Liquid-crystalline media having homeotropic alignment

Abstract

A liquid-crystalline media (LC media) containing a low-molecular-weight, non-polymer component, and a combination of self-alignment additives for vertical alignment of two or more of the specified kinds (formulae IA to IM). The combination of two or more self-alignment additives affect homeotropic (vertical) alignment of the LC media at a surface or the cell surfaces of a liquid-crystal display (LC display).

Claims

1. A liquid-crystal (LC) medium comprising a low-molecular-weight, non-polymerizable liquid-crystalline component and a combination of self-alignment additives for vertical alignment selected from the group consisting of formulae IG and IL ##STR00460## combined with one or more compounds selected from the group consisting of formulae IE, IF, IJ and IK ##STR00461## in which A.sup.4, A.sup.5, A.sup.6 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which optionally contains fused rings, and which is optionally mono-or polysubstituted by a group L or -Sp-P, A.sup.7, A.sup.8, A.sup.9 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which optionally contains fused rings, and which is optionally mono-or polysubstituted by a group L or -Sp-P, P denotes a polymerizable group, Sp denotes a spacer group or a single bond, wherein formulae IE, IF and IG independently comprise one polymerizable group P each, and wherein formulae IJ, IK and IL independently comprise two or more polymerizable groups P each, L in each case, independently of one another, denotes H, F, CI, Br, I, —CN, —NO.sub.2, —NCO, —NCS, —OCN, —SCN, —C(═O)N(R.sup.0).sub.2, —C(═O)R.sup.0, optionally substituted silyl, optionally substituted aryl or cycloalkyl having 3 to 20 C atoms, or straight-chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 3 to 25 C atoms, in which one or more H atoms are each optionally replaced by F or CI, Z.sup.2, Z.sup.3 in each case, independently of one another, denotes a single bond, —O—, —S—, —CO—, —CO—O—, —OCO—, —O—CO—O—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —(CH.sub.2).sub.n1—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —(CF.sub.2).sub.n1—, —CH═CH—, —CF═CF—, —C═C—, —CH═CH—COO—, —OCO—CH═CH—, —(CR.sup.0R.sup.00).sub.n1—, —CH(—Sp-P)—, —CH.sub.2CH(—Sp-P)—, or —CH(—Sp-P)CH(—Sp-P)—, n1 denotes 1, 2, 3 or 4, m denotes 0, 1, 2, 3, 4, 5 or 6, n denotes 0 or 1, R.sup.0 in each case, independently of one another, denotes alkyl having 1 to 12 C atoms, R.sup.00 in each case, independently of one another, denotes H or alkyl having 1 to 12 C atoms, R.sup.1 denotes H, halogen, straight-chain alkyl having 1 to 25 C atoms, or branched or cyclic alkyl having 3 to 25 C atoms, in which one or more non-adjacent CH.sub.2 groups are each optionally replaced by —O—, —S—, —CO—, —CH═CH—, —C≡C—, —CO—O—, —O—CO—, or —O—CO—O— in such a way that O and/or S atoms are not linked directly to one another and in which one or more H atoms are each optionally replaced by F or Cl, or denotes a group -Sp-P, X.sup.1 each, independently of one another, denotes —OH, —SH, or —NH.sub.2, R.sup.22 denotes alkyl having 1 to 12 C atoms, and Sp.sup.a, Sp.sup.c each, independently of one another, denotes a spacer group or a single bond.

2. The liquid-crystal (LC) medium according to claim 1 comprising any of the following combinations of a first and a second self-alignment additive of formulae: IE and IG, IF and IG, IJ and IG, IJ and IL, IK and IL, IE and IL, IG and IK, or IF and IL.

3. The liquid-crystal (LC) medium according to claim 1, wherein said two or more alignment additives each comprise one, two or more polymerizable groups.

4. The liquid-crystal (LC) medium according to claim 1, comprising one or more self-alignment additives selected from the group consisting of formulae IE and IJ and one or more self-alignment additives selected from the group consisting of formulae IG and IL.

5. The liquid-crystal (LC) medium according to claim 1, comprising one or more self-alignment additives of formula IJ and one or more compounds of formula IL.

6. The LC medium according to claim 1, further comprising a polymerizable or polymerized compound other than compounds of formulae IG, IL, IE, IF, IJ and IK, where the polymerized component is obtainable by polymerization of a polymerizable component.

7. The medium according to claim 1, wherein, in any of formulae IG, IL, IE, IF, IJ and IK, A.sup.4, A.sup.5, A.sup.6, A.sup.7, A.sup.8, A.sup.9, each, independently of one another, denote 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, in which one or more CH groups are each optionally replaced by N, cyclohexane-1,4-diyl, in which one or more non-adjacent CH.sub.2 groups are each optionally replaced by O or S, 3,3′-bicyclobutylidene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, piperidine-1,4-diyl, decahydro-naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl, octahydro-4,7-methanoindane-2,5-diyl, or perhydrocyclopenta[a]phenanthrene-3,17-diyl, where any of which is unsubstituted or mono- or polysubstituted by a group L, and A.sup.4 to A.sup.6 is optionally substituted by a group -Sp-P, and A.sup.7 to A.sup.9 is optionally substituted by one, two or three groups -Sp-P.

8. The medium according to claim 1, wherein the compound of formula IJ is a compound of formula IJ1, ##STR00462## in which R.sup.1, A.sup.7, A.sup.8, A.sup.9, Z.sup.2, Z.sup.3, m, n, L, Sp.sup.a, X.sup.1, Sp and P independently are defined as for the compound of formula IJ, p1 is 2, and r1, r2, r3 independently are 0, 1, 2 or 3.

9. The medium according to claim 1, wherein the compound of formula IK is a compound of formula IK1, ##STR00463## in which R.sup.1, A.sup.7, A.sup.8, A.sup.9, Z.sup.2, Z.sup.3, m, n, L, Sp.sup.a, Sp.sup.c, X.sup.1, Sp and P independently are defined as for the compound of formula IK, P.sup.1 is 2, and r1, r2, r3 independently are 0, 1, 2 or 3.

10. The medium according to claim 1, wherein the one or more compounds of formula IJ are compounds of formulae IJ1-1 to IJ1-9: ##STR00464## in which R.sup.1, Z.sup.2, Z.sup.3, L, Sp and P independently are as defined as for the compound of formula IJ, and x is 0 or 1, n is 1, 2, 3, 4, 5, 6, 7 or 8, p1 is 2, and r1, r2, r3, r3″ independently denote 0, 1, 2 or 3.

11. The medium according to claim 1, wherein the one or more compounds of formula IK are compounds of formulae IK1-1 to IK1-9: ##STR00465## in which R.sup.1, Z.sup.2, Z.sup.3, L, Sp, Spy and P independently are as defined as for the compound of formula IK, and x is 0 or 1, n is 1, 2, 3, 4, 5, 6, 7 or 8, p1 is 2, and r1, r2, r3, r3″ independently denote 0, 1, 2 or 3.

12. The medium according to claim 1, wherein the compound of formula IJ is a compound of formula IJ1, ##STR00466## in which R.sup.1, A.sup.7, A.sup.8, A.sup.9, Z.sup.2, Z.sup.3, m, n, L, Sp.sup.a, X.sup.1, Sp and P independently are defined as for the compound of formula IJ, p1 is 2, r1, r3 independently are 0, 1, 2 or 3, and r2 is 2, or wherein the compound of formula IK is a compound of formula IK1, ##STR00467## in which R.sup.1, A.sup.7, A.sup.8, A.sup.9, Z.sup.2, Z.sup.3, m, n, L, Spa, Spy, X.sup.1, Sp and P independently are defined as for the compound of formula IK, p1 is 2, r1, r3 independently are 0, 1, 2 or 3, and r2 is 2.

13. The medium according to one or more of claim 1, comprising one or more alignment additives selected from the group consisting of formulae IJ1-3 and IJ 1-7, ##STR00468## in which R.sup.1, Z.sup.2, Z.sup.3, L, Sp and P independently are as defined as for the compound of formula IJ, and x is 0 or 1, n is 1, 2, 3, 4, 5, 6, 7 or 8, p1 is 2, and r1, r2, r3 independently denote 0, 1, 2 or 3, and one or more additives selected from the group consisting of formulae IK1-1 and IK1-5 ##STR00469## in which R.sup.1, Z.sup.2, Z.sup.3, L, Sp, Sp.sup.C and P independently are as defined as for the compound of formula IK, and x is 0 or 1, n is 1, 2, 3, 4, 5, 6, 7 or 8, p1 is 2, and r1, r2, r3 independently denote 0, 1, 2 or 3.

14. The medium according to claim 1, wherein for the compounds of formulae IG, IL, IE, IF, IJ and IK the groups Z.sup.2 are single bonds.

15. The medium according to claim 1, which comprises compounds of formula IJ in a concentration of 0.1 or more and less than 0.4% by weight.

16. The medium according to claim 1, which comprises one or more compounds of formula IK in a total concentration of 0.2 or more and less than 0.8% by weight.

17. The medium according to claim 1, which further comprises one or more compounds selected from the group consisting of the compounds of formulae IIA, IIB and IIC: ##STR00470## in which R.sup.2A, R.sup.2B and R.sup.2C each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms, which is unsubstituted, monosubstituted by CN or CF.sub.3 or at least monosubstituted by halogen, in which one or more CH.sub.2 groups are optionally replaced by —O—, —S—, ##STR00471## —C≡C—, —CF.sub.2O—, —OCF.sub.2—, —OC—O—or —O—CO—in such a way that 0 atoms are not linked directly to one another, L.sup.1-4 each, independently of one another, denote F, Cl, CF.sub.3 or CHF.sub.2, Z.sup.2 and Z.sup.2′each, independently of one another, denote a single bond, —CH.sub.2CH.sub.2—, —CH═CH—, —CF.sub.2O—, —OCF.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —COO—, —OCO—, —C.sub.2F.sub.4—, —CF═CF—, or —CH═CHCH.sub.2O—, P denotes 0, 1 or 2, q denotes 0 or 1, and v denotes 1 to 6.

