BIPHENYLYL ETHANES AND THEIR USE IN LIQUID CRYSTAL MATERIALS AND DEVICES

Abstract: Novel compounds having a general formula: where m, n are 0 or 1, R₁ represents hydrogen, alkyl, alkoxy, alkoxy substituted alkyl, alkanoyl, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy, represent cyclic groups, each of X, Y, Z is hydrogen or fluorine, at least one being fluorine, B is F, CL or CF₃. Preferred compounds have a formula where R₁ is C₁-12 alkyl or alkoxy, B is fluorine. The compounds may be used as components of liquid crystal compositions, having a low viscosity and high clearing point.

Description: This invention relates to biphenylyl ethanes and their use in liquid crystal materials and devices. The use of liquid crystal materials to exhibit electro-optical effects in display devices such as digital calculators, watches, meters and simple word displays is now well know. However, known liquid crystal materials are not ideal in all respects and a considerable amount of work is currently being carried out in the art to improve their properties. Liquid crystal materials normally consist of specially selected mixture compositions and improved materials are obtained by forming new mixtures having an improved combination of properties, e.g. by the provision of new compounds for incorporation in the mixtures. Preferably, such compounds are nematogenic or chiral nematogenic in nature. The present invention, in particular, relates to fluorinated biphenylyl ethanes. Some fluorinated analogues of these compounds have been investigated, for example, fluorinated compounds such as as described in DE A 3233641, and as described in EP A 205998, and as described in Chemical Abstracts, Vol. 104, 159751h (1986). To date, the extent to which fluorinated compounds for use as liquid crystal compounds could be investigated has been hampered by the unavailability of suitable starting materials, and the difficulties of organofluorine chemistry. The present inventors have investigated the field of fluorinated biphenylyl ethanes and have identified a range of novel compounds which are useful components of liquid crystal materials. The compounds are considered novel due to the presence of lateral fluorine substituents which project sideways from the molecule causing a substantial difference to the molecular shape and transverse dipole of the essentially cylindrical non-laterally substituted molecules described above. According to the present invention there is provided a fluorobiphenylyl ethane suitable for use in liquid crystal materials which has a formula : wherein : m represents 0 or 1; n represents 0 or 1; R₁ represents hydrogen or an alkyl, alkoxy, alkoxy substituted alkyl, alkanoyl, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy group; each of represents a group selected from 1,4-disubstituted cyclohexane with the substituents in the trans configuration; 1,4-disubstituted bicyclo (2,2,2) octane; 2,5-disubstituted 1,3-dioxan with the substituents in the trans configuration; 1,4-disubstituted benzene optionally substituted with fluorine, e.g. in the 2 and/or 3 positions, 2,5-disubstituted 1,3-pyrimidine and 3,6-disubstituted 1,2-pyridazine; each of X, Y and Z represent hydrogen or fluorine in the 2,3,5 and 6 benzene ring positions provided that at least one of X, Y and Z represents fluorine in at least one ring position; and B represents a terminal group selected from: fluoro, chloro and CF₃; with the proviso that if rings are cyclohexane, and X is hydrogen and Y is fluorine in the 3-position and B is fluorine and R₁ is alkyl, then R₁ is selected from C₄₋₁₂ chiral alkyl or if m and n are both O then R₁ is selected from n-butyl, n-pentyl, n-hexyl and n-octyl, or if m is 1 and n is 0 then R₁ is selected from n-propyl, n-butyl, n-pentyl, n-hexyl and n-octyl. B is preferably fluoro. R₁ is preferably alkyl or alkoxy. Examples of certain sub-classes of compounds falling within formula I are listed in table 1. Examples of preferred sub-classes of compounds falling within formula I are listed in table 1a i.e. compounds having a general formula Ia; wherein R₁, m and B are as defined in formula I, and where at least one of X or Y is fluorine. In formula Ia, R₁ is preferably C₁₋₁₂ alkyl or alkoxy and B is preferably fluorine, and one of X or Y is fluorine, and provided that if Y is fluorine in the 3-position and R₁ is alkyl then either R₁ is C₄₋₁₂ chiral alkyl, or if m is 0 then R₁ is selected from n-butyl, n-pentyl, n-hexyl and n-octyl, or if m is 1 then R₁ is selected from n-propyl, n-butyl, n-pentyl, n-hexyl and n-octyl. In the compounds of Formula I where an alkyl group is contained within the group R₁ it preferably has from 1 to 12 carbon atoms, and it is preferably an n-alkyl group (where it contains more than 2 carbon atoms). An alkyl group contained