Title of Invention	METHOD OF MAKING COMPOUNDS, IN PARTICULAR LIQUID CRYSTALLINE COMPOUNDS FOR THE MANUFACTURE OF OPTICAL COMPONENTS
Abstract	A compound is of formula (I): wherein: MG<1> and MG<3> each independently represent an optionally-substituted aliphatic group with 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; or an optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring system, with 1 to 80 C-atoms; and MG<2> represents a group comprising at least two and up to four optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring systems, with 1 to 80 C-atoms, wherein, when MG<2> represents a group comprising four optionally-substituted ring systems, at least three of the ring systems are aligned in between B<1> and B<2>. The groups MG<1>, MG<2> and MG<3> in these new "staircase molecules" may be selected so that each has one or more of the properties which are required in an LCP material prepared by polymerising the compound.

Title of Invention

METHOD OF MAKING COMPOUNDS, IN PARTICULAR LIQUID CRYSTALLINE COMPOUNDS FOR THE MANUFACTURE OF OPTICAL COMPONENTS

Abstract

A compound is of formula (I): wherein: MG<1> and MG<3> each independently represent an optionally-substituted aliphatic group with 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; or an optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring system, with 1 to 80 C-atoms; and MG<2> represents a group comprising at least two and up to four optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring systems, with 1 to 80 C-atoms, wherein, when MG<2> represents a group comprising four optionally-substituted ring systems, at least three of the ring systems are aligned in between B<1> and B<2>. The groups MG<1>, MG<2> and MG<3> in these new "staircase molecules" may be selected so that each has one or more of the properties which are required in an LCP material prepared by polymerising the compound.

