Liquid crystal compounds

Abstract

The invention relates to novel polymerizable liquid crystals of formula (I), ##STR00001##
to LCP mixtures comprising these compounds and to their uses for optical and electro-optical devices.

Claims

1. A compound of formula (I) ##STR00026## wherein the ring A is an unsubstituted or substituted phenylene group, naphthalene group or biphenylene group, AA.sup.1 is selected from the groups (a), (b) and (c): ##STR00027## AA.sup.2 is selected from the groups (a), (b), (c), (d) and (e): ##STR00028## wherein AA.sup.1 and AA.sup.2 are independently from each other unsubstituted or substituted with one or two substituents selected from the group consisting of F, Cl, Br, I, CN, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.1-C.sub.6alkoxy and C.sub.1-C.sub.6alkenyloxy, Q.sup.1 is an unsubstituted or substituted homocyclic or heterocyclic group, or Q.sup.1 is selected from unsubstituted or substituted groups of formulae (Ia), (Ib), (Ic) and (Id):
COOSP.sup.2BB(Ia),
OCOSP.sup.2BB(Ib),
COSP.sup.2BB(Ic) and
OSP.sup.2BB(Id), with the proviso that the substituents of Q.sup.1 are selected from the group consisting of F, Cl, Br, I, CN, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.1-C.sub.6alkoxy and C.sub.1-C.sub.6alkenyloxy; and with the proviso that if the ring A is a naphthalene group Q.sup.1 has the above given meaning or is hydrogen; SP.sup.1, SP.sup.2 and SP.sup.3 independently from each other represents a single bond or a spacer group of the formula (CH.sub.2) p- in which p is an integer of 1 to 18 and in which one, two, three or four CH.sub.2 groups are unreplaced or replaced by a group selected from the group consisting of CHCH, O, S, CO, COO, CONR, OCOO, OCONR, NR, CONR, OCOO, OCONR, wherein R is selected from the group consisting of hydrogen, a C.sub.1-C.sub.6 alkyl group and a C.sub.1-C.sub.6 alkenyl group; with the proviso that the spacer group does not contain two adjacent heteroatoms; n is 0 or 1, BP is a polymerizable group or F, Cl, Br, I, CN, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.1-C.sub.6alkoxy or C.sub.1-C.sub.6alkenyloxy, P.sup.1 is a polymerizable group, with the proviso that if BP and P.sup.1 are polymerizable groups, they are identical or different; BB is hydrogen or a group of formula (II) ##STR00029## in which A and B independently represent an unsubstituted or substituted six membered homocyclic or heterocyclic group or a naphthalene group; C is selected from the group consisting of a five and six membered homocyclic or heterocyclic group or a naphthalene group; n.sup.1 and n.sup.2 are 0 or 1 with the proviso that firstly 1n.sup.1+n.sup.22 and secondly, when C is a naphthalene group 0n.sup.1+n.sup.22; Z.sup.1 is selected from the group consisting of O, S, COO, OOC, CO, CONR, NRCO, OCOO, OCONR, NRCOO and a single bond; in which R is selected from the group consisting of hydrogen, a C.sub.1-C.sub.6 alkyl group and a C.sub.1-C.sub.6 alkenyl group; with the proviso that the SP.sup.2Z.sup.1 group does not contain two adjacent heteroatoms; Z.sup.2 and Z.sup.3 are independently from each other selected from the group consisting of single bond, COO, OOC, CH.sub.2CH.sub.2, CH.sub.2O, OCH.sub.2, CHCH, CC, (CH.sub.2).sub.4 and (CH.sub.2).sub.3O; R.sup.1 is selected from the group consisting of H, CN, COR, COOR, OCOR, CONRR, NRCOR, OCOOR, OCONRR, NRCOOR, F, Cl, I, CF.sub.3, OCF.sub.3, OR, in which R is selected from the group consisting of hydrogen, a C.sub.1-C.sub.6 alkyl group and a C.sub.1-C.sub.6 alkenyl group, and R is selected from the group consisting of hydrogen, a C.sub.1-18alkyl group and a C.sub.4-18alkenyl group with the double bond at 3-position or higher.

2. A compound according to claim 1, wherein the polymerizable groups of BP and P.sup.1 independently from each other are preferably selected from the group consisting of CH.sub.2C(Ph)-, CH.sub.2CWCOO, CH.sub.2CHCOO-Ph-, CH.sub.2CWCONH, CH.sub.2CHO, CH.sub.2CHOOC, Ph-CHCH, CH.sub.2CH-Ph-, CH.sub.2CH-Ph-O, R.sub.6-Ph-CHCHCOO, R.sub.6OOCCHCH-Ph-O and 2-W-epoxyethyl, in which W represents hydrogen, chloride, aryl or a C.sub.1-C.sub.6alkyl, R.sub.6 represents a C.sub.1-C.sub.6alkyl with the proviso that when R.sub.6 is attached to an aryl group it may also represent hydrogen or a C.sub.1-C.sub.6alkoxy.

3. A compound according to claim 1, in which SP.sup.1 and SP.sup.3 each independently from each other represents a single bond or a spacer group of the formula (CH.sub.2)p- in which p is an integer of 1 to 12, and in which one CH.sub.2 group is unreplaced or replaced by a group selected from the group consisting of O or S; and SP.sup.2 represents a single bond or a spacer group of the formula (CH.sub.2)p- in which p is an integer of 1 to 12, preferably an integer from 1 to 10, and in which one CH.sub.2 group is unreplaced or replaced by a group selected from the group consisting of O or S.

4. A compound according to claim 1, in which BB is hydrogen or a group of formula (II) ##STR00030## in which A and B independently represent an unsubstituted or substituted 1,4-phenylene group or naphthalene group; C is unsubstituted or substituted 1,4-phenylene group or naphthalene group; n.sup.1 and n.sup.2 are 0 or 1 with the proviso that firstly 1n.sup.1+n.sup.22 and secondly, when C is a naphthalene group 0n.sup.1+n.sup.22; with the proviso that the SP.sup.2Z.sup.1 group does not contain two adjacent heteroatoms; Z.sup.2 and Z.sup.3 are independently selected from the group consisting of a single bond, COO and OOC; R.sup.1 is selected from the group consisting of H, CN and I.

5. A compound according to claim 1, in which BP is a polymerizable group, or C.sub.1-C.sub.4alkyl, I or CN.

6. A compound according to claim 1, in which n is 1, BP is a polymerizable group.

7. A LCP mixture comprising the compound of formula (I) according to claim 1.

8. A LCP network comprising a compound according to claim 1.

9. A method comprising use of a compound according to claim 1, in the manufacture of an optical or an electro-optical device.

10. An optical or electro-optical device including a compound according to claim 1.

11. A LCP network comprising a mixture according to claim 7 in cross-linked or polymerised form.

12. A method comprising using a mixture according to claim 7 in the manufacture of an optical or an electro-optical device.