18. The medium according to claim 1, which additionally comprises one or more polymerizable compounds of formula M or a (co)polymer comprising one or more compounds of formula M: P.sup.1-Sp.sup.1-A.sup.2-(Z.sup.1-A.sup.1).sub.n-Sp.sup.2-P.sup.2 M in which P.sup.1, P.sup.2 each independently denote a polymerizable group, Sp.sup.1, Sp.sup.2 each independently denote a spacer group, A.sup.1, A.sup.2 each, independently of one another, denotes a) trans-1,4-cyclohexylene, 1,4-cyclohexenylene or 4,4″-bicyclohexylene, in which one or more non-adjacent CH.sub.2 groups are each optionally replaced by —O— or —S— and in which one or more H atoms are each optionally replaced by a group L, or is ##STR00472## b) 1,4-phenylene or 1,3-phenylene, in which one or two CH groups are each optionally replaced by N and in which one or more H atoms are each optionally replaced by a group L or -Sp.sup.3-P, c) tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl or selenophene-2,5-diyl, each of which is optionally mono-or polysubstituted by a group L, d) a saturated, partially unsaturated or fully unsaturated, and optionally substituted, polycyclic radical having 5 to 20 cyclic C atoms, one or more of which are optionally replaced by heteroatoms, P.sup.3 denotes a polymerizable group, Sp.sup.3 denotes a spacer group, n denotes 0, 1, 2 or 3, Z.sup.1 in each case, independently of one another, denotes —CO—O—, —O—CO—, —CH.sub.2O—, —OCH.sub.2—, —CF.sub.2O—, —OCF.sub.2—, —(CH.sub.2).sub.n,—where n* is 2, 3 or 4, —O—, —CO—, —C(R.sup.cR.sup.d)—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—or a single bond, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF.sub.5 or a straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxy-carbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or a branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 3 to 12 C atoms, R.sup.c and R.sup.d each, independently of one another, denote H, F, CF.sub.3, or alkyl having 1 to 6 C atoms, where one or more of the groups P.sup.1-Sp.sup.1-, -Sp.sup.2-P.sup.2 and -Sp.sup.3-P.sup.3 optionally denote a radical R.sup.aa, with the proviso that at least one of the groups P.sup.1-Sp.sup.1-, -Sp.sup.2-P.sup.2 and -Sp.sup.3-P.sup.3 present does not denote R.sup.aa, R.sup.aa denotes H, F, CI, CN or straight-chain alkyl having 1 to 25 C atoms, or branched alkyl having 3 to 25 C atoms, in which one or more non-adjacent CH.sub.2 groups are each optionally replaced, independently of one another, by)C(R.sup.0)═C(R.sup.00) -, —C≡C—, —O—, —S—, —CO—, —CO—O—, —O—CO—, or —O—CO—O— in such a way that 0 and/or S atoms are not linked directly to one another, and in which one or more H atoms are each optionally replaced by F, Cl or CN, and R.sup.0, R.sup.00 each, independently of one another, denote H, F or straight-chain alkyl having 1 to 12 C atoms, or branched alkyl having 3 to 12 C atoms, in which one or more H atoms are each optionally replaced by F.

19. The medium according to claim 18, wherein the polymerizable or polymerized component comprises 0.01 to 1.5% by weight of one or more compounds of formula M.

20. A liquid-crystal (LC) display comprising an LC cell having two substrates and at least two electrodes, where at least one substrate is transparent to light and at least one substrate has one or two electrodes, and having a layer of an LC medium according to claim 1 located between the substrates, where the combination of self-alignment additives for vertical alignment are selected from the group consisting of two or more of formulae IE, IF, IG, IJ, IK and IL for affecting homeotropic alignment of the LC medium with respect to the substrate surfaces.

21. The display according to claim 20, wherein at least one of the substrates has no alignment layer.

22. The display according to claim 20, wherein one or two of the substrates is coated with indium-tin oxide.

23. The display according to claim 20, which is a VA display containing an LC medium having negative dielectric anisotropy and electrodes arranged on opposite substrates.

24. A process for preparing a liquid-crystal medium, comprising mixing a combination of self-alignment additives for vertical alignment selected from the group consisting of two or more of formulae IE, IF, IG, IJ, IK and IL according to claim 1 with a low-molecular-weight liquid-crystalline component, and optionally adding one or more polymerizable compounds, and/or other additives.

25. A method for affecting homeotropic alignment of a liquid-crystal medium with respect to a surface delimiting the liquid-crystal medium, comprising adding to said medium a combination of self-alignment additives for vertical alignment selected from the group consisting of two or more of formulae IE, IF, IG, IJ, IK and IL according to claim 1 and optionally polymerizing the same.

26. A process for preparing an LC display comprising an LC cell having two substrates and at least two electrodes, where at least one substrate is transparent to light and at least one substrate has one or two electrodes, said process comprising filling the cell with a liquid-crystal medium according to claim 1, where homeotropic alignment of the liquid-crystal medium with respect to the substrate surfaces is established, optionally heating the medium, and optionally polymerizing the polymerizable component(s), optionally with application of a voltage to the cell or under the action of an electric field.

27. The medium according to claim 1, wherein R.sup.22 denotes alkyl having 2 to 5 C atoms.

Description

SYNTHESIS EXAMPLES

Example 1. 2-Methyl-acrylic acid 3-[4″-(3,3-bis-hydroxymethyl-heptyloxy)-2′-ethyl-5″-[3-(2-methyl-acryloyloxy)-propyl]-4-(4-pentyl-cyclohexyl)[1,1′;4′,1″]terphenyl-3″-yl]-propyl ester

(1) ##STR00390##

Step 1.1. Synthesis of 4-bromo-2-ethyl-4′-(4-pentyl-cyclohexyl)-biphenyl

(2) ##STR00391##

(3) A solution of 4-bromo-2-ethyl-1-iodobenzene (27.2 g, 87.5 mmol)) and [4-(4-pentylcyclohexyl)-phenyl]-boronic acid (24.0 g, 87.5 mmol) in toluene (370 mL) was added to a stirred solution of sodium carbonate (13.9 g, 131.3 mmol) in water (90 mL). The resulted mixture was treated with bis(triphenylphosphine)-palladium(II) chloride (0.3 g, 0.44 mmol) and stirred at 85° C. for 4 h, before it was cooled down to the room temperature, treated with water and methyl tert-butyl ether. Organic phase was separated; aqueous phase was extracted with methyl tert-butyl ether. The combined organic phase was washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) to give the desired product (27.8 g) as white crystals.

Step 1.2. Synthesis of 2′-ethyl-4-(4-pentyl-cyclohexyl)-[1,1′;4′,1″]terphenyl-4″-ol

(4) ##STR00392##

(5) A solution of bromide 1.1 (27.7 g, 67 mmol) in tetrahydrofuran (130 mL) was added to a stirred solution of potassium carbonate (15.5 g, 112.2 mmol) in water (80 mL). The resulted mixture was heated up to 60° C. and treated with butyldi-1-adamantylphosphine(di-(1-adamantyl)-butylphosphine) (0.5 g, 1.3 mmol) and with tris(dibenzylidenacetone)-dipalladium(0) (0.6 g, 0.66 mmol), followed an addition of a solution of 4-hydroxyphenyl boronic acid (10.0 g, 72.6 mmol) in tetrahydrofuran (130 mL) at 65° C. The reaction mixture was stirred overnight under reflux, before it was cooled to the room temperature, treated with water and methyl tert-butyl ether and acidified with 2N HCl solution (to pH 6). Phases were separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) to give phenol (26.7 g) as yellow solid.

Step 1.3. Synthesis of 3″,5″-dibromo-2′-ethyl-4-(4-pentyl-cyclohexyl)[1,1′;4′,1″]terphenyl-4″-ol

(6) ##STR00393##

(7) N-Bromosuccinimide (17.6 g, 98.9 mmol) was added portionswise to a stirred solution of phenol 1.2 (21.4 g, 50.2 mmol) and diisopropyl amine (1.5 ml, 10.3 mmol) in tetrahydrofuran (500 mL) at −5° C. The reaction mixture was allowed to warm to room temperature and stirred overnight, before it was quenched with sodium hydrogensulfite (250 mL, 39% solution). Phases were separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo to give dibromide (33.2 g) as an orange oil.

Step 1.4. Synthesis of 4″-[3,3-bis-(tert-butyl-dimethyl-silanyloxymethyl)heptyloxy]-3″,5″-dibromo-2′-ethyl-4-(4-pentyl-cyclohexyl)-[1,1′;4′,1″]terphenyl

(8) ##STR00394##

(9) Triphenylphosphine (7.1 g, 27.1 mmol) was added to a stirred solution of dibromide 1.3 (13.0 g, 22.2 mmol) and 3,3-bis-(tert-butyl-dimethylsilanyloxymethyl)-heptan-1-ol (11.5 g, 28.3 mmol) in tetrahydrofuran (150 mL), followed by the addition of diisopropyl azodicarboxylate (5.3 mL, 27.1 mmol) at room temperature. The reaction mixture was stirred overnight, before it was concentrated under the reduced pressure, treated with heptane (100 mL) and filtered. The mother liquor was concentrated in vacuo and the residue was purified by flash chromatography (heptane/toluene) to give the desired product (17.7 g) as a colorless oil.

Step 1.5. Synthesis of 3-[4″-[3,3-bis-(tert-butyl-dimethyl-silanyloxymethyl)heptyloxy]-2′-ethyl-5″-(3-hydroxy-propyl)-4-(4-pentyl-cyclohexyl)[1,1′;4′,1″]terphenyl-3″-yl]-propan-1-ol

(10) ##STR00395##

(11) A solution of dibromide 1.4 (25.7 g, 25.4 mmol) and 2-butoxy-1,2-oxaborolane (13.7 g, 96.4 mmol) in tetrahydrofuran (400 mL) was added to a stirred solution of potassium phosphate monohydrate (30.7 g, 126.8 mmol) in water (80 mL). The resulted mixture was treated with palladium(II) acetate (0.1 g, 0.5 mmol) and 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl (0.5 g, 1.0 mmol) at room temperature. The reaction mixture was stirred overnight at 65° C., before it was cooled to the room temperature and treated with water and methyl tert-butyl ether. Phases were separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) to give the desired diol (19.0 g) as a yellowish oil.

Step 1.6. Synthesis of 2-methyl-acrylic acid 3-[4″-[3,3-bis-(tert-butyldimethyl-silanyloxymethyl)-heptyloxy]-2′-ethyl-5″-[3-(2-methyl-acryloyloxy)propyl]-4-(4-pentyl-cyclohexyl)-[1,1′;4′,1″]terphenyl-3″-yl]-propyl ester

(12) ##STR00396##

(13) A solution of diol 1.5 (19.0 g, 20.32 mmol) in dichloromethane (220 mL) was treated with methacrylic acid (8.6 mL, 101.6 mmol) and 4-(dimethylamino)pyridine (0.5 g, 4.1 mmol) at room temperature, followed by treatment with a solution of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (17.5 mL, 101.6 mmol) in dichloromethane (90 mL) at 3° C. The reaction mixture was allowed to warm to the room temperature and was stirred overnight, before it was concentrated in vacuo. The residue was purified with flash chromatography (dichloromethane/methyl tert-butyl ether) to give the desired product (10.7 g) as a colorless oil.