Full Text	FORM 2 THE PATENTS ACT, 1970 (39 of 1970) & THE PATENS RULES, 2003 COMPLETE SPECIFICATION [See section 10, Rule 13] METHOD OF MAKING COMPOUNDS, IN PARTICULAR LIQUID CRYSTALLINE COMPOUNDS FOR THE MANUFACTURE OF OPTICAL COMPONENTS; ROLIC AG, A CORPORATION ORGANIZED AND EXISTING UNDER THE LAWS OF SWITZERLAND, WHOSE ADDRESS IS CHAMERSTRASSE 50, 6301 ZUG, SWITZERLAND. THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES THE INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED. Liquid crystalline compounds The invention relates to new liquid crystalline compounds, mixtures of those compounds and their application in optical devices. More particularly, it relates to the use of a component of a polymerisable liquid crystalline mixture in the production of orientated liquid crystalline polymers; compounds used as components in polymer¬isable liquid crystalline mixtures; liquid crystalline mixtures comprising these components, liquid crystalline polymers prepared from such components; and liquid crystalline devices comprising those compounds. Liquid crystal polymers (LCPs) are used in the manufacture of optical components such as waveguides, optical gratings, filters, retarders, piezoelectric cells and non-linear optical cells and films. The choice of LCP for use in any one of the aforementioned optical components depends upon its associated optical properties such as the optical anisotropy, refractive index, transparency and dispersion. Optical filters, for example, contain LCPs having a large anisotropy (An) and a low dispersion (n = In some applications there is a requirement to produce LCPs in which the component molecules adopt a specific tilt angle or orientation with respect to the plane of the substrate or to a plane perpendicular to the substrate. These LCP materials can be used as optical components such as compensation layers and retarders. Such optical components may be used in the production of liquid crystal devices (LCDs) with improved viewing angles, for example. LCPs are manufactured by orientating a layer of a polymerisable liquid crystal single compound or mixture on an orientated substrate and cross-linking the mesogenic layer to form a liquid crystal polymer (LCP) network. Polymerisable LC compounds used in the manufacture of the LCPs need to be chemically and thermally stable, stable to electromagnetic radiation, soluble in standard solvents and miscible with other LC components, and to exhibit liquid crystalline properties over the range 25 to 150 °C, preferably 25 to 80 °C. The configuration imposed by the orientation layer on the polymerisable LC single compound or mixture becomes fixed or frozen into the LCP network formed upon cross-linking. The resulting LCP films have a high viscosity and are stable to mechanical stresses, temperature and light exposure. There is therefore a need for a liquid crystalline single compound or mixture which exhibits a broad liquid-crystalline thermal range and which can be orientated on a substrate prior to cross-linking in such a way that the orientation of the LC single compound or mixture on the substrate remains stable over the period required for manufacturing the LCP network. Components which may be used in photo--crosslinkable liquid crystalline layers are particularly desirable. Compounds known from the prior art include those disclosed in EP-A-0675186, EP-A-0700981 and EP-A-0748852 (all F. Hoffmann-La Roche AG). The three earlier documents disclose compounds such as (taken from EP-A-0675186): O >=0 ° US 3971824 (Van Meter et al. / Eastman Kodak Company) discloses in its broadest 20 aspect compounds of the following formula: X where X is chlorine. Previous strategies used for obtaining the desired thermal and optical properties with a given LCP material have mainly relied upon mixtures of compounds comprising at least one liquid crystalline polymerisable monomer and the combination of their individual properties. However due to the general incompatibility of the latter components at the molecular scale, the thermodynamic behaviour of their corresponding mixtures is generally undesirable (for example, a depression of the clearing point, a reduction of the liquid crystalline range etc.), besides some problems of miscibility between the different components of the mixture leading to difficulties in achieving a uniform orientation of the LCP material. To ameliorate this situation, a new concept of obtaining LCP materials of special thermal and optical properties was investigated. This concept uses chemical junctions at lateral positions of different molecules, at least one of them being mesogenic, having each one or more of the properties which are required in the final LCP material. Depending on the application, these properties can be selectively induced from at least one of the mesogenic stairs of the new "staircase molecules". Thus the invention provides chiral or achiral "staircase" compounds of formula I: wherein: A1 to A6 each independently represent hydrogen; an optionally-substituted methyl group; or an optionally-substituted hydrocarbon group of 2 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; B1 and B2 each independently represent a single bond, an oxygen atom or an optionally-substituted hydrocarbon group of 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; MG1 and MG3 each independently represent an optionally-substituted aliphatic group with 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; or an optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring system, with 1 to 80 C-atoms; MG2 represents a group comprising at least two and up to four optionally-substituted aromatic or non-aromatic carbocyciic or heterocyclic ring systems, with 1 to 80 C-atoms, wherein, when MG2 represents a group comprising four optionally-substituted ring systems, at least three of the ring systems are aligned in between B! and B"; nl and n2 are each independently 1 or 2, where "nl = 2" (or "n2 = 2") indicates the presence of two separate linkages via the groups B1 (or the groups B~) between the groups MG1 and MG2 (or MG2 and MG3); and n3 is a positive integer up to 1000; with the proviso that: when. A3 and A4 both represent hydrogen, then both MG1 and MG represent an araliphatic group with 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, or an optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring system, with 1 to 80 C-atoms; and at least two of A , A, A and A -each independently represent an optionally-substituted hydrocarbon group of 3 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom; when A1, A2, A5 and A6 all represent hydrogen, then A3 and A4 both represent an optionally-substituted hydrocarbon group of 3 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom; and optionally-substituted ring systems, then neither of A3 and A4 when MG" represents a group comprising two or three optionally-substituted rinj includes an aromatic ring. The term "aliphatic" includes straight-chain and branched alkylene, as well as saturated and unsaturated groups. Possible substituents include alkyl, aryl (thus giving an araliphatic group) and cycloalkyl, as well as amino, cyano, epoxy, halogen, hydroxy, nitro, oxo etc. Possible heteroatoms which may replace carbon atoms include nitrogen, oxygen and sulphur. In the case of nitrogen further substitution is possible with groups such as alkyl, aryl and cycloalkyl. Likewise, the terms "alkyl" and "alkylene", as used herein, includes straight-chain and branched groups, as well as saturated and unsaturated groups. When MG2 represents a group comprising four optionally-substituted ring systems, at least three of the ring systems are aligned in between B1 and B2. Thus, at least three of the rings are all in a discrete identifiable block positioned in between B and B , not in an arbitrarily defined region with some of the rings protruding from the axis of the molecule connecting B1 with B2. Comparison may be made with compounds such as Compound I-a of EP-A-0675186: When MG2 represents a group comprising two or three optionally-substituted ring systems, then neither of A and A includes an aromatic ring. This again makes it clear that with compounds such as Compound I-a of US 5567349 fall outside the scope of the present invention. It is not possible to produce the present invention by arbitrarily labelling parts of molecules known from the prior art. The groups MG1, MG2 and MG3 in the new "stairc&se molecules" may be selected so that each has one OT more of the properties which are Teqaiicu in 1he fma^ LCP material. To an expert in liquid crystals, the molecular architecture of compounds of formula I would not have been thought to be favourable for obtaining a liquid crystalline mesophase, because a bulky substituent at a position lateral to a mesogenic core would have been thought to cause a loss of mesogenic character. However we have now discovered that the compounds of formula I were surprisingly found to be liquid crystalline over a broad thermal range. Besides, they are suitable for producing a ; I" high tilt and high optical birefringence together with well oriented LCP films. MG" may be either a mesogenic group or otherwise. It is advantageous for the liquid crystalline compounds to be photo-crossIinkabJe, so that for example they may be used in a crosslinked state in optical devices. Thus preferably at least one of A1 to A6 includes a polymerisable group. In such a case, when A3 and A4 both represent hydrogen then at least one of A , A , A5 and A6 would include a polymerisable group; whereas when A1, A2, A3 and A all represent hydrogen then at least one of AJ and A4 would include a polymerisable group. In a first preferred embodiment of the present invention, each or any of the groups A1 to A may be selected from a residue of formula (II): p-tSp^KX1),,- (ii) wherein: P is hydrogen or a polymerisable group selected from groups comprising CH2=CW-, CH2=W-0-, CH2-CW-COO-, CH2=C(Ph)-COO-, CH?=CH-COO-Ph-, CH2-CW-CO-NH-, CH2=C(Ph)-CONH-, CH2=C(COOR")-CH2-COCK CH2-CH-O-, CH2=CH-OOC-5 (Ph)-CH=CH-, wherein: W represents H, F, CI, Br or I or a Ci-s alkyl group; m3 is an integer having a value of from 1 to 9; m4 is an integer having a value of 0 or 1, R" represents a Ci_5 alkyl group; and R" represents a Ci_s alkyl group, methoxy, cyano, F, CI, Br or I; Sp" represents an optionally-substituted Cj_2o alkylene group, in which one or more C-atoms may be replaced by a heteroatom; k1 is an integer having a value of from 0 to 4; X1 represents -0-, -S-, -NH-, N(CH3)-, -CH(OH)-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -S02-, -CH2(S02)-, -COO-, -OCO-, -OCO-0-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH2-CH2-, -OCH2-, -CH20-, -CH=CH-, or -C=C-; and t1 is an integer having a value of 0 or 1; with the proviso that at least one of the groups A1 to A6 is not a hydrogen atom. In relation to the residue of formula (II), the term Ph is to be understood as denoting phenylene and (Ph) as denoting phenyl. The C1_2o alkylene group Sp1 may comprise branched or straight chain alkylene groups and may be unsubstituted, mono- or polysubstituted by F, CI, Br, I or CN. Alternatively or in addition one or more of CH2 groups present in the hydrocarbon chain may be replaced, independently, by one or more groups selected from -O-, -S-, -NH-, N(CH3)-, -CH(OH)-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -S02-, -CH2(S02)-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -C=C-, -(CF2K , -(CD2)S- or C(W )=C(W)-, with the proviso that no two oxygen atoms are directly linked to each other. W and W~ each represent, independently, H, H-(CH2)qr or CI. The integers r, s and ql each independently represent a number of between 1 and 15. More preferably, A to A each independently represent a group of formula (III): P2-Sp5-X4- (III); wherein: X4 represents -0-, -CO-, -COO-, -OCO-, -CsC-, or a single bond, especially -0-, -COO-, -OCO- or single bond; Sp5 represents a C1-20 straight-chain alkylene group, especially ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, or dodecylene; and P2 represents hydrogen, CH2-CW5- or CH2=CW5-(CO)v20-, wherein: W5 represents H, CH3, F, CI, Br or I; and v2 is 0 or 1. One or more of A1 to A6 may also represent a C1-C20-alkyl, Ci-C20-alkoxy, Ci-C2o-alkoxycarbonyl, Cj-Cio-alkylcarbonyl or Ci-C2o-alkylcarbonyloxy group, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, methoxy, ethoxy, «-propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxy-carbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, acetyl, propionyl, butyryl, valeryl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, terdecanoyl, acetoxy, propionyloxy, butyryloxy, valeryloxy, hexanoyloxy, heptanoyloxy, octanoyioxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, terdecanoyloxy