13. An optical or electro-optical device including a mixture according to claim 7.

14. An optical or electro-optical device including a network according to claim 8.

15. A compound according to claim 3, in which in which SP.sup.1 and SP.sup.3 each independently from each other represents a single bond or a spacer group of the formula (CH.sub.2)p- in which p is an integer from 1 to 6, and in which one CH.sub.2 group is unreplaced or replaced by a group selected from the group consisting of O or S; and SP.sup.2 represents a single bond or a spacer group of the formula (CH.sub.2)p- in which p is an integer of 1 to 12, and in which one CH.sub.2 group is unreplaced or replaced by a group selected from the group consisting of O or S.

16. A compound according to claim 3, in which in which SP.sup.1 and SP.sup.3 each independently from each other represents a single bond or a spacer group of the formula (CH.sub.2)p- in which p is an integer of 1 to 12, and in which one CH.sub.2 group is unreplaced or replaced by a group selected from the group consisting of O or S; and SP.sup.2 represents a single bond or a spacer group of the formula (CH.sub.2)p- in which p is an integer from 1 to 10, and in which one CH.sub.2 group is unreplaced or replaced by a group selected from the group consisting of O or S.

17. A compound according to claim 3, in which in which SP.sup.1 and SP.sup.3 each independently from each other represents a single bond or a spacer group of the formula (CH.sub.2)p- in which p is an integer from 1 to 6, and in which one CH.sub.2 group is unreplaced or replaced by a group selected from the group consisting of O or S; and SP.sup.2 represents a single bond or a spacer group of the formula (CH.sub.2)p- in which p is an integer from 1 to 10, and in which one CH.sub.2 group is unreplaced or replaced by a group selected from the group consisting of O or S.

Description

EXAMPLES

Definitions Used in the Examples

(1) .sup.1H NMR: .sup.1H nuclear magnetic resonance spectroscopy DMSO-d.sub.6: dimethylsulfoxid deuterated 300 MHz: 300 MegaHertz m: multiplet, d: doublet, dd: doublet doublet, t: triplet, s: singulet DMF: dimethylformamide HCl: hydrochloric acid DBU: 2,3,4,6,7,8,9,10-Octahydropyrimidol[1,2-a]azepine THF: tetrahydrofuran Na.sub.2SO.sub.4: sodium sulfate Pd(PPh.sub.3).sub.2Cl.sub.2: Bis(triphenylphosphine)palladium dichloride DCC: N,N-Dicyclohexylcarbodiimide DMAP: 4-Dimethylaminopyridine CH.sub.2Cl.sub.2: dichloromethane THF: tetrahydrofuran NMP: N-Methyl-2-pyrrolidon CuI: Copper iodide MgSO.sub.4: magnesium sulfate

(2) In the following examples, the thermotropic phases are abbreviated as follow: T.sub.(CrN): transition temperature from crystal phase to nematic phase T.sub.(NI): transition temperature from nematic phase to isotropic phase

Example 1: Preparation of 6-(4-iodophenoxy)-hexan-1-ol Compound 1

(3) A mixture of 4-iodophenol (40.0 g, 0.182 mol) and potassium carbonate (32.6 g, 0.236 mol) in 600 ml of DMF is heated to 90 C. 6-chlorohexan-1-ol (37.2 g, 0.272 mol) in 120 ml of DMF and potassium iodide (3.0 g, 0.018 mol) are added dropwise. The mixture is then stirred at 90 C. for 12 h. Then, the solution is cooled down to room temperature and poured onto 2.5 L of ice water containing 1.3 equivalent of HCl. The precipitate is filtered off, washed two times with 2 L of water and dried under vacuum at 40 C. to give the title compound (56.67 g, 0.177 mol) as an off-white powder.

Example 2: Preparation of 6-[4-(2-trimethylsilylethynyl])phenoxyl-hexan-1-ol Compound 2

(4) 6-(4-iodophenoxy)-hexan-1-ol (24.09 g, 0.075 mol), Pd(PPh.sub.3).sub.2Cl.sub.2 (2.64 g, 3.76 mmol), copper iodide (1.43 g, 7.52 mmol) and triphenylphosphine (1.97 g, 7.52 mmol) are suspended in 100 ml of triethylamine (100 ml). Trimethylsilylacetylene (11.08 g, 0.113 mol) is added dropwise. The resulting mixture is then heated to 60 C. for 5 h before cooling it to 25 C. A filtration over Hyflo is followed by evaporation of the solvents. The residue is dissolved in ethyl acetate and washed with acidic H.sub.2O, brine and then dried over Na.sub.2SO.sub.4. The residue is purified by flash chromatography over silica gel using a 1:1 mixture of heptane/ethyl acetate to provide the title compound (19.53 g, 0.067 mol) as a brown oil.

Example 3: Preparation of 6-(4-ethynylphenoxy)-hexan-1-ol Compound 3

(5) To a solution of 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol (19.53 g, 0.067 mol) in 500 ml of methanol, potassium carbonate (19.13 g, 0.134 mol) is added. The reaction mixture is stirred at ambient temperature for 2 h. After evaporation of the solvent, 1 L of H.sub.2O is added and the suspension is extracted with ethyl acetate. A purification by flash chromatography over silica gel using a 1:1 mixture of heptane/ethyl acetate provides the title compound (9.55 g, 0.044 mol) as a brown oil which crystalizes after some minutes.

Example 4: Preparation of methyl 2,5-dihydroxybenzoate Compound 4

(6) To a solution of 2,5-dihydroxybenzoic acid (10.0 g, 0.065 mol) in 50 ml of methanol, 5 ml of concentrated sulfuric acid is added, leading to an increase of the temperature to 40 C. The mixture is refluxed for 24 h and allowed then to cool to 25 C. The solution is poured onto H.sub.2O and extracted with ethyl acetate. The organic layers are dried over Na.sub.2SO.sub.4 and filtered off. The solution is concentrated under vacuum to give the title compound (10.7 g, 0.063 mol) as a white powder.

Example 5: Preparation of methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate Compound 5

(7) Methyl 2,5-dihydroxybenzoate (8.4 g, 0.05 mol), 4-iodobenzoic acid (24.8 g, 0.1 mol) and DMAP (1.22 g, 0.01 mol) are suspended in 450 ml of dichloromethane. DCC (25.8 g, 0.125 mol) dissolved in 80 ml of dichloromethane is added dropwise. After complete addition, the suspension is stirred at 25 C. for 3 h. The suspension is then filtered off over Hyflo, which is washed with 250 ml of dichloromethane. The solution is concentrated under vacuum and a purification by recrystallization in 250 ml of methanol gives the title compound (21.55 g, 0.034 mol) as a white powder.

