described in GBA 8905422.5, eg of formula X where R. and R, are independently C,-C 12 alkyl or alkoxy. The phenyl -pyrimidines described in WO 86/00087 . eg of formula XI including those compounds where R. is C 3 ~C 12 alkyl and R„ is given by the general formula (CH 2 )„-CHXCH.CH,, where n is 1 to 5 and X is CN or Cl. The compounds described by R. Eidenschink et. al . in Cyclohexanederivative mit Getilteneten Smektischen Phasen at the 16 th Freiberg Liquid Crystal Conference. Freiberg, Germany, p8. Available from E. Merck Ltd.. Germany, eg of formula XII. inciudir.g those compounds where and R 2 are independently C 1 -C lc alkyl. The difluoro-phenyl pyrimidines described in European Patent Application EP 0 332 02-4 Al, including the following: F F including those compounds where R. and R 2 are independently C^-C,. alkyl. An example of the use of a compound of Formula I in a liquid crystal material and device embodying the present invention will now be described with reference to Figure 10. The liquid crystal device consists of two transparent plates, 1 and 2, in this case made from glass. These plates are coated on their internal face with transparent: conducting electrodes 3 and 4. An alignment layer is introduced onto the internal faces of the cell so that a planar orientation of the molecules making up the liquid crystalline material will be approximately parallel to the glass plates 1 and 2. This is done by coating the glass plates 1,2 complete with conducting electrodes 3,4 with layers of film 5 and 6 of a suitable polymer, eg polyimide. The electrodes 3,4 may be formed into row and column electrodes so that the intersections between each column and row form an x. y matrix of addressable elements or pixels. Prior to the construction of the cell the films 5.6 are rubbed with a soft tissue in a given direction, the rubbing directions being arranged parallel (same or opposite direction) upon construction of the cell. A spacer 7 eg of polymethyl ethacrylate separates the glass plates 1 and 2 to a suitable distance eg 2 microns. Liquid crystal material 8 is introduced between glass plates 1. 2 by filling the space in between them. The spacer 7 is sealed with an adhesive 9 in a vacuum using an existing technique. Polarisers 10, 11 may be arranged in front of and behind the cell. The device may operate in a transmissive or reflective mode. In the former, light passing through the device, eg from a tungsten bulb, is selectively transmitted or blocked to form the desired display. In the reflective mode a mirror (12) is placed behind the second polariser 11 to reflect ambient light back through the cell and two polarisers. By making the mirror partly reflecting the device may be operated both in a transmissive and reflective mode. Compound 10 K 105.1 S A 117.9 (°C) Compound 15 15 a R = H, R 1 = Et K 98.8 S A 111-7 I (°C) 15 b R«Me. f-V -Et K 67.8 S A 69.3 I (X) Compound 20 20 a R = H, R 1 = Et K 92.5 S A 131 1 I (°C) 20 b R = e. R 1 = Et K 72.1 S A 80.1 I (°C) Compound 26 26 a R-H, R 1 = Et K 97.4 S A 152.6 I (°C) Compound 30 30 a R = H, R 1 - Et K 63.4 S A 136.3 I (°C*) Optical rotation = -11.73° at 28°C 30 b R = Me, R 1 = Et K 53.2 S A 64.8 I (°C) Optical rotation = -8.73° at 28°C 30 c R = Me,R 1 = C 6 H 13 K 46.2 S A 101.2 I (°C) Compound 33 K94.5S A 103.8 I (°C) K 98.9 S A 125.4 I (°C) Optical rotation = -9.2° at 22°C K98.1 S A 134.2I(°C) K83.1 S A 124.2I(°C) Optical rotation = +4.24° at 22°C The compounds of the present invention may be added to host materials. For example, HI is a 1:1:1 mixture of the following: R. = C 3 H 17 . R 2 = C.H.. R. = 0C 8 H. 7 , R 2 = C.H n R, 1 = 0C. iH.1. ->. R.2 = C,7H,15. The host is a commercially available host