Step 1.7. Synthesis of 2-methyl-acrylic acid 3-[4″-(3,3-bis-hydroxymethylheptyloxy)-2′-ethyl-5″-[3-(2-methyl-acryloyloxy)-propyl]-4-(4-pentyl-cyclohexyl)-[1,1′;4′,1″]terphenyl-3″-yl]-propyl ester

(14) ##STR00397##

(15) A solution of tetrabutyl ammonium fluoride (1M in THF, 32 mL, 32 mmol) was added dropwise to a stirred solution of compound 1.6 (10.6 g, 12.7 mmol) in tetrahydrofuran (80 mL) at 3° C. The reaction mixture was allowed to warm to room temperature, was stirred overnight, cooled to 0° C. and treated with methyl tert-butyl ether and aqueous NaHCO.sub.3 solution (to pH 9). Phases were separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) to give the desired diol (5.5 g) as a colorless oil. .sup.1H NMR (Chloroform-d): δ 7.47 (d, J=1.9 Hz, 1H), 7.40 (dd, J=7.9, 2.0 Hz, 1H), 7.33 (s, 2H), 7.29 (d, J=4.7 Hz, 5H), 6.15 (t, J=1.3 Hz, 2H), 5.59 (p, J=1.6 Hz, 2H), 4.29 (t, J=6.6 Hz, 4H), 3.97 (t, J=6.4 Hz, 2H), 3.71 (d, J=5.2 Hz, 4H), 2.87-2.76 (m, 6H), 2.71 (q, J=7.5 Hz, 2H), 2.55 (tt, J=12.0, 3.4 Hz, 1H), 2.16-2.07 (m, 4H), 2.04-1.88 (m, 12H), 1.53 (qd, J=12.9, 3.3 Hz, 2H), 1.43-1.23 (m, 15H), 1.24-1.04 (m, 5H), 1.01-0.86 (m, 6H).

Example 2. 2-Methyl-acrylic acid 3-[4-(3,3-bis-hydroxymethyl-heptyloxy)-2′-cyclopropyl-5-[3-(2-methyl-acryloyloxy)-propyl]-4″-(4-pentyl-cyclohexyl)[1,1′;4′,1″]terphenyl-3-yl]-propyl ester

(16) ##STR00398##

Step 2.1. Synthesis of 4′-bromo-2′-chloro-biphenyl-4-ol

(17) ##STR00399##

(18) A solution of 4-bromo-2-chloro-iodobenzene (46.0 g, 142.1 mmol) and 4-hydroxyphenyl boronic acid (20.2 g, 142.1 mmol) in 1,4-dioxane (480 mL) was added to a stirred solution of Na.sub.2CO.sub.3 (32.1 g, 302.6 mmol) in water (150 mL). The resulted mixture was treated with [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (11) (3.1 g, 4.3 mmol) and stirred overnight at 80° C., before it was cooled to the room temperature, treated with water and methyl tert-butyl ether and acidified with 2N HCl solution (to pH 7). The suspension was filtered through a pad of Celite, phases were separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) to give phenol (23.4 g) as a brownish solid.

Step 2.2. Synthesis of 2′-chloro-4″-(4-pentyl-cyclohexyl)-[1,1′;4′,1″]terphenyl-4-ol

(19) ##STR00400##

(20) A solution of bromide 2.1 (21.4 g, 67.5 mmol) in tetrahydrofuran (200 mL) was added to a stirred solution of potassium carbonate (15.8 g, 114.7 mmol) in water (60 mL). The resulted mixture was heated up to 60° C. and treated with butyldi-1-adamantylphosphine(di-(1-adamantyl)-butylphosphine) (0.51 g, 1.4 mmol) and with Tris(dibenzylidenacetone)-dipalladium (0) (0.6 g, 0.67 mmol), followed an addition of a solution of [4-(4-pentylcyclohexyl)-phenyl]-boronic acid (18.6 g, 67.5 mmol) in tetrahydrofuran (40 mL) at 65° C. The reaction mixture was stirred overnight under reflux, before it was cooled to the room temperature, treated with water and methyl tert-butyl ether and acidified with 2N HCl solution (to pH 3). Phases were separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (dichloromethane/methyl tert-butyl ether) to give phenol (29.8 g) as a yellow solid.

Step 2.3. Synthesis of 2′-cyclopropyl-4″-(4-pentyl-cyclohexyl)[1,1′;4′,1″]terphenyl-4-ol

(21) ##STR00401##

(22) Palladium (II) acetate (0.46 g, 2.0 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (1.9 g, 4.1 mmol) were added to a stirred solution of potassium carbonate (28.0 g, 202.7 mmol), phenol 2.2 (30.6 g, 67.6 mmol) and cyclopropyl boronic acid (12.2 g, 135.1 mmol) in water (80 mL) and toluene (450 mL). The reaction mixture was stirred overnight under reflux, before it was cooled to the room temperature, treated with water and methyl tert-butyl ether and acidified with 2N HCl solution (to pH 3). Phases were separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) and recrystallization (1-chlorobutane) to give the desired phenol (17.7 g) as a brownish solid.

Step 2.4. Synthesis of 3,5-dibromo-2′-cyclopropyl-4″-(4-pentyl-cyclohexyl)[1,1′;4′,1″]terphenyl-4-ol

(23) ##STR00402##

(24) A solution of N-bromosuccinimide (13.9 g, 78.2 mmol) in dichloromethane (100 mL) was added dropwise to a stirred solution of phenol 2.3 (17.2 g, 39.1 mmol) and diisopropyl amine (1.1 ml, 8.2 mmol) in dichloromethane (200 mL) at −5° C. The reaction mixture was allowed to warm to room temperature and stirred overnight, before it was quenched with sodium hydrogensulfite (250 mL, 39% solution). Phases were separated, and the aqueous phase was extracted with dichloromethane. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo to give dibromide (22.3 g) as brown oil.

Step 2.5. Synthesis of 4-[3,3-bis-(tert-butyl-dimethyl-silanyloxymethyl)heptyloxy]-3,5-dibromo-2′-cyclopropyl-4″-(4-pentyl-cyclohexyl)[1,1′;4′,1″]terphenyl

(25) ##STR00403##

(26) Triphenylphosphine (12.0 g, 45.7 mmol) was added to a stirred solution of dibromide 2.4 (22.3 g, 37.4 mmol) and 3,3-bis-(tert-butyl-dimethylsilanyloxymethyl)-heptan-1-ol (19.3 g, 47.6 mmol) in tetrahydrofuran (250 mL), followed by the addition of diisopropyl azodicarboxylate (9.0 mL, 45.7 mmol) at room temperature. The reaction mixture was stirred overnight, before it was concentrated under the reduced pressure, treated with heptane (400 mL) and filtered. The mother liquor was concentrated in vacuo and the residue was purified by flash chromatography (heptane/toluene) to give the desired product (19.1 g) as a colorless oil.

Step 2.6. Synthesis of 3-[4-[3,3-bis-(tert-butyl-dimethyl-silanyloxymethyl)heptyloxy]-2′-cyclopropyl-5-(3-hydroxy-propyl)-4″-(4-pentyl-cyclohexyl)[1,1′;4′,1″]terphenyl-3-yl]-propan-1-ol

(27) ##STR00404##

(28) A solution of dibromide 2.5 (19.4 g, 19.7 mmol) and 2-butoxy-1,2-oxaborolane (10.6 g, 74.8 mmol) in tetrahydrofuran (300 mL) was added to a stirred solution of potassium phosphate monohydrate (23.9 g, 98.4 mmol) in water (60 mL). The resulted mixture was treated with palladium(II) acetate (0.09 g, 0.39 mmol) and 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl (0.39 g, 0.79 mmol) at room temperature. The reaction mixture was stirred for 4.5 h at 65° C., before it was cooled to the room temperature and treated with water and methyl tert-butyl ether. Phases were separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) to give the desired diol (17.8 g) as a yellowish oil.

Step 2.7. Synthesis of 2-methyl-acrylic acid 3-[4-[3,3-bis-(tert-butyl-dimethylsilanyloxymethyl)-heptyloxy]-2′-cyclopropyl-5-[3-(2-methyl-acryloyloxy)propyl]-4″-(4-pentyl-cyclohexyl)-[1,1′;4′,1″]terphenyl-3-yl]-propyl ester

(29) ##STR00405##

(30) A solution of diol 2.6 (17.8 g, 18.8 mmol) in dichloromethane (140 mL) was treated with methacrylic acid (8.0 mL, 94.0 mmol) and 4-(dimethylamino)pyridine (0.46 g, 3.8 mmol) at room temperature, followed by treatment with a solution of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (16.0 mL, 94.0 mmol) in dichloromethane (50 mL) at 3° C. The reaction mixture was allowed to warm to the room temperature and was stirred overnight, before it was concentrated in vacuo. The residue was purified with flash chromatography (dichloromethane) to give the desired product (13.7 g) as a colorless oil.

Step 2.8. Synthesis of 2-methyl-acrylic acid 3-[4-(3,3-bis-hydroxymethylheptyloxy)-2′-cyclopropyl-5-[3-(2-methyl-acryloyloxy)-propyl]-4″-(4-pentyl-cyclohexyl)-[1,1′;4′,1″]terphenyl-3-yl]-propyl ester

(31) ##STR00406##

(32) A solution of tetrabutyl ammonium fluoride (1M in THF, 40 mL, 40 mmol) was added dropwise to a stirred solution of compound 2.7 (13.7 g, 12.7 mmol) in tetrahydrofuran (100 mL) at 2° C. The reaction mixture was allowed to warm to room temperature, was stirred overnight, cooled to 0° C. and treated with methyl tert-butyl ether and aqueous NaHCO.sub.3 solution (to pH 8). Phases were separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with saturated NaCl solution, dried over Na.sub.2SO.sub.4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (heptane/ethyl acetate) to give the desired diol (6.1 g) as a colorless oil. .sup.1H NMR (Chloroform-d): δ 7.56-7.51 (m, 2H), 7.42 (dd, J=7.9, 1.9 Hz, 1H), 7.34-7.30 (m, 2H), 7.28 (d, J=7.9 Hz, 1H), 7.21 (s, 2H), 7.14 (d, J=1.8 Hz, 1H), 6.13 (t, J=1.3 Hz, 2H), 5.58 (p, J=1.6 Hz, 2H), 4.27 (t, J=6.6 Hz, 4H), 4.00 (t, J=6.4 Hz, 2H), 3.71 (d, J=5.3 Hz, 4H), 2.89-2.74 (m, 6H), 2.54 (tt, J=12.1, 3.3 Hz, 1H), 2.13-2.05 (m, 4H), 2.04-1.88 (m, 13H), 1.52 (qd, J=12.7, 3.0 Hz, 2H), 1.41-1.22 (m, 15H), 1.10 (qd, J=12.8, 3.1 Hz, 2H), 0.97-0.87 (m, 8H), 0.82-0.76 (m, 2H).

(33) According to the synthetic procedures, described for example, in the documents WO 2012/038026 A1, EP 2918658, WO 2016/015803, WO 2017/041893, WO 2017/045740 and the above shown synthesis pathway the following compounds have been synthesized:

Example 3

(34) ##STR00407##

(35) White crystals. Melting point: 58° C. (K 58 l).