Example 6: Preparation of methyl 5-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy-2-(4-iodobenzoyl)oxy-benzoate Compound 6

(8) Under N.sub.2 atmosphere, 6-(4-ethynylphenoxy)-hexan-1-ol (4.17 g, 0.019 mol), methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate (12.0 g, 0.019 mol), Pd(PPh.sub.3).sub.2Cl.sub.2 (0.67 g, 0.95 mmol), copper iodide (0.36 g, 1.9 mmol) and triphenylphosphine (0.5 g, 1.9 mmol) are suspended in 200 ml of triethylamine. The mixture is stirred at 40 C. for 5 h. After cooling down to 25 C., 6-(4-ethynylphenoxy)-hexan-1-ol (0.83 g, 0.004 mol) is added. After stirring 24 h, the reaction mixture is poured onto 500 ml of H.sub.2O and acidified with HCl to pH 1. The precipitate is filtered off and the residue dissolved with 1 L of ethyl acetate. The solution is passed through Hyflo and then concentrated under vacuum. A purification by flash chromatography over silica gel using a 1:2 mixture of heptane/ethyl acetate results in the title compound (3.5 g, 0.005 mol) as a dark orange solid.

Example 7: Preparation of methyl 2-(4-iodobenzoyl)oxy-5-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy-benzoate Compound 7

(9) ##STR00009##

(10) To a solution of methyl 5-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy-2-(4-iodobenzoyl)oxy-benzoate (3.5 g, 0.005 mol) in 150 ml of tetrahydrofuran cooled to 0 C., triethylamine (1.47 g, 0.014 mol) is added. 2-Propenoyl chloride (2.2 g, 0.024 mol) is added dropwise to the reaction mixture followed by DMAP (0.122 g, 0.97 mmol). After stirring 4 h at 0-5 C., the mixture is allowed to warm to 25 C. The solution is then diluted with acetonitrile and a purification by flash chromatography over silica gel using ethyl acetate affords a brown residue. The former oil is suspended in acetonitrile. The obtained precipitate is filtered off and dried under vacuo to result in the title compound (1.12 g, 1.45 mmol) as a grey solid.

(11) Liquid crystal phase Transition: Compound 7 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 82 C. (T.sub.(CrN)) and the isotropic phase appears to be above 184 C. (T.sub.(NI)).

(12) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.16 (m, 2H), 8.03 (m, 2H), 7.90 (m, 3H), 7.74 (m, 3H), 7.55 (m, 3H), 7.01 (m, 3H), 6.32 (m, 1H), 6.17 (m, 1H), 5.93 (m, 1H), 4.12 (t, 2H), 4.02 (t, 2H), 3.69 (s, 3H), 1.74 (m, 2H), 1.64 (m, 2H), 1.42 (m, 4H).

Example 8: Preparation of methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate Compound 8

(13) Under N.sub.2 atmosphere, 6-(4-ethynylphenoxy)-hexan-1-ol (17.46 g, 0.08 mol), methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate (25.13 g, 0.04 mol), Pd(PPh.sub.3).sub.2Cl.sub.2 (2.81 g, 0.004 mol), copper iodide (1.52 g, 0.008 mol) and triphenylphosphine (2.1 g, 0.008 mol) are suspended in 500 ml of triethylamine. The reaction mixture is stirred at 60 C. for 12 h and then cooled to room temperature. The obtained precipitate is filtered off and purified by flash chromatography over silica gel using a 1:2 mixture of heptane/ethyl acetate to give the title compound (10.41 g, 0.013 mol) as a yellow solid.

Example 9: Preparation of methyl 2,5-bis[[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]-ethynyl]benzoyl]oxy]benzoate Compound 9

(14) ##STR00010##

(15) Methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate (10.0 g, 0.012 mol) is suspended in 400 ml of tetrahydrofuran and triethylamine (5.15 g, 0.051 mol) is added. The mixture is cooled down to 0 C. and then 2-propenoyl chloride (6.9 g, 0.076 mol) is added dropwise followed by DMAP (0.311 g, 2.5 mmol). The reaction mixture is stirred at 0-5 C. for 5 h. The suspension is then filtered off and the resulting organic solution is concentrated under vacuum to give a yellow oil. The former residue is suspended in ethyl acetate and cooled to 5 C. for 20 h. The precipitate is filtered off and a purification by flash chromatography over silica gel using ethyl acetate provides the title compound (0.72 g, 0.78 mmol) as a yellow solid.

(16) Liquid crystal phase Transition: Compound 9 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 76 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(17) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.17 (m, 4H), 7.95 (d, 1H), 7.74 (m, 5H), 7.56 (m, 5H), 7.01 (m, 4H), 6.32 (m, 2H), 6.17 (m, 2H), 5.93 (m, 2H), 4.12 (t, 4H), 4.02 (m, 4H), 3.71 (s, 3H), 1.74 (m, 4H), 1.62 (m, 4H), 1.41 (m, 8H).

Example 10: Preparation of 3-(4-iodophenoxy)-propan-1-ol Compound 10

(18) The title compound 10 is prepared according to the process described in example 1 for compound 1 with the proviso that 6-chlorohexanol is replaced by 3-chloropropanol.

Example 11: Preparation of 3-(4-bromophenyl-sulfanylpropan-1-ol Compound 11

(19) The title compound 11 is prepared according to the process described in example 1 for compound 1 with the proviso that 6-chlorohexanol and 4-iodophenol are respectively replaced by 3-chloropropanol and 4-bromobenzenethiol.

Example 12: Preparation of 6-(4-bromophenyl)-sulfanylhexan-1-ol Compound 12

(20) The title compound 12 is prepared according to the process described in example 1 for compound 1 with the proviso that 4-iodophenol is replaced by 4-bromobenzenethiol.

Example 13: Preparation of 6-[(6-bromo-2-naphthyl)oxy]-hexan-1-ol Compound 13

(21) The title compound 13 is prepared according to the process described in example 1 for compound 1 with the proviso that 4-iodophenol is replaced by 6-bromonaphthalen-2-ol.

Example 14: Preparation of 3-[(6-bromo-2-naphthyl)oxy]-propan-1-ol, Compound 14

(22) The title compound 14 is prepared according to the process described in example 1 for compound 1 with the proviso that 6-chlorohexanol is replaced by 3-chloropropanol and 4-iodophenol is replaced by 6-bromonaphthalen-2-ol.

Example 15: Preparation of 3-[4-(2-trimethylsilylethynyl)phenoxy]-propan-1-ol Compound 15

(23) The title compound 15 is prepared according to the process described in example 2 for compound 2 with the proviso that 6-(4-iodophenoxy)-hexan-1-ol is replaced by 3-(4-iodophenoxy)-propan-1-ol compound 10.

Example 16: Preparation of 3-[4-(2-trimethylsilylethynyl)phenyl]-sulfanylpropan-1-ol Compound 16

(24) The title compound 16 is prepared according to the process described in example 2 for compound 2 with the proviso that 6-(4-iodophenoxy)-hexan-1-ol is replaced by 3-(4-bromophenyl)-sulfanylpropan-1-ol compound 11.

Example 17: Preparation of 6-[4-(2-trimethylsilylethynyl)phenyl]-sulfanylhexan-1-ol Compound 17

(25) The title compound 17 is prepared according to the process described in example 2 for compound 2 with the proviso that 6-(4-iodophenoxy)-hexan-1-ol is replaced by 6-(4-bromophenyl)-sulfanylhexan-1-ol compound 12.

