Liquid crystal compounds

Abstract

The present invention relates to novel polymerizable liquid crystals of formula (I), LCP mixtures containing these compounds, and their use for optical and electro-optical devices. TIFF2024546732000033.tif35161

Description

[Technical field]

[0001] The present invention relates to laterally substituted curable liquid crystals (LCPs) having high optical anisotropy, and the use of such LCPs in the fabrication of substantially uniform or patterned films in which the alignment of the LCP molecules can be controlled.

[0002] In the display industry, optical LCP films are used to provide or enhance optical or electro-optical effects, for example for polarizers. As displays become thinner and thinner, the industry is demanding thinner optical LCP films that provide the desired optical or electro-optical effects, such as retardation films.

[0003] A retardation film is a type of optical element that changes the polarization state of light passing through it. When light passes through a phase retarder, its polarization direction changes due to the birefringence and thickness of the phase retarder. One of the biggest challenges in fabricating phase retarders is to fabricate high-performance films with a small cost. By using liquid crystals with high birefringence, the required retardation value can be achieved with a small amount of liquid crystal compound. LCP materials with high birefringence may provide a way to thin optical films, especially thin retardation films.

[0004] Therefore, the task of this invention was to explore new LCP materials with high birefringence applicable to optical films.

[0005] The first aspect of the present invention is a compound of formula (I) [ka] [In the formula, Ring A is an unsubstituted or substituted phenylene group, naphthalene group or biphenylene group, preferably, ring A is an unsubstituted or substituted 1,4-phenylene group, 2,6-naphthalene group, 1,4-naphthalene group, 1,5-naphthalene group or 4,4'-biphenylene group; more preferably, ring A is an unsubstituted or substituted 1,4-phenylene group or 1,4-naphthalene group; AA 1 is selected from the group of compounds: [ka] AA 2 is the following compound or is selected from the following group of compounds: [ka] Here, A.A. 1 and A.A. 2 are, independently of each other, unsubstituted or substituted with one or two substituents selected from the group consisting of F, Cl, Br, I, CN, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkoxy and C1-C6 alkenyloxy; Q 1 is an unsubstituted or substituted monocyclic or heterocyclic group, preferably selected from the group consisting of 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, 1,4-naphthalenediyl and 2,6-naphthalenediyl, benzofuran, benzothiazole and benzimidazole; more preferably, Q is 1 is selected from the group consisting of 1,4-phenylene, 1,4-naphthalenediyl, 2,6-naphthalenediyl, benzofuran, benzothiazole and benzimidazole; 1 is selected from benzofuran, benzothiazole, benzimidazole; or, among others, most preferred Q 1is a benzothiazole or benzimidazole; or Q 1 are represented by the formulas (Ia), (Ib), (Ic) and (Id): -COO-SP 2 -BB(Ia), -OCO-SP 2 -BB(Ib), -CO-SP 2 -BB(Ic) and -O-SP 2 Among the most preferred Q are selected from the group of unsubstituted or substituted compounds represented by the formula: 1 -COO-SP 2 -BB (Ia); However, as a condition, Q 1 the substituents are selected from the group consisting of F, Cl, Br, I, CN, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkoxy and C1-C6 alkenyloxy; and As a condition, if ring A is a naphthalene group, Q 1 has the meaning given above or is hydrogen; SP 1 , S.P. 2 and S.P. 3 represent, independently of one another, a single bond or a spacer group of formula -(CH2)p-, where p is an integer from 1 to 18, and one, two, three or four -CH2- groups are unreplaced or replaced by a group selected from the group consisting of -CH=CH-, -O-, -S-, -CO-, -COO-, -CONR'-, -OCOO-, -OCONR', -NR'-, -CONR'-, -OCOO-, -OCONR', where R' is selected from the group consisting of hydrogen, C1-C6 alkyl groups and C1-C6 alkenyl groups; with the proviso that the spacer group does not contain two adjacent heteroatoms; preferably SP 1 and S.P. 3each independently represents a single bond or a spacer group represented by the formula -(CH2)p-, where p is an integer from 1 to 12, preferably an integer from 1 to 6, and one -CH2- group is unsubstituted or is replaced by a group selected from the group consisting of -O- or -S-; preferably, SP 2 represents a single bond or a spacer group represented by the formula -(CH2)p-, where p is an integer from 1 to 12, preferably an integer from 1 to 10, and one -CH2- group is unsubstituted or is replaced by a group selected from the group consisting of -O- or -S-; n is 0 or 1, preferably 1; BP is a polymerizable group or F, Cl, Br, I, CN, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkoxy or C1-C6 alkenyloxy, preferably BP is CN, I or a polymerizable group; P 1 is a polymerizable group, However, as a condition, BP and P 1 are polymerizable groups, they may be the same or different; BB is hydrogen or a group represented by the formula (II) [ka] (In the formula, A and B independently represent an unsubstituted or substituted 6-membered monocyclic or heterocyclic group or a naphthalene group; C is selected from the group consisting of 5- and 6-membered monocyclic or heterocyclic groups or naphthalene groups; n 1 and n 2 is 0 or 1, with the first condition that 1≦n 1 +n 2 ≦2, and secondly, when C is a naphthalene group, 0≦n 1 +n 2 Preferably, n 1 is 1, and n 2 is 0; Z 1is selected from the group consisting of -O-, -S-, -COO-, -OOC-, -CO-, -CONR'-, -NR'CO-, -OCOO-, -OCONR'-, -NR'COO- and a single bond; R' is selected from the group consisting of hydrogen, C1-C6 alkyl groups, and C1-C6 alkenyl groups; preferably, Z 1 is -O-, -COO-, -OOC- or a single bond; However, as a condition, -SP 2 -Z 1 The - group shall not contain two adjacent heteroatoms; Z 2 and Z 3 are each independently selected from the group consisting of a single bond, -COO-, -OOC-, -CH2-CH2-, -CHO-, -OCH2-, -CH=CH-, -C≡C-, -(CH2)4- and -(CH2)3O-; preferably, Z 2 and Z 3 is independently selected from the group consisting of a single bond, -COO-, and -OOC-; R 1 is selected from the group consisting of H, -CN, -COR, -COOR, -OCOR, -CONR'R, -NR'COR, OCOOR, -OCONR'R, -NR'COOR, -F, -Cl, I, -CF3, -OCF3, -OR, preferably selected from the group consisting of H, -CN and I, where R' is selected from the group consisting of hydrogen, C1-C6 alkyl groups and C1-C6 alkenyl groups, R is selected from the group consisting of hydrogen, C1-C6 alkyl groups and C1-C6 alkenyl groups, 1-18 C with alkyl group and double bond at 3-position or higher 4-18 alkenyl groups, preferably the higher positions are 4, 5, 6, 7, 8, 9, and 10). is a compound represented by the formula: The present invention provides a compound, preferably a liquid crystal, represented by the formula:

[0006] Spacer group SP 1 , S.P. 2 and S.P. 3are each, independently of the other, unsubstituted or substituted by one or more fluorine or chlorine atoms. Spacer groups without any substituents are preferred.

[0007] The groups A and B are saturated, unsaturated alicyclic or aromatic groups. They are unsubstituted or substituted with one or two substituents selected from the group consisting of F, Cl, CN, lower alkyl, lower alkenyl, lower alkoxy and lower alkenyloxy. Preferably, the groups A and B each contain only one substituent. It is particularly preferred that the groups A and B do not contain any substituents.

[0008] The radicals A and B are preferably selected from the group consisting of 1,4-phenylene, biphenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene or trans-1,3-dioxane-2,5-diyl, bicyclohexylene, 1,4-naphthalenediyl and 2,6-naphthalenediyl. It is especially preferred that A and B are selected from the group consisting of 1,4-phenylene, trans-1,4-cyclohexylene and 2,6-naphthalenediyl.

[0009] The group C is a saturated, unsaturated alicyclic or aromatic group. It is optionally substituted with one or two substituents selected from the group consisting of F, Cl, CN, lower alkyl, lower alkenyl, lower alkoxy and lower alkenyloxy. It is preferred that the group C contains at most one substituent. It is especially preferred that the group C does not contain any substituents.