within the group R₁ may alternatively be a chiral alkyl group having from 4 to 12 carbon atoms, eg (+)-2-methylbutyl. Preferably, the group R₁ has between 1 and 8 carbon atoms. Generally speaking, the compounds of Formula I are nematogenic or chiral nematogenic (where R₁ is chiral) showing a high clearing point (liquid crystal to isotropic liquid transition temperature) and, where n = 0 and m = 0 a relatively low melting point (> 100°C), a good chemical and photochemical stability and a positive dielectric anisotropy. They may also advantageously show a reduction in the tendency to form smectic phases by themselves and in admixture with nematogenic compounds of smaller dielectric anisotropy compared with the tendency to form such phases shown by unfluorinated compounds of comparable structure. They may also show a high clearing point combined with a relatively low viscosity, thus enabling them to be used to raise the clearing point of a liquid crystal mixture in which they are contained. The compounds of Formula I are therefore useful compounds of liquid crystal compositions for electro-optical displays. As the compounds of Formula I have a positive dielectric anisotropy they may be added to other liquid crystal materials of positive dielectric anisotropy, or to materials having a lower dielectric anisotropy in order to produce a mixture having amongst other things a suitable dielectric anisotropy. As is well known to those skilled in the art the dielectric anisotropy of the liquid crystal material is necessary to give electro-optical operation and its sign (for a given frequency) is chosen according to the kind of electro-optical device in which the material is to be used. Compounds of reasonably low melting point are preferred as high dielectric anisotropy components. For example, the low melting compounds of the known classes listed in table 2 are suitable as positive materials for admixture with the compounds of Formula I. In table 2 each R is independently n-alkyl or n-alkoxy and each R A is independently n-alkyl. As noted above, the compounds of Formula I may have added to them small dielectric anisotropy compounds, eg to reduce mixture melting point, viscosity or to improve multiplexibility. The classes listed in table 3 are examples of such small dielectric anisotropy compounds. In table 3 each R is independently n-alkyl or n-alkoxy; each R A is independently n-alkyl; each R′ is independently n-alkyl, n-alkoxy or hydrogen; x = H or F; and Q = halogen, eg Cl or F. In general, one or more compounds of Formula I is likely to be added to one or more compounds of Formula IIIa to IIIi optionally together with one or more compounds of Formula IIa to IIi to form suitable liquid crystal mixtures. Additional high clearing point compounds may be included in such mixtures eg one or more compounds selected from the classes shown in table 4. In table 4 R, R A , and X are as specified above (each one being independently selected). Other specific known additives, eg low melting chiral additives, such as where R C = (+)-methylbutyl and R D = (+)-2-methylbutoxy, may be incorporated in the mixture where required. One or more of compounds according to Formula I may be used in any of the following applications (where material having a positive dielectric anisotropy is referred to as 'positive' material: (i) as one or more components of a positive nematic material for use in twisted nematic effect devices including multiplexed devices; an example of such a device is given below; (ii) as one or more components of a positive nematic material, preferably also with a pleochroic dye, for use in Freedericksz effect devices (positive nematic type) in which the molecular arrangement may be changed from the homogeneous texture (OFF state) to the homeotropic texture (ON state) by an electric field; (iii) as one or more components of a positive material which is a long helical molecular pitch (eg 3 µm) cholesteric (chiral nematic), preferably together also with a pleochroic dye, in cholesteric-to-nematic phase change effect devices (negative contrast type) in which the molecular arrangement may be changed from a scattering focal conic texture (OFF state) to a clear homeotropic texture (ON state) by an electric field; (iv) as one or more components of a positive nematic material in two frequency switching effect devices (which may be twisted nematic effect devices) in which the dielectric anisotropy of the material may be changed form (at low frequency) positive (OFF state) to negative (ON state) by the application of a high frequency electric field. (v) As one or more components of a device as described in UK Patent Application No 8317355 Publication No GB 2123163A. The construction and operation of the above devices and the general kinds of material