and the like. In a second preferred embodiment of the present invention each or either of the groups B1 and/or B2 comprises a group of formula (IV): (XV(Sp2)k2-(X3)t3 (IV) wherein: Sp represents a Cj_2o alkylene group; X2andX3 each independently represent -0-, -S-, -NH-, N(CH3)-, -CH(OH)-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -S02-, -CH2(S02)-; -COO-, -OCO-, -OCO-0-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH2-CH2-, -OCH2-, -CH2O-, -CH=CH-, -C=C- or a single bond; k2 is an integer, having a value of 0 or 1; t2 and t3 are integers, each independently having a value of 0 or 1; with the proviso that oxygen atoms are not linked one to another. Preferably B1 and B2 each independently represent a group of formula (IV), wherein: X2 to X3 each independently represent -0-, -CO-, -COO-, -OCO-, -C=C-, or a single bond, especially -0-, -COO-, -OCO- or a single bond; and Sp2 represents a C\|_2o straight-chain alkylene group, especially ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene or dodecylene. An especially preferred compound is that in which B and B each independently represent a group of formula (IV) and A to A each independently represent a group of formula (III). The invention is particularly useful when MG2 is a mesogenic group and the groups of MG1 and MG3 also impart mesogenic properties to the molecule, in addition to those properties imparted by the mesogenic group MG . Thus preferably MG2 and at least one of MG1 and MG3 represents a mesogenic group comprising at least two J optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring systems. Preferably MG represents a mesogenic group comprising 2 to 4 aromatic or non--aromatic carbocyclic or heterocyclic ring systems and optionally up to 3 bridging 25 groups, and at least one of MG! and MGJ represent a mesogenic group comprising 1 to 4 aromatic or non-aromatic carbocyclic or heterocyclic ring systems and optionally up to 3 bridging groups. These are more preferably selected from the meanings of formulae V: 30 C"-(Z,-C2)al-(Z2-C3)a2-(23-C4)a3 (V), in which: C1 to C4 are in each case independently optionally-substituted non-aromatic, aromatic, carbocyclic or heterocyclic groups; Z]toZ3 are independently from each other -COO-, -OCO-, -CH2-CH2-, -OCH2-, -CH2O-, -CH-CH-, -OC-, -CH=CH-COO-5 -OCO-CH=CH-or a single bond; and al, a2 and a3 are independently integers 0 to 3, such that al + a2 + a3 \ ■ ■; ^ with: L being -CH3, -COCH3, -N02, CN, or halogen ul being 0,1,2, 3, or 4, u2 being 0,1,2, or 3, and u3 being 0, l,or2. More especially preferred are those in which C1 to C4 are selected from cyclohexylene, phenylene, naphthylene or phenanthrylene. For ease of synthesis, the molecules may possess some symmetrical aspects. Thus: A1 and A2 may be identical; A5 and A6 may be identical; A1—MG1—A2 and A5—MG3—A6 may be identical; A3 and A4 may be identical; or nl, n2 and n3 may equal 1 and B1 and B2 may be identical. The compounds of the invention may be readily prepared using methods that are well known to the person skilled in the art, such as those documented in Houben-Weyl, Methoden der Organischen Chemie, Thieme-Verlag, Stuttgart. The compounds may for example be made according to the following reaction schemes: Scheme 1: Cr03/H2S04/H20 Acetone Scheme 1 fcoutinued): Scheme 1 (continued): CH3S02CI Et3N THF ffchcmc 2; Scheme 2 (continued); o To a solution of 4,4"-dipentyl[l,l";4,,r]terphenyl-2",5"-diol (0.11 g), 2,5-di-[4-(6-acryl-oyloxyhexyloxy)benzoyloxy]benzoic acid (0.42 g) and 4-dimethylaminopyridine (DMAP) (7 mg) in dichloromethane (8 ml), cooled at 0°C, a solution of N.N"-dicyclohexylcarbodiimide (DCC) (0.12 g) in dichloromethane (2 ml) is added dropwise. After complete addition, the reaction mixture is stirred at room temperature for 6 h then evaporated under reduced pressure. The obtained crude white residue is chromatographed on silica (dichloromethane/diethyl ether : 19/1) to afford pure 2,5-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 5"-[2,5-bis[4-(6-acryloyl-oxyhexyloxy)benzoyloxy3ben20yioxy]-4,4"-dipentyl[l,r;4",l"]terphenyl-2"-yl ester as white crystalline material. Yield: 0.32 g. This compound has the following thermotropic sequence: K 172°C I, Example 2: 1) 4,4"-Dinony loxy [ 1,1";4",1 "jterpheny 1-3,3 "-dicarbaldehyde 2,5-Bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 3-[2,5-bis-[4-(6-acryloyl-oxyhexyloxy)benzoyloxy]benzoyloxy]-4,4"-bisnonyloxy [1,1 ";4", 1 "]terphenyl-3 "-yl ester. To a well degassed mixture of 1,4-benzenediboronic acid (1.4 g), 5-bromo--2-nonyloxybenzaldehyde (5.50 g), Na2C03 2M (40 ml), ethanol (15 ml) and toluene (40 ml), tetrakis(triphenylphosphine)palladium(0) (0.62 g) and CuI (5 mg) are added. The obtained mixture is maintained under argon atmosphere and vigorously stirred at reflux for 12 h. After cooling the organic layer is separated and the aqueous phase is extracted with 2 x 60 ml of ether and the combined organic extracts are dried over magnesium sulphate and evaporated to dryness. The obtained black residue is 3 0 chromatographed on silica using CH2CI2 / hexane : 3/1 as eluant. The obtained yellow crystalline material is dissolved in minimum of CH2CI2 (30 ml) and poured into 200 ml of acetone. The obtained solution is half-concentrated and cooled at 0°C for 2 h. The pure 4,4"-dmonyloxy[l,r;4",l"]terphenyl-3,3"-dicarbaldehyde crystallises as white powder. 1 J Yield: 3.8 g. 2) 4,4"-Dinony loxy [ 1,1 ";4", 1 "]terphenyi-3,3 "-diol A solution of 4,4"-dinonyloxy[l,r;4",r"]terphenyl-3,3"-dicarbaldehyde (3.42 g) in CH2CI2 (120 ml) is cooled at 0°C and treated with two crops addition of w-chloroperbenzoic acid (3.83 g). The mixture is stirred at room temperature for 3 h. It is then quenched with saturated solution of NaHC03 (50 ml) and extracted twice with ether (2 x 200 ml). The combined organic extracts are further washed with saturated solution of NaHC03 (100 ml), with saturated solution of NaCl, dried over magnesium sulphate and evaporated to afford a yellow crystalline residue. This residue is dissolved in ethanol / dichloromethane : "50 ml / 30 ml and treated with 75 ml of 1.5 M KOH at 55°C for 20 min. The resulting mixture is then concentrated and extracted with ether (3 x 150 ml). The ether extracts are washed with sat. NaCl (2 x 200 ml), dried over magnesium sulphate and evaporated to dryness. This affords the dihydroxy compound as yellow crystalline material which is purified by recrystallisation in ethanol to give .") 454"-dinonyloxy[l,r;4",l"]terphenyl-3,3"-diol as a slightly yellow crystalline material. Yield: 3.1 g. 3) 2;5-Bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 3-[2,5-bis--[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoyloxy]-4,4"-bisnonyloxyl-[1,1 ,;4,,r,]terphenyl-3"-yl ester. A solution of mesyl chloride (0.73 g) in 10 ml of dry THF is dropwise added to a solution of 2",5"-bis-[2,5-di-(4-(6-acryloyloxyhexyloxy)benzoyloxy)]benzoic acid (4.50 g) and triethylamine (3.6 ml) in 50 ml of dry THF, cooled at -25 °C and maintained and ". under argon atmosphere. After complete addition (15 min), the reaction mixture is further stirred for 120 min at -25 DC then treated with a solution of 4,4"-dmonyloxy[l,r;4",r]terphenyl-3,3"-diol in 60 ml of dry THF containing 78 mg of DMAP and the reaction mixture is further stirred at -25°C for 2 h. The temperature is then allowed to reach room temperature and stirring is continued overnight. The reaction mixture is poured into 120 ml of water, extracted with 2 x 200 ml of ether and 120 ml of dichloromethane. The combined organic extracts are washed with HC1 3JV (200 ml) then with a half saturated NaCl solution (2 x 100 ml), dried over MgS04 and evaporated to dryness to afford a slightly yellow pasty material. This is dissolved in 25 ml of THF and reprecipitated from 300 of methanol, then flash chromatographed over a short silica column. Pure 2?5-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 3-[2,5-bis--[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoyloxy]-4,4"-bisnonyloxy [1,1 ";4", 1 "]-terphenyl-3"-yl ester is obtained as a white crystalline material. Yield: 4.7 g. This compound has the following thermotropic sequence: K 105.5 °C N 122.6 °C I. When the sample is quickly cooled from the isotropic state, the nematic mesophase still occurs at room temperature for 2 hours before the crystallisation. Example 3: 2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-5-(rran5,-4-pentylcyclohexanecarbonyloxy)-benzoic acid 3-[2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-5-(/ra«5-4-pentylcyclo-hexanecarbonyloxy)]benzoyloxy]-4,4"-bisnonyloxy [ 1,1";4",1 "]terphenyl-3 "-yl ester. 1) 2-[4-(6-Acryloyloxyhexyloxy)benzoyloxy]-5-(4-rra«i--pentylcyclohexane-carbonyloxy)benzaldehyde A solution of mesyl chloride (1.14 g) in 10 ml of dry THF is drop wise added to a cooled (-40 to -25°C) solution of 4-(6-acryloyloxyhexyloxy)benzoic acid (2.78 g) and trJethylamine (6 ml) in 40 ml of dry THF and under argon. After complete addition (15 rain), the reaction mixture was further stirred for 60 min at -25 °C then treated with a solution of 2,5-dihydroxybenzaldehyde (1.38 g) in 10 ml of dry THF and the reaction mixture is further stirred at -25 °C for 2 h. This mixture was then treated with a suspension of triethyl-(rran5-4-pentylcyclohexynecarbonyl)ammonium; chloride (prepared from rra7M-4-pentylcyclohexanecarboxylic acid (2.26 g), triethylamine (6 .. ml) and mesyl chloride (1.14 g) in THF(35 ml)) in dry THF (35 ml), followed by one-crop addition of DMAP (0.24 g). Stirring is continued for 3 h at -25°c and for 30 min at room temperature. The reaction mixture is then poured into 80 ml of saturated NaHC03, extracted with 2 x 100 ml of ether . The combined organic extracts are washed with HC1 3N (100 ml) then with half saturated NaCl solution (2 x 100 ml), dried over MgS04, filtered and evaporated to dryness to afford a slightly yellow pasty material. This is flash chromatographed over a short silica-gel column (CH2CI2). The obtained white residue (2.3 g) was dissolved in CH2CI2 (5 ml) then reprecipitated from ethanol (50 ml). This affords pure 2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]--5-(4-?m«i--pentylcyclohexanecarbonyloxy)benzaldehyde as white crystalline material. Yield 1.3 g. 2) 2-[4-(6-Aciyloyloxyhexyloxy)berizoyloxy]-5-(4-fra«s,-pentylcyclohexane-carbonyloxy)benzoic acid Jones oxidant (Cr03/H2S04/H:>0) (8 m!) is added dropwise to a ice-cooled solution of 2-[4-(6-acryloyloxyhex>"lox>")benzoyIox\]-5-(4-/rflns-pentylcyciohexariecarbonyloxy)- benzaldehyde (1.21 g) in acetone/dichloromethane (40 ml/20 ml). After complete addition (10 min), stirring is continued at room temperature overnight. The green-orange mixture is then filtered off and the green precipitate is washed with 150 ml of ether. The combined organic solutions are then washed with water until the orange coloration is removed (fix 100 ml). The obtained colourless organic solution is washed with saturated NaCl solution (2 x 80 ml), dried over MgS04, filtered and evaporated to dryness. 2-[4-(6-acryloyloxyhexyIoxy)benzoyloxy]-5-(4-/rara,-pentyl-cyclohexanecarbonyloxy)benzoic acid as white crystalline material Yield 1.18 g. 3) 2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-5-(rran5-4-pentyIcyclohexane- carbonyloxy)benzoic acid 3-[2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]--5-(fra«s-4-pentylcyclohexanecarbonyloxy)]benzoyloxy]-4,4"-bisnonyloxy-[1,1 ";4",1 "]terphenyl-3"-yl ester. Following the procedure described in Example 2, the reaction was performed with 1.1 g of 2-[4-(6-Acryloyloxyhexyloxy)benzoyloxy]-5-(4-?raHs-pentylcyclohexane-carbonyloxy)benzoic acid , 0.37 g of 4,4"-dinonyloxy[l5r;4",r"]terphenyl-373"-diol, 0.02 g of DMAP, 2 ml of triethylamine and 0.2 g of mesyl chloride affording the t desired compound as white crystalline material. Yield 0.81 g. This compound presents the nematic mesophase as a single liquid-crystalline phase at a temperature above 90 °C and thermally polymerises at this temperature. Example 4: 2,5-Bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoie acid 3-[3-[2,5-bis-[4-(6-acryI-oyloxyhexyloxy)benzoyloxy]benzoyloxy]phenylethynyl]phenyl ester. 