[0010] The group C is furan-2,4-diyl, furan-2,5-diyl, tetrahydrofuran-2,4-diyl, tetrahydrofuran-2,5-diyl, dioxolane-2,4-diyl, dioxolane-2,5-diyl, oxazole-2,4-diyl, oxazole-2,5-diyl, cyclopentane-1,3-diyl, cyclopentane-1,4-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, Preferably, C is selected from trans-1,4-cyclohexylene or dioxane-2,5-diyl, 1,4-naphthalenediyl, 1,3-naphthalenediyl, 1,5-naphthalenediyl, 1,6-naphthalenediyl, 1,7-naphthalenediyl, 2,3-naphthalenediyl, 2,4-naphthalenediyl, 2,5-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, and 2,8-naphthalenediyl. It is especially preferred that C is selected from the group consisting of furan-2,5-diyl, tetrahydrofuran-2,5-diyl, oxazole-2,5-diyl, 1,4-phenylene, trans-1,4-cyclohexylene, and 2,6-naphthalenediyl, and especially more preferred C is 1,4-phenylene.

[0011] BP and P 1 are each independently of one another and are preferably selected from the group consisting of CH2=C(Ph)-, CH2=CW-COO-, CH2=CH-COO-Ph-, CH2=CW-CO-NH-, CH2=CH-O-, CH2=CH-OOC-, Ph-CH=CH-, CH2=CH-Ph-, CH2=CH-Ph-O-, R6-Ph-CH=CH-COO-, R6-OOC-CH=CH-Ph-O- and 2-W-epoxyethyl, where W represents hydrogen, chloride, aryl or C1-C6 alkyl.

[0012] R6 represents C1-C6 alkyl, with the proviso that when R6 is attached to an aryl group, R6 may also represent hydrogen or C1-C6 alkoxy.

[0013] BP and P 1are, independently of one another, particularly preferably selected from the group consisting of CH2=CW-COO-, CH2=CH-O-, and CH2=CH-OOC-, where W represents hydrogen, chloride, aryl or C1-C6 alkyl, preferably hydrogen or C1-C6 alkyl.

[0014] The term "lower alkyl" refers to C 1-6 Examples of lower alkyl groups which may be present in the compounds of this invention include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like.

[0015] The term "lower alkenyl" refers to a C alkyl group in which the double bond is at position 2 or higher. 3-6 Examples of lower alkenyl groups which may be present in the compounds of the invention include 2-propenyl, 3-butenyl, 3-isopentenyl, 4-pentenyl, 5-hexenyl, 4-isohexenyl, and the like.

[0016] The term "lower alkoxy" refers to C 1-6 Examples of lower alkoxy groups which may be present in the compounds of this invention include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and the like.

[0017] The term "alkenyloxy" refers to a C alkyl group having a double bond at or above the 2-position. 3-6 Examples of lower alkenyloxy groups which may be present in the compounds of the invention include 2-propenyloxy, 3-butenyloxy, 4-pentenyloxy, 5-hexenyloxy, and the like.

[0018] Starting materials are either commercially available or readily prepared and are well known to those skilled in the art.

[0019] Preferably, the present invention relates to a method for producing ... composition comprising the steps of: Ring A is an unsubstituted or substituted phenylene group, preferably a 1,4-phenylene group, or a naphthalene group; AA 1 is selected from the group of compounds: [ka] AA 2 is selected from the group consisting of C1-C4 alkylene, alicyclic groups, or the following compounds: [ka] Q 1 is an unsubstituted or substituted group selected from the group consisting of benzofuran, benzothiazole and benzimidazole; preferably, Q 1 is benzothiazole or benzimidazole, or Q 1 Formula (Ia): -COO-SP 2 -BB group, However, as a condition, Q 1 is selected from the group consisting of F, Cl, Br, I, CN, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkoxy and C1-C6 alkenyloxy; with the proviso that if ring A is a naphthalene group, then Q 1 has the meaning given above or is hydrogen; SP 1 and S.P. 3 represent, independently of each other, a single bond or a spacer group of formula -(CH2)p-, where p is an integer from 1 to 12, preferably an integer from 1 to 6, and one -CH2- group is unsubstituted or replaced by a group selected from the group consisting of -O- or -S-; and SP 2represents a single bond or a spacer group represented by the formula -(CH2)p-, where p is an integer from 1 to 12, preferably an integer from 1 to 10, and one -CH2- group is unsubstituted or is replaced by a group selected from the group consisting of -O- or -S-; n is 0 or 1, and BP is a polymerizable group, or C1-C4 alkyl, I, or -CN; P 1 is a polymerizable group, wherein the polymerizable group is selected from the group consisting of CH2=C(Ph)-, CH2=CW-COO-, CH2=CH-COO-Ph-, CH2=CW-CO-NH-, CH2=CH-O-, CH2=CH-OOC-, Ph-CH=CH-, CH2=CH-Ph-, CH2=CH-Ph-O-, R6-Ph-CH=CH-COO-, R6-OOC-CH=CH-Ph-O- and 2-W-epoxyethyl, wherein W represents hydrogen, chloride, aryl or C1-C6 alkyl, preferably W is hydrogen; more preferably the polymerizable group is CH2=CW-COO-, wherein W represents hydrogen, R6 represents C1-C6 alkyl, with the proviso that when R6 is attached to an aryl group, R6 may also represent hydrogen or C1-C6 alkoxy; However, as a condition, BP and P 1 are polymerizable groups, they may be the same or different, and BB is hydrogen or a group represented by the formula (II) [ka] (In the formula, A and B independently represent an unsubstituted or substituted 1,4-phenylene or naphthalene group; preferably, A and B independently represent an unsubstituted or substituted 1,4-phenylene group; C is an unsubstituted or substituted 1,4-phenylene or naphthalene group; preferably, C is an unsubstituted or substituted 1,4-phenylene group; n 1 and n 2 is 0 or 1, with the first condition that 1≦n 1 +n 2 ≦2, and secondly, when C is a naphthalene group, 0≦n 1 +n 2 Preferably, n 1 is 1, and n 2 is 0, Z 1 is selected from the group consisting of -O-, -COO-, -OOC-, -CO- and a single bond; However, as a condition, -SP 2 -Z 1 The - group shall not contain two adjacent heteroatoms; Z 2 and Z 3 is independently selected from the group consisting of a single bond, -COO- and -OOC-; preferably, Z 2 and Z 3 are independently a single bond, and R 1 is selected from the group consisting of H, -CN and I, preferably R 1 is -CN) The present invention provides a compound, preferably a liquid crystal, of formula (I), which is a compound of the formula:

[0020] More preferably, the present invention relates to a method for producing 1 and A.A. 2 , S.P. 1 and S.P. 1 and P 1 and BP is the same or AA 2 is 1,4-phenylene, n is 0, and rings A and AA 1 , Q 1 , S.P. 1 , S.P. 2 , S.P. 3 , B.P. and P. 1 has the meaning as given above, and preferably BP represents a halogen I.

[0021] LCP material as used within the context of this application shall mean a liquid crystal material comprising liquid crystal monomers and / or liquid crystal oligomers and / or liquid crystal polymers and / or crosslinked liquid crystals. When the liquid crystal material comprises liquid crystal monomers, such monomers can typically be polymerized after anisotropy is created in the LCP material, for example by contact with an alignment layer. Polymerization can be initiated by heat treatment or by exposure to actinic radiation, preferably including UV light. The LCP material may comprise only one type of liquid crystal compound, but may also comprise additional polymerizable and / or non-polymerizable compounds, not all of which need to be liquid crystal compounds. Furthermore, the LCP material may contain antioxidants, initiators, such as photoinitiators, accelerators, dyes, inhibitors, activators, fillers, chain transfer inhibitors, pigments, antistatic agents, flame retardants, thickeners, thixotropic agents, surfactants, viscosity modifiers, extender oils, plasticizers, tackifiers, catalysts, sensitizers, stabilizers, such as phenol derivatives, such as 4-ethoxyphenol or 2,6-di-tert-butyl-4-methyl-phenol (BHT), leveling agents; dispersing agents; polymer binders and / or monomeric compounds which can be converted into polymer binders by polymerization, or, in the case of emulsion paints and printing inks, dispersing aids, as disclosed in U.S. Pat. No. 5,798,147; hydrophobizing agents, adhesives, flow improvers, defoamers, degassing agents, diluents, adjuvants, colorants, dyes and pigments, cure inhibitors, such as hydroquinone, p-tert.-butylcatechol; 2,6-di It may contain additives including, but not limited to, tert.-butyl-p-methylphenol; phenothiazine; N-phenyl-2-naphthylamine; or photoalignable monomers or oligomers or polymers as described in EP 1 090 325 B, chiral additives, isotropic or anisotropic fluorescent and / or non-fluorescent dyes, especially dichroic dyes.