which are suitable for use in them are themselves known. Compositions incorporating the compounds of Formula I for use in the above applications may for example contain the following components. Component A: one or more compounds of Formula I, especially formula Ia, optionally plus one or more compounds IIa to IIi, Component B: one or more compounds of Formula IIIa to IIIq; Component C: one or more compounds of Formula IVa to IVo; Component D: one or more low melting chiral additives. For the twisted nematic effect and Freedericksz (positive nematic) effect the following percentages of the various components may be used in the material (the overall sum of the percentages adding to 100%). Component A: 5 to 95% by weight (typically 5 to 75% by weight) Component B: 0 to 90% by weight (typically 5 to 25% by weight) Component C: 0 to 30% by weight (typically 0 to 20% by weight) Component D: 0 to 5% by weight (typically 0 to 1% by weight) For the Freedericksz (positive nematic) and phase change (negative contrast type) effects a pleochroic dye forming from ±0.5 to 15% of the overall mixture is preferably added to the liquid crystal material. Suitable dyes are described in published UK Patent Application Nos 2081736A, 208219A and 2093475A. Typically, each dye compound incorporated forms 1 to 3% by weight of the overall mixture. Liquid crystal mixtures including compounds of Formula I may be formed in a known way, eg simply by heating the constituent compounds together in the correct weight proportion to form an overall isotropic liquid(eg at about 100°C). To provide a more general example of a mixture embodying the invention at least one compound according to Formula I above may be mixed together with one more compounds in any one or more of the known families listed in table 5 for use in one or more of the applications given above (the actual application(s) depending on the mixture's properties). In table 5 X is a 1,4 phenylene group, a 4,4′ biphenylyl group, a 2,6 naphthyl group or a trans-1,4-disubstituted cyclohexane ring, and Y is CN, or R′ or halogen or CO.O-X-Y¹ where Y¹ is CN, or R′ or OR′; where R and R′ are alkyl groups. The compound may alternatively be a derivative of one of these wherein H is replaced by a halogen, eg F, in one of the benzene rings. Preferably, the compound(s) of Formula I comprises between 5 and 95% by weight of the mixture. In addition to one or more compounds of formula I, especially of Formula Ia eg the compounds listed in Table 1a, preferred mixtures according to this aspect of the invention contain one or more compounds of formula xxvii and / or xxviii of table 5, particularly where the substituent is -OR′. These preferred mixtures may also contain other liquid crystal compounds, especially those in table 5 having formulae i, iv, v, vi, viii and xxix. According to the present invention in a second aspect a liquid crystal device includes two dielectric substrates at least one of which is optically transparent, a layer of liquid crystal material sandwiched between the substrates and electrodes on the inner surfaces of the substrates to enable an electric field to be applied across the layer of liquid crystal material to provide an electro-optic effect therein, characterised in that the liquid crystal material consists of or includes a compound according to Formula I above. The device according to the second aspect may be a twisted nematic effect device, which may or may not be operated in a multiplexed fashion, a cholesteric-to-nematic phase change effect device, a Freedericksz effect device or a two-frequency switching effect device, all constructed in a known manner or any of the other devices mentioned above. The various ways in which compounds according to Formula I may be used in these devices are outlined above and will be further apparent to those skilled in the art Compounds of Formula I may be produced by preparative routes in which the individual steps are known per se, the overall route being new. The preparation of laterally mono-fluorinated biphenyls of Formula I containing a halogen Q selected from fluorine and chlorine in the 4′ - position of the biphenylyl ring and a single ring A (=A₂ in Formula I) may be carried out using one of Routes 1 to 4 as shown in Figures 1 to 4 respectively. The starting materials for these Routes may be made by Routes 5 and 6 as shown in Figures 5 and 6. The preparation of laterally di-fluorinated biphenyls of Formula I containing a halogen Q in the 4′-position of the biphenylyl ring may be carried out for example using Route 7 illustrated in Figure 7 or Route 8 illustrated in Figure 8. The starting material for Route 8 may be made by Route 9 shown in Figure 9 or Route 10 shown in Figure 10. The preparation of laterally fluorinated terphenyls of Formula I containing