1) 3-(3-Ethynylphenoxy)tetrahydropyran: To a well degassed solution of 3-(3-bromophenoxy)tetrahydropyran (5.14 g), triphenylphosphine {204 mg), copper(I) iodide (38 mg) and bis(triphenylphosphine)-palladium(II) dichloride (3.93 g) in triethylamine (40 ml), maintained under argon atmosphere, trimethylsilylacetylene is added and the mixture is stirred at 85°C for 3 h. The precipitated ammonium salts was removed by filtration and the filtrate was evaporated to dryness. This affords a yellowish oil which is dissolved in 30 ml of THF containing 3 ml of water, then cooled at 0°C and treated by dropwise addition of 5 ml of tetrabutylammonium fluoride (1M in THF). After stirring for 30 min the reaction was complete and the obtained brownish solution was filtered over a short silica-gel column and concentrated to yield a brownish residue, which was chromatographed on silica-gel column affording 3-(3-ethynylphenoxy)tetrahydropyran as yellowish crystals. Yield 3.8 g. 2) 1,2-Bis-(3-hydroxyphenyl)ethyne: HO OH Following the above procedure, the reaction was performed with 3-(3-bromophenoxy)-tetrahydropyran (2.57 g), 3-(3-ethynylphenoxy)tetrahydropyran (2.02 g), triphenyl¬phosphine (105 mg), copper(I) iodide (19 mg) and bis(triphenyiphosphine)-palladium(II) dichloride (70 mg) in triethylamine (40 ml). The crude dark residue obtained after filtration over silica-gel column is dissolved in a mixture of dichloromethane (10 ml) and methanol (40 ml), then treated with 150 mg pyridinium p-toluene sulphonate at 60 °C for 2 h. The transparent reaction solution was then diluted with 100 ml of ether and washed twice with 40 ml of water then with 50 ml of saturated NaCl solution, dried over MgS04 and evaporated to dryness to afford l,2-bis-(3-hydroxyphenyl)ethyne as yellowish solid. Yield 1.66 g. 3) 2,5-Bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 3-[3-[2,5-bis--[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoyloxy]phenylethynyI]phenyl ester. Following the procedure described in Example 2, the reaction was performed with 1.4 g of 2",5"-bis-[2,5-di-(4-(6-acryloyloxyhexyloxy)benzoyloxy)]benzoic acid, 0.14 g of l,2-bis-(3-hydroxyphenyl)ethyne, 0.012 g of DMAP, 1.4 ml of triethylamine and 0.23 g of mesyl chloride affording the desired compound as white pasty material. Yield 0.64 g. This compound present the following thermotropic sequence: N Example 5: A mixture is formulated consisting of: 50% 1,4-butanediol diacrylate; Aldrich 10% To this mixture 500 p.p.m. inhibitor 2,6-di-/er/-butyl-4-methylphenol (BHT) is added to prevent premature polymerisation. For the radical photo-polymerisation we use 500 p.p.m. initiator: IRGACURE™ 369 (commercially available from Ciba Geigy, Basle, Switzerland). These mixture were solved in anisole with a ratio of 20 : 80. After stirring at room temperature, this mixture were spin-coated on a glass plate with an orientation layer on top to form a layer of ca. 800 nm. This film is then dried at 80°C for 1 or 2 minutes and photo-polymerised by irradiation with UV light using Mercury lamp for 5 minutes at room temperature in a N2-atmosphere. The film shows well oriented nematic mesophase with exclusion of any defects. In addition this film exhibits a great tilt angle w.r.t. to plane, as shown by ellipsometric measurements. CLAIM A compound of formula A5-MG3—A6 wherein; A1 to. A" each independently represent hydrogen; an optionally-substituted methyl group; or an optionally-substituted hydrocarbon group of 2 to 80 C-aloms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; B1 and B2 each independently represent a single bond, an oxygen atom or an optionally-substituted hydrocarbon group of 1 to 80 C-atoms, ; in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; MG1 and MG"1 each independently represent an optionally-substituted aliphatic group with 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; or an optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring system, with 1 to 80 C-atoms; MG2 represents a group comprising at least two and up to four optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring systems, with 1 to 80 C-atoms, wherein, when MG2 represents a group comprising four optionally-substituted ring systems, at least three of" the ring systems aic aliened in between IJ and tt"; nl and n2 are each independently 1 or 2, where "nl = 2" (or "n2 = 2") indicates the presence of two separate linkages via the groups 13" (or the groups B2) between the groups MG1 and MG2 (or MG2 and MG3); and n3 is a positive integer up to 1000; with the proviso that: when A3 and A"1 both represent hydrogen, then both MG1 and MG1 represent an araliphalie group with 1 to 80 C-atorus, in which one or more C-atoms may be replaced by a heteroatom, or an optionally-substituted aromatic or non-aromatic carbocyciic or heterocyclic ring system, with 1 to 80"C-atoms; and at least two of A1, A2, A" and A6 each independently represent an optionally-substituted hydrocarbon group of 3 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom; when A1, A2, A" and A6 all represent hydrogen, then A"1 and A"1 both represent an optionally-substituted hydrocarbon group of 3 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom; and when MG2 represents a group comprising two or three i optionally-substituted ring systems, then neither of A3 and A4 includes an aromatic ring. 2. A compound as claimed in claim 1, wherein at least one of A1 lo A" includes a polymeiisable group. 3. A compound as claimed in claim 2, wherein each or any of the groups A1 to A6 is selected from a residue of formula (II): P-(Sp")u-(X,)11- (II) wherein: P is VvfdYogen w a YwvtymeirHsaWe. g,TO\vp aetettesl ftwfi £TO\ips coTrrprisVng CII2=CW-, CU2=W-0-, CM2=CW-COO-, CIb=C(Ph)-COO-, CIl2=CM-COO-Ph-, CH2=CW-CO-NH-, CH2=C(Ph)-CONH-, CIl2=C(COOR>CU2-COG)-, Cll2=CII-0, Clb-CU-OOC-, (Ph)-CH=CH-, CFl3-C=N-(CII2),„r, HO-, JIS-, MO-(CII2)m3-, HS-(CI!2W, HO(CII2)m,COO-, HS(CHa)m3COO-, MWN-, MOC(O)-, CH2=CH-Ph-(0)n,, HWcPcH- , U^)V-CH==CH- or a^\--CH==COO- wherein: i i W ., represents II, F, CI, Br or I or a Ci_5 alkyl group; m3 is an integer having « value of from 1 to 0; i i m4 is on integer having a value of 0 or 1, ■ I ! i i . \ [ 1 ...;{ I" R represents a C,_5 alkyl group; and ..! " ! ■ , "I ! : \ R" . represents a.Qi-s alkyl group, methoxy, cyano, F, CI, Br or 1; Sp ,„ ^represents an optionally-substituted Ci_2o alkylene group, in which one or more , C-aU\\ws,vwav V«. rcpUiced. hy a UeAeraaUxm/, k1 is an integer having a value of from 0 It) 4; X" represents -O, -S-, -Nil-, N(C113)-, -Cll(Oll)-, -CO-, -CI l2(CO)-, -SO, * -CH2(SO)-, -SO2-, -CH2(S02)-, -COO-, -OCO-, -OCO-0-, -S-CO-, -CO-S-, -SOO-, -0S0-, -SOS-, -CI I2-CH2-, -OCH2-, -CH2O-, -C1-1=CI 1-, or -OC-; and I1 is an integer having a value of 0 or 1; in which the term Ph denotes phcnylene and the term (Ph) denotes phenyl; with the proviso that at least one of the groups A1 to Af" is not a hydrogen atom. 4. A compound as clainicd in claim 3, wherein A1 to A6 each independently represent a group of formula (111): P2-Sp5-X4- (111); wherein: X4 represents -0-, -CO-, -COO-, -OCO-, -C=C-, or a single bond, especially -O-, -COO-, -OCO- or single bond; Sp" represents a C^2o straight-chain alkylene group, especially ethylene, 1 propylene, butylcnc, pentylcne, hexylene, heptylcne, oclylenc, nonylene, decylenc, undecylene, or dodecylene; and P2 represents hydrogen, CI12=CWS- or Cll2=CW5-(CO)v20-? wherein: % Ws represents 11, CH3, F, CI, Br or 1; and v2 is (I or 1 5. A compound as claimed in any preceding claim, wherein B1 and/or B2 comprises a group of formula (IV): (X2)l2-(Sp2)k2 -(X3),3 (IV) wherein: Sp" represents a C\|_2o alkylene group;* X2andX3 each independently represent -O-, -S-, -Nil-, N(CII3)-, -CH(OII)-, -co-, -ci i2(co)-, -so-, -cn2(so)-, -SO2-, -cn2(so2)-, -coo-, -oco-, -OCO-0-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH2-CH2-, -OCH2-, -CH20-, -CM=CI I-, -CsC- or a single bond; k2 is an integer, having a value of() or 1; t2 and t3 are integers, each independently having a value of 0 or 1; with the proviso that oxygen atoms are not linked one to another. 6. A compound as claimed in claim 5, wherein: X2andX3 each independently represent -0-, -CO-, -COO-, -OCO-, -CsC-, or a single bond; and Sp2 represents a C1-20 straight-chain alkylene group. 7. : A compound as claimed in claim 6, wherein X" and X3 each independently represent -O-, -COO-, -OCO- or a single bond. A compound as claimed in claim 6 or claim 7, wherein Sp2 represents ethylene, propylene, butylenc, pcnlylene, hexylcne, heptylene, octylene, nonylene, decylcne, undecylene or dodecylcne 9- A compound as claimed in any preceding claim, wherein MG2 and at least one of MG1 and MG3 represents a mesogenic group comprising at least two optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring systems. 10. A compound as claimed in any preceding claim, wherein: MG represents a mesogenic group comprising 2 to A aromatic or non-aromatic carbocyclic or heterocyclic ring systems and optionally up to 3 bridging groups; and at least one of MG1 and MG3 represent a mesogenic group comprising 1 to 4 aromatic or. non-aromatic carbocyclic or heterocyclic ring systems and optionally up to 3 bridging groups. 11. A compound as claimed in claim 10, wherein one or more of MG1, MG2 and MG represents a mesogenic group selected from the meanings of formulae V: in which: C toC are in each case independently optionally-substituted non-aromatic, aromatic, carbocyclic or heterocyclic groups; Z loZ are independently from each other -COO-, -OCO-, -CH2-CH2- -OCH2-, -CH2O-, -CH=CH-, -C=C-, -CH=CI-l-COO-, -OCO-CH=CH-or a single bond; and al, u2 and a.3 are independently inicgcr.s 0 to 3, such thai a I -I- a2 ) a3 3. 12. A compound as claimed in claim 1 1, wherein C to C4 are selected from: N with: L. being -CH3, -COCM3, -NO?, CN, or halogen ul being 0, 1,2, 3, or 4, u2 being 0, I, 2, or 3, and u3 being 0, 1, or 2. 13. A compound as claimed in claim 12, wlierein C1 to C4 are selected from cyclo-hexylene, phenylcne, naphlhylene or phenanthrylene. 14. A compound as claimed in any preceding claim, wherein A1 and A- are identical. 15. A compound as claimed in any preceding claim, wherein A-s and A6 arc identical. - 16. A compound as claimed in any preceding claim, wherein A" — MG.1 —A2 and A5—MQ-3—A6) arc identical. 17. A compound as claimed in any preceding claim, wherein A3 and A4 are identical. 18. A compound as claimed in any preceding claim, wherein nl, n2 and n3 equal 1 and B1 and B2 arc identical. 19. A liquid crystalline mixture comprising at least one compound as claimed in any one of claims 1 to 18. 20. A polymer network comprising at least one compound as claimed in any one of claims 1 lo 18. 21. A polymer network as claimed in claim 20, essentially consisting of: i) at least one chiral or/and achiral mesogenic polymerisable compound; ii) at least one "staircase" compound of formula 1; and iii) an initiator. 22. A polymer network as claimed in claim 21 further comprising one or more further polymerisable compounds, stabilisers and/or dyes. 23. A liquid crystalline polymer film comprising a compound as claimed in any one of claims 1 to 18. 24 A liquid crystalline polymer film obtainable by polymerisation of a liquid crystalline mixture as claimed in claim 19. 25. A process for the preparation of a liquid crystalline polymer film as claimed in claim 24 comprising the steps of: (a) forming the polymerisable liquid crystalline mixture according to claim 19 into a thin film preferably on a substrate; and (b) subsequent curing of this film, preferably by means of UV light. 26. An optical or electro-optical component containing a liquid crystalline polymer film as claimed in claim 24. 27. Method of making a compound of formula (I) according to any of the claims 1 to 18, comprising the steps of: (a) preparing, preferentially, first elements A"-MG-A2, A3 - MG - A4 AND A5-MG3-A6 and (b) subsequently, joining by means of second elements (B1) n1 and (B2) ,l2. precursors of which second elements preferably form part of said first elements. 28. Method of making a liquid crystalline mixture according to claim 19, wherein a compound of formula (I) according to any of the claims 1 to 18 is admixed with an additional mesogenic component, which is miscible with said compound of formula (I). 29. Method of making a polymer network according to any of the claims 20 - 22, wherein a compound of formula (I) according to any of the claims 1 to 18 is used, and wherein preferentially, I) at least one chiral or / and achiral mesogenic polymerisable compound, ii) at least one "staircase" compound of formula(l), and iii) an initiator are copolymerised to form the polymer network. 30. Method of making a liquid crystalline polymer film according to any of claims 23 - 24 or of making an optical or electro-optical component according to claim 26, wherein a film comprising a compound of formula (I) according to any of the claims 1 to 18 is formed on a substrate and subsequently polymerized and cross-linked. Dated this 27th day of September, 2001. FOR ROLIC AG BY their Agent (MANISH SAURASTRI) KRISHNA SAURASTRI