[0022] It will be understood that the compounds of the present invention may be used in the preparation of LCP mixtures. Such mixtures may be prepared by mixing the compounds of formula (I) with one or more additional components. Organic solvents may be used in the preparation of these mixtures.

[0023] Thus, a second aspect of the present invention provides an LCP mixture comprising a compound of formula (I) and one or more additional components. The LCP mixture may also include a suitable organic solvent.

[0024] The one or more additional components present in the LCP mixture may be further compounds of formula (I), other mesogenic compounds, compounds compatible with the mesogenic molecular structure, or chiral dopants for inducing helical pitch. The LCP mixture may also include a suitable organic solvent.

[0025] Examples of solvents that may be used in the preparation of such liquid crystal mixtures include, but are not limited to, acetone, cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone, N-vinylpyrrolidone, N,N-dimethylacetamide (AN), tetrahydrofuran (THF), 1,3-dioxolane (DXG), ethylene glycol, dipropylene glycol, butyl carbitol, ethyl carbitol acetate, dipropylene glycol monomethyl ether, ethyl acetate (EA), 1-methoxy-2-propanol acetate (MPA), gamma-butyrolactone (BL), propylene glycol monoacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dimethyl sulfoxide (DMSO).

[0026] Most preferred are cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), ethyl acetate (EA), 1-methoxy-2-propanol acetate (MPA), 1,3-dioxolane (DXG), and dimethyl sulfoxide (DMSO).

[0027] The dichroic dye refers to a dye whose absorbance varies between the long axis direction and the short axis direction of the molecule. The dichroic dye preferably absorbs visible light. Examples of the dichroic dye include azo dyes, acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, and anthraquinone dyes. These dichroic dyes can be used individually or in combination. The amount of the dichroic dye used relative to 100 parts by weight of the liquid crystal mixture is 0.01 parts by weight to 40 parts by weight, preferably 0.05 parts by weight to 15 parts by weight.

[0028] The compounds of the present invention may also be used in forming an LCP layer by casting an LCP compound according to the first aspect of the invention or an LCP mixture according to the third aspect of the invention onto a substrate.

[0029] Thus, a third aspect of the invention is a method of forming an LCP network, preferably an LCP film, comprising the steps of: forming an LCP layer comprising a compound of formula (I) or preferably an LCP mixture comprising a compound of formula (I); and Polymerizing the LCP layer The present invention provides a method comprising:

[0030] The present invention also includes, in a fourth aspect, a crosslinked LCP network comprising a compound of formula (I) or an LCP mixture in crosslinked form.

[0031] The LCP network, preferably the LCP film, has a birefringence preferably in the range of 0.27-0.45 (±0.01-0.02), more preferably in the range of 0.28-0.40 (±0.01), most preferably in the range of 0.30-0.40 (±0.01), especially most preferably in the range of 0.31-0.38 (±0.01). The birefringence (Δn) was obtained from the determined retardation (here at 550 nm) and thickness values ​​by measurement with an ellipsometer according to the formula (Δn=retardation / thickness). The thickness of the sample is measured by a stylus step gauge.

[0032] A fifth aspect of the present invention provides the use of a compound of formula (I) in the preparation of an optical or electro-optical device. Also included in this aspect of the present invention is the use of a liquid crystal mixture in the preparation of an optical or electro-optical device.

[0033] A sixth aspect of the present invention provides an optical or electro-optical device comprising a compound of formula (I) in crosslinked form. Also included in this aspect of the present invention is an optical or electro-optical device comprising an LCP liquid crystal mixture according to the third aspect of the present invention in crosslinked form.

[0034] The LCP mixture can be applied onto a support. The support can be rigid or flexible and can have any form or shape. For example, the support can be an object with a complex surface. In principle, the support can be made of any material. Preferably, the support comprises plastic, glass or metal, or is a silicon wafer. If the support is flexible, the support is preferably a plastic or metal foil. Preferably, the surface of the support is flat. In some applications, the support can include local surface structures, such as microstructures, such as microlenses or microprisms, or structures that show abrupt changes in shape, such as rectangular structures. Preferably, the support is transparent.

[0035] The support may move during deposition of the LCP mixture. For example, a layer of the LCP mixture may be produced in a continuous roll-to-roll process by depositing the material composition on a moving flexible foil, preferably made of plastic or metal. The resulting film may then be wound onto a roll together with the support foil, or the film may be peeled off from the support, and the film may then be wound as a free-standing film without the support.

[0036] The support may have additional layers, such as organic layers, dielectric layers or metal layers. The layers may have various functions, for example, the organic layer may be coated as a primer layer to enhance the compatibility of the coated material with the support. The metal layer may be used as an electrode when used in electro-optical devices, such as displays, or may have the function of a reflector. The support may also be an optical element or device with a specific function, such as a substrate for an LCD, which may include thin film transistors, electrodes or color filters. In another example, the support is a device that includes an OLED layer structure. The support may also be a retarder film, a polarizer, such as a polarizing film or sheet polarizer, a reflective polarizer, such as the commercially available Vikuity™ DBEF film.

[0037] The LCP mixture can be applied to the support by any suitable method, such as extrusion, casting, molding, 2D or 3D printing or coating. Suitable coating methods are, for example, spin coating, blade coating, knife coating, kiss roll coating, die coating, dipping, brushing, casting with a bar, roller coating, flow coating, wire coating, spray coating, dip coating, curtain coating, air knife coating, reverse roll coating, gravure coating, metering rod (Meyer bar) coating, slot die (extrusion) coating, roller coating, flexographic coating. Suitable printing methods include silk screen printing, relief printing, such as flexographic printing, jet printing, intaglio printing, such as direct gravure printing or offset gravure printing, lithographic printing, such as offset printing, or stencil printing, such as screen printing.

[0038] The layer of the LCP mixture need not cover the entire surface of the support: rather, the layer may be applied in the form of a pattern, for example by printing, or may be treated after deposition to have the form of a pattern, for example by photolithographic methods.

[0039] The alignment of LCPs can be achieved by any known means for aligning liquid crystals. For example, the support can have an alignment surface, which means that the surface has the ability to align liquid crystals. The support can be pre-aligned without further processing. For example, when a plastic substrate is used as the support, the support can be aligned on the surface due to the manufacturing method, such as extrusion or stretching of the substrate. It is also possible to brush the support or imprint a directional microstructure to create alignment capabilities. Alternatively, a thin layer of material can be coated on a support specifically designed for alignment capabilities. The layer can be further brushed or treated to have a directional microstructure on the surface, for example by imprinting. If the thin layer comprises a photoalignable material, the alignment can be created by exposure to alignment light.

[0040] To define an alignment pattern of the liquid crystal in the LCP layer, the alignment surface of the substrate may exhibit a pattern of alignment directions. Preferably, an alignment layer comprising a photoalignable material is used for this purpose, and the alignment pattern is induced by selective exposure to alignment light of different polarized planes.

[0041] In the present invention, new compounds of the present invention represented by formula I have been found, which have high birefringence. Furthermore, the compounds of formula I can be aligned with low energy by an alignment layer, preferably by using photoalignment materials, which provides a way to a more economical process with less energy consumption.

[0042] In addition, it has surprisingly been found that the compounds of formula I exhibit very good alignment qualities without crystallization.

[0043] Furthermore, the compounds of formula I can be oriented at low energies (<250 mJ). They show very good alignment quality without crystallization.

[0044] The present invention will now be described with reference to the following non-limiting examples, which are provided for illustrative purposes only. Variations to these examples which fall within the scope of the invention will be apparent to those of ordinary skill in the art.

[0045] The present invention will now be described with reference to the following non-limiting examples, which are provided for illustrative purposes only. Variations to these examples which fall within the scope of the invention will be apparent to those of ordinary skill in the art. EXAMPLES

[0046] Definitions used in the examples: 1 H NMR: 1 H nuclear magnetic resonance spectroscopy DMSO-d6: Deuterated dimethyl sulfoxide 300MHz: 300 megahertz m: multiplet, d: doublet, dd: doublet doublet, t: triplet, s: singlet DMF: Dimethylformamide HCl: Hydrochloric acid DBU: 2,3,4,6,7,8,9,10-octahydropyrimidol [1,2-a] azepine THF: tetrahydrofuran Na2SO4: Sodium sulfate Pd(PPh3)2Cl2: Bis(triphenylphosphine)palladium dichloride DCC: N,N'-dicyclohexylcarbodiimide DMAP: 4-dimethylaminopyridine CH2Cl2: Dichloromethane THF: tetrahydrofuran NMP: N-methyl-2-pyrrolidone CuI: Copper iodide MgSO4: Magnesium sulfate

[0047] In the following examples, the thermotropic phases are abbreviated as follows: T (Cr-N) : Transition temperature from crystalline phase to nematic phase T (N-I) : Transition temperature from nematic phase to isotropic phase

[0048] Example 1: Preparation of 6-(4-iodophenoxy)-hexan-1-ol Compound 1 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) and potassium iodide (3.0 g, 0.018 mol) in 120 ml of DMF are added dropwise. The mixture is then stirred at 90 °C for 12 h. The solution is then cooled to room temperature and poured into 2.5 L of ice water containing 1.3 equivalents of HCl. The precipitate is filtered off, washed twice with 2 L of water and dried in vacuum at 40 °C to give the title compound (56.67 g, 0.177 mol) as an off-white powder.