Example 18: Preparation of 6-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-hexan-1-ol Compound 18

(26) The title compound 18 is prepared according to the process described in example 2 for compound 2 with the proviso that 6-(4-iodophenoxy)-hexan-1-ol is replaced by 6-[(6-bromo-2-naphthyl)oxy]-hexan-1-ol compound 13.

Example 19: Preparation of 3-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-propan-1-ol Compound 19

(27) The title compound 19 is prepared according to the process described in example 2 for compound 2 with the proviso that 6-(4-iodophenoxy)-hexan-1-ol is replaced by 3-[(6-bromo-2-naphthyl)oxy]-propan-1-ol compound 14.

Example 20: Preparation of 3-(4-ethynylphenoxy)-propan-1-ol Compound 20

(28) The title compound 20 is prepared according to the process described in example 3 for compound 3 with the proviso that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced by 3-[4-(2-trimethylsilylethynyl)phenoxy]-propan-1-ol compound 15.

Example 21: Preparation of 3-(4-ethynylphenyl)-sulfanylpropan-1-ol, Compound 21

(29) The title compound 21 is prepared according to the process described in example 3 for compound 3 with the proviso that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced by 3-[4-(2-trimethylsilylethynyl)phenyl]-sulfanylpropan-1-ol compound 16.

Example 22: Preparation of 6-(4-ethynylphenyl)-sulfanylhexan-1-ol, Compound 22

(30) The title compound 22 is prepared according to the process described in example 3 for compound 3 with the proviso that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced by 6-[4-(2-trimethylsilylethynyl)phenyl]-sulfanylhexan-1-ol compound 17.

Example 23: Preparation of 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol, Compound 23

(31) The title compound 23 is prepared according to the process described in example 3 for compound 3 with the proviso that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced by 6-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-hexan-1-ol compound 18.

Example 24: Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]-propan-1-ol, Compound 24

(32) The title compound 24 is prepared according to the process described in example 3 for compound 3 with the proviso that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced by 3-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-propan-1-ol compound 19.

Example 25: Preparation of ethyl 2,5-dihydroxybenzoate, Compound 25

(33) The title compound 25 is prepared according to the process described in example 4 for compound 4 with the proviso that methanol is replaced by ethanol.

Example 26: Preparation of buthyl 2,5-dihydroxybenzoate, Compound 26

(34) The title compound 26 is prepared according to the process described in example 4 for compound 4 with the proviso that methanol is replaced by butanol.

Example 27: Preparation of 2-(1,3-benzothiazol-2-yl)benzene-1,4-diol, Compound 27

(35) To a suspension of 2-aminobenzenethiol (24.0 g, 0.192 mol) in 1.5 L of H.sub.2O, 2,5-dihydroxybenzaldehyde (26.52 g, 0.192 mol) is added dropwise. The reaction mixture is heated to 110 C. for 8 h. After cooling down to 25 C., the obtained precipitate is filtered off and purified by flash chromatography over silica gel using a 1:1 mixture of heptane/ethyl acetate to give the title compound (13.97 g, 0.057 mol) as a yellow solid.

Example 28: Preparation of 4-[4-(11-hydroxyundecoxy)phenyl]-benzonitrile, Compound 28

(36) The title compound 28 is prepared according to the process described in example 1 for compound 1 with the proviso that 6-chlorohexanol and 4-iodophenol are respectively replaced by 11-bromoundecanol and by 4-(4-hydroxyphenyl)benzonitrile.

Example 29: Preparation of 4-[4-(10-hydroxydecoxy)phenyl]-benzonitrile, Compound 29

(37) The title compound 29 is prepared according to the process described in example 1 for compound 1 with the proviso that 6-chlorohexanol and 4-iodophenol are respectively replaced by 10-bromodecanol and by 4-(4-hydroxyphenyl)benzonitrile.

Example 30: Preparation of 4-[4-(8-hydroxyoctoxy)phenyl]-benzonitrile, Compound 30

(38) The title compound 30 is prepared according to the process described in example 1 for compound 1 with the proviso that 6-chlorohexanol and 4-iodophenol are respectively replaced by 8-bromooctanol and by 4-(4-hydroxyphenyl)benzonitrile.

Example 31: Preparation of 11-[4-(4-cyanophenyl)phenoxy]undecyl methanesulfonate Compound 31

(39) To a suspension of 4-[4-(11-hydroxyundecoxy)phenyl]-benzonitrile (60.6 g, 0.165 mol) in 500 ml of THF, triethylamine (50.6 g, 0.495 mol) is added dropwise. The reaction is cooled down to 0 C. Methanesulfonylchloride (22.8 g, 0.198 mol) is slowly added and the mixture is stirred at 0-5 C. for 2 h. After filtration over Hyflo, the solvent is evaporated under vacuum to provide the title compound (72.0 g, 0.162 mol) as an off-white solid.

Example 32: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl methanesulfonate Compound 32

(40) The title compound 32 is prepared according to the process described in example 31 for compound 31 with the proviso that 4-[4-(11-hydroxyundecoxy)phenyl]-benzonitrile is replaced by 4-[4-(10-hydroxydecoxy)phenyl]-benzonitrile compound 29.

Example 33: Preparation of 8-[4-(4-cyanophenyl)phenoxy]octyl methanesulfonate Compound 33

(41) The title compound 33 is prepared according to the process described in example 31 for compound 31 with the proviso that 4-[4-(11-hydroxyundecoxy)phenyl]-benzonitrile is replaced by 4-[4-(8-hydroxyoctoxy)phenyl]-benzonitrile compound 30.

Example 34: Preparation of 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-dihydroxybenzoate, Compound 34

(42) To a solution of 2,5-dihydroxybenzoic acid (27.2 g, 0.173 mol) in 180 ml of DMF, DBU (26.4 g, 0.170 mol) is dropwise added. The solution is stirred 0.5 h at room temperature. Afterwards, sodium iodide (7.45 g, 0.050 mol) and a solution of 11-[4-(4-cyanophenyl)phenoxy]undecyl methanesulfonate (72.0 g, 0.162 mol) in 180 ml of DMF are slowly added. The resulting reaction mixture is heated to 70 C. for 16 h. After filtration over Hyflo, the filtrate is added to 2 L of ice water. The obtained precipitate is filtered off and purified by recrystallization in 600 ml of acetonitrile to give the title compound (61.8 g, 0.123 mol) as a white powder.

Example 35: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-dihydroxybenzoate, Compound 35

(43) The title compound 35 is prepared according to the process described in example 34 for compound 34 with the proviso that 11-[4-(4-cyanophenyl)phenoxy]undecyl methanesulfonate is replaced by 10-[4-(4-cyanophenyl)phenoxy]decyl methanesulfonate compound 32.

Example 36: Preparation of 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-dihydroxybenzoate Compound 36

(44) The title compound 35 is prepared according to the process described in example 34 for compound 34 with the proviso that 11-[4-(4-cyanophenyl)phenoxy]undecyl methanesulfonate is replaced by 8-[4-(4-cyanophenyl)phenoxy]oct methanesulfonate compound 33.