Full Text

FORM 2
THE PATENTS ACT, 1970 (39 of 1970)
& THE PATENS RULES, 2003
COMPLETE SPECIFICATION
[See section 10, Rule 13]
METHOD OF MAKING COMPOUNDS, IN PARTICULAR LIQUID CRYSTALLINE COMPOUNDS FOR THE MANUFACTURE OF OPTICAL COMPONENTS;
ROLIC AG, A CORPORATION ORGANIZED AND EXISTING UNDER THE LAWS OF SWITZERLAND, WHOSE ADDRESS IS CHAMERSTRASSE 50, 6301 ZUG, SWITZERLAND.
THE FOLLOWING SPECIFICATION
PARTICULARLY DESCRIBES THE
INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED.

Liquid crystalline compounds
The invention relates to new liquid crystalline compounds, mixtures of those compounds and their application in optical devices. More particularly, it relates to the use of a component of a polymerisable liquid crystalline mixture in the production of orientated liquid crystalline polymers; compounds used as components in polymer¬isable liquid crystalline mixtures; liquid crystalline mixtures comprising these components, liquid crystalline polymers prepared from such components; and liquid crystalline devices comprising those compounds.
Liquid crystal polymers (LCPs) are used in the manufacture of optical components such as waveguides, optical gratings, filters, retarders, piezoelectric cells and non-linear optical cells and films. The choice of LCP for use in any one of the aforementioned optical components depends upon its associated optical properties such as the optical anisotropy, refractive index, transparency and dispersion. Optical filters, for example, contain LCPs having a large anisotropy (An) and a low dispersion (n =

In some applications there is a requirement to produce LCPs in which the component molecules adopt a specific tilt angle or orientation with respect to the plane of the substrate or to a plane perpendicular to the substrate. These LCP materials can be used as optical components such as compensation layers and retarders. Such optical components may be used in the production of liquid crystal devices (LCDs) with improved viewing angles, for example.
LCPs are manufactured by orientating a layer of a polymerisable liquid crystal single compound or mixture on an orientated substrate and cross-linking the mesogenic layer to form a liquid crystal polymer (LCP) network. Polymerisable LC compounds used in the manufacture of the LCPs need to be chemically and thermally stable, stable to electromagnetic radiation, soluble in standard solvents and miscible with other LC components, and to exhibit liquid crystalline properties over the range 25 to 150 °C,

preferably 25 to 80 °C. The configuration imposed by the orientation layer on the polymerisable LC single compound or mixture becomes fixed or frozen into the LCP network formed upon cross-linking. The resulting LCP films have a high viscosity and are stable to mechanical stresses, temperature and light exposure.
There is therefore a need for a liquid crystalline single compound or mixture which exhibits a broad liquid-crystalline thermal range and which can be orientated on a substrate prior to cross-linking in such a way that the orientation of the LC single compound or mixture on the substrate remains stable over the period required for manufacturing the LCP network. Components which may be used in photo--crosslinkable liquid crystalline layers are particularly desirable.
Compounds known from the prior art include those disclosed in EP-A-0675186, EP-A-0700981 and EP-A-0748852 (all F. Hoffmann-La Roche AG). The three earlier documents disclose compounds such as (taken from EP-A-0675186):

O >=0 °

US 3971824 (Van Meter et al. / Eastman Kodak Company) discloses in its broadest 20 aspect compounds of the following formula:

X
where X is chlorine.
Previous strategies used for obtaining the desired thermal and optical properties with a given LCP material have mainly relied upon mixtures of compounds comprising at least one liquid crystalline polymerisable monomer and the combination of their individual properties. However due to the general incompatibility of the latter components at the molecular scale, the thermodynamic behaviour of their corresponding mixtures is generally undesirable (for example, a depression of the clearing point, a reduction of the liquid crystalline range etc.), besides some problems of miscibility between the different components of the mixture leading to difficulties in achieving a uniform orientation of the LCP material. To ameliorate this situation, a new concept of obtaining LCP materials of special thermal and optical properties was investigated. This concept uses chemical junctions at lateral positions of different molecules, at least one of them being mesogenic, having each one or more of the properties which are required in the final LCP material. Depending on the application, these properties can be selectively induced from at least one of the mesogenic stairs of the new "staircase molecules".
Thus the invention provides chiral or achiral "staircase" compounds of formula I:

wherein:
A1 to A6 each independently represent hydrogen; an optionally-substituted
methyl group; or an optionally-substituted hydrocarbon group of 2 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another;
B1 and B2 each independently represent a single bond, an oxygen atom or
an optionally-substituted hydrocarbon group of 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another;
MG1 and MG3 each independently represent an optionally-substituted aliphatic
group with 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; or an optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring system, with 1 to 80 C-atoms;
MG2 represents a group comprising at least two and up to four
optionally-substituted aromatic or non-aromatic carbocyciic or heterocyclic ring systems, with 1 to 80 C-atoms, wherein, when MG2 represents a group comprising four optionally-substituted ring systems, at least three of the ring systems are aligned in between B! and B";

nl and n2 are each independently 1 or 2, where "nl = 2" (or "n2 = 2")
indicates the presence of two separate linkages via the groups B1 (or the groups B~) between the groups MG1 and MG2 (or MG2 and MG3); and
n3 is a positive integer up to 1000;
with the proviso that:
when. A3 and A4 both represent hydrogen, then both MG1 and MG represent an araliphatic group with 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, or an optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring system, with 1 to 80 C-atoms; and at least two of A , A, A and A -each independently represent an optionally-substituted hydrocarbon group of 3 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom;
when A1, A2, A5 and A6 all represent hydrogen, then A3 and A4 both represent an optionally-substituted hydrocarbon group of 3 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom; and

optionally-substituted ring systems, then neither of A3 and A4
when MG" represents a group comprising two or three optionally-substituted rinj includes an aromatic ring.

The term "aliphatic" includes straight-chain and branched alkylene, as well as saturated and unsaturated groups. Possible substituents include alkyl, aryl (thus giving an araliphatic group) and cycloalkyl, as well as amino, cyano, epoxy, halogen, hydroxy, nitro, oxo etc. Possible heteroatoms which may replace carbon atoms include

nitrogen, oxygen and sulphur. In the case of nitrogen further substitution is possible with groups such as alkyl, aryl and cycloalkyl. Likewise, the terms "alkyl" and "alkylene", as used herein, includes straight-chain and branched groups, as well as saturated and unsaturated groups.
When MG2 represents a group comprising four optionally-substituted ring systems, at least three of the ring systems are aligned in between B1 and B2. Thus, at least three of the rings are all in a discrete identifiable block positioned in between B and B , not in an arbitrarily defined region with some of the rings protruding from the axis of the molecule connecting B1 with B2. Comparison may be made with compounds such as Compound I-a of EP-A-0675186:

When MG2 represents a group comprising two or three optionally-substituted ring systems, then neither of A and A includes an aromatic ring. This again makes it clear that with compounds such as Compound I-a of US 5567349 fall outside the scope of the present invention. It is not possible to produce the present invention by arbitrarily labelling parts of molecules known from the prior art.

The groups MG1, MG2 and MG3 in the new "stairc&se molecules" may be selected so that each has one OT more of the properties which are Teqaiicu in 1he fma^ LCP material. To an expert in liquid crystals, the molecular architecture of compounds of formula I would not have been thought to be favourable for obtaining a liquid crystalline mesophase, because a bulky substituent at a position lateral to a mesogenic core would have been thought to cause a loss of mesogenic character. However we have now discovered that the compounds of formula I were surprisingly found to be liquid crystalline over a broad thermal range. Besides, they are suitable for producing a ; I" high tilt and high optical birefringence together with well oriented LCP films.
MG" may be either a mesogenic group or otherwise.
It is advantageous for the liquid crystalline compounds to be photo-crossIinkabJe, so that for example they may be used in a crosslinked state in optical devices. Thus preferably at least one of A1 to A6 includes a polymerisable group. In such a case, when A3 and A4 both represent hydrogen then at least one of A , A , A5 and A6 would include a polymerisable group; whereas when A1, A2, A3 and A all represent hydrogen then at least one of AJ and A4 would include a polymerisable group.
In a first preferred embodiment of the present invention, each or any of the groups A1 to A may be selected from a residue of formula (II):
p-tSp^KX1),,- (ii)
wherein:
P is hydrogen or a polymerisable group selected from groups comprising
CH2=CW-, CH2=W-0-, CH2-CW-COO-, CH2=C(Ph)-COO-,
CH?=CH-COO-Ph-, CH2-CW-CO-NH-, CH2=C(Ph)-CONH-,
CH2=C(COOR")-CH2-COCK CH2-CH-O-, CH2=CH-OOC-5 (Ph)-CH=CH-,

wherein:
W represents H, F, CI, Br or I or a Ci-s alkyl group;
m3 is an integer having a value of from 1 to 9;
m4 is an integer having a value of 0 or 1,
R" represents a Ci_5 alkyl group; and
R" represents a Ci_s alkyl group, methoxy, cyano, F, CI, Br or I;
Sp" represents an optionally-substituted Cj_2o alkylene group, in which one or more C-atoms may be replaced by a heteroatom;
k1 is an integer having a value of from 0 to 4;
X1 represents -0-, -S-, -NH-, N(CH3)-, -CH(OH)-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -S02-, -CH2(S02)-, -COO-, -OCO-, -OCO-0-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH2-CH2-, -OCH2-, -CH20-, -CH=CH-, or -C=C-; and
t1 is an integer having a value of 0 or 1;
with the proviso that at least one of the groups A1 to A6 is not a hydrogen atom.

In relation to the residue of formula (II), the term Ph is to be understood as denoting phenylene and (Ph) as denoting phenyl.
The C1_2o alkylene group Sp1 may comprise branched or straight chain alkylene groups and may be unsubstituted, mono- or polysubstituted by F, CI, Br, I or CN. Alternatively or in addition one or more of CH2 groups present in the hydrocarbon chain may be replaced, independently, by one or more groups selected from -O-, -S-, -NH-, N(CH3)-, -CH(OH)-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -S02-, -CH2(S02)-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -C=C-, -(CF2K , -(CD2)S- or C(W )=C(W)-, with the proviso that no two oxygen atoms are directly linked to each other. W and W~ each represent, independently, H, H-(CH2)qr or CI. The integers r, s and ql each independently represent a number of between 1 and 15.
More preferably, A to A each independently represent a group of formula (III):
P2-Sp5-X4- (III);
wherein:
X4 represents -0-, -CO-, -COO-, -OCO-, -CsC-, or a single bond,
especially -0-, -COO-, -OCO- or single bond;
Sp5 represents a C1-20 straight-chain alkylene group, especially ethylene,
propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, or dodecylene; and
P2 represents hydrogen, CH2-CW5- or CH2=CW5-(CO)v20-,
wherein:
W5 represents H, CH3, F, CI, Br or I; and