[0049] Example 2: Preparation of 6-[4-(2-trimethylsilylethynyl])phenoxy]-hexan-1-ol Compound 2 6-(4-Iodophenoxy)-hexan-1-ol (24.09 g, 0.075 mol), Pd(PPh3)2Cl2 (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 hours, after which it is cooled to 25° C. Following filtration through Hyflo®, the solvent is evaporated. The residue is dissolved in ethyl acetate, washed with acidic H2O, brine and then dried over Na2SO4. The residue is purified by silica gel flash chromatography using a 1:1 mixture of heptane / ethyl acetate to give the title compound (19.53 g, 0.067 mol) as a brown oil.

[0050] Example 3: Preparation of 6-(4-ethynylphenoxy)-hexan-1-ol compound 3 To a solution of 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol (19.53 g, 0.067 mol) in 500 ml of methanol is added potassium carbonate (19.13 g, 0.134 mol). The reaction mixture is stirred at ambient temperature for 2 h. After evaporation of the solvent, 1 L of H2O is added and the suspension is extracted with ethyl acetate. Purification by flash chromatography on 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 crystallizes after a few minutes.

[0051] Example 4: Preparation of methyl 2,5-dihydroxybenzoate compound 4 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 and the temperature rises to 40° C. The mixture is refluxed for 24 h and then allowed to cool to 25° C. The solution is poured into H2O and extracted with ethyl acetate. The organic layer is dried over Na2SO4 and filtered off. The solution is concentrated under vacuum to give the title compound (10.7 g, 0.063 mol) as a white powder.

[0052] Example 5: Preparation of methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 5 Methyl 2,5-dihydroxybenzoate (8.4 g, 0.05 mol), 4-iodobenzoate (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 the addition is complete, the suspension is stirred at 25° C. for 3 hours. The suspension is then filtered through Hyflo®, which is washed with 250 ml of dichloromethane. The solution is concentrated under vacuum and purification by recrystallization in 250 ml of methanol gives the title compound (21.55 g, 0.034 mol) as a white powder.

[0053] Example 6: Preparation of methyl 5-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy-2-(4-iodobenzoyl)oxy-benzoate compound 6 Under N2 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(PPh3)2Cl2 (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 to 25 °C, 6-(4-ethynylphenoxy)-hexan-1-ol (0.83 g, 0.004 mol) is added. After stirring for 24 h, the reaction mixture is poured into 500 ml of H2O and acidified to pH 1 with HCl. The precipitate is filtered off and the residue is dissolved in 1 L of ethyl acetate. The solution is passed through Hyflo® and then concentrated under vacuum. Purification by flash chromatography on silica gel using a 1:2 mixture of heptane / ethyl acetate gives the title compound (3.5 g, 0.005 mol) as a dark orange solid.

[0054] Example 7: Preparation of methyl 2-(4-iodobenzoyl)oxy-5-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy-benzoate compound 7 [ka] 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 at 0-5 °C for 4 h, the mixture is allowed to warm to 25 °C. The solution is then diluted with acetonitrile, and purification by silica gel flash chromatography using ethyl acetate gives a brown residue. The previous oil is suspended in acetonitrile. The resulting precipitate is filtered off and dried under vacuum to give the title compound (1.12 g, 1.45 mmol) as a grey solid.

[0055] Liquid crystal phase transition: Compound 7 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes to a temperature above 82 °C (T (Cr-N) ) to a nematic phase, and the isotropic phase at 184°C (T (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0056] Example 8: Preparation of methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate compound 8 Under N2 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(PPh3)2Cl2 (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 resulting precipitate is filtered off and purified by silica gel flash chromatography using a 1:2 mixture of heptane / ethyl acetate to give the title compound (10.41 g, 0.013 mol) as a yellow solid.

[0057] Example 9: Preparation of methyl 2,5-bis[[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]-ethynyl]benzoyl]oxy]benzoate compound 9 [ka] 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 to 0 °C, 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 purification by silica gel flash chromatography using ethyl acetate provides the title compound (0.72 g, 0.78 mmol) as a yellow solid.

[0058] Liquid crystal phase transition: Compound 9 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes at 76 °C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0059] Example 10: Preparation of 3-(4-iodophenoxy)-propan-1-ol compound 10 The title compound 10 is prepared following the process described in Example 1 for compound 1, except substituting 3-chloropropanol for 6-chlorohexanol.

[0060] Example 11: Preparation of 3-(4-bromophenyl)-sulfanylpropan-1-ol compound 11 The title compound 11 is prepared according to the process described in Example 1 for compound 1, except substituting 3-chloropropanol and 4-bromobenzenethiol for 6-chlorohexanol and 4-iodophenol, respectively.

[0061] Example 12: Preparation of 6-(4-bromophenyl)-sulfanylhexan-1-ol compound 12 The title compound 12 is prepared following the process described in Example 1 for compound 1, except substituting 4-bromobenzenethiol for 4-iodophenol.

[0062] Example 13: Preparation of 6-[(6-bromo-2-naphthyl)oxy]-hexan-1-ol compound 13 The title compound 13 is prepared following the process described in Example 1 for compound 1, except substituting 6-bromonaphthalen-2-ol for 4-iodophenol.

[0063] Example 14: Preparation of 3-[(6-bromo-2-naphthyl)oxy]-propan-1-ol, compound 14 The title compound 14 is prepared following the process for compound 1 described in Example 1, except substituting 3-chloropropanol for 6-chlorohexanol and 6-bromonaphthalen-2-ol for 4-iodophenol.

[0064] Example 15: Preparation of 3-[4-(2-trimethylsilylethynyl)phenoxy]-propan-1-ol Compound 15 The title compound 15 is prepared following the process for compound 2 described in Example 2, except substituting 3-(4-iodophenoxy)-propan-1-ol compound 10 for 6-(4-iodophenoxy)-hexan-1-ol.

[0065] Example 16: Preparation of 3-[4-(2-trimethylsilylethynyl)phenyl]-sulfanylpropan-1-ol compound 16 The title compound 16 is prepared following the process for compound 2 described in Example 2, except substituting 3-(4-bromophenyl)-sulfanylpropan-1-ol compound 11 for 6-(4-iodophenoxy)-hexan-1-ol.

[0066] Example 17: Preparation of 6-[4-(2-trimethylsilylethynyl)phenyl]-sulfanylhexan-1-ol compound 17 The title compound 17 is prepared following the process described in Example 2 for compound 2, except substituting 6-(4-bromophenyl)-sulfanylhexan-1-ol compound 12 for 6-(4-iodophenoxy)-hexan-1-ol.

[0067] Example 18: Preparation of 6-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-hexan-1-ol compound 18 The title compound 18 is prepared according to the process for compound 2 described in Example 2, except that 6-(4-iodophenoxy)-hexan-1-ol is replaced with 6-[(6-bromo-2-naphthyl)oxy]-hexan-1-ol compound 13.

[0068] Example 19: Preparation of 3-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-propan-1-ol Compound 19 The title compound 19 is prepared according to the process for compound 2 described in Example 2, except that 6-(4-iodophenoxy)-hexan-1-ol is replaced with 3-[(6-bromo-2-naphthyl)oxy]-propan-1-ol compound 14.

[0069] Example 20: Preparation of 3-(4-ethynylphenoxy)-propan-1-ol compound 20 The title compound 20 is prepared according to the process for compound 3 described in Example 3, except that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced with 3-[4-(2-trimethylsilylethynyl)phenoxy]-propan-1-ol compound 15.

[0070] Example 21: Preparation of 3-(4-ethynylphenyl)-sulfanylpropan-1-ol, compound 21 The title compound 21 is prepared according to the process for compound 3 described in Example 3, except that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced with 3-[4-(2-trimethylsilylethynyl)phenyl]-sulfanylpropan-1-ol compound 16.