a halogen Q in the 4″-position of the terphenylyl ring may be carried out for example using route 11 illustrated in Figure 11. In figure 11 W, X, Y, Z, Y¹ and Z¹ are all H or F at least one being F in at least one ring position. Q is F or Cℓ. Figures 12 and 13 illustrate Routes 12 and 13 respectively for the preparation of -CF₃ terminated compounds of Formula I. The cyano-terminated compounds used in Step12a may be produced by cyanation of the corresponding bromo-terminated compounds (eg as produced by Route 9 or Route 10) or produced by Route 14 or Route 15 shown in Figures 14 and 15 respectively where ring A is heterocyclic. Compounds wherein in Formula I m is 1 may be made by analogous routes which will be apparent to those skilled in the art of synthesis of organic compounds. One such route is route 16 shown in fig. 16. In figs. 1 - 16 R is alkyl or alkoxy and R A is alkyl. The invention will now be described by way of example only with reference to the accompanying drawings in which: Figures 1-16 show preparative routes for the compounds of Formula I. In this description: K, N, S, I represent respectively solid crystal, Nematic liquid crystal, Smectic liquid crystal and Isotropic liquid. All transition temperatures are in °C. Example 1 Preparation of compound of formula: using route 16. 3,4 - Difluorobromobenzene (9.65g) in tetrahydrofuran (10 ml) were added to magnesium (1.23g) in tetrahydrofuran (30 ml) in the absence of atmospheric oxygen and moisture. The reaction mixture was boiled under reflux until all the magnesium had dissolved. The mixture was cooled to room temperature and was then added, under ice cooling, to a solution of zinc chloride (3.4g) in tetrahydrofuran (25 ml). After 30 minutes dichloro-bistriphenylphosphine-nickel (II) (0.33g) was added, followed by a solution of p-[trans-4-(trans-4-n-propylcyclohexyl)-cyclohexylethyl]-bromobenzene (20.5g) in tetrahydrofuran. After 24 hours standing at room temperature the reaction mixture was worked up in the usual way to yield 4-[trans-4-(trans-4-n-propylcyclohexyl)-cyclohexylethyl]-3¹,4¹-difluorobiphenyl. Mpt 82°C, clearing point 216°C. This compound had an extrapolated viscosity of 28.0 cp at 20°C. This is quite low and thus the compound may be used to reduce the viscosity whilst raising the clearing point of a liquid crystal composition in which it is contained. By a completely analogous route the following compounds were prepared, of general formula R₁ X Y X Y methyl H F F H ethyl " " " " n-butyl " " " " n-pentyl " " " " n-hexyl " " " " n-heptyl " " " " n-octyl " " " " n-nonyl " " " " n-decyl " " " " n-undecyl " " " " n-dodecyl " " " " 2-methylbutyl (+), (-) and (±) " " " " 3-methylpentyl (+), (-) and (±) " " " " 4-methylhexyl (+), (-) and (±) " " " " methoxy " " " " ethoxy " " " " n-propyloxy " " " " n-butyloxy " " " " n-pentyloxy " " " " n-hexyloxy " " " " n-heptyloxy " " " " n-octyloxy " " " " n-nonyloxy " " " " n-decyloxy " " " " n-undecyloxy " " " " 2-methylbutyloxy (+), (-) and (±) " " " " 3-methylheptyloxy (+), (-) and (±) " " " " 4-methylhexyloxy (+), (-) and (±) " " " " Example 2 Preparation of compounds of general formula: where one of Z and Y is F and the other H. These compounds were prepared by a method analogous to that of example 1, but using p-[trans-4-alkyl or alkoxy cyclohexylethyl]-bromobenzene so that only one cyclohexyl ring is introduced into the molecule. The properties of some of these compounds, where X is hydrogen and Y is fluorine are listed below: R₁ K-N°C N-I°C ethyl 35.2 61.6 n-propyl 64.1 88.7 n-butyl 50.6 87.0 n-pentyl 74.8 95.9 n-hexyl 48.2 92.0 By a completely analogous route to that of example 2, the compounds listed in table 7 were prepared. R₁ X Y X Y methyl H F H F ethyl F H n-propyl F H n-butyl F H n-pentyl F H n-hexyl F H n-octyl F H H F n-nonyl " " " " n-decyl " " " " n-undecyl " " " " n-dodecyl " " " " 2-methylbutyl (+), (-) and (±) " " " " 3-methylpentyl (+), (-) and (±) " " " " 4-methylhexyl (+), (-) and (±) " " " " 5-methylheptyl (+), (-) and (±) " " " " methoxy " " " " ethoxy " " " " n-propyloxy " " " " n-butyloxy " " " " n-pentyloxy " " " " n-hexyloxy " " " " n-heptyloxy " " " " n-octyloxy " " " " n-nonyloxy " " " " n-decyloxy " " " " 2-methylbutyloxy (+), (-) and (±) " " " " 3-methylpentyloxy (+), (-) and (±) " " " " 4-methylhexyloxy (+), (-) and (±) " " " " n-undecyloxy " " " " n-dodecyloxy " " " " The compounds referred to above may for example be used in the devices particularly described with reference to the drawings in published UK Patent Application No 2121406A, the above compounds (either alone or in mixture form) replacing the compound 1-(4-cyano-phenyl)-2-(4-n-pentylphenyl)ethane in mixtures 1, 2 and 3 specified in that application. Example 3. Nematic liquid crystal mixtures containing compounds of formula I.