v2 is 0 or 1.
One or more of A1 to A6 may also represent a C1-C20-alkyl, Ci-C20-alkoxy, Ci-C2o-alkoxycarbonyl, Cj-Cio-alkylcarbonyl or Ci-C2o-alkylcarbonyloxy group, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, methoxy, ethoxy, «-propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxy-carbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, acetyl, propionyl, butyryl, valeryl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, terdecanoyl, acetoxy, propionyloxy, butyryloxy, valeryloxy, hexanoyloxy, heptanoyloxy, octanoyioxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, terdecanoyloxy and the like.
In a second preferred embodiment of the present invention each or either of the groups B1 and/or B2 comprises a group of formula (IV):
(XV(Sp2)k2-(X3)t3 (IV)
wherein:
Sp represents a Cj_2o alkylene group;
X2andX3 each independently represent -0-, -S-, -NH-, N(CH3)-, -CH(OH)-, -CO-, -CH2(CO)-, -SO-, -CH2(SO)-, -S02-, -CH2(S02)-; -COO-, -OCO-, -OCO-0-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH2-CH2-, -OCH2-, -CH2O-, -CH=CH-, -C=C- or a single bond;
k2 is an integer, having a value of 0 or 1;
t2 and t3 are integers, each independently having a value of 0 or 1;

with the proviso that oxygen atoms are not linked one to another.
Preferably B1 and B2 each independently represent a group of formula (IV), wherein:
X2 to X3 each independently represent -0-, -CO-, -COO-, -OCO-, -C=C-, or a
single bond, especially -0-, -COO-, -OCO- or a single bond; and
Sp2 represents a C|_2o straight-chain alkylene group, especially ethylene,
propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene or dodecylene.
An especially preferred compound is that in which B and B each independently represent a group of formula (IV) and A to A each independently represent a group of formula (III).
The invention is particularly useful when MG2 is a mesogenic group and the groups of MG1 and MG3 also impart mesogenic properties to the molecule, in addition to those properties imparted by the mesogenic group MG . Thus preferably MG2 and at least one of MG1 and MG3 represents a mesogenic group comprising at least two J optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring systems.
Preferably MG represents a mesogenic group comprising 2 to 4 aromatic or non--aromatic carbocyclic or heterocyclic ring systems and optionally up to 3 bridging 25 groups, and at least one of MG! and MGJ represent a mesogenic group comprising 1 to 4 aromatic or non-aromatic carbocyclic or heterocyclic ring systems and optionally up to 3 bridging groups. These are more preferably selected from the meanings of formulae V:
30 C"-(Z,-C2)al-(Z2-C3)a2-(23-C4)a3 (V),
in which:

C1 to C4 are in each case independently optionally-substituted non-aromatic,
aromatic, carbocyclic or heterocyclic groups;
Z]toZ3 are independently from each other -COO-, -OCO-, -CH2-CH2-,
-OCH2-, -CH2O-, -CH-CH-, -OC-, -CH=CH-COO-5 -OCO-CH=CH-or a single bond; and
al, a2 and a3 are independently integers 0 to 3, such that al + a2 + a3
\
■ ■; ^

with:
L being -CH3, -COCH3, -N02, CN, or halogen
ul being 0,1,2, 3, or 4,
u2 being 0,1,2, or 3, and

u3 being 0, l,or2.
More especially preferred are those in which C1 to C4 are selected from cyclohexylene, phenylene, naphthylene or phenanthrylene.
For ease of synthesis, the molecules may possess some symmetrical aspects. Thus:
A1 and A2 may be identical;
A5 and A6 may be identical;
A1—MG1—A2 and A5—MG3—A6 may be identical;
A3 and A4 may be identical; or
nl, n2 and n3 may equal 1 and B1 and B2 may be identical.
The compounds of the invention may be readily prepared using methods that are well known to the person skilled in the art, such as those documented in Houben-Weyl, Methoden der Organischen Chemie, Thieme-Verlag, Stuttgart. The compounds may for example be made according to the following reaction schemes:

Scheme 1:

Cr03/H2S04/H20 Acetone

Scheme 1 fcoutinued):

Scheme 1 (continued):

CH3S02CI
Et3N THF

ffchcmc 2;

Scheme 2 (continued);

o

To a solution of 4,4"-dipentyl[l,l";4,,r*]terphenyl-2",5"-diol (0.11 g), 2,5-di-[4-(6-acryl-oyloxyhexyloxy)benzoyloxy]benzoic acid (0.42 g) and 4-dimethylaminopyridine (DMAP) (7 mg) in dichloromethane (8 ml), cooled at 0°C, a solution of N.N"-dicyclohexylcarbodiimide (DCC) (0.12 g) in dichloromethane (2 ml) is added dropwise. After complete addition, the reaction mixture is stirred at room temperature for 6 h then evaporated under reduced pressure. The obtained crude white residue is chromatographed on silica (dichloromethane/diethyl ether : 19/1) to afford pure 2,5-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 5"-[2,5-bis[4-(6-acryloyl-oxyhexyloxy)benzoyloxy3ben20yioxy]-4,4"-dipentyl[l,r;4",l"]terphenyl-2"-yl ester as white crystalline material. Yield: 0.32 g. This compound has the following thermotropic sequence: K 172°C I,
Example 2:
1) 4,4"-Dinony loxy [ 1,1";4",1 "jterpheny 1-3,3 "-dicarbaldehyde

2,5-Bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 3-[2,5-bis-[4-(6-acryloyl-oxyhexyloxy)benzoyloxy]benzoyloxy]-4,4"-bisnonyloxy [1,1 ";4", 1 "]terphenyl-3 "-yl ester.

To a well degassed mixture of 1,4-benzenediboronic acid (1.4 g), 5-bromo--2-nonyloxybenzaldehyde (5.50 g), Na2C03 2M (40 ml), ethanol (15 ml) and toluene (40 ml), tetrakis(triphenylphosphine)palladium(0) (0.62 g) and CuI (5 mg) are added. The obtained mixture is maintained under argon atmosphere and vigorously stirred at reflux for 12 h. After cooling the organic layer is separated and the aqueous phase is extracted with 2 x 60 ml of ether and the combined organic extracts are dried over magnesium sulphate and evaporated to dryness. The obtained black residue is
3 0 chromatographed on silica using CH2CI2 / hexane : 3/1 as eluant. The obtained yellow crystalline material is dissolved in minimum of CH2CI2 (30 ml) and poured into 200 ml of acetone. The obtained solution is half-concentrated and cooled at 0°C for 2 h. The pure 4,4"-dmonyloxy[l,r;4",l"]terphenyl-3,3"-dicarbaldehyde crystallises as white powder.
1 J Yield: 3.8 g.
2) 4,4"-Dinony loxy [ 1,1 ";4", 1 "]terphenyi-3,3 "-diol

A solution of 4,4"-dinonyloxy[l,r;4",r"]terphenyl-3,3"-dicarbaldehyde (3.42 g) in CH2CI2 (120 ml) is cooled at 0°C and treated with two crops addition of w-chloroperbenzoic acid (3.83 g). The mixture is stirred at room temperature for 3 h. It

is then quenched with saturated solution of NaHC03 (50 ml) and extracted twice with ether (2 x 200 ml). The combined organic extracts are further washed with saturated solution of NaHC03 (100 ml), with saturated solution of NaCl, dried over magnesium sulphate and evaporated to afford a yellow crystalline residue. This residue is dissolved in ethanol / dichloromethane : "50 ml / 30 ml and treated with 75 ml of 1.5 M KOH at 55°C for 20 min. The resulting mixture is then concentrated and extracted with ether (3 x 150 ml). The ether extracts are washed with sat. NaCl (2 x 200 ml), dried over magnesium sulphate and evaporated to dryness. This affords the dihydroxy compound as yellow crystalline material which is purified by recrystallisation in ethanol to give .") 454"-dinonyloxy[l,r;4",l"]terphenyl-3,3"-diol as a slightly yellow crystalline material. Yield: 3.1 g.
3) 2;5-Bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 3-[2,5-bis--[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoyloxy]-4,4"-bisnonyloxyl-[1,1 ,;4,,r,]terphenyl-3"-yl ester.
A solution of mesyl chloride (0.73 g) in 10 ml of dry THF is dropwise added to a solution of 2",5"-bis-[2,5-di-(4-(6-acryloyloxyhexyloxy)benzoyloxy)]benzoic acid (4.50 g) and triethylamine (3.6 ml) in 50 ml of dry THF, cooled at -25 °C and maintained and ". under argon atmosphere. After complete addition (15 min), the reaction mixture is further stirred for 120 min at -25 DC then treated with a solution of 4,4"-dmonyloxy[l,r;4",r]terphenyl-3,3"-diol in 60 ml of dry THF containing 78 mg of DMAP and the reaction mixture is further stirred at -25°C for 2 h. The temperature is then allowed to reach room temperature and stirring is continued overnight. The reaction mixture is poured into 120 ml of water, extracted with 2 x 200 ml of ether and 120 ml of dichloromethane. The combined organic extracts are washed with HC1 3JV (200 ml) then with a half saturated NaCl solution (2 x 100 ml), dried over MgS04 and evaporated to dryness to afford a slightly yellow pasty material. This is dissolved in 25 ml of THF and reprecipitated from 300 of methanol, then flash chromatographed over a short silica column.

Pure 2?5-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 3-[2,5-bis--[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoyloxy]-4,4"-bisnonyloxy [1,1 ";4", 1 "]-terphenyl-3"-yl ester is obtained as a white crystalline material. Yield: 4.7 g.
This compound has the following thermotropic sequence: K 105.5 °C N 122.6 °C I.
When the sample is quickly cooled from the isotropic state, the nematic mesophase still occurs at room temperature for 2 hours before the crystallisation.
Example 3:
2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-5-(rran5,-4-pentylcyclohexanecarbonyloxy)-benzoic acid 3-[2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-5-(/ra«5-4-pentylcyclo-hexanecarbonyloxy)]benzoyloxy]-4,4"-bisnonyloxy [ 1,1";4",1 "]terphenyl-3 "-yl ester.