[0071] Example 22: Preparation of 6-(4-ethynylphenyl)-sulfanylhexan-1-ol, compound 22 The title compound 22 is prepared according to the process for compound 3 described in Example 3, except that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced with 6-[4-(2-trimethylsilylethynyl)phenyl]-sulfanylhexan-1-ol compound 17.

[0072] Example 23: Preparation of 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol, compound 23 The title compound 23 is prepared according to the process for compound 3 described in Example 3, except that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced with 6-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-hexan-1-ol compound 18.

[0073] Example 24: Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]-propan-1-ol, compound 24 The title compound 24 is prepared according to the process for compound 3 described in Example 3, except that 6-[4-(2-trimethylsilylethynyl)phenoxy]-hexan-1-ol is replaced with 3-[(6-(2-trimethylsilylethynyl)-2-naphthyl)oxy]-propan-1-ol compound 19.

[0074] Example 25: Preparation of ethyl 2,5-dihydroxybenzoate, compound 25 The title compound 25 is prepared following the process for compound 4 described in Example 4, except substituting ethanol for methanol.

[0075] Example 26: Preparation of butyl 2,5-dihydroxybenzoate, compound 26 The title compound 26 is prepared following the process for compound 4 described in Example 4, except substituting butanol for methanol.

[0076] Example 27: Preparation of 2-(1,3-benzothiazol-2-yl)benzene-1,4-diol, compound 27 To a suspension of 2-aminobenzenethiol (24.0 g, 0.192 mol) in 1.5 L of HO is added dropwise 2,5-dihydroxybenzaldehyde (26.52 g, 0.192 mol). The reaction mixture is heated to 110° C. for 8 h. After cooling to 25° C., the resulting precipitate is filtered off and purified by silica gel flash chromatography using a 1:1 mixture of heptane / ethyl acetate to give the title compound (13.97 g, 0.057 mol) as a yellow solid.

[0077] Example 28: Preparation of 4-[4-(11-hydroxyundecoxy)phenyl]-benzonitrile, compound 28 The title compound 28 is prepared according to the process for compound 1 described in Example 1, except that 6-chlorohexanol and 4-iodophenol are replaced with 11-bromoundecanol and 4-(4-hydroxyphenyl)benzonitrile, respectively.

[0078] Example 29: Preparation of 4-[4-(10-hydroxydecoxy)phenyl]-benzonitrile, compound 29 The title compound 29 is prepared according to the process for compound 1 described in Example 1, except that 6-chlorohexanol and 4-iodophenol are replaced with 10-bromodecanol and 4-(4-hydroxyphenyl)benzonitrile, respectively.

[0079] Example 30: Preparation of 4-[4-(8-hydroxyoctoxy)phenyl]-benzonitrile, compound 30 The title compound 30 is prepared according to the process for compound 1 described in Example 1, except that 6-chlorohexanol and 4-iodophenol are replaced with 8-bromooctanol and 4-(4-hydroxyphenyl)benzonitrile, respectively.

[0080] Example 31: Preparation of 11-[4-(4-cyanophenyl)phenoxy]undecyl methanesulfonate compound 31 To a suspension of 4-[4-(11-hydroxyundecoxy)phenyl]-benzonitrile (60.6 g, 0.165 mol) in 500 ml of THF, add triethylamine (50.6 g, 0.495 mol) dropwise. Cool the reaction to 0 °C. Slowly add methanesulfonyl chloride (22.8 g, 0.198 mol) and stir the mixture at 0-5 °C for 2 h. After filtration through Hyflo®, the solvent is evaporated under vacuum to provide the title compound (72.0 g, 0.162 mol) as an off-white solid.

[0081] Example 32: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl methanesulfonate compound 32 The title compound 32 is prepared according to the process for compound 31 described in Example 31, except that 4-[4-(11-hydroxyundecoxy)phenyl]-benzonitrile is replaced with 4-[4-(10-hydroxydecoxy)phenyl]-benzonitrile compound 29.

[0082] Example 33: Preparation of 8-[4-(4-cyanophenyl)phenoxy]octyl methanesulfonate compound 33 The title compound 33 is prepared according to the process for compound 31 described in Example 31, except that 4-[4-(11-hydroxyundecoxy)phenyl]-benzonitrile is replaced with 4-[4-(8-hydroxyoctoxy)phenyl]-benzonitrile compound 30.

[0083] Example 34: Preparation of 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-dihydroxybenzoate, compound 34 DBU (26.4 g, 0.170 mol) is added dropwise to a solution of 2,5-dihydroxybenzoic acid (27.2 g, 0.173 mol) in 180 ml of DMF. The solution is stirred at room temperature for 0.5 h. Then, 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 through Hyflo®, the filtrate is added to 2 L of ice water. The resulting 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.

[0084] Example 35: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-dihydroxybenzoate, compound 35 The title compound 35 is prepared according to the process for compound 34 described in Example 34, except that 11-[4-(4-cyanophenyl)phenoxy]undecyl methanesulfonate is replaced with 10-[4-(4-cyanophenyl)phenoxy]decyl methanesulfonate compound 32.

[0085] Example 36: Preparation of 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-dihydroxybenzoate compound 36 The title compound 35 is prepared according to the process for compound 34 described in Example 34, except that 11-[4-(4-cyanophenyl)phenoxy]undecyl methanesulfonate is replaced with 8-[4-(4-cyanophenyl)phenoxy]octyl methanesulfonate compound 33.

[0086] Example 37: Preparation of ethyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, compound 37 The title compound 37 is prepared following the process for compound 5 described in Example 5, except substituting ethyl 2,5-dihydroxybenzoate compound 25 for methyl 2,5-dihydroxybenzoate.

[0087] Example 38: Preparation of butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, compound 38 The title compound 38 is prepared following the process for compound 5 described in Example 5, except substituting butyl 2,5-dihydroxybenzoate compound 26 for methyl 2,5-dihydroxybenzoate.

[0088] Example 39: Preparation of [3-(1,3-benzothiazol-2-yl)-4-(4-iodobenzoyl)oxy-phenyl] 4-iodobenzoate, compound 39 The title compound 39 is prepared by following the process for compound 5 described in Example 5, except substituting 2-(1,3-benzothiazol-2-yl)benzene-1,4-diol compound 27 for methyl 2,5-dihydroxybenzoate.

[0089] Example 40: Preparation of [4-(4-iodobenzoyl)oxy-1-naphthyl] 4-iodobenzoate compound 40 The title compound 40 is prepared following the process for compound 5 described in Example 5, except substituting naphthalene-1,4-diol for methyl 2,5-dihydroxybenzoate.

[0090] Example 41: Preparation of 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, compound 41 The title compound 41 is prepared by following the process for compound 5 described in Example 5, except substituting 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-dihydroxybenzoate compound 34 for methyl 2,5-dihydroxybenzoate.

[0091] Example 42: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, compound 42 The title compound 42 is prepared by following the process for compound 5 described in Example 5, except that methyl 2,5-dihydroxybenzoate is replaced with 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-dihydroxybenzoate compound 35.

[0092] Example 43: Preparation of 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate, compound 43 The title compound 43 is prepared according to the process for compound 5 described in Example 5, except that methyl 2,5-dihydroxybenzoate is replaced with 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-dihydroxybenzoate compound 36.

[0093] Example 44: Preparation of ethyl 2-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate, compound 44 The title compound 44 is prepared according to the process for compound 6 described in Example 6, except that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced with ethyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 37.

[0094] Example 45: Preparation of ethyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate, compound 45 The title compound 45 is prepared according to the process for compound 8 described in Example 8, except that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced with ethyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 37.

[0095] Example 46: Preparation of butyl 2-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate, compound 46 The title compound 46 is prepared by following the process for compound 6 described in Example 6, except that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced with butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

[0096] Example 47: Preparation of butyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate, compound 47 The title compound 47 is prepared by following the process for compound 8 described in Example 8, except that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced with butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

[0097] Example 48: Preparation of butyl 2-[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate, compound 48 The title compound 48 is prepared according to the process for compound 6 described in Example 6, except replacing 6-(4-ethynylphenoxy)-hexan-1-ol with 3-(4-ethynylphenoxy)-propan-1-ol compound 20 and replacing methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate with butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

[0098] Example 49: Preparation of butyl 2,5-bis[[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate, compound 49 The title compound 49 is prepared according to the process for compound 8 described in Example 8, except replacing 6-(4-ethynylphenoxy)-hexan-1-ol with 3-(4-ethynylphenoxy)-propan-1-ol compound 20 and replacing methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate with butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

[0099] Example 50: Preparation of methyl 2,5-bis[[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]-ethynyl]benzoyl]oxy]benzoate, compound 50 The title compound 50 is prepared according to the process for compound 8 described in Example 8, except that 6-(4-ethynylphenoxy)-hexan-1-ol is replaced with 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol compound 23.