(36) .sup.1H NMR (Chloroform-d): δ 7.59-7.55 (m, 2H), 7.49-7.42 (m, 2H), 7.38 (dd, J=12.1, 1.5 Hz, 1H), 7.35-7.32 (m, 2H), 7.30 (d, J=1.4 Hz, 2H), 6.13 (t, J=1.3 Hz, 2H), 5.59 (p, J=1.6 Hz, 2H), 4.28 (t, J=6.5 Hz, 4H), 3.98 (t, J=6.4 Hz, 2H), 3.70 (s, 4H), 2.87-2.70 (m, 6H), 2.55 (tt, J=12.1, 3.3 Hz, 1H), 2.15-2.04 (m, 4H), 2.05-1.88 (m, 12H), 1.52 (qd, J=12.8, 3.0 Hz, 2H), 1.41-1.22 (m, 15H), 1.10 (qd, J=13.1, 12.7, 2.8 Hz, 2H), 0.94 (q, J=6.9 Hz, 6H).

Example 4

(37) ##STR00408##

(38) White crystals. Melting point: 76° C. (K 76 SmA 91 l).

(39) .sup.1H NMR (500 MHz, Chloroform-d): δ 7.60-7.54 (m, 2H), 7.49-7.43 (m, 2H), 7.38 (dd, J=12.0, 1.6 Hz, 1H), 7.35-7.32 (m, 2H), 7.30 (d, J=1.4 Hz, 2H), 6.13 (t, J=1.4 Hz, 2H), 5.59 (p, J=1.6 Hz, 2H), 4.28 (t, J=6.6 Hz, 4H), 4.01-3.89 (m, 4H), 3.82 (dd, J=10.8, 6.7 Hz, 2H), 2.84-2.75 (m, 4H), 2.70 (br.s., 2H), 2.55 (tt, J=12.2, 3.4 Hz, 1H), 2.18-2.03 (m, 5H), 2.02-1.85 (m, 12H), 1.52 (qd, J=12.8, 3.0 Hz, 2H), 1.43-1.23 (m, 9H), 1.10 (qd, J=13.1, 12.7, 2.8 Hz, 2H), 0.93 (t, J=7.1 Hz, 3H).

Example 5

(40) ##STR00409##

(41) White crystals. Melting point: 58° C. (K 58 l).

(42) .sup.1H NMR (Chloroform-d): δ 7.61-7.56 (m, 2H), 7.53 (d, J=1.9 Hz, 1H), 7.45 (dd, J=7.9, 2.0 Hz, 1H), 7.34-7.31 (m, 2H), 7.24 (d, J=7.9 Hz, 1H), 7.07 (s, 2H), 6.13 (t, J=1.3 Hz, 2H), 5.58 (p, J=1.6 Hz, 2H), 4.26 (t, J=6.6 Hz, 4H), 4.00 (t, J=6.3 Hz, 2H), 3.71 (s, 4H), 2.89-2.76 (m, 6H), 2.67 (q, J=7.5 Hz, 2H), 2.55 (tt, J=12.1, 3.4 Hz, 1H), 2.11-2.04 (m, 4H), 2.04-1.86 (m, 12H), 1.53 (qd, J=12.9, 3.2 Hz, 2H), 1.44-1.23 (m, 11H), 1.18 (t, J=7.5 Hz, 3H), 1.11 (qd, J=12.8, 3.2 Hz, 2H), 0.95 (td, J=7.1, 3.0 Hz, 6H).

Example 6

(43) ##STR00410##

(44) White crystals. Melting point: 40° C. (K 40 l).

(45) .sup.1H NMR (Chloroform-d): δ 7.61-7.55 (m, 2H), 7.53 (d, J=1.9 Hz, 1H), 7.45 (dd, J=7.9, 2.0 Hz, 1H), 7.35-7.30 (m, 2H), 7.24 (d, J=7.9 Hz, 1H), 7.06 (s, 2H), 6.13 (t, J=1.3 Hz, 2H), 5.58 (p, J=1.6 Hz, 2H), 4.26 (t, J=6.6 Hz, 4H), 3.99 (t, J=6.3 Hz, 2H), 3.76-3.64 (m, 4H), 2.86-2.74 (m, 6H), 2.66 (q, J=7.6 Hz, 2H), 2.59-2.48 (m, 1H), 2.11-2.04 (m, 4H), 2.04-1.88 (m, 12H), 1.53 (qd, J=12.8, 3.1 Hz, 2H), 1.41-1.23 (m, 17H), 1.18 (t, J=7.5 Hz, 3H), 1.10 (qd, J=12.9, 3.1 Hz, 2H), 0.93 (td, J=7.0, 5.4 Hz, 6H).

Example 7

(46) ##STR00411##

(47) White Crystals: Tg −18° C., melting point: 52° C.

(48) .sup.1H NMR (400 MHz, Chloroform-d) δ 7.49-7.34 (m, 2H), 7.10-6.97 (m, 2H), 6.10 (t, J=1.4 Hz, 1H), 5.55 (p, J=1.6 Hz, 1H), 4.24 (t, J=6.6 Hz, 2H), 3.97 (t, J=6.4 Hz, 1H), 3.68 (d, J=5.6 Hz, 2H), 2.83-2.72 (m, 3H), 2.63 (q, J=7.5 Hz, 1H), 2.10-1.91 (m, 8H), 1.89 (t, J=6.5 Hz, 1H), 1.60 (s, 2H), 1.55-1.40 (m, 1H), 1.36-1.28 (m, 5H), 1.28-1.18 (m, 2H), 1.18-0.99 (m, 3H), 0.97-0.86 (m, 3H).

Example 8

(49) ##STR00412##

(50) White Crystals: Tg −28° C., melting point: 54° C.

(51) .sup.1H NMR (400 MHz, Chloroform-d) δ 7.49-7.34 (m, 1H), 7.03 (s, 1H), 6.10 (t, J=1.3 Hz, 1H), 5.56 (p, J=1.6 Hz, 1H), 4.24 (t, J=6.6 Hz, 2H), 3.97-3.86 (m, 2H), 3.80 (ddd, J=10.9, 6.7, 5.4 Hz, 1H), 2.79-2.70 (m, 2H), 2.68-2.58 (m, 2H), 2.15-2.01 (m, 2H), 2.01-1.90 (m, 4H), 1.87 (q, J=6.2 Hz, 1H), 1.58 (s, 1H), 1.56-1.40 (m, 1H), 1.38-1.18 (m, 4H), 1.18-0.99 (m, 2H), 0.90 (t, J=6.9 Hz, 1H).

Example 9

(52) ##STR00413##

(53) White Crystals: Tg −17° C., melting point: 74° C.

(54) 1H NMR (400 MHz, Chloroform-d) δ 7.49-7.34 (m, 1H), 7.03 (s, 1H), 6.10 (t, J=1.3 Hz, 1H), 5.56 (p, J=1.6 Hz, 1H), 4.24 (t, J=6.6 Hz, 2H), 3.97-3.86 (m, 2H), 3.80 (ddd, J=10.9, 6.7, 5.4 Hz, 1H), 2.79-2.70 (m, 2H), 2.68-2.58 (m, 2H), 2.15-2.01 (m, 2H), 2.01-1.90 (m, 4H), 1.87 (q, J=6.2 Hz, 1H), 1.58 (s, 1H), 1.56-1.40 (m, 1H), 1.38-1.18 (m, 4H), 1.18-0.99 (m, 2H), 0.90 (t, J=6.9 Hz, 1H).

Example 10

(55) ##STR00414##

(56) White Crystals: Tg −18° C., melting point: 45° C.

(57) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.45-7.38 (m, 1H), 7.13-7.01 (m, 2H), 6.13 (t, J=1.3 Hz, 1H), 5.58 (p, J=1.6 Hz, 1H), 4.26 (t, J=6.5 Hz, 2H), 3.99 (t, J=6.4 Hz, 1H), 3.73-3.69 (m, 2H), 2.83-2.73 (m, 3H), 2.66 (q, J=7.6 Hz, 1H), 2.12-2.04 (m, 2H), 2.04-1.95 (m, 5H), 1.92 (dd, J=13.3, 3.2 Hz, 1H), 1.55-1.33 (m, 4H), 1.33-1.22 (m, 3H), 1.20-1.02 (m, 3H), 0.96-0.89 (m, 3H).

Example 11

(58) ##STR00415##

(59) White Crystals: Tg −26° C., melting point: 85° C.

(60) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.61-7.56 (m, 2H), 7.53 (d, J=1.9 Hz, 1H), 7.45 (dd, J=7.8, 2.0 Hz, 1H), 7.32 (d, J=8.2 Hz, 2H), 7.21-7.14 (m, 2H), 6.91 (d, J=8.3 Hz, 1H), 6.11 (p, J=1.1 Hz, 1H), 5.58 (p, J=1.6 Hz, 1H), 4.24 (t, J=6.9 Hz, 2H), 4.13 (t, J=6.0 Hz, 2H), 3.95 (dd, J=10.8, 4.0 Hz, 2H), 3.81 (dd, J=10.8, 7.0 Hz, 2H), 2.78 (dd, J=8.5, 6.6 Hz, 2H), 2.69 (q, J=7.5 Hz, 2H), 2.55 (tt, J=12.0, 3.4 Hz, 2H), 2.15 (ddp, J=10.9, 7.1, 3.9, 3.4 Hz, 1H), 2.10-2.02 (m, 2H), 2.02-1.87 (m, 9H), 1.59-1.45 (m, 2H), 1.42-1.22 (m, 9H), 1.21-1.03 (m, 5H), 0.93 (t, J=7.1 Hz, 3H).

Example 12

(61) ##STR00416##

(62) White Crystals: Tg −15° C.

(63) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.58 (d, J=8.2 Hz, 2H), 7.45 (dd, J=7.9, 2.0 Hz, 1H), 7.32 (d, J=8.3 Hz, 2H), 7.26 (d, J=7.9 Hz, 1H), 7.22-7.14 (m, 2H), 6.95 (d, J=8.3 Hz, 1H), 4.24 (t, J=6.6 Hz, 2H), 4.17 (t, J=6.3 Hz, 2H), 3.77-3.67 (m, 4H), 2.78 (dd, J=8.5, 6.6 Hz, 2H), 2.68 (q, J=7.5 Hz, 2H), 2.59-2.50 (m, 3H), 2.05 (dq, J=8.8, 6.7 Hz, 2H), 2.01-1.88 (m, 9H), 1.59-1.42 (m, 7H), 1.40-1.22 (m, 9H), 1.21-1.04 (m, 5H), 0.98-0.90 (m, 6H).

Example 13

(64) ##STR00417##

(65) White Crystals Tg −30° C. TM=52° C.