Example 37: Preparation of ethyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, Compound 37

(45) The title compound 37 is prepared according to the process described in example 5 for compound 5 with the proviso that methyl 2,5-dihydroxybenzoate is replaced by ethyl 2,5-dihydroxybenzoate compound 25.

Example 38: Preparation of butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, Compound 38

(46) The title compound 38 is prepared according to the process described in example 5 for compound 5 with the proviso that methyl 2,5-dihydroxybenzoate is replaced by butyl 2,5-dihydroxybenzoate compound 26.

Example 39: Preparation of [3-(1,3-benzothiazol-2-yl)-4-(4-iodobenzoyl)oxy-phenyl]4-iodobenzoate, Compound 39

(47) The title compound 39 is prepared according to the process described in example 5 for compound 5 with the proviso that methyl 2,5-dihydroxybenzoate is replaced by 2-(1,3-benzothiazol-2-yl)benzene-1,4-diol compound 27.

Example 40: Preparation of [4-(4-iodobenzoyl)oxy-1-naphthyl]4-iodobenzoate Compound 40

(48) The title compound 40 is prepared according to the process described in example 5 for compound 5 with the proviso that methyl 2,5-dihydroxybenzoate is replaced by naphthalene-1,4-diol.

Example 41: Preparation of 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, Compound 41

(49) The title compound 41 is prepared according to the process described in example 5 for compound 5 with the proviso that methyl 2,5-dihydroxybenzoate is replaced by 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-dihydroxybenzoate compound 34.

Example 42: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, Compound 42

(50) The title compound 42 is prepared according to the process described in example 5 for compound 5 with the proviso that methyl 2,5-dihydroxybenzoate is replaced by 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-dihydroxybenzoate compound 35.

Example 43: Preparation of 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, Compound 43

(51) The title compound 43 is prepared according to the process described in example 5 for compound 5 with the proviso that methyl 2,5-dihydroxybenzoate is replaced by 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-dihydroxybenzoate compound 36.

Example 44: Preparation of ethyl 2-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate, Compound 44

(52) The title compound 44 is prepared according to the process described in example 6 for compound 6 with the proviso that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by ethyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 37.

Example 45: Preparation of ethyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate, Compound 45

(53) The title compound 45 is prepared according to the process described in example 8 for compound 8 with the proviso that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by ethyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 37.

Example 46: Preparation of butyl 2-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate, Compound 46

(54) The title compound 46 is prepared according to the process described in example 6 for compound 6 with the proviso that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

Example 47: Preparation of butyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate, Compound 47

(55) The title compound 47 is prepared according to the process described in example 8 for compound 8 with the proviso that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

Example 48: Preparation of butyl 2-[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate, Compound 48

(56) The title compound 48 is prepared according to the process described in example 6 for compound 6 with the proviso that 6-(4-ethynylphenoxy)-hexan-1-ol is replaced by 3-(4-ethynylphenoxy)-propan-1-ol compound 20 and methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

Example 49: Preparation of butyl 2,5-bis[[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate, Compound 49

(57) The title compound 49 is prepared according to the process described in example 8 for compound 8 with the proviso that 6-(4-ethynylphenoxy)-hexan-1-ol is replaced by 3-(4-ethynylphenoxy)-propan-1-ol compound 20 and methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

Example 50: Preparation of methyl 2,5-bis[[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]-ethynyl]benzoyl]oxy]benzoate, Compound 50

(58) The title compound 50 is prepared according to the process described in example 8 for compound 8 with the proviso that 6-(4-ethynylphenoxy)-hexan-1-ol is replaced by 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol compound 23.

Example 51: Preparation of butyl 2,5-bis[[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]-ethynyl]benzoyl]oxy]benzoate, Compound 51

(59) The title compound 51 is prepared according to the process described in example 8 for compound 8 with the proviso that 6-(4-ethynylphenoxy)-hexan-1-ol is replaced by 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol compound 23 and methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

Example 52: Preparation of methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexylsulfanyl)phenyl]-ethynyl]benzoyl]oxy]benzoate, Compound 52

(60) The title compound 52 is prepared according to the process described in example 8 for compound 8 with the proviso that 6-(4-ethynylphenoxy)-hexan-1-ol is replaced by 6-(4-ethynylphenyl)-sulfanylhexan-1-ol compound 22.

Example 53: Preparation of butyl 2,5-bis[[4-[2-[4-(3-hydroxypropylsulfanyl)phenyl]-ethynyl]benzoyl]oxy]benzoate, Compound 53

(61) The title compound 53 is prepared according to the process described in example 8 for compound 8 with the proviso that 6-(4-ethynylphenoxy)-hexan-1-ol is replaced by 3-(4-ethynylphenyl)-sulfanylpropan-1-ol compound 21 and methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

Example 54: Preparation of [3-(1,3-benzothiazol-2-yl)-4-[4-[2-[4-(6-hydroxyhexoxy)-phenyl]ethynyl]benzoyl]oxy-phenyl]-4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoate, compound 54

(62) The title compound 54 is prepared according to the process described in example 8 for compound 8 with the proviso that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by [3-(1,3-benzothiazol-2-yl)-4-(4-iodobenzoyl)oxy-phenyl]4-iodobenzoate compound 39.

Example 55: Preparation of [4-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy-1-naphthyl]4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoate, Compound 55

(63) The title compound 55 is prepared according to the process described in example 8 for compound 8 with the proviso that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by [4-(4-iodobenzoyl)oxy-1-naphthyl]4-iodobenzoate compound 40.

Example 56: Preparation of 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate, Compound 56

(64) The title compound 56 is prepared according to the process described in example 8 for compound 8 with the proviso that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 41.

Example 57: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate, Compound 57

(65) The title compound 57 is prepared according to the process described in example 8 for compound 8 with the proviso that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 42.

Example 58: Preparation of 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate, Compound 58

(66) The title compound 58 is prepared according to the process described in example 8 for compound 8 with the proviso that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 43.

Example 59: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]benzoyl]oxy]benzoate, Compound 59

(67) The title compound 59 is prepared according to the process described in example 8 for compound 8 with the proviso that 6-(4-ethynylphenoxy)-hexan-1-ol is replaced by 3-(4-ethynylphenoxy)-propan-1-ol compound 20 and methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced by 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 42.

Example 60: Preparation of ethyl 5-(4-iodobenzoyl)oxy-2-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy-benzoate, Compound 60

(68) The title compound 60 is prepared according to the process described in example 7 for compound 7 with the proviso that 5-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy-2-(4-iodobenzoyl)oxy-benzoate is replaced by ethyl 2-[4-[2-[4-(6-hydroxyhexoxy)phenyl]-ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate compound 44.

Example 61: Preparation of ethyl 2,5-bis[[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]-ethynyl]benzoyl]oxy]benzoate, Compound 61

(69) ##STR00011##

(70) The title compound 61 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by ethyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate compound 45. Purification by flash chromatography over silica gel using ethyl acetate provides the title compound (3.18 g, 3.41 mmol, 47%) as an off-white solid.