[0100] Example 51: Preparation of butyl 2,5-bis[[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]-ethynyl]benzoyl]oxy]benzoate, compound 51 The title compound 51 is prepared according to the process for compound 8 described in Example 8, except replacing 6-(4-ethynylphenoxy)-hexan-1-ol with 6-[(6-ethynyl-2-naphthyl)oxy]-hexan-1-ol compound 23 and replacing methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate with butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

[0101] Example 52: Preparation of methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexylsulfanyl)phenyl]-ethynyl]benzoyl]oxy]benzoate, compound 52 The title compound 52 is prepared following the process for compound 8 described in Example 8, except substituting 6-(4-ethynylphenoxy)-hexan-1-ol for 6-(4-ethynylphenyl)-sulfanylhexan-1-ol compound 22.

[0102] Example 53: Preparation of butyl 2,5-bis[[4-[2-[4-(3-hydroxypropylsulfanyl)phenyl]-ethynyl]benzoyl]oxy]benzoate, compound 53 The title compound 53 is prepared according to the process for compound 8 described in Example 8, except replacing 6-(4-ethynylphenoxy)-hexan-1-ol with 3-(4-ethynylphenyl)-sulfanylpropan-1-ol compound 21 and replacing methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate with butyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 38.

[0103] 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 The title compound 54 is prepared by following the process for compound 8 described in Example 8, except that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced with [3-(1,3-benzothiazol-2-yl)-4-(4-iodobenzoyl)oxy-phenyl]4-iodobenzoate compound 39.

[0104] 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 The title compound 55 is prepared according to the process for compound 8 described in Example 8, except that methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate is replaced with [4-(4-iodobenzoyl)oxy-1-naphthyl]4-iodobenzoate compound 40.

[0105] 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 The title compound 56 is prepared by following the process for compound 8 described in Example 8, except substituting 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 41 for methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate.

[0106] 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 The title compound 57 is prepared by following the process for compound 8 described in Example 8, except substituting 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 42 for methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate.

[0107] 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 The title compound 58 is prepared by following the process for compound 8 described in Example 8, except substituting 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 43 for methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate.

[0108] 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 The title compound 59 is prepared according to the process for compound 8 described in Example 8, except replacing 6-(4-ethynylphenoxy)-hexan-1-ol with 3-(4-ethynylphenoxy)-propan-1-ol compound 20 and replacing methyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate with 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[(4-iodobenzoyl)oxy]benzoate compound 42.

[0109] Example 60: Preparation of ethyl 5-(4-iodobenzoyl)oxy-2-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy-benzoate, compound 60 The title compound 60 is prepared according to the process for compound 7 described in Example 7, except substituting ethyl 2-[4-[2-[4-(6-hydroxyhexoxy)phenyl]-ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate compound 44 for 5-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy-2-(4-iodobenzoyl)oxy-benzoate.

[0110] Example 61: Preparation of ethyl 2,5-bis[[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]-ethynyl]benzoyl]oxy]benzoate, compound 61 [ka] The title compound 61 is prepared by following the process for compound 9 described in Example 9, except substituting ethyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate compound 45 for methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate compound. Purification by flash chromatography on silica gel using ethyl acetate provides the title compound (3.18 g, 3.41 mmol, 47%) as an off-white solid.

[0111] Liquid crystal phase transition: Compound 61 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes to a temperature above 70 °C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0112] Example 62: Preparation of butyl 5-(4-iodobenzoyl)oxy-2-[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]ethynyl]benzoyl]oxy-benzoate, compound 62 [ka] The title compound 62 is prepared according to the process for compound 7 described in Example 7, but replacing 5-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy-2-(4-iodobenzoyl)oxy-benzoate with butyl 2-[4-[2-[4-(6-hydroxyhexoxy)phenyl]-ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate compound 46. Purification by silica gel flash chromatography using ethyl acetate gives a brown oily residue, which is suspended in acetonitrile. The resulting precipitate is filtered off and dried under vacuum to give the title compound (1.53 g, 1.87 mmol, 94%) as a grey solid.

[0113] Liquid crystal phase transition: Compound 62 was observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increased, the crystalline phase was observed at 80 °C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appeared in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0114] Example 63: Butyl 2,5-bis[[4-[2-[4-(6-prop-2-enoyloxyhexoxy)phenyl]-ethynyl]benzoyl]oxy]benzoate Preparation of compound 63 [ka] The title compound 63 is prepared by following the process for compound 9 described in Example 9, except substituting butyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate compound 47 for methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate compound. Purification by flash chromatography on silica gel using ethyl acetate provides the title compound (0.64 g, 0.67 mmol, 57%) as a white solid.

[0115] Liquid crystal phase transition: Compound 63 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes to a temperature above 117°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0116] Example 64: Preparation of butyl 5-(4-iodobenzoyl)oxy-2-[4-[2-[4-(3-prop-2-enoyloxypropoxy)phenyl]ethynyl]benzoyl]oxy-benzoate, compound 64 [ka] The title compound 64 is prepared according to the process for compound 7 described in Example 7, but replacing 5-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy-2-(4-iodobenzoyl)oxy-benzoate with butyl 2-[4-[2-[4-(3-hydroxypropoxy)phenyl]-ethynyl]-benzoyl]oxy-5-(4-iodobenzoyl)oxy-benzoate compound 48. Purification by silica gel flash chromatography using ethyl acetate gives a brown oily residue, which is suspended in acetonitrile. The resulting precipitate is filtered off and dried under vacuum to give the title compound (1.18 g, 1.53 mmol, 44%) as a brownish solid.

[0117] Liquid crystal phase transition: Compound 64 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes to a temperature above 85°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0118] Example 65: Preparation of butyl 2,5-bis[[4-[2-[4-(3-prop-2-enoyloxypropoxy)phenyl]-ethynyl]benzoyl]oxy]benzoate, compound 65 [ka] The title compound 65 is prepared by following the process for compound 9 described in Example 9, except substituting butyl 2,5-bis[[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate compound 49 for methyl 2,5-bis[[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]-benzoyl]oxy]benzoate compound. Purification by flash chromatography on silica gel using ethyl acetate provides the title compound (4.9 g, 5.6 mmol, 71%) as a white solid.

[0119] Liquid crystal phase transition: Compound 65 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes to a phase transition temperature of 115°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0120] Example 66: Preparation of methyl 2,5-bis[[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]benzoyl]oxy]benzoate, compound 66 [ka] The title compound 66 is prepared by following the process described in Example 9 for compound 9, except substituting methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate compound 50 for methyl 2,5-bis[[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]-ethynyl]benzoyl]oxy]benzoate.

[0121] Liquid crystal phase transition: Compound 66 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes at 164°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in CD2Cl2-d2: 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)

[0122] Example 67: Preparation of butyl 2,5-bis[[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]benzoyl]oxy]benzoate, compound 67 [ka] The title compound 67 is prepared by following the process for compound 9 described in Example 9, except substituting butyl 2,5-bis[[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]-ethynyl]benzoyl]oxy]benzoate compound 51 for methyl 2,5-bis[[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]-ethynyl]benzoyl]oxy]benzoate.

[0123] Liquid crystal phase transition: Compound 67 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes from 120°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1H NMR (300MHz) in CD2Cl2-d2: 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)

[0124] Example 69: Preparation of butyl 2,5-bis[[4-[2-[4-(3-prop-2-enoyloxypropylsulfanyl)-phenyl]ethynyl]benzoyl]oxy]benzoate, compound 69 [ka] The title compound 69 is prepared by following the process for compound 9 described in Example 9, except substituting butyl 2,5-bis[[4-[2-[4-(3-hydroxypropylsulfanyl)phenyl]-ethynyl]benzoyl]oxy]benzoate compound 53 for methyl 2,5-bis[[4-[2-[4-(3-hydroxypropylsulfanyl)phenyl]-ethynyl]benzoyl]oxy]benzoate compound. Purification by flash chromatography on silica gel using ethyl acetate provides the title compound (1.05 g, 1.15 mmol, 57%) as a white sticky solid.