(66) H NMR (500 MHz, Chloroform-d) δ 7.60-7.52 (m, 2H), 7.50 (d, J=1.9 Hz, 1H), 7.42 (dd, J=7.9, 1.9 Hz, 1H), 7.30 (d, J=1.8 Hz, 2H), 7.22 (d, J=7.9 Hz, 1H), 7.03 (s, 2H), 6.11 (t, J=1.3 Hz, 2H), 5.55 (p, J=1.6 Hz, 2H), 4.24 (t, J=6.5 Hz, 4H), 4.00 (t, J=5.9 Hz, 2H), 3.95 (t, J=5.8 Hz, 2H), 2.84-2.73 (m, 4H), 2.64 (q, J=7.6 Hz, 2H), 2.52 (tt, J=12.1, 3.4 Hz, 1H), 2.06 (ddq, J=12.7, 9.7, 6.2 Hz, 6H), 1.99-1.84 (m, 11H), 1.50 (qd, J=12.8, 3.1 Hz, 2H), 1.40-1.20 (m, 9H), 1.18-1.02 (m, 5H), 0.91 (t, J=7.0 Hz, 3H).

Example 14

(67) ##STR00418##

(68) White Crystals Tg −24° C. Tm=51° C.

(69) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.61-7.56 (m, 2H), 7.53 (d, J=1.9 Hz, 1H), 7.46 (dd, J=7.9, 2.0 Hz, 1H), 7.34-7.27 (m, 2H), 7.25 (d, J=7.9 Hz, 1H), 7.23-7.17 (m, 2H), 6.93 (d, J=8.3 Hz, 1H), 6.15 (d, J=1.3 Hz, 1H), 5.54 (t, J=1.6 Hz, 1H), 4.45 (t, J=7.3 Hz, 2H), 4.15 (t, J=5.9 Hz, 2H), 3.94 (dd, J=10.7, 4.1 Hz, 2H), 3.82 (dd, J=10.8, 6.8 Hz, 2H), 3.08 (t, J=7.3 Hz, 2H), 2.72-2.63 (m, 4H), 2.33 (tdd, J=8.8, 6.9, 1.4 Hz, 2H), 2.18 (ddp, J=11.0, 7.0, 4.0, 3.5 Hz, 1H), 1.91 (q, J=6.2 Hz, 2H), 1.75-1.61 (m, 2H), 1.39 (dq, J=7.2, 4.0, 3.3 Hz, 4H), 1.17 (t, J=7.5 Hz, 3H), 1.08 (t, J=7.4 Hz, 3H), 0.98-0.88 (m, 3H).

Example 15

(70) ##STR00419##

(71) White Crystals Tg −17° C. Tm=50° C.

(72) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.60-7.52 (m, 2H), 7.50 (d, J=1.9 Hz, 1H), 7.42 (dd, J=7.8, 2.0 Hz, 1H), 7.31 (s, 2H), 7.22 (d, J=7.9 Hz, 1H), 7.04 (s, 2H), 6.10 (s, 2H), 5.56 (t, J=1.8 Hz, 2H), 4.24 (t, J=6.5 Hz, 4H), 3.97 (t, J=6.3 Hz, 2H), 3.69 (s, 4H), 2.91-2.69 (m, 5H), 2.64 (q, J=7.6 Hz, 2H), 2.52 (tt, J=12.2, 3.4 Hz, 1H), 2.15-1.76 (m, 16H), 1.50 (qd, J=12.7, 3.1 Hz, 2H), 1.39-1.19 (m, 13H), 1.15 (t, J=7.5 Hz, 3H), 1.08 (qd, J=12.8, 3.1 Hz, 2H), 0.92 (dt, J=14.2, 6.4 Hz, 6H).

Example 16

(73) ##STR00420##

(74) White Crystals Tg −18° C. Tm=52° C.

(75) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.61-7.53 (m, 2H), 7.50 (d, J=1.9 Hz, 1H), 7.42 (dd, J=7.9, 1.9 Hz, 1H), 7.30 (d, J=8.3 Hz, 2H), 7.22 (d, J=7.9 Hz, 1H), 7.04 (s, 2H), 6.10 (t, J=1.3 Hz, 2H), 5.56 (p, J=1.6 Hz, 2H), 4.24 (t, J=6.5 Hz, 4H), 4.00 (t, J=6.3 Hz, 2H), 3.66 (s, 4H), 2.80-2.73 (m, 4H), 2.64 (q, J=7.5 Hz, 2H), 2.52 (tt, J=12.1, 3.4 Hz, 1H), 2.04 (ddt, J=18.1, 8.3, 6.4 Hz, 6H), 1.98-1.83 (m, 10H), 1.50 (qd, J=12.8, 3.1 Hz, 4H), 1.39-1.18 (m, 10H), 1.15 (t, J=7.5 Hz, 3H), 1.08 (qd, J=12.8, 3.1 Hz, 2H), 0.95-0.86 (m, 6H).

Example 17

(76) ##STR00421##

(77) White Crystals Tg −28° C. Tm=37° C.

(78) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.58-7.53 (m, 2H), 7.50 (d, J=1.9 Hz, 1H), 7.43 (dd, J=7.9, 2.0 Hz, 1H), 7.30 (d, J=8.2 Hz, 2H), 7.22 (d, J=7.9 Hz, 1H), 7.04 (s, 2H), 6.11 (t, J=1.3 Hz, 2H), 5.56 (p, J=1.6 Hz, 2H), 4.24 (t, J=6.5 Hz, 4H), 3.97 (t, J=6.4 Hz, 2H), 3.68 (d, J=4.6 Hz, 4H), 2.85-2.70 (m, 6H), 2.64 (q, J=7.5 Hz, 2H), 2.52 (tt, J=12.1, 3.4 Hz, 1H), 2.10-2.01 (m, 4H), 2.00-1.86 (m, 12H), 1.50 (qd, J=12.8, 3.1 Hz, 2H), 1.40 (q, J=7.6 Hz, 2H), 1.37-1.18 (m, 10H), 1.15 (t, J=7.5 Hz, 3H), 1.08 (qd, J=13.0, 3.1 Hz, 2H), 0.94-0.83 (m, 6H).

Example 18

(79) ##STR00422##

(80) White Crystals Tg −18° C. Tm=40° C.

(81) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.46 (d, J=1.6 Hz, 1H), 7.43-7.34 (m, 2H), 7.22 (d, J=7.9 Hz, 1H), 7.07 (dd, J=8.0, 1.7 Hz, 1H), 7.02 (d, J=17.6 Hz, 3H), 6.10 (t, J=1.3 Hz, 2H), 5.56 (p, J=1.6 Hz, 2H), 4.24 (t, J=6.5 Hz, 4H), 3.97 (t, J=6.3 Hz, 2H), 3.68 (s, 4H), 2.82-2.71 (m, 6H), 2.63 (q, J=7.5 Hz, 2H), 2.51 (tt, J=12.3, 3.5 Hz, 1H), 2.09-2.01 (m, 4H), 2.01-1.84 (m, 12H), 1.53-1.40 (m, 2H), 1.38-1.17 (m, 15H), 1.14 (t, J=7.5 Hz, 3H), 1.07 (qd, J=13.0, 3.2 Hz, 2H), 0.96-0.78 (m, 6H).

Example 19

(82) ##STR00423##

(83) White Crystals Tg −24° C. Tm=67° C.

(84) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.59-7.53 (m, 2H), 7.50 (d, J=1.9 Hz, 1H), 7.42 (dd, J=7.9, 1.9 Hz, 1H), 7.30 (d, J=8.2 Hz, 2H), 7.22 (d, J=7.8 Hz, 1H), 7.03 (s, 2H), 6.15-6.04 (m, 2H), 5.56 (p, J=1.6 Hz, 2H), 4.24 (t, J=6.6 Hz, 4H), 3.92 (dt, J=8.8, 5.2 Hz, 4H), 3.80 (dd, J=10.8, 6.7 Hz, 2H), 2.81-2.70 (m, 4H), 2.64 (q, J=7.5 Hz, 3H), 2.52 (tt, J=12.2, 3.4 Hz, 2H), 2.12 (tt, J=6.5, 4.1 Hz, 1H), 2.08-2.00 (m, 4H), 1.98-1.82 (m, 12H), 1.50 (qd, J=12.8, 3.1 Hz, 2H), 1.38-1.19 (m, 7H), 1.15 (t, J=7.5 Hz, 3H), 1.08 (qd, J=12.9, 3.2 Hz, 2H), 0.97-0.84 (m, 3H).

Example 20

(85) ##STR00424##

(86) White Crystals Tg −26° C. Tm=72° C.

(87) .sup.1H NMR (500 MHz, Chloroform-d) δ 7.59-7.52 (m, 2H), 7.50 (d, J=1.9 Hz, 1H), 7.42 (dd, J=7.9, 2.0 Hz, 1H), 7.30 (d, J=8.3 Hz, 2H), 7.22 (d, J=7.9 Hz, 1H), 7.03 (s, 2H), 6.10 (t, J=1.4 Hz, 2H), 5.56 (p, J=1.6 Hz, 2H), 4.24 (t, J=6.6 Hz, 4H), 3.92 (dt, J=8.9, 5.2 Hz, 4H), 3.80 (dd, J=10.8, 6.7 Hz, 2H), 2.80-2.70 (m, 4H), 2.64 (q, J=7.5 Hz, 3H), 2.52 (tt, J=12.2, 3.4 Hz, 2H), 2.12 (tt, J=6.6, 4.2 Hz, 1H), 2.08-1.99 (m, 4H), 1.98-1.77 (m, 12H), 1.50 (qd, J=12.8, 3.1 Hz, 2H), 1.39-1.18 (m, 11H), 1.15 (t, J=7.6 Hz, 3H), 1.08 (qd, J=12.8, 3.1 Hz, 2H), 0.90 (t, J=6.9 Hz, 3H).

Example 21

(88) ##STR00425##

(89) White Crystals Tg −18° C. Tm=67° C.

(90) .sup.1H NMR (500 MHz, Chloroform-d) b 7.60-7.51 (m, 2H), 7.50 (d, J=1.9 Hz, 1H), 7.43 (dd, J=7.9, 1.9 Hz, 1H), 7.30 (d, J=8.2 Hz, 2H), 7.22 (d, J=7.9 Hz, 1H), 7.04 (s, 2H), 6.11 (t, J=1.3 Hz, 2H), 5.56 (p, J=1.6 Hz, 2H), 4.24 (t, J=6.6 Hz, 4H), 3.97 (t, J=6.3 Hz, 2H), 3.69 (s, 4H), 2.91-2.68 (m, 6H), 2.64 (q, J=7.5 Hz, 2H), 2.52 (tt, J=12.2, 3.4 Hz, 1H), 2.10-2.01 (m, 4H), 2.01-1.84 (m, 12H), 1.50 (qd, J=12.8, 3.1 Hz, 2H), 1.40-1.19 (m, 13H), 1.15 (t, J=7.5 Hz, 3H), 1.08 (qd, J=12.9, 3.2 Hz, 2H), 0.92 (h, J=3.7 Hz, 6H).