(71) Liquid crystal phase Transition: Compound 61 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 70 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(72) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.18 (m, 4H), 7.95 (d, 1H), 7.74 (m, 5H), 7.55 (m, 5H), 7.01 (m, 4H), 6.32 (m, 2H), 6.17 (m, 2H), 5.93 (m, 2H), 4.12 (m, 6H), 4.02 (m, 4H), 1.74 (m, 4H), 1.65 (m, 4H), 1.42 (m, 8H), 1.04 (t, 3H).

Example 62: Preparation of butyl 5-(4-iodobenzoyl)oxy-2-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy-benzoate, Compound 62

(73) ##STR00012##

(74) The title compound 62 is prepared according to the process described in example 7 for compound 7 with the proviso that 5-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy-2-(4-iodobenzoyl)oxy-benzoate is replaced by butyl 2-[4-[2-[4-(6-hydroxyhexoxy)phenyl]-ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate compound 46. A purification by flash chromatography over silica gel using ethyl acetate affords a brown oily residue which is suspended in acetonitrile. The obtained precipitate is filtered off and dried under vacuo to result in the title compound (1.53 g, 1.87 mmol, 94%) as a grey solid.

(75) Liquid crystal phase Transition: Compound 62 was observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increased, the crystalline phase changed into nematic phase at 80 C. (T.sub.(CrN)) and the isotropic phase appeared to be above 140 C. (T.sub.(NI)).

(76) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.16 (m, 2H), 8.03 (m, 2H), 7.90 (m, 3H), 7.75 (m, 2H), 7.70 (m, 1H), 7.54 (m, 3H), 7.01 (m, 2H), 6.32 (m, 1H), 6.17 (m, 1H), 5.93 (m, 1H), 4.12 (m, 4H), 4.01 (t, 2H), 1.74 (m, 2H), 1.68 (m, 2H), 1.45 (m, 6H), 1.18 (m, 2H), 0.73 (t, 3H).

Example 63: Preparation of butyl 2,5-bis[[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]-ethynyl]benzoyl]oxy]benzoate Compound 63

(77) ##STR00013##

(78) The title compound 63 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by butyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate compound 47. A purification by flash chromatography over silica gel using ethyl acetate provides the title compound (0.64 g, 0.67 mmol, 57%) as a white solid.

(79) Liquid crystal phase Transition: Compound 63 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 117 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(80) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.17 (m, 4H), 7.93 (d, 1H), 7.74 (m, 5H), 7.56 (m, 5H), 7.01 (m, 4H), 6.32 (m, 2H), 6.17 (m, 2H), 5.93 (m, 2H), 4.12 (m, 6H), 4.02 (m, 4H), 1.74 (m, 4H), 1.64 (m, 4H), 1.41 (m, 10H), 1.22 (m, 2H), 0.73 (t, 3H).

Example 64: Preparation of butyl 5-(4-iodobenzoyl)oxy-2-[4-[2-[4-(3-prop-2-enoyloxypropoxy)phenyl]ethynyl]benzoyl]oxy-benzoate, Compound 64

(81) ##STR00014##

(82) The title compound 64 is prepared according to the process described in example 7 for compound 7 with the proviso that 5-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy-2-(4-iodobenzoyl)oxy-benzoate is replaced by butyl 2-[4-[2-[4-(3-hydroxypropoxy)phenyl]-ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate compound 48. A purification by flash chromatography over silica gel using ethyl acetate affords a brown oily residue which is suspended in acetonitrile. The obtained precipitate is filtered off and dried under vacuo to result in the title compound (1.18 g, 1.53 mmol, 44%) as a brownish solid.

(83) Liquid crystal phase Transition: Compound 64 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 85 C. (T.sub.(CrN)) and the isotropic phase appears to be above 115 C. (T.sub.(NI)).

(84) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.17 (m, 2H), 8.03 (m, 2H), 7.91 (m, 3H), 7.74 (m, 3H), 7.55 (m, 3H), 7.02 (m, 2H), 6.34 (m, 1H), 6.19 (m, 1H), 5.95 (m, 1H), 4.28 (t, 2H), 4.12 (m, 4H), 2.10 (m, 2H), 1.19 (m, 4H), 0.72 (t, 3H).

Example 65: Preparation of butyl 2,5-bis[[4-[2-[4-(3-prop-2-enoyloxypropoxy)phenyl]-ethynyl]benzoyl]oxy]benzoate, Compound 65

(85) ##STR00015##

(86) The title compound 65 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by butyl 2,5-bis[[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate compound 49. A purification by flash chromatography over silica gel using ethyl acetate provides the title compound (4.9 g, 5.6 mmol, 71%) as a white solid.

(87) Liquid crystal phase Transition: Compound 65 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 115 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(88) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.17 (m, 4H), 7.93 (d, 1H), 7.75 (m, 5H), 7.56 (m, 5H), 7.03 (m, 4H), 6.34 (m, 2H), 6.19 (m, 2H), 5.95 (m, 2H), 4.28 (t, 4H), 4.12 (m, 6H), 2.10 (m, 4H), 1.38 (m, 2H), 1.21 (m, 2H), 0.73 (t, 3H).

Example 66: Preparation of methyl 2,5-bis[[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]benzoyl]oxy]benzoate, Compound 66

(89) ##STR00016##

(90) The title compound 66 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by methyl 2,5-bis[[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]-ethynyl]benzoyl]oxy]benzoate compound 50.

(91) Liquid crystal phase Transition: Compound 66 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 164 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(92) .sup.1H NMR (300 MHz) in CD.sub.2Cl.sub.2-d.sub.2: 8.22 (m, 4H), 8.04 (m, 3H), 7.94 (m, 2H), 7.75 (m, 7H), 7.56 (m, 2H), 7.35 (d, 1H), 7.17 (m, 4H), 6.41 (m, 2H), 6.13 (m, 2H), 5.86 (m, 2H), 4.13 (m, 8H), 3.76 (s, 3H), 1.86 (m, 2H), 1.73 (m, 2H), 1.53 (m, 4H).

Example 67: Preparation of butyl 2,5-bis[[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]benzoyl]oxy]benzoate, Compound 67

(93) ##STR00017##

(94) The title compound 67 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by butyl 2,5-bis[[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]-ethynyl]benzoyl]oxy]benzoate compound 51.

(95) Liquid crystal phase Transition: Compound 67 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 120 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(96) .sup.1H NMR (300 MHz) in CD.sub.2Cl.sub.2-d.sub.2: 8.23 (m, 4H), 8.03 (m, 3H), 7.93 (m, 2H), 7.74 (m, 7H), 7.55 (m, 2H), 7.34 (m, 1H), 7.18 (m, 4H), 6.37 (m, 2H), 6.12 (m, 2H), 5.81 (m, 2H), 4.15 (m, 10H), 1.86 (m, 4H), 1.73 (m, 4H), 1.52 (m, 10H), 1.28 (m, 2H), 0.83 (t, 3H).