[0125] Liquid crystal phase transition: Compound 69 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes from 110°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1H NMR (300MHz) in DMSO-d6: 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)

[0126] 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 [ka] The title compound 70 is prepared by following the process for compound 9 described in Example 9, but substituting [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 for methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)-phenyl]ethynyl]benzoyl]oxy]benzoate. Purification by silica gel flash chromatography using ethyl acetate provides the title compound (2.23 g, 2.24 mmol) as an off-white solid.

[0127] Liquid crystal phase transition: Compound 70 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes at 135°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1H NMR (300MHz) in DMSO-d6: 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)

[0128] 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 [ka] The title compound 71 is prepared by following the process for compound 9 described in Example 9, except substituting [4-[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate for methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy-1-naphthyl]4-[2-[4-(6-hydroxyhexoxy)phenyl]-ethynyl]benzoate compound 55. Purification by silica gel flash chromatography using ethyl acetate provides the title compound (4.69 g, 5.16 mmol) as a grey solid.

[0129] Liquid crystal phase transition: Compound 71 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes at 177°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1H NMR (300MHz) in DMSO-d6: 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)

[0130] 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 [ka] The title compound 72 is prepared according to the process for compound 9 described in Example 9, except substituting 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate compound 56 for methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]benzoate.

[0131] Liquid crystal phase transition: Compound 72 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes to a temperature above 105°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in CD2Cl2-d2: 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)

[0132] 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 [ka] The title compound 73 is prepared by following the process for compound 9 described in Example 9, except substituting 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]-benzoate compound 57 for methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]-benzoate compound. Purification by flash chromatography on silica gel using ethyl acetate provides the title compound (3.24 g, 2.62 mmol) as a white solid.

[0133] Liquid crystal phase transition: Compound 73 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes from 125°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0134] 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 [ka] The title compound 74 is prepared by following the process for compound 9 described in Example 9, except substituting 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]-benzoate compound 58 for methyl 2,5-bis[[4-[2-[4-(6-hydroxyhexoxy)phenyl]ethynyl]benzoyl]oxy]-benzoate compound. Purification by silica gel flash chromatography using ethyl acetate provides the title compound (6.28 g, 5.19 mmol) as a white solid.

[0135] Liquid crystal phase transition: Compound 74 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes from 110°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0136] 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 [ka] The title compound 75 is prepared by following the process for compound 9 described in Example 9, except substituting 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]benzoyl]oxy]-benzoate compound 59 for methyl 2,5-bis[[4-[2-[4-(3-hydroxypropoxy)phenyl]ethynyl]benzoyl]oxy]-benzoate compound. Purification by silica gel flash chromatography using ethyl acetate provides the title compound (3.41 g, 2.95 mmol) as a white solid.

[0137] Liquid crystal phase transition: Compound 9 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes to a temperature above 116 °C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0138] 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 [ka] 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(PPh3)2Cl2 (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 cooled to 25° C. before being poured into ice water. The precipitate is filtered off and purified by silica gel flash chromatography using a 2:1 mixture of heptane / ethyl acetate to give the title compound (0.25 g, 0.32 mmol) as a white solid.

[0139] Liquid crystal phase transition: Compound 76 is observed under crossed polarizers using a polarizing microscope to determine its phase transition temperature. As a result, as the temperature increases, the crystalline phase changes to a temperature above 117°C (T (Cr-N) ) changes to a nematic phase, and the isotropic phase changes to (N-I) ) appears in Super. 1 H NMR (300MHz) in DMSO-d6: 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)

[0140] Example 77: Preparation of alignment layer using photoalignment material A glass substrate is spin-coated with a photoalignment composition (photoalignment material at 3% solids in cyclopentanone as described in patent publication WO2012 / 085048: a photoactive polymer material is used as an alignment layer for the liquid crystal). The film is dried at 180 °C for 10 min, resulting in a film thickness of about 100 nm. The film is then exposed to alignment light, which is parallel linearly polarized UV (LPUV) light (280-320 nm), at 500 mJ / cm. 2 The plane of polarization is at 0° relative to the reference edge on the substrate.

[0141] Example 78: Preparation of Optical Films from Compound 7 A 15.0 w% solution is prepared by mixing 14.775 w% of compound 7, 0.150 w% of Irgacure® 369 (having the chemical structure 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), and 0.075 w% of Tinuvin® 123 (having the chemical structure bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) in cyclopentanone and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on a glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film is dried at 180° C. for 5 minutes on a temperature-controlled hot plate. The sample is cooled to room temperature and then photopolymerized by irradiating UV light at room temperature for approximately 2 minutes under a N2 atmosphere using a mercury lamp to fix the alignment state of the liquid crystal.

[0142] The resulting film exhibited a very well-ordered nematic mesophase at room temperature.

[0143] Example 79: Preparation of optical films from compound 9 A 15.0 w% solution is prepared by mixing 14.775 w% Compound 9, 0.150 w% Irgacure® 369, and 0.075 w% Tinuvin® 123 in cyclopentanone, and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on the glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film is dried on a temperature-controlled hot plate at different temperatures for different times. The sample is cooled to room temperature, and then photopolymerized by irradiating UV light using a mercury lamp under N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0144] The resulting films exhibit a moderately ordered nematic mesophase at room temperature.

[0145] Example 80: Preparation of Optical Films from Compound 61 A 15.0 w% solution is prepared by mixing 14.775 w% Compound 61, 0.150 w% Irgacure® 369, and 0.075 w% Tinuvin® 123 in cyclopentanone, and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on the glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film is dried at 150°C for 3 seconds on a temperature-controlled hot plate. The sample is cooled to room temperature, and then photopolymerized by irradiating UV light using a mercury lamp under a N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0146] The resulting film exhibited a very well-ordered nematic mesophase at room temperature.

[0147] Example 81: Preparation of Optical Films from Compound 62 A 15.0 w% solution is prepared by mixing 14.775 w% of Compound 62, 0.150 w% of Irgacure® 369, and 0.075 w% of Tinuvin® 123 in cyclopentanone, and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on the glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film is dried at 130°C for 3 minutes on a temperature-controlled hot plate. The sample is cooled to room temperature, and then photopolymerized by irradiating UV light using a mercury lamp under a N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0148] The resulting film exhibited a very well-ordered nematic mesophase at room temperature.

[0149] Example 82: Preparation of Optical Films from Compound 63 A 15.0 w% solution is prepared by mixing 14.775 w% Compound 63, 0.150 w% Irgacure® 369, and 0.075 w% Tinuvin® 123 (BASF) in cyclopentanone, and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on the glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film is dried at 180°C for 3 seconds on a temperature-controlled hot plate. The sample is cooled to room temperature, and then photopolymerized by irradiating UV light using a mercury lamp under a N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0150] The resulting film exhibited a very well-ordered nematic mesophase at room temperature.

[0151] Example 83: Preparation of Optical Films from Compound 64 A 15.0 w% solution is prepared by mixing 14.775 w% Compound 64, 0.150 w% Irgacure® 369, and 0.075 w% Tinuvin® 123 in cyclopentanone, and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on the glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film is dried at 130°C for 3 seconds on a temperature-controlled hot plate. The sample is cooled to room temperature, and then photopolymerized by irradiating UV light using a mercury lamp under a N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0152] The resulting film exhibited a very well-ordered nematic mesophase at room temperature.

[0153] Example 84: Preparation of Optical Films from Compound 65 A 15.0 w% solution is prepared by mixing 14.775 w% Compound 65, 0.150 w% Irgacure® 369, and 0.075 w% Tinuvin® 123 in cyclopentanone, and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on the glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film is dried at 180°C for 5 seconds on a temperature-controlled hot plate. The sample is cooled to room temperature, and then photopolymerized by irradiating UV light using a mercury lamp under a N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0154] The resulting film exhibited a very well-ordered nematic mesophase at room temperature.

[0155] Example 85: Preparation of Optical Films from Compound 69 A 15.0 w% solution is prepared by mixing 14.520 w% Compound 69, 0.300 w% Irgacure® 369, 0.150 w% Tinuvin® 123 and 0.030 w% BYK® 378 (a polyether-modified polydimethylsiloxane from BYK used as a surface additive) in cyclopentanone and thoroughly stirring at room temperature until the solids are completely dissolved. The above polymer solution is spin-coated on a glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film is dried at 120°C for 1 minute on a temperature-controlled hot plate. The sample is photopolymerized by irradiating UV light using a mercury lamp under a N2 atmosphere at 120°C for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0156] The resulting film exhibited a very well-ordered nematic mesophase at room temperature.