Example 23

(91) ##STR00426##

(92) Tg −24° C.

(93) H NMR (500 MHz, Chloroform-d) δ 7.60-7.52 (m, 2H), 7.50 (d, J=1.8 Hz, 1H), 7.42 (dd, J=7.9, 1.9 Hz, 1H), 7.30 (d, J=8.3 Hz, 2H), 7.22 (d, J=7.9 Hz, 1H), 7.04 (s, 2H), 6.10 (d, J=1.6 Hz, 2H), 5.56 (p, J=1.6 Hz, 2H), 4.24 (t, J=6.6 Hz, 4H), 3.97 (t, J=6.3 Hz, 2H), 3.69 (s, 4H), 2.83-2.71 (m, 6H), 2.64 (q, J=7.5 Hz, 2H), 2.52 (tt, J=12.1, 3.4 Hz, 1H), 2.09-2.01 (m, 4H), 2.01-1.83 (m, 12H), 1.50 (qd, J=12.8, 3.1 Hz, 2H), 1.39-1.21 (m, 17H), 1.15 (t, J=7.5 Hz, 3H), 1.08 (qd, J=12.9, 3.2 Hz, 2H), 0.91 (dt, J=10.3, 6.9 Hz, 6H).

EXAMPLES

(94) The compounds employed, if not commercially available, are synthesized by standard laboratory procedures. The LC media originate from Merck KGaA, Germany.

A) Mixture Examples

(95) LC media according to the invention are prepared using the following liquid-crystalline mixtures consisting of low-molecular-weight components in the percentage proportions by weight indicated.

(96) TABLE-US-00005 H1: Nematic host mixture (Δε < 0) CY-3-O2 15.50% Clearing point [° C.]: 75.1 CCY-3-O3 8.00% Δn (589 nm, 20° C.): 0.098 CCY-4-O2 10.00% Δε (1 kHz, 20° C.): −3.0 CPY-2-O2 5.50% ε.sub.|| (1 kHz, 20° C.): 3.4 CPY-3-O2 11.50% ε.sub.⊥ (1 kHz, 20° C.): 6.4 CC-3-4 9.25% K.sub.1 (20° C.) [pN]: 13.1 CC-2-3 24.50% K.sub.3 (20° C.) [pN]: 13.3 PYP-2-3 8.75% γ.sub.1 (20° C.) [mPa .Math. s]: 113 CP-3-O1 7.00% V.sub.0 (20° C.) [V]: 2.22

(97) TABLE-US-00006 H2: Nematic host mixture (Δε < 0) CPP-3-2 10.5%  Clearing point [° C.]: 74.5 CC-3-4 9.0% Δn (589 nm, 20° C.): 0.109 CC-3-5 9.0% Δε (1 kHz, 20° C.): −3.4 CCP-3-1 8.0% ε.sub.|| (1 kHz, 20° C.): 3.7 CCY-3-O2 9.5% ε.sub.⊥ (1 kHz, 20° C.): 7.0 CCY-4-O2 5.5% K.sub.1 (20° C.) [pN]: 14.0 CPY-3-O2 5.5% K.sub.3 (20° C.) [pN]: 15.7 CY-3-O2  15% γ.sub.1 (20° C.) [mPa .Math. s]: 128 CY-5-O2 5.0% V.sub.0 (20° C.) [V]: 2.25 CP-3-O1 7.0% PY-3-O2  16%

(98) TABLE-US-00007 H3: Nematic host mixture (Δε < 0) CC-3-V1 9.00% Clearing point [° C.]: 74.7 CC-2-3 18.00% Δn (589 nm, 20° C.): 0.098 CC-3-4 3.00% Δε (1 kHz, 20° C.): −3.4 CC-3-5 7.00% ε.sub.|| (1 kHz, 20° C.): 3.5 CCP-3-1 5.50% ε.sub.⊥ (1 kHz, 20° C.): 6.9 CCY-3-O2 11.50% K.sub.1 (20° C.) [pN]: 14.9 CPY-2-O2 8.00% K.sub.3 (20° C.) [pN]: 15.9 CPY-3-O2 11.00% γ.sub.1 (20° C.) [mPa .Math. s]: 108 CY-3-O2 15.50% V.sub.0 (20° C.) [V]: 2.28 PY-3-O2 11.50%

(99) TABLE-US-00008 H4: Nematic host mixture (Δε < 0) CY-3-O2 10.0% Clearing point [° C.]: 81 CCY-3-O1 8.0% Δn (589 nm, 20° C.): 0.103 CCY-3-O2 11.0% Δε (1 kHz, 20° C.): −3.8 CCY-4-O2 5.0% K.sub.1 (20° C.) [pN]: 13.9 CCY-5-O2 2.0% K.sub.3 (20° C.) [pN]: 15.0 CPY-2-O2 9.0% γ.sub.1 (20° C.) [mPa .Math. s]: 133 CPY-3-O2 9.0% V.sub.0 (20° C.) [V]: 2.10 CC-3-4 9.0% CC-2-3 17.5% CP-3-O1 9.0% PYP-2-3 2.5% PY-3-O2 8.0%

(100) TABLE-US-00009 H5: Nematic host mixture (Δε < 0) CY-3-O4 14.00% Clearing point [° C.]: 80.0 CCY-3-O2 9.00% Δn (589 nm, 20° C.): 0.090 CCY-3-O3 9.00% Δε (1 kHz, 20° C.): −3.3 CPY-2-O2 10.00% ε.sub.|| (1 kHz, 20° C.): 3.4 CPY-3-O2 10.00% ε.sub.⊥ (1 kHz, 20° C.): 6.7 CCY-3-1 8.00% K.sub.1 (20° C.) [pN]: 15.1 CC-3-4 9.00% K.sub.3 (20° C.) [pN]: 14.6 CC-3-5 6.00% γ.sub.1 (20° C.) [mPa .Math. s]: 140 CP-5-3 10.00% V.sub.0 (20° C.) [V]: 2.23 CC-3-O1 6.00% CC-3-O3 9.00%

(101) TABLE-US-00010 H6: Nematic host mixture (Δε < 0) CPP-3-2 6.5% Clearing point [° C.]: 74.7 CC-3-V1 8.0% Δn (589 nm, 20° C.): 0.104 CC-2-3  17% Δε (1 kHz, 20° C.): −3.0 CC-3-4 6.5% ε.sub.|| (1 kHz, 20° C.): 3.38 CCY-3-O1 3.5% ε.sub.⊥ (1 kHz, 20° C.): 6.33 CCY-3-O2 12.5%  K.sub.1 (20° C.) [pN]: 14.8 CPY-2-O2 5.5% K.sub.3 (20° C.) [pN]: 15.8 CPY-3-O2  10% γ.sub.1 (20° C.) [mPa .Math. s]: 106 CY-3-O2 15.5%  V.sub.0 (20° C.) [V]: 2.43 CP-3-O1 4.5% PP-1-2V1 5.0% PY-3-O2 5.5%

(102) TABLE-US-00011 H7: Nematic host mixture (Δε < 0) CC-3-V 37.50% Clearing point [° C.]: 74.8 CC-3-V1 2.00% Δn (589 nm, 20° C.): 0.099 CCY-4-O2 14.50% Δε (1 kHz, 20° C.): −2.9 CPY-2-O2 10.50% ε.sub.|| (1 kHz, 20° C.): 3.7 CPY-3-O2 9.50% ε.sub.⊥ (1 kHz, 20° C.): 6.6 CY-3-O2 15.00% K.sub.1 (20° C.) [pN]: 12.2 CY-3-O4 4.50% K.sub.3 (20° C.) [pN]: 13.4 PYP-2-4 5.50% γ.sub.1 (20° C.) [mPa .Math. s]: 92 PPGU-3-F 1.00% V.sub.0 (20° C.) [V]: 2.28

(103) TABLE-US-00012 H8: Nematic host mixture (Δε < 0) CC-2-3 20.00% Clearing point [° C.]: 74.8 CC-3-O1 6.00% Δn (589 nm, 20° C.): 0.105 CC-3-4 6.00% Δε (1 kHz, 20° C.): −3.2 CCP-3-1 3.00% ε.sub.|| (1 kHz, 20° C.): 3.5 CCY-3-O2 11.00% ε.sub.⊥ (1 kHz, 20° C.): 6.8 CPY-2-O2 12.00% K.sub.1 (20° C.) [pN]: 12.7 CPY-3-O2 11.00% K.sub.3 (20° C.) [pN]: 13.6 CY-3-O2 14.00% γ.sub.1 (20° C.) [mPa .Math. s]: 120 CY-3-O4 4.00% V.sub.0 (20° C.) [V]: 2.16 CP-3-O1 4.00% PYP-2-3 9.00%

(104) TABLE-US-00013 H9: Nematic host mixture (Δε < 0) CC-4-V 17.00% Clearing point [° C.]: 106.1 CCP-V-1 15.00% Δn (589 nm, 20° C.): 0.120 CCZPC-3-3 2.50% Δε (1 kHz, 20° C.): −3.6 CCY-3-O2 4.00% ε.sub.|| (1 kHz, 20° C.): 3.5 CCY-3-O3 5.00% ε.sub.⊥ (1 kHz, 20° C.): 7.0 CCY-4-O2 5.00% K.sub.1 (20° C.) [pN]: 16.8 CLY-3-O2 3.50% K.sub.3 (20° C.) [pN]: 17.3 CLY-3-O3 2.00% γ.sub.1 (20° C.) [mPa .Math. s]: 207 CPY-2-O2 8.00% V.sub.0 (20° C.) [V]: 2.33 CPY-3-O2 10.00% CY-3-O4 17.00% PYP-2-3 11.00%

(105) TABLE-US-00014 H10: Nematic host mixture (Δε < 0) CY-3-O2 15.00% Clearing point [° C.]: 75.5 CCY-4-O2 9.50% Δn (589 nm, 20° C.): 0.108 CCY-5-O2 5.00% Δε (1 kHz, 20° C.): −3.0 CPY-2-O2 9.00% ε.sub.|| (1 kHz, 20° C.): 3.5 CPY-3-O2 9.00% ε.sub.⊥ (1 kHz, 20° C.): 6.5 CC-3-4 9.00% K.sub.1 (20° C.) [pN]: 12.9 CC-2-3 22.00% K.sub.3 (20° C.) [pN]: 13.0 PYP-2-3 7.00% γ.sub.1 (20° C.) [mPa .Math. s]: 115 PYP-2-4 7.50% V.sub.0 (20° C.) [V]: 2.20 CP-3-O1 7.00%