1) 2-[4-(6-Acryloyloxyhexyloxy)benzoyloxy]-5-(4-rra«i--pentylcyclohexane-carbonyloxy)benzaldehyde

A solution of mesyl chloride (1.14 g) in 10 ml of dry THF is drop wise added to a cooled (-40 to -25°C) solution of 4-(6-acryloyloxyhexyloxy)benzoic acid (2.78 g) and trJethylamine (6 ml) in 40 ml of dry THF and under argon. After complete addition (15 rain), the reaction mixture was further stirred for 60 min at -25 °C then treated with a solution of 2,5-dihydroxybenzaldehyde (1.38 g) in 10 ml of dry THF and the reaction mixture is further stirred at -25 °C for 2 h. This mixture was then treated with a suspension of triethyl-(rran5-4-pentylcyclohexynecarbonyl)ammonium; chloride (prepared from rra7M-4-pentylcyclohexanecarboxylic acid (2.26 g), triethylamine (6 .. ml) and mesyl chloride (1.14 g) in THF(35 ml)) in dry THF (35 ml), followed by one-crop addition of DMAP (0.24 g). Stirring is continued for 3 h at -25°c and for 30 min at room temperature. The reaction mixture is then poured into 80 ml of saturated NaHC03, extracted with 2 x 100 ml of ether . The combined organic extracts are washed with HC1 3N (100 ml) then with half saturated NaCl solution (2 x 100 ml), dried over MgS04, filtered and evaporated to dryness to afford a slightly yellow pasty material. This is flash chromatographed over a short silica-gel column (CH2CI2). The obtained white residue (2.3 g) was dissolved in CH2CI2 (5 ml) then reprecipitated from ethanol (50 ml). This affords pure 2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]--5-(4-?m«i--pentylcyclohexanecarbonyloxy)benzaldehyde as white crystalline material. Yield 1.3 g.
2) 2-[4-(6-Aciyloyloxyhexyloxy)berizoyloxy]-5-(4-fra«s,-pentylcyclohexane-carbonyloxy)benzoic acid

Jones oxidant (Cr03/H2S04/H:>0) (8 m!) is added dropwise to a ice-cooled solution of 2-[4-(6-acryloyloxyhex>"lox>")benzoyIox\]-5-(4-/rflns-pentylcyciohexariecarbonyloxy)-

benzaldehyde (1.21 g) in acetone/dichloromethane (40 ml/20 ml). After complete addition (10 min), stirring is continued at room temperature overnight. The green-orange mixture is then filtered off and the green precipitate is washed with 150 ml of ether. The combined organic solutions are then washed with water until the orange coloration is removed (fix 100 ml). The obtained colourless organic solution is washed with saturated NaCl solution (2 x 80 ml), dried over MgS04, filtered and evaporated to dryness. 2-[4-(6-acryloyloxyhexyIoxy)benzoyloxy]-5-(4-/rara,-pentyl-cyclohexanecarbonyloxy)benzoic acid as white crystalline material Yield 1.18 g.
3) 2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-5-(rran5-4-pentyIcyclohexane-
carbonyloxy)benzoic acid 3-[2-[4-(6-acryloyloxyhexyloxy)benzoyloxy]--5-(fra«s-4-pentylcyclohexanecarbonyloxy)]benzoyloxy]-4,4"-bisnonyloxy-[1,1 ";4",1 "]terphenyl-3"-yl ester.
Following the procedure described in Example 2, the reaction was performed with 1.1 g of 2-[4-(6-Acryloyloxyhexyloxy)benzoyloxy]-5-(4-?raHs-pentylcyclohexane-carbonyloxy)benzoic acid , 0.37 g of 4,4"-dinonyloxy[l5r;4",r"]terphenyl-373"-diol, 0.02 g of DMAP, 2 ml of triethylamine and 0.2 g of mesyl chloride affording the t desired compound as white crystalline material. Yield 0.81 g.
This compound presents the nematic mesophase as a single liquid-crystalline phase at a temperature above 90 °C and thermally polymerises at this temperature.
Example 4:
2,5-Bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoie acid 3-[3-[2,5-bis-[4-(6-acryI-oyloxyhexyloxy)benzoyloxy]benzoyloxy]phenylethynyl]phenyl ester.

1) 3-(3-Ethynylphenoxy)tetrahydropyran:

To a well degassed solution of 3-(3-bromophenoxy)tetrahydropyran (5.14 g), triphenylphosphine {204 mg), copper(I) iodide (38 mg) and bis(triphenylphosphine)-palladium(II) dichloride (3.93 g) in triethylamine (40 ml), maintained under argon atmosphere, trimethylsilylacetylene is added and the mixture is stirred at 85°C for 3 h. The precipitated ammonium salts was removed by filtration and the filtrate was evaporated to dryness. This affords a yellowish oil which is dissolved in 30 ml of THF containing 3 ml of water, then cooled at 0°C and treated by dropwise addition of 5 ml of tetrabutylammonium fluoride (1M in THF). After stirring for 30 min the reaction was complete and the obtained brownish solution was filtered over a short silica-gel column and concentrated to yield a brownish residue, which was chromatographed on silica-gel column affording 3-(3-ethynylphenoxy)tetrahydropyran as yellowish crystals. Yield 3.8 g.
2) 1,2-Bis-(3-hydroxyphenyl)ethyne:

HO

OH

Following the above procedure, the reaction was performed with 3-(3-bromophenoxy)-tetrahydropyran (2.57 g), 3-(3-ethynylphenoxy)tetrahydropyran (2.02 g), triphenyl¬phosphine (105 mg), copper(I) iodide (19 mg) and bis(triphenyiphosphine)-palladium(II) dichloride (70 mg) in triethylamine (40 ml). The crude dark residue

obtained after filtration over silica-gel column is dissolved in a mixture of dichloromethane (10 ml) and methanol (40 ml), then treated with 150 mg pyridinium p-toluene sulphonate at 60 °C for 2 h. The transparent reaction solution was then diluted with 100 ml of ether and washed twice with 40 ml of water then with 50 ml of saturated NaCl solution, dried over MgS04 and evaporated to dryness to afford l,2-bis-(3-hydroxyphenyl)ethyne as yellowish solid. Yield 1.66 g.
3) 2,5-Bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoic acid 3-[3-[2,5-bis--[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzoyloxy]phenylethynyI]phenyl ester.
Following the procedure described in Example 2, the reaction was performed with 1.4 g of 2",5"-bis-[2,5-di-(4-(6-acryloyloxyhexyloxy)benzoyloxy)]benzoic acid, 0.14 g of l,2-bis-(3-hydroxyphenyl)ethyne, 0.012 g of DMAP, 1.4 ml of triethylamine and 0.23 g of mesyl chloride affording the desired compound as white pasty material. Yield 0.64 g.
This compound present the following thermotropic sequence: N Example 5:
A mixture is formulated consisting of:

50%

1,4-butanediol diacrylate; Aldrich 10%
To this mixture 500 p.p.m. inhibitor 2,6-di-/er/-butyl-4-methylphenol (BHT) is added to prevent premature polymerisation. For the radical photo-polymerisation we use 500 p.p.m. initiator: IRGACURE™ 369 (commercially available from Ciba Geigy, Basle, Switzerland). These mixture were solved in anisole with a ratio of 20 : 80.
After stirring at room temperature, this mixture were spin-coated on a glass plate with an orientation layer on top to form a layer of ca. 800 nm. This film is then dried at 80°C for 1 or 2 minutes and photo-polymerised by irradiation with UV light using Mercury lamp for 5 minutes at room temperature in a N2-atmosphere.
The film shows well oriented nematic mesophase with exclusion of any defects. In addition this film exhibits a great tilt angle w.r.t. to plane, as shown by ellipsometric measurements.

CLAIM
A compound of formula

A5-MG3—A6 wherein;
A1 to. A" each independently represent hydrogen; an optionally-substituted
methyl group; or an optionally-substituted hydrocarbon group of 2 to 80 C-aloms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another;
B1 and B2 each independently represent a single bond, an oxygen atom or
an optionally-substituted hydrocarbon group of 1 to 80 C-atoms,
; in which one or more C-atoms may be replaced by a heteroatom,
in such a way that oxygen atoms are not linked to one another;
MG1 and MG"1 each independently represent an optionally-substituted aliphatic
group with 1 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom, in such a way that oxygen atoms are not linked to one another; or an optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring system, with 1 to 80 C-atoms;
MG2 represents a group comprising at least two and up to four
optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring systems, with 1 to 80 C-atoms, wherein, when MG2 represents a group comprising four optionally-substituted

ring systems, at least three of" the ring systems aic aliened in between IJ and tt";
nl and n2 are each independently 1 or 2, where "nl = 2" (or "n2 = 2")
indicates the presence of two separate linkages via the groups 13" (or the groups B2) between the groups MG1 and MG2 (or MG2 and MG3); and
n3 is a positive integer up to 1000;
with the proviso that:
when A3 and A"1 both represent hydrogen, then both MG1 and MG1 represent an araliphalie group with 1 to 80 C-atorus, in which one or more C-atoms may be replaced by a heteroatom, or an optionally-substituted aromatic or non-aromatic carbocyciic or heterocyclic ring system, with 1 to 80"C-atoms; and at least two of A1, A2, A" and A6 each independently represent an optionally-substituted hydrocarbon group of 3 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom;
when A1, A2, A" and A6 all represent hydrogen, then A"1 and A"1 both represent an optionally-substituted hydrocarbon group of 3 to 80 C-atoms, in which one or more C-atoms may be replaced by a heteroatom; and
when MG2 represents a group comprising two or three
i optionally-substituted ring systems, then neither of A3 and A4
includes an aromatic ring.
2. A compound as claimed in claim 1, wherein at least one of A1 lo A*" includes a
polymeiisable group.