[0157] Example 86: Preparation of Optical Films from Compound 70 A 13.0 w% solution is prepared by mixing 12.584 w% Compound 70, 0.260 w% Irgacure® 369, 0.130 w% Tinuvin® 123 and 0.026 w% BYK® 378 in 1,3-dioxolane and thoroughly stirring at 80°C until the solids are completely dissolved. The above polymer solution is spin-coated on a glass plate with the alignment layer of Example 1 to form a liquid crystal film. The film is dried on a temperature-controlled hot plate at 120°C for 2 minutes. The sample is photopolymerized by irradiating UV light using a mercury lamp under a N2 atmosphere at room temperature for approximately 2 minutes to fix the alignment state of the liquid crystal.

[0158] The resulting film exhibited a very well-ordered nematic mesophase at room temperature.

[0159] Example 87: The retardation at 550 nm of the samples described in Example 78, Example 80, Example 81, Example 82, Example 83, Example 84, Example 85, Example 86 is measured by ellipsometer. The thickness of the samples is measured by stylus step gauge. The birefringence (Δn) is obtained from the determined retardation and thickness values ​​according to the formula (Δn=retardation / thickness). The values ​​are listed in Table 1.

[0160] [Table 1]

[0161] The films of Examples 78, 80, 82, 83, 84, and 86 have high birefringence, with values ​​exceeding 0.29. These new LCPs can be used to make phase retarder optical films as quarter wave plates (QWPs) and half wave plates (HWPs). Retarder transmits light and changes its polarization state, and is widely used in various display applications or security elements. The particularly high birefringence of these new LCPs results in significant thickness reduction of retarder films.

[0162] As an example, Table 2 shows the thicknesses required to obtain a quarter-wave plate (λ / 4) retarder (QWP) and a half-wave plate (λ / 2) retarder (HWP) at 550 nm for Examples 78, 80, 81, 82, 83, 84 and 86 using Compounds 7, 61, 62, 63, 64, 65, 70, respectively.

[0163] [Table 2]

Claims

1. Formula (I) 【Chemistry 25】 [In the formula, Ring A is an unsubstituted or substituted phenylene group, naphthalene group or biphenylene group; A.A. １ is a divalent radical of a compound selected from the group of compounds below: 【Chemistry 26】 A.A. ２ is a C 1 -C 4 alkylene, an alicyclic group, or a divalent radical of a compound selected from the group of compounds: 【Chemistry 27】 Here, A.A. １ and A.A. ２ are, independently of one another, unsubstituted or selected from the group consisting of F, Cl, Br, I, CN, C １ -C ６ Alkyl, C １ -C ６ Alkenyl, C １ -C ６ Alkoxy and C １ -C ６ substituted with one or two substituents selected from the group consisting of alkenyloxy; Q １ is an unsubstituted or substituted monocyclic or heterocyclic group, or Q １ are represented by the formulas (Ia), (Ib), (Ic) and (Id): -COO-SP ２ -BB(Ia), -OCO-SP ２ -BB(Ib), -CO-SP ２ -BB(Ic) and -O-SP ２ -BB(Id) However, as a condition, Q １ The substituents are F, Cl, Br, I, CN, C １ -C ６ Alkyl, C １ -C ６ Alkenyl, C １ -C ６ Alkoxy and C １ -C ６ alkenyloxy; and With the proviso that when ring A is a naphthalene group, Q １ has the meaning given above or is hydrogen; SP １ , SP ２ and SP ３ are each independently a single bond or a group of the formula -(CH ２ )p-, where p is an integer of 1 to 18, and 1, 2, 3, or 4 —CH ２ The - group is unsubstituted or replaced by a group selected from the group consisting of -CH=CH-, -O-, -S-, -CO-, -COO-, -CONR'-, -OCOO-, -OCONR', -NR'-, -CONR'-, -OCOO-, and -OCONR', where R' is hydrogen, C １ -C ６ Alkyl group and C １ -C ６ alkenyl groups; 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 １ -C ６ Alkyl, C １ -C ６ Alkenyl, C １ -C ６ Alkoxy or C １ -C ６ alkenyloxy, P １ is a polymerizable group, However, as a condition, BP and P １ are polymerizable groups, they may be the same or different; BB is hydrogen or a group of formula (II) 【Chemistry 28】 (In the formula, A and B independently represent an unsubstituted or substituted 6-membered monocyclic or heterocyclic group or a naphthalene group; C is selected from the group consisting of 5- and 6-membered monocyclic or heterocyclic groups or naphthalene groups; n １ and n ２ is 0 or 1, provided that, first, 1≦n １ +n ２ ≦2, and secondly, when C is a naphthalene group, 0≦n １ +n ２ ≦2; Z １ is selected from the group consisting of —O—, —S—, —COO—, —OOC—, —CO—, —CONR′—, —NR′CO—, —OCOO—, —OCONR′—, —NR′COO— and a single bond; R' is hydrogen, C １ -C ６ Alkyl group and C １ -C ６ alkenyl groups; However, as a condition, -SP ２ -Z １ - groups shall not contain two adjacent heteroatoms; Z ２ and Z ３ are each independently a single bond, —COO—, —OOC—, or —CH ２ -CH ２ -, -CH ２ O-, -OCH ２ -, -CH=CH-, -C≡C-, -(CH ２ ) ４ - and -(CH ２ ) ３ selected from the group consisting of O-; R １ is H, -CN, -COR, -COOR, -OCOR, -CONR'R, -NR'COR, OCOOR, -OCONR'R, -NR'COOR, -F, -Cl, I, -CF ３ , -OCF ３ , —OR, R' is hydrogen, C １ -C ６ Alkyl group and C １ -C ６ alkenyl groups, and R is selected from the group consisting of hydrogen, C １－１８ C having an alkyl group and a double bond at the 3-position or higher ４－１８ alkenyl groups) is a compound represented by the formula: A compound represented by the formula:

2. BP and P １ are independent of each other and ２ =C(Ph)-, CH ２ =CW-COO-, CH ２ =CH-COO-Ph-, CH ２ =CW-CO-NH-, CH ２ =CH-O-, CH ２ =CH-OOC-, Ph-CH=CH-, CH ２ =CH-Ph-, CH ２ =CH-Ph-O-, R ６ -Ph-CH=CH-COO-, R ６ -OOC-CH=CH-Ph-O- and 2-W-epoxyethyl, W is hydrogen, chloride, aryl or C １ -C ６ represents alkyl, R ６ But C １ -C ６ represents alkyl, with the proviso that R ６ When R is attached to an aryl group, ６ is hydrogen or C １ -C ６ 2. The compound of claim 1, which may also represent alkoxy.

3. SP １ and SP ３ are each independently a single bond or a group of the formula -(CH ２ )p-, where p is an integer of 1 to 12, one —CH ２ - group is unsubstituted or replaced by a group selected from the group consisting of -O- or -S-; SP ２ is a single bond or a group of the formula -(CH ２ )p-, where p is an integer of 1 to 12, one —CH ２ 2. The compound of claim 1, wherein the - group is unsubstituted or is replaced by a group selected from the group consisting of -O- or -S-.

4. BB is hydrogen or a group represented by formula (II) 【Chemistry 29】 [In the formula, A and B independently represent an unsubstituted or substituted 1,4-phenylene or naphthalene group; C is an unsubstituted or substituted 1,4-phenylene or naphthalene group; n １ and n ２ is 0 or 1, provided that, first, 1≦n １ +n ２ ≦2, and secondly, when C is a naphthalene group, 0≦n １ +n ２ ≦2; However, as a condition, -SP ２ -Z １ - groups shall not contain two adjacent heteroatoms; Z ２ and Z ３ is independently selected from the group consisting of a single bond, —COO—, and —OOC—; R １ is selected from the group consisting of H, —CN and I. The compound according to claim 1, which is a compound represented by the formula:

5. BP is a polymerizable group or C １ -C ４ The compound of claim 1, wherein the aryl group is alkyl, I, or —CN.

6. 2. The compound of claim 1, wherein n is 1 and BP is a polymerizable group.

7. An LCP mixture comprising a compound represented by formula (I) according to claim 1.

8. An LCP network comprising a compound according to any one of claims 1 to 6 or a mixture according to claim 7 in crosslinked or polymerized form.

9. Use of a compound according to any one of claims 1 to 6 or a mixture according to claim 7 in the manufacture of an optical or electro-optical device.

10. An optical or electro-optical device comprising a compound according to any one of claims 1 to 6 or a mixture according to claim 7.

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