(106) TABLE-US-00015 H11: Nematic host mixture (Δε < 0) CY-3-O2 15.00% Clearing point [° C.]: 74.7 CY-5-O2 6.50% Δn (589 nm, 20° C.): 0.108 CCY-3-O2 11.00% Δε (1 kHz, 20° C.): −3.0 CPY-2-O2 5.50% ε.sub.|| (1 kHz, 20° C.): 3.6 CPY-3-O2 10.50% ε.sub.⊥ (1 kHz, 20° C.): 6.6 CC-3-V 28.50% K.sub.1 (20° C.) [pN]: 12.9 CC-3-V1 10.00% K.sub.3 (20° C.) [pN]: 15.7 PYP-2-3 12.50% γ.sub.1 (20° C.) [mPa .Math. s]: 97 PPGU-3-F 0.50% V.sub.0 (20° C.) [V]: 2.42

(107) TABLE-US-00016 H12: Nematic host mixture (Δε < 0) CC-3-5 9.50% Clearing point [° C.]: 79.1 CC-5-O1 5.00% Δn (589 nm, 20° C.): 0.091 CCY-2-1 9.50% Δε (1 kHz, 20° C.): −3.6 CCY-3-1 10.50% ε.sub.|| (1 kHz, 20° C.): 3.5 CCY-3-O2 10.50% ε.sub.⊥ (1 kHz, 20° C.): 7.1 CCY-5-O2 9.50% K.sub.1 (20° C.) [pN]: 14.6 CPY-2-O2 12.00% K.sub.3 (20° C.) [pN]: 14.5 CY-3-O4 9.00% γ.sub.1 (20° C.) [mPa .Math. s]: 178 CY-5-O4 11.00% V.sub.0 (20° C.) [V]: 2.12 CP-5-3 13.50%

(108) TABLE-US-00017 H13: Nematic host mixture (Δε < 0) CPP-3-2 4.00% Clearing point [° C.]: 74.8 CC-3-V1 8.00% Δn (589 nm, 20° C.): 0.106 CC-2-3 13.00% Δε (1 kHz, 20° C.): −3.5 CC-3-4 7.00% ε.sub.|| (1 kHz, 20° C.): 3.6 CC-3-5 7.00% ε.sub.⊥ (1 kHz, 20° C.): 7.1 CCY-3-O2 13.00% K.sub.1 (20° C.) [pN]: 14.8 CPY-2-O2 7.00% K.sub.3 (20° C.) [pN]: 15.8 CPY-3-O2 12.00% γ.sub.1 (20° C.) [mPa .Math. s]: 115 CY-3-O2 12.00% V.sub.0 (20° C.) [V]: 2.23 CP-3-O1 2.00% PY-3-O2 15.00%

(109) TABLE-US-00018 H14: Nematic host mixture (Δε < 0) CY-3-O4 22.00% Clearing point [° C.]: 86.9 CY-5-O4 12.00% Δn (589 nm, 20° C.): 0.111 CCY-3-O2 6.00% Δε (1 kHz, 20° C.): −4.9 CCY-3-O3 6.00% ε.sub.|| (1 kHz, 20° C.): 3.8 CCY-4-O2 6.00% ε.sub.⊥ (1 kHz, 20° C.): 8.7 CPY-2-O2 10.00% K.sub.1 (20° C.) [pN]: 14.9 CPY-3-O2 10.00% K.sub.3 (20° C.) [pN]: 15.9 PYP-2-3 7.00% γ.sub.1 (20° C.) [mPa .Math. s]: 222 CC-3-V1 7.00% V.sub.0 (20° C.) [V]: 1.91 CC-5-V 10.00% CCZPC-3-3 2.00% CCZPC-3-5 2.00%

(110) TABLE-US-00019 H15: Nematic host mixture (Δε < 0) CY-3-O4 12.00% Clearing point [° C.]: 86.0 CY-5-O2 10.00% Δn (589 nm, 20° C.): 0.110 CY-5-O4 8.00% Δε (1 kHz, 20° C.): −5.0 CCY-3-O2 8.00% ε.sub.|| (1 kHz, 20° C.): 3.8 CCY-4-O2 7.00% ε.sub.⊥ (1 kHz, 20° C.): 8.8 CCY-5-O2 6.00% K.sub.1 (20° C.) [pN]: 14.7 CCY-2-1 8.00% K.sub.3 (20° C.) [pN]: 16.0 CCY-3-1 7.00% γ.sub.1 (20° C.) [mPa .Math. s]: 250 CPY-3-O2 9.00% V.sub.0 (20° C.) [V]: 1.90 CPY-3-O2 9.00% CPP-3-2 6.00% CP-5-3 10.00%

(111) TABLE-US-00020 H16: Nematic host mixture (Δε < 0) CC-3-V1 10.25% Clearing point [° C.]: 74.7 CC-2-3 18.50% Δn (589 nm, 20° C.): 0.103 CC-3-5 6.75% Δε (1 kHz, 20° C.): −3.1 CCP-3-1 6.00% ε.sub.|| (1 kHz, 20° C.): 3.4 CCY-3-1 2.50% ε.sub.⊥ (1 kHz, 20° C.): 6.4 CCY-3-O2 12.00% K.sub.1 (20° C.) [pN]: 15.4 CPY-2-O2 6.00% K.sub.3 (20° C.) [pN]: 16.8 CPY-3-O2 9.75% γ.sub.1 (20° C.) [mPa .Math. s]: 104 CY-3-O2 11.50% V.sub.0 (20° C.) [V]: 2.46 PP-1-2V1 3.75% PY-3-O2 13.00%

(112) TABLE-US-00021 H17: Nematic host mixture (Δε < 0) CC-3-V 27.50% Clearing point [° C.]: 74.7 CC-3-V1 10.00% Δn (589 nm, 20° C.): 0.104 CC-3-5 8.00% Δε (1 kHz, 20° C.): −3.0 CCY-3-O2 9.25% ε.sub.|| (1 kHz, 20° C.): 3.4 CLY-3-O2 10.00% ε.sub.⊥ (1 kHz, 20° C.): 6.4 CPY-3-O2 11.75% K.sub.1 (20° C.) [pN]: 15.3 PY-3-O2 14.00% K.sub.3 (20° C.) [pN]: 16.2 PY-4-O2 9.00% γ.sub.1 (20° C.) [mPa .Math. s]: 88 PYP-2-4 0.50% V.sub.0 (20° C.) [V]: 2.44

(113) TABLE-US-00022 H18: Nematic host mixture (Δε < 0) B-2O-O5 4.00% Clearing point [° C.]: 74.2 CPP-3-2 8.00% Δn (589 nm, 20° C.): 0.1091 CC-3-V1 9.00% Δε (1 kHz, 20° C.): −3.1 CC-3-O1 2.00% ε.sub.|| (1 kHz, 20° C.): 3.6 CC-3-4 8.00% ε.sub.⊥ (1 kHz, 20° C.): 6.7 CC-3-5 7.00% K.sub.1 (20° C.) [pN]: 14.5 CCP-3-1 8.00% K.sub.3 (20° C.) [pN]: 16.5 CCP-V2-1 5.00% γ.sub.1 (20° C.) [mPa .Math. s]: 108 CCY-3-O2 10.50% V.sub.0 (20° C.) [V]: CLY-3-O2 1.00% CPY-3-O2 2.50% CY-3-O2 11.50% CP-301 5.50% PY-3-O2 18.00%

(114) TABLE-US-00023 H19: Nematic host mixture (Δε < 0) CC-3-V 15.00% Clearing point [° C.]: 74.4 CC-3-V1 9.00% Δn (589 nm, 20° C.): 0.1086 CC-2-3 8.00% Δε (1 kHz, 20° C.): −3.2 CC-3-4 7.50% ε.sub.|| (1 kHz, 20° C.): 3.5 CCY-3-O2 10.00% ε.sub.⊥ (1 kHz, 20° C.): 6.7 CCY-5-O2 8.00% K.sub.1 (20° C.) [pN]: 14.3 CPY-2-O2 3.00% K.sub.3 (20° C.) [pN]: 15.7 CPY-3-O2 8.50% γ.sub.1 (20° C.) [mPa .Math. s]: 102 CY-3-O2 7.00% V.sub.0 (20° C.) [V]: PY-3-O2 16.00% PYP-2-3 8.00%

(115) TABLE-US-00024 H20: Nematic host mixture (Δε < 0) CC-3-V1 8.00% Clearing point [° C.]: 74.6 CC-2-3 15.00% Δn (589 nm, 20° C.): 0.0899 CC-3-4 5.00% Δε (1 kHz, 20° C.): −3.3 CC-3-5 6.00% ε.sub.|| (1 kHz, 20° C.): 3.5 CCP-3-1 3.00% ε.sub.⊥ (1 kHz, 20° C.): 6.8 CCY-3-O1 8.00% K.sub.1 (20° C.) [pN]: 13.9 CCY-3-O2 10.00% K.sub.3 (20° C.) [pN]: 14.6 CCY-3-O3 6.00% γ.sub.1 (20° C.) [mPa .Math. s]: 114 CCY-4-O2 6.00% V.sub.0 (20° C.) [V]: CY-3-O2 12.00% CY-3-O4 3.75% CP-301 3.00% PY-3-O2 2.75% PY-4-O2 6.50% PYP-2-3 5.00%

(116) TABLE-US-00025 H21: Nematic host mixture (Δε < 0) CC-3-V1 3.00% Clearing point [° C.]: 74.8 CP-3-O1 9.00% Δn (589 nm, 20° C.): 0.0891 CC-3-O3 5.00% Δε (1 kHz, 20° C.): −3.2 CC-3-4 9.00% ε.sub.|| (1 kHz, 20° C.): 3.5 CC-3-5 9.00% ε.sub.⊥ (1 kHz, 20° C.): 6.7 CCP-3-1 8.00% K.sub.1 (20° C.) [pN]: 14.2 CCY-3-O2 11.50% K.sub.3 (20° C.) [pN]: 16.3 CCY-5-O2 9.00% γ.sub.1 (20° C.) [mPa .Math. s]: 115 CPY-3-O2 6.00% V.sub.0 (20° C.) [V]: CY-3-O2 15.00% CP-3-01 4.50% PY-3-O2 11.00%

(117) TABLE-US-00026 H22: Nematic host mixture (Δε < 0) CPP-3-2 6.00% Clearing point [° C.]: 74.8 CC-3-V1 6.00% Δn (589 nm, 20° C.): 0.1066 CC-3-4 9.00% Δε (1 kHz, 20° C.): −3.3 CC-3-5 7.00% ε.sub.|| (1 kHz, 20° C.): 3.6 CCP-3-1 8.00% ε.sub.⊥ (1 kHz, 20° C.): 6.9 CCP-3-3 3.00% K.sub.1 (20° C.) [pN]: 14.2 CCY-3-1 2.00% K.sub.3 (20° C.) [pN]: 16.5 CCY-3-O2 10.50% γ.sub.1 (20° C.) [mPa .Math. s]: 118 CCY-4-O2 5.00% V.sub.0 (20° C.) [V]: CPY-3-O2 3.50% CY-3-O2 14.00% CP-3-01 5.50% PY-1-O4 6.50% PY-3-O2 14.00%

(118) The following self-alignment additives are particularly used. They are synthesized as provided in the examples above or in analogy thereof, or according to prior publications including WO 2012/038026 A1, WO 2014/094959 A1, WO 2013/004372 A1 or EP 2918658 A2. The numbering below is used within the mixture examples:

(119) TABLE-US-00027 No. Structure  1  2  3  4 0  5  6  7  8  9 10 11 12 13 14 0 15 16 17 18 19 20 21 22 23 24 0 25 26 27 28 29 30 31 32

(120) The following polymerizable compound is used:

(121) ##STR00459##

MIXTURE EXAMPLE 1

(122) Self-alignment additives 1 (2% by weight) and 2 (0.03% by weight) are added to a nematic LC medium H1 of the VA-type (Δε<0) and the mixture is homogenized.