and is widely used in ferroelectric liquid crystal mixtures. Some of the compounds described by the current invention were mixed with HI and the effect on the S A to S c transition temperature was as follows: Dopant Reduction in S A -S C transition temp per wt % of dopant added 30a 1.34 30b 2.07 26a 1.46 35 2.22 The following compound showed a 1.52* reduction of S A -S C transition temperature per wt % of dopant added: The following compounds were also made according to the present invention: K 96.9 S A 136.3 N* 140.2 K 77.5 S A 138.2 K79.9S A 138.8I K 81.4 S A 139.3 I K62.4 K 63.3 I (+) K 81.6 I K 56.9 I K 105.1 S A 117.9

Claims: CLAIMS 1. A compound having formula I wherein R is C.. l6 alkyl or alkoxy; X is selected from F and Cl and indicates that one or more of the phenyl rings may be laterally substituted is selected from 0-3; A and B are independently selected from C0 2 , OCO, C__C and single bond R. and R 2 are independently selected from H and C l _ l6 alkyl provided that R. and R 2 are different; n is 0 or 1 provided that if n is zero then B is single bond. A compound according to claim 1 wherein X is F; A and B are selected from CO,. OCO and single bond; X is F and „ is 1 or 2; n is 1. 3- A liquid crystal mixture comprising at least one of the compounds of claim 1. ■*•**. A ferroelectric liquid crystal mixture comprising at least one of the compounds of claim 1. 5. A liquid crystal device comprising a layer of liquid crystal material contained between two spaced cell walls each bearing electrode structures and surface treated on facing surfaces to align liquid crystal material molecules, characterised in that the liquid crystal material includes the mixture as described in claim 3 or claim -4. 6. A liquid crystal mixture containing any of the compounds of claim 1 and a host material of the following general formula: where R. and 2 are independently C,-C 12 alkyl or alkoxy. A liquid crystal mixture containing any of the compounds of claim 1 and a host material of the following general formula ^ where R. and R 2 are independently C 3 -C χ2 alkyl or alkoxy, x is 1 and F may be on any one of the available substitution positions on the phenyl ring specified. A liquid crystal mixture containing any of the compounds of claim 1 and a host material of the following general formula: where R. and R 2 are independently C 3 *-C 12 alkyl or alkoxy. 9. A liquid crystal mixture containing any of the compounds of claim 1 and a host material of the following general formula: where R. is C^-C l 2 alkyl and R 2 is given by the general formula (CH,j.)' n- * CHXO--.CH-, * . where n is 1 to 5*^ and X is CN or Cl. 10. A liquid crystal mixture containing any of the compounds of claim 1 and a host material of the following general formula where R. and R, are independently C j -C alkyl or alkoxy. 11. A liquid crystal mixture containing any of the compounds of claim 1 and a host material of the following general formula where R ; and R, are independently C 3 *-C 8 alkyl or alkoxy. 12. A device as described in claim 5 including any of the host materials specified m claims 6-11.

Inventors: CARRICK BENJAMIN ROSS, GOODBY JOHN WILLIAM, HIRD MICHAEL, MCDONNELL DAMIEN GERARD, TOYNE KENNETH JOHNSON, CARRICK, BENJAMIN, ROSS, GOODBY, JOHN, WILLIAM, HIRD, MICHAEL, MCDONNELL, DAMIEN, GERARD, TOYNE, KENNETH, JOHNSON
Applicants: CARRICK BENJAMIN ROSS, GOODBY JOHN WILLIAM, HIRD MICHAEL, MCDONNELL DAMIEN GERARD, SECR DEFENCE, TOYNE KENNETH JOHNSON, CARRICK, BENJAMIN, ROSS, GOODBY, JOHN, WILLIAM, HIRD, MICHAEL, MCDONNELL, DAMIEN, GERARD, THE SECRETARY OF STATE FOR DEFENCE, TOYNE, KENNETH, JOHNSON
Application year: 1996
Main classification: C09K19
IPC codes: C07C255, C09K19, G02F1