Claims: Claims for the following Contracting States : AT, BE, FR, GB, IT, NL, SE A compound suitable for use in liquid crystal materials having a formula: wherein: m represents 0 or 1; n represents 0 or 1; R₁ represents hydrogen or an alkyl, alkoxy, alkoxy substituted alkyl, alkanoyl, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy group; each of represents a group selected from 1,4-disubstituted cyclohexane with the substituents in the trans -configuration; 1,4-disubstituted bicyclo (2,2,2) octane; 2,5-disubstituted 1,3-dioxan with the substituents in the trans -configuration; 1,4-disubstituted benzene optionally substituted with fluorine, eg in the 2 and/or 3 positions, 2,5-disubstituted 1,3 pyrimidine and 3,6-disubstituted 1,2 pyridazine; each of X, Y and Z represent hydrogen and fluorine in the 2,3,5 and 6 benzene ring positions provided that at least one of X, Y and Z represents fluorine in at least one ring position; and B represents a terminal group selected from: fluoro, chloro and CF₃. A compound according to claim 1, having a formula: where at least one of X and Y is fluorine. A compound according to claim 1 or 2 characterised in that R₁ is C₁₋₁₂ alkyl or alkoxy and B is fluorine. A compound according to claim 3 having a formula A compound according to claim 4 characterised in that R₁ contains 2-6 carbon atoms. A compound according to claim 3 having a formula A compound according to claim 6 characterised in that R₁ is n-propyl. A liquid crystal material having at least two components characterised in that at least one component is a compound as claimed in any one of the preceding claims. A liquid crystal material according to claim 8 characterised in that it contains a compound of formula where R and R' are alkyl groups. A liquid crystal electro-optical display device characterised in that it incorporates a material as claimed in claim 8 or 9. Claims for the following Contracting States : CH, DE, LI A compound suitable for use in liquid crystal materials characterised by a formula: wherein: m represents 0 or 1; n represents 0 or 1; R₁ represents hydrogen or an alkyl, alkoxy, alkoxy substituted alkyl, alkanoyl, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy group; each of represents a group selected from 1,4-disubstituted cyclohexane with the substituents in the trans -configuration; 1,4-disubstituted bicyclo (2,2,2) octane; 2,5-dissubstituted 1,3-dioxan with the substituents in the trans -configuration; 1,4-dissubstituted benzene optionally substituted with fluorine, eg in the 2 and/or 3 positions, 2,5-disubstituted 1,3 pyrimidine and 3,6-dissubstituted 1,2 pyridazine; each of X, Y and Z represents hydrogen and fluorine in the 2,3,5 and 6 benzene ring positions provided that at least one of X, Y and Z represents fluorine in at least one ring position; and B represents a terminal group selected from: fluoro, chloro and CF₃ ; with the proviso that if rings are cyclohexane, and X is hydrogen and Y is fluorine in the 3- position and B is fluorine and R₁ is alkyl, then R₁ is selected from C₄₋₁₂ chiral alkyl or if m and n are both 0 then R₁ is selected from n-butyl, n-pentyl, n-hexyl and n-octyl, or if m is I and n is 0 then R₁ is selected from n-propyl, n-butyl, n-pentyl, n-hexyl and n-octyl. A compound according to claim 1 characterised by a formula: wherein at least one X or Y is fluorine. A compound according to claim 2 characterised in that, R₁ is C₁₋₁₂ alkyl or alkoxy, B is fluorine and one of X or Y is fluorine, and provided that if Y is fluorine in the 3- position and R₁ is alkyl then either R₁ is C₄₋₁₂ chiral alkyl, or if m is 0 then R₁ is selected from n-butyl, n-pentyl, n-hexyl and n-octyl, or if m is 1 then R₁ is selected from n-propyl, n-butyl, n-pentyl, n-hexyl and n-octyl-. A compound according to claim 2 characterised by a formula: wherein R₁ is selected from n-butyl, n-pentyl, n-hexyl and n-octyl. A compound according to claim 2 characterised by a formula: wherein R₁ is selected from N-propyl, n-butyl, n-pentyl, n-hexyl and n-octyl. A compound according to claim 5 characterised in that R₁ is n-propyl. A liquid crystal material having at least two components characterised in that at least one component is a compound as claimed in any one of the preceding claims. A liquid crystal material according to claim 7 characterised in that it contains a compound of formula where R and R' are alkyl groups. A liquid crystal electro-optical display device characterised in that it incorporates a material as claimed in claim 7 or 8

Inventors: GRAY, GEORGE WILLIAM, LACEY, DAVID, POETSCH, EIKE, TOYNE, KENNETH JOHNSON, WEBER, GEORG
Applicants: THE SECRETARY OF STATE FOR DEFENCE IN HER BRITANNIC MAJESTY'S GOVERNMENT OF THE UNITED KINGDOM OF GREAT BRITAIN AND
Application year: 1987
Main classification: C07C25
IPC codes: C07C25, C07C43, C09K19