Example 69: Preparation of butyl 2,5-bis[[4-[2-[4-(3-prop-2-enoyloxypropylsulfanyl)-phenyl]ethynyl]benzoyl]oxy]benzoate, Compound 69

(97) ##STR00018##

(98) The title compound 69 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by butyl 2,5-bis[[4-[2-[4-(3-hydroxypropylsulfanyl)phenyl]-ethynyl]benzoyl]oxy]benzoate compound 53. A purification by flash chromatography over silica gel using ethyl acetate provides the title compound (1.05 g, 1.15 mmol, 57%) as a white sticky solid.

(99) Liquid crystal phase Transition: Compound 69 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 110 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(100) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.18 (m, 4H), 7.93 (d, 1H), 7.74 (m, 5H), 7.57 (m, 5H), 7.40 (m, 4H), 6.35 (m, 2H), 6.19 (m, 2H), 5.96 (m, 2H), 4.22 (m, 4H), 4.13 (m, 2H), 3.12 (m, 4H), 1.96 (m, 4H), 1.40 (m, 2H), 1.19 (m, 2H), 0.73 (t, 3H).

Example 70: Preparation of [3-(1,3-benzothiazol-2-yl)-4-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy-phenyl]4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoate, compound 70

(101) ##STR00019##

(102) The title compound 70 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by [3-(1,3-benzothiazol-2-yl)-4-[4-[2-[4-(6-hydroxyhexoxy)-phenyl]ethynyl]benzoyl]oxy-phenyl]-4-[2-[4-(6-hydroxy-hexoxy)phenyl]ethynyl]-benzoate compound 54. A purification by flash chromatography over silica gel using ethyl acetate provides the title compound (2.23 g, 2.24 mmol) as an off-white solid.

(103) Liquid crystal phase Transition: Compound 70 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 135 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(104) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.29 (m, 4H), 8.12 (d, 1H), 7.89 (d, 1H), 7.80 (m, 4H), 7.71 (m, 2H), 7.50 (m, 6H), 6.32 (m, 2H), 6.19 (m, 2H), 5.92 (m, 2H), 4.13 (m, 4H), 4.02 (m, 4H), 1.74 (m, 4H), 1.68 (m, 4H), 1.45 (m, 8H).

Example 71: Preparation of [4-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]-benzoyl]oxy-1-naphthyl]4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoate Compound 71

(105) ##STR00020##

(106) The title compound 71 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by [4-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy-1-naphthyl]4-[2-[4-(6-hydroxyhexoxy)phenyl]-ethynyl]benzoate compound 55. A purification by flash chromatography over silica gel using ethyl acetate provides the title compound (4.69 g, 5.16 mmol) as a grey solid.

(107) Liquid crystal phase Transition: Compound 71 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 177 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(108) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.30 (m, 3H), 8.06 (m, 2H), 7.98 (m, 2H), 7.80 (m, 4H), 7.68 (m, 2H), 7.58 (m, 5H), 7.02 (m, 4H), 6.33 (m, 2H), 6.17 (m, 2H), 5.93 (m, 2H), 4.12 (t, 4H), 4.03 (m, 4H), 1.74 (m, 4H), 1.65 (m, 4H), 1.43 (m, 8H).

Example 72: Preparation of 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-bis[[4-[2-[4-(6-Prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate Compound 72

(109) ##STR00021##

(110) The title compound 72 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]-oxy]benzoate compound 56.

(111) Liquid crystal phase Transition: Compound 72 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 105 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(112) .sup.1H NMR (300 MHz) in CD.sub.2Cl.sub.2-d.sub.2: 8.19 (m, 4H), 7.92 (d, 1H), 7.68 (m, 8H), 7.53 (m, 7H), 7.32 (d, 1H), 6.97 (m, 2H), 6.90 (m, 4H), 6.37 (m, 2H), 6.13 (m, 2H), 5.81 (m, 2H), 4.15 (m, 6H), 3.99 (m, 6H), 1.70 (m, 8H), 1.48 (m, 12H), 1.25 (m, 14H).

Example 73: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate, Compound 73

(113) ##STR00022##

(114) The title compound 73 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]-benzoate compound 57. A purification by flash chromatography over silica gel using ethyl acetate provides the title compound (3.24 g, 2.62 mmol) as a white solid.

(115) Liquid crystal phase Transition: Compound 73 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 125 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(116) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.18 (m, 4H), 7.92 (d, 1H), 7.84 (m, 4H), 7.75 (m, 4H), 7.68 (m, 2H), 7.55 (m, 5H), 6.99 (m, 7H), 6.32 (m, 2H), 6.17 (m, 2H), 5.93 (m, 2H), 4.10 (m, 6H), 4.02 (m, 2H), 3.95 (m, 4H), 1.66 (m, 8H), 1.27 (m, 24H).

Example 74: Preparation of 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-bis[[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate, Compound 74

(117) ##STR00023##

(118) The title compound 74 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]-benzoate compound 58. A purification by flash chromatography over silica gel using ethyl acetate provides the title compound (6.28 g, 5.19 mmol) as a white solid.

(119) Liquid crystal phase Transition: Compound 74 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 110 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(120) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.17 (m, 4H), 7.93 (d, 1H), 7.83 (m, 4H), 7.74 (m, 4H), 7.65 (m, 2H), 7.53 (m, 5H), 6.98 (m, 7H), 6.33 (m, 2H), 6.17 (m, 2H), 5.93 (m, 2H), 4.12 (m, 6H), 4.02 (m, 2H), 3.93 (m, 4H), 1.67 (m, 8H), 1.36 (m, 12H), 1.15 (m, 8H).

Example 75: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-[2-[4-(3-prop-2-enoyloxypropoxy)phenyl]ethynyl]benzoyl]oxy]benzoate, Compound 75

(121) ##STR00024##

(122) The title compound 75 is prepared according to the process described in example 9 for compound 9 with the proviso that methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate is replaced by 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]benzoyl]oxy]-benzoate compound 59. A purification by flash chromatography over silica gel using ethyl acetate provides the title compound (3.41 g, 2.95 mmol) as a white solid.

(123) Liquid crystal phase Transition: Compound 9 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 116 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(124) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.17 (m, 4H), 7.93 (d, 1H), 7.84 (m, 4H), 7.76 (m, 4H), 7.66 (m, 2H), 7.55 (m, 5H), 7.01 (m, 7H), 6.33 (m, 2H), 6.20 (m, 2H), 5.95 (m, 2H), 4.26 (m, 4H), 4.12 (m, 6H), 3.96 (m, 2H), 2.08 (m, 4H), 1.67 (m, 2H), 1.23 (m, 14H).