3. A compound as claimed in claim 2, wherein each or any of the groups A1 to A6
is selected from a residue of formula (II):
P-(Sp")u-(X,)11- (II)
wherein:
P is VvfdYogen w a YwvtymeirHsaWe. g,TO\vp aetettesl ftwfi £TO\ips coTrrprisVng
CII2=CW-, CU2=W-0-, CM2=CW-COO-, CIb=C(Ph)-COO-,
CIl2=CM-COO-Ph-, CH2=CW-CO-NH-, CH2=C(Ph)-CONH-,
CIl2=C(COOR>CU2-COG)-, Cll2=CII-0, Clb-CU-OOC-, (Ph)-CH=CH-, CFl3-C=N-(CII2),„r, HO-, JIS-, MO-(CII2)m3-, HS-(CI!2W, HO(CII2)m,COO-, HS(CHa)m3COO-, MWN-, MOC(O)-, CH2=CH-Ph-(0)n,,

HWcPcH- , U^)V-CH==CH- or a^\--CH==COO-
wherein:
i i
W ., represents II, F, CI, Br or I or a Ci_5 alkyl group;
m3 is an integer having « value of from 1 to 0;
i i m4 is on integer having a value of 0 or 1,
■ I !
i i .
\ [
1 ...;{ I"
R represents a C,_5 alkyl group; and
..! " ! ■ , "I ! : \ R" . represents a.Qi-s alkyl group, methoxy, cyano, F, CI, Br or 1;
Sp ,„ ^represents an optionally-substituted Ci_2o alkylene group, in which one or more , C-aU\\ws,vwav V«. rcpUiced. hy a UeAeraaUxm/,

k1 is an integer having a value of from 0 It) 4;
X" represents -O, -S-, -Nil-, N(C113)-, -Cll(Oll)-, -CO-, -CI l2(CO)-, -SO,
* -CH2(SO)-, -SO2-, -CH2(S02)-, -COO-, -OCO-, -OCO-0-, -S-CO-, -CO-S-, -SOO-, -0S0-, -SOS-, -CI I2-CH2-, -OCH2-, -CH2O-, -C1-1=CI 1-, or -OC-; and
I1 is an integer having a value of 0 or 1;
in which the term Ph denotes phcnylene and the term (Ph) denotes phenyl;
with the proviso that at least one of the groups A1 to Af" is not a hydrogen atom.
4. A compound as clainicd in claim 3, wherein A1 to A6 each independently
represent a group of formula (111):
P2-Sp5-X4- (111);
wherein:
X4 represents -0-, -CO-, -COO-, -OCO-, -C=C-, or a single bond,
especially -O-, -COO-, -OCO- or single bond;
Sp" represents a C^2o straight-chain alkylene group, especially ethylene,
1 propylene, butylcnc, pentylcne, hexylene, heptylcne, oclylenc, nonylene, decylenc, undecylene, or dodecylene; and
P2 represents hydrogen, CI12=CWS- or Cll2=CW5-(CO)v20-?
wherein:
%
Ws represents 11, CH3, F, CI, Br or 1; and

v2 is (I or 1
5. A compound as claimed in any preceding claim, wherein B1 and/or B2
comprises a group of formula (IV):
(X2)l2-(Sp2)k2 -(X3),3 (IV)
wherein:
Sp" represents a C|_2o alkylene group;*
X2andX3 each independently represent -O-, -S-, -Nil-, N(CII3)-, -CH(OII)-,
-co-, -ci i2(co)-, -so-, -cn2(so)-, -SO2-, -cn2(so2)-, -coo-, -oco-,
-OCO-0-, -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH2-CH2-, -OCH2-, -CH20-, -CM=CI I-, -CsC- or a single bond;
k2 is an integer, having a value of() or 1;
t2 and t3 are integers, each independently having a value of 0 or 1;
with the proviso that oxygen atoms are not linked one to another.
6. A compound as claimed in claim 5, wherein:
X2andX3 each independently represent -0-, -CO-, -COO-, -OCO-, -CsC-, or a single bond; and
Sp2 represents a C1-20 straight-chain alkylene group.
7. : A compound as claimed in claim 6, wherein X" and X3 each independently
represent -O-, -COO-, -OCO- or a single bond.

A compound as claimed in claim 6 or claim 7, wherein Sp2 represents ethylene,
propylene, butylenc, pcnlylene, hexylcne, heptylene, octylene, nonylene, decylcne, undecylene or dodecylcne
9- A compound as claimed in any preceding claim, wherein MG2 and at least one
of MG1 and MG3 represents a mesogenic group comprising at least two optionally-substituted aromatic or non-aromatic carbocyclic or heterocyclic ring systems.
10. A compound as claimed in any preceding claim, wherein:
MG represents a mesogenic group comprising 2 to A aromatic or non-aromatic carbocyclic or heterocyclic ring systems and optionally up to 3 bridging groups; and
at least one of MG1 and MG3 represent a mesogenic group comprising 1 to 4 aromatic or. non-aromatic carbocyclic or heterocyclic ring systems and optionally up to 3 bridging groups.
11. A compound as claimed in claim 10, wherein one or more of MG1, MG2 and MG represents a mesogenic group selected from the meanings of formulae V:

in which:
C toC are in each case independently optionally-substituted non-aromatic,
aromatic, carbocyclic or heterocyclic groups;
Z loZ are independently from each other -COO-, -OCO-, -CH2-CH2-
-OCH2-, -CH2O-, -CH=CH-, -C=C-, -CH=CI-l-COO-, -OCO-CH=CH-or a single bond; and

al, u2 and a.3 are independently inicgcr.s 0 to 3, such thai a I -I- a2 ) a3 3.
12. A compound as claimed in claim 1 1, wherein C to C4 are selected from:

N

with:
L. being -CH3, -COCM3, -NO?, CN, or halogen
ul being 0, 1,2, 3, or 4,
u2 being 0, I, 2, or 3, and
u3 being 0, 1, or 2.
13. A compound as claimed in claim 12, wlierein C1 to C4 are selected from cyclo-hexylene, phenylcne, naphlhylene or phenanthrylene.
14. A compound as claimed in any preceding claim, wherein A1 and A- are identical.
15. A compound as claimed in any preceding claim, wherein A-s and A6 arc

identical. -

16. A compound as claimed in any preceding claim, wherein A" — MG.1 —A2 and A5—MQ-3—A6) arc identical.
17. A compound as claimed in any preceding claim, wherein A3 and A4 are identical.
18. A compound as claimed in any preceding claim, wherein nl, n2 and n3 equal 1 and B1 and B2 arc identical.
19. A liquid crystalline mixture comprising at least one compound as claimed in any one of claims 1 to 18.
20. A polymer network comprising at least one compound as claimed in any one of claims 1 lo 18.
21. A polymer network as claimed in claim 20, essentially consisting of: i) at least one chiral or/and achiral mesogenic polymerisable compound; ii) at least one "staircase" compound of formula 1; and
iii) an initiator.
22. A polymer network as claimed in claim 21 further comprising one or more further polymerisable compounds, stabilisers and/or dyes.
23. A liquid crystalline polymer film comprising a compound as claimed in any one of claims 1 to 18.
24 A liquid crystalline polymer film obtainable by polymerisation of a liquid crystalline mixture as claimed in claim 19.

25. A process for the preparation of a liquid crystalline polymer film as claimed
in claim 24 comprising the steps of:
(a) forming the polymerisable liquid crystalline mixture according to claim 19 into a thin film preferably on a substrate; and
(b) subsequent curing of this film, preferably by means of UV light.

26. An optical or electro-optical component containing a liquid crystalline polymer film as claimed in claim 24.
27. Method of making a compound of formula (I) according to any of the claims 1 to 18, comprising the steps of:
(a) preparing, preferentially, first elements A"-MG-A2, A3 - MG - A4 AND
A5-MG3-A6 and
(b) subsequently, joining by means of second elements (B1) n1 and (B2) ,l2.
precursors of which second elements preferably form part of said first
elements.
28. Method of making a liquid crystalline mixture according to claim 19, wherein a compound of formula (I) according to any of the claims 1 to 18 is admixed with an additional mesogenic component, which is miscible with said compound of formula (I).
29. Method of making a polymer network according to any of the claims 20 - 22, wherein a compound of formula (I) according to any of the claims 1 to 18 is used, and wherein preferentially, I) at least one chiral or / and achiral mesogenic polymerisable compound, ii) at least one "staircase" compound of formula(l), and iii) an initiator are copolymerised to form the polymer network.
30. Method of making a liquid crystalline polymer film according to any of claims 23 - 24 or of making an optical or electro-optical component according to claim 26, wherein a film comprising a compound of formula (I) according to any of the claims 1 to 18 is formed on a substrate and subsequently polymerized and cross-linked.
Dated this 27th day of September, 2001.
FOR ROLIC AG BY their Agent
(MANISH SAURASTRI) KRISHNA SAURASTRI

Documents:

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in-pct-2001-51-mum-cancelled pages(27-10-2005).pdf

in-pct-2001-51-mum-claims(granted)-(27-10-2005).doc

in-pct-2001-51-mum-claims(granted)-(27-10-2005).pdf

in-pct-2001-51-mum-correspondence(27-10-2005).pdf

in-pct-2001-51-mum-correspondence(ipo)-(12-10-2006).pdf

in-pct-2001-51-mum-form 1(11-1-2001).pdf

in-pct-2001-51-mum-form 19(27-1-2004).pdf

in-pct-2001-51-mum-form 1a(22-6-2004).pdf

in-pct-2001-51-mum-form 2(granted)-(27-10-2005).doc

in-pct-2001-51-mum-form 2(granted)-(27-10-2005).pdf

in-pct-2001-51-mum-form 3(11-1-2001).pdf

in-pct-2001-51-mum-form 3(22-6-2004).pdf

in-pct-2001-51-mum-form 5(11-1-2001).pdf

in-pct-2001-51-mum-form 5(22-6-2001).pdf

in-pct-2001-51-mum-form-pct-ipea-409(11-1-2001).pdf

in-pct-2001-51-mum-form-pct-isa-210(11-1-2001).pdf

in-pct-2001-51-mum-petition under rule137(22-6-2004).pdf

in-pct-2001-51-mum-petition under rule138(22-6-2004).pdf

in-pct-2001-51-mum-power of attorney(11-1-2001).pdf

in-pct-2001-51-mum-power of attorney(22-6-2004).pdf

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Patent Number

211428

Indian Patent Application Number

IN/PCT/2001/00051/MUM

PG Journal Number

45/2007

Publication Date

09-Nov-2007

Grant Date

29-Oct-2007

Date of Filing

11-Jan-2001

Name of Patentee

ROLIC AG

Applicant Address

CHAMERSTRASSE 50, 6301 ZUG.

Inventors:

#	Inventor's Name	Inventor's Address
1	CARSTEN BENECKE	VIERTHAUEN 9, 79576 WEIL AM RHEIN.
2	ZOUBAIR MOHAMMED CHERKAOUI	DURRENMATTWEG 9, 4123 ALLSCHWIL, SWITZERLAND.

PCT International Classification Number

C07C 69/92, C09K 19/20, C09K 19/34

PCT International Application Number

PCT/IB99/01419

PCT International Filing date

1999-08-09

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	9817272.9	1998-08-07	U.K.