(123) Use in Test Cells without Pre-Alignment Layer:

(124) The mixture formed is introduced into a test cell (without polyimide alignment layer, layer thickness d=4.0 μm, ITO coated center on both sides, without passivation layer). The LC medium spontaneously achieves a stable vertical alignment (dark region between crossed polarizers). The VA cell formed can be switched reversibly by application of a voltage.

(125) The overall amount of self-alignment additives 1+2 can be considerably reduced in comparison to a mixture containing only additive 1 (see Comparative Mixture Example 1a/b), while maintaining the same level of alignment.

Comparative Mixture Example 1a

(126) Self-alignment additives 1 (3% by weight) is added to a nematic LC medium H1 of the VA-type (Δε<0) and the mixture is homogenized.

(127) Use in test cell is made as described for Mixture Example 1.

Comparative Mixture Example 1b

(128) Self-alignment additives 1 (2% by weight) is added to a nematic LC medium H.sub.1 of the VA-type (Δε<0) and the mixture is homogenized.

(129) Use in test cell is made as described for Mixture Example 1.

(130) Heat stability of Mixture Example 1 and comparison:

(131) As a stress test a heat load of 120° C. for 1 hour is applied.

(132) TABLE-US-00028 TABLE 1 Stability of vertical alignment after heat load. Mixture Example Additive(s) Alignment after heat stress 1 1 + 2 (Σ 2.03%) Complete Comparative 1a 1 (3%) Complete Comparative 1b 1 (2%) Partially incomplete by inspection
Voltage Holding Ratio (VHR):

(133) UV process for VHR measurements: Metal halide lamp, (100 mW/cm3, with 320 nm cut filter for 60 min) at 40° C. in fully ITO covered test cells.

(134) VHR measurements are performed with a Toyo VHR instrument: VHR of the cells is measured one hour after the UV process of the test cells with the following conditions: frequency: 0.6 Hz, 60° C.

(135) TABLE-US-00029 TABLE 2 Results of VHR tests after UV load (0.6 Hz, 60° C.). Mixture Example Additive(s) VHR after back light stress 1 1 + 2 95.0% Comparative 1a 1 93.9%

(136) Mixture 1 and 1a, which have both sufficient heat stability, are compared in view of VHR. Mixture 1 has higher value of VHR than the comparative.

MIXTURE EXAMPLE 2

(137) Self-alignment additive 4 (0.2% by weight), self-alignment additive 5 (0.6% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H2 of the VA type (Δε<0) and the mixture is homogenized.

(138) Use in Test Cells without Pre-Alignment Layer:

(139) The mixture formed is introduced into a test cell (without polyimide alignment layer, layer thickness d=4.0 μm, ITO coated center on both sides, without passivation layer). The LC medium spontaneously achieves a stable vertical alignment (dark region between crossed polarizers). The VA cell formed can be switched reversibly by application of a voltage.

(140) Polymer Stabilization:

(141) UV-curing process is performed by applying irradiation from a metal halide lamp (100 mW/cm.sup.3, with 320 nm cut filter for 60 min) at 40° C. whilst applying a square wave alternating voltage of 20 Vpp at 200 Hz. The quality of the vertical alignment is not affected by the UV-step.

Comparative Mixture Example 2

(142) Self-alignment additive 5 (0.6% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H2 of the VA type (Δε<0) and the mixture is homogenized.

(143) The LC medium is further used and tested like Mixture Example 2.

(144) Results for Mixture Example 2 and Comparative Mixture 2:

(145) Additive Spreading:

(146) Method for spreading measurement: Test cells (8 cm×4 cm) are filled with the LC medium. The lower part of the cell in vicinity to the injection hole shows good vertical alignment. The upper part of the cell, opposite the filling entrance shows a variable portion of the cell area which is not perfectly aligned, characterized by higher transmission between crossed polarizers. The size of the area, usually a small stripe, depends on the type and concentration of the additive(s). The alignment is assessed through crossed polarizers. The percentage of area with good alignment is a criterion for the advantageous spreading behavior of the additives. The results are provided in the table below.

(147) TABLE-US-00030 TABLE 3 Results for alignment in spreading measurement. Cell area showing vertical Mixture Example Additive(s) orientation 2 4 + 5   97% Comparative 2 5 93.5%

(148) The reliability of the polymerized test cell is tested with respect to LTS (low temperature stability), VHR (voltage holding ratio) and tilt stability (Tables below).

(149) Voltage Holding Ratio (VHR):

(150) UV process for VHR measurements: Metal halide lamp, (100 mW/cm.sup.3, with 320 nm cut filter for 60 min) at 40° C. in fully ITO covered test cells.

(151) VHR measurements are performed with a Toyo VHR instrument: VHR of the cells is measured one hour after the UV process of the test cells with the following conditions: Frequency: 0.6 Hz, 60° C.

(152) TABLE-US-00031 TABLE 4 Results of VHR tests after UV load (0.6 Hz, 60° C.). Mixture Example Additive(s) VHR after back light stress 2 4 + 5 87% Comparative 2 5 83%
Low Temperature Stability (LTS):

(153) The low temperature stability of Mixture Example 1 was as good as the comparative Mixture Example 1, despite its higher total content of additives.

(154) Tilt Stability:

(155) Test cells after polymer stabilization are stressed with 60 Vpp for 60 hours at room temperature. The difference in pre-tilt before and after this stress is used to assess the stability of the pre-tilts. A higher change in pre-tilt after stress indicates a less stable pre-tilt.

(156) The change in the tilt angle after stress test is 0.2 degrees for Mixture Example 1. The tilt stability is higher than for the use of additive 4 alone, and similar to the use of additive 5 alone.

MIXTURE EXAMPLE 3

(157) Self-alignment additives 3 (0.27% by weight), 9 (0.41% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H3 of the VA-type (Δε<0) and the mixture is homogenized.

(158) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

Comparative Mixture Example 3

(159) Self-alignment additive 3 (0.55% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H3 of the VA-type (Δε<0) and the mixture is homogenized.

Results for Mixture Example 3 and Comparative Mixture 3

(160) TABLE-US-00032 TABLE 5 Results of VHR tests after UV load (0.6 Hz, 60° C.). Mixture Example Additive(s) VHR after back light stress 3 3 + 9   97% Comparative 3 3 94.8%

(161) The VHR value for a 1:1 mixture by moles of the two additives 3 and 9 is significantly higher than the midpoint of values for the sole additives.

(162) Tilt generation: The behavior in tilt generation and tilt stability is similar to the comparative mixture.

(163) In summary, the Mixture 3 with mixed additives has improved VHR compared to the sole additive, while tilt and spreading remain unaffected.

MIXTURE EXAMPLE 4

(164) Self-alignment additives 4 (0.2% by weight), 5 (0.6% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(165) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(166) Cell area showing vertical orientation: 97%

(167) Low temperature stability (LTS): 120 h (−20° C.)

(168) The mixture shows superior tilt stability of 0.2°.

MIXTURE EXAMPLE 5

(169) Self-alignment additives 4 (0.2% by weight), 8 (0.6% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(170) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(171) Cell area showing vertical orientation: 98%

(172) Low temperature stability (LTS): 380 h (−20° C.)

(173) The mixture shows superior tilt stability of 0.4°.

MIXTURE EXAMPLE 6

(174) Self-alignment additives 7 (0.2% by weight), 8 (0.6% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(175) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(176) Cell area showing vertical orientation: 99%

(177) Low temperature stability (LTS): 380 h (−20° C.)

(178) The mixture shows superior tilt stability of 0.4°.

MIXTURE EXAMPLE 7

(179) Self-alignment additives 7 (0.2% by weight), 5 (0.6% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(180) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(181) Cell area showing vertical orientation: 99%

(182) Low temperature stability (LTS): 120 h (−20° C.)

(183) The mixture shows superior tilt stability of 0.5°.

MIXTURE EXAMPLE 8

(184) Self-alignment additives 3 (0.15% by weight), 4 (0.75% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(185) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(186) Cell area showing vertical orientation: 99%

(187) Low temperature stability (LTS): 700 h (−20° C.)

(188) The mixture shows superior tilt stability of 0.4°.

MIXTURE EXAMPLE 9

(189) Self-alignment additives 5 (0.6% by weight), 10 (0.2% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(190) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(191) Cell area showing vertical orientation: 99%

(192) Low temperature stability (LTS): 1000 h (−20° C.)

(193) The mixture shows superior tilt stability of 0.5°.

MIXTURE EXAMPLE 10

(194) Self-alignment additives 9 (0.35% by weight), 4 (0.75% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(195) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(196) Cell area showing vertical orientation: 94%

(197) Low temperature stability (LTS): 1000 h (−20° C.)

(198) The mixture shows superior tilt stability of 0.2°.

MIXTURE EXAMPLE 11

(199) Self-alignment additives 3 (0.15% by weight), 9 (0.35% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(200) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(201) Cell area showing vertical orientation: 94%

(202) Low temperature stability (LTS): 1000 h (−20° C.)

MIXTURE EXAMPLE 12

(203) Self-alignment additives 5 (0.15% by weight), 9 (0.35% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(204) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(205) Cell area showing vertical orientation: 93%

(206) Low temperature stability (LTS): 1000 h (−20° C.)

MIXTURE EXAMPLE 13

(207) Self-alignment additives 6 (0.15% by weight), 8 (0.35% by weight) and RM-1 (0.3% by weight) are added to a nematic LC medium H4 of the VA-type (Δε<0) and the mixture is homogenized.

(208) Use in test cells without pre-alignment layer and polymer stabilization are performed like for Mixture Example 2.

(209) Cell area showing vertical orientation: 92%

(210) Low temperature stability (LTS): 800 h (−20° C.)

(211) The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

(212) Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. From the description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

(213) The entire disclosure[s] of all applications, patents and publications, cited herein and of corresponding European application No. EP 17208758.7, filed Dec. 20, 2017 are incorporated by reference herein.