Example 76: Preparation of methyl 5-[4-[2-(4-cyanophenyl)ethynyl]benzoyl]oxy-2-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy-benzoate, Compound 76

(125) ##STR00025##

(126) 2-(4-Iodobenzoyl)oxy-5-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy-benzoate (1.0 g, 1.29 mmol), 4-ethynylbenzonitrile (0.2 g, 1.55 mmol), Pd(PPh.sub.3).sub.2Cl.sub.2 (0.05 g, 0.07 mmol), copper iodide (0.025 g, 0.13 mmol) and triphenylphosphine (0.034 g, 0.13 mmol) are suspended in 40 ml of triethylamine. The mixture is stirred at 40 C. for 5 h and after cooling to 25 C. poured onto ice water. The precipitation is filtered off and purified by flash chromatography over silica gel using a 2:1 mixture of heptane/ethyl acetate to give the title compound (0.25 g, 0.32 mmol) as a white solid.

(127) Liquid crystal phase Transition: Compound 76 is observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increases, the crystalline phase changes into nematic phase at 117 C. (T.sub.(CrN)) and the isotropic phase appears to be above 200 C. (T.sub.(NI)).

(128) .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.19 (m, 4H), 7.94 (m, 3H), 7.84 (m, 4H), 7.75 (m, 3H), 7.56 (m, 3H), 7.01 (m, 2H), 6.32 (m, 1H), 6.18 (m, 1H), 5.94 (m, 1H), 4.12 (t, 2H), 4.02 (t, 2H), 3.71 (s, 3H), 1.69 (m, 4H), 1.42 (m, 4H).

Example 77: Preparation of an Orientation Layer Using Photoalignment Materials

(129) A glass substrate is spin-coated with a Photoalignment Composition (3% solid content of a photoaligning material in cyclopentanone as described in the patent publication WO2012/085048: photoactive polymer materials use as orienting layer for liquid crystals). The film is dried at 180 C. for 10 min and the resulting film thickness is about 100 nm. Then, the film is exposed to aligning light, which is collimated and linearly polarized UV (LPUV) light (280-320 nm) with 500 mJ/cm.sup.2. The plane of polarization is 0 with regard to a reference edge on the substrate.

Example 78: Preparation of Optical Film from Compound 7

(130) A 15.0 w % solution is prepared by mixing the 14.775 w % compound 7, 0.150 w % of Irgacure369 (having the chemical structure of 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), 0.075 w % of Tinuvin123 (having the chemical structure of Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate) in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 1 to form a liquid crystal film. This film is dried at 180 C. for 5 min onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

(131) The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 79: Preparation of Optical Film from Compound 9

(132) A 15.0 w % solution is prepared by mixing the 14.775 w % compound 9, 0.150 w % of Irgacure 369, 0.075 w % of Tinuvin123 in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 1 to form a liquid crystal film. This film is dried at different temperatures for different amounts of time onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

(133) The resulting films exhibit a medium oriented nematic mesophase at room temperature.

Example 80: Preparation of Optical Film from Compound 61

(134) A 15.0 w % solution is prepared by mixing the 14.775 w % compound 61, 0.150 w % of Irgacure 369, 0.075 w % of Tinuvin123 in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 1 to form a liquid crystal film. This film is dried at 150 C. for 3 sec onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

(135) The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 81: Preparation of Optical Film from Compound 62

(136) A 15.0 w % solution is prepared by mixing the 14.775 w % compound 62, 0.150 w % of Irgacure 369, 0.075 w % of Tinuvin123 in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 1 to form a liquid crystal film. This film is dried at 130 C. for 3 min onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

(137) The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 82: Preparation of Optical Film from Compound 63

(138) A 15.0 w % solution is prepared by mixing the 14.775 w % compound 63, 0.150 w % of Irgacure 369, 0.075 w % of Tinuvin123 (from BASF) in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 1 to form a liquid crystal film. This film is dried at 180 C. for 3 sec onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

(139) The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 83: Preparation of Optical Film from Compound 64

(140) A 15.0 w % solution is prepared by mixing the 14.775 w % compound 64, 0.150 w % of Irgacure 369, 0.075 w % of Tinuvin123 in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 1 to form a liquid crystal film. This film is dried at 130 C. for 3 sec onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

(141) The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 84: Preparation of Optical Film from Compound 65

(142) A 15.0 w % solution is prepared by mixing the 14.775 w % compound 65, 0.150 w % of Irgacure 369, 0.075 w % of Tinuvin123 in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 1 to form a liquid crystal film. This film is dried at 180 C. for 5 sec onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

(143) The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 85: Preparation of Optical Film from Compound 69

(144) A 15.0 w % solution is prepared by mixing the 14.520 w % compound 69, 0.300 w % of Irgacure 369, 0.150 w % of Tinuvin123 and 0.030 w % of BYK378 (Polyether-modified polydimethylsiloxane from BYK used as surface additive) in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 1 to form a liquid crystal film. This film is dried at 120 C. for 1 min onto a temperature controlled hot plate. The sample is photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at 120 C. under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

(145) The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 86: Preparation of Optical Film from Compound 70

(146) A 13.0 w % solution is prepared by mixing the 12.584 w % compound 70, 0.260 w % of Irgacure 369, 0.130 w % of Tinuvin123 and 0.026 w % of BYK378 in 1,3-dioxolane and stirred thoroughly till the solid is completely dissolved at 80 C. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 1 to form a liquid crystal film. This film is dried at 120 C. for 2 min onto a temperature controlled hot plate. The sample is photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

(147) The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 87

(148) The retardation at 550 nm of the sample described in example 78, example 80, example 81, example 82, example 83, example 84, example 85, example 86 are measured with an Ellipsometer. The thicknesses of the samples are measured by a contact stylus profilometer. The birefringence (n) was obtained from the determined retardation and thickness values according to the formula (n=Retardation/Thickness). The values are listed in Table 1.

(149) TABLE-US-00001 TABLE 1 Thickness Retardation at Example [nm] 550 nm [nm] n at 550 nm 78 (compound 7) 585 30 176.1 0.31 0.01 80 (compound 61) 670 30 229.1 0.34 0.01 81 (compound 62) 465 30 124.8 0.27 0.02 82 (compound 63) 520 30 169.4 0.33 0.02 83 (compound 64) 390 30 113.1 0.29 0.02 84 (compound 65) 685 30 231.5 0.34 0.01 86 (compound 70) 1000 30 297.3 0.30 0.01

(150) The films of Example 78, 80, 82, 83, 84, 86 have high birefringence with values above 0.29. These new LCPs could be used for preparing phase retarder optical films as Quarter-Waveplate (QWP) and Half-Waveplate (HWP). A retarder transmits light and modifies its polarization state and is widely used in various display application or in security elements. The particularly high birefringence of these new LCPs leads to a significant thickness reduction of the retarder's films.

(151) As an example, Table 2 shows the required thickness to get a quarter waveplate (/4) retarder (QWP) and Half-Waveplate (/2) retarder (HWP) at 550 nm with the compounds 7, 61, 62, 63, 64, 65, 70 used in respectively example 78, 80, 81, 82, 83, 84 and 86.

(152) TABLE-US-00002 TABLE 2 Required Thickness for Required Thickness for Example QWP at 550 nm (nm) HWP at 550 nm (nm) 78 444 888 80 404 808 81 509 1018 82 417 834 83 474 948 84 404 808 86 458 916