Liquid-crystalline media having homeotropic alignment

Abstract

The present invention relates to liquid-crystalline media (LC media) having negative or positive dielectric anisotropy, comprising a low-molecular-weight component and a polymerizable component. The polymerizable component comprises self-aligning, polymerizable mesogens (polymerizable self-alignment additives) which effect homeotropic (vertical) alignment of the LC media at a surface or the cell walls of a liquid-crystal display (LC display). The invention therefore also encompasses LC displays having homeotropic alignment of the LC medium without alignment layers. The invention discloses novel structures for self-alignment additives which have a certain position of the functional groups.

Claims

1. A liquid-crystal medium comprising a low-molecular-weight, non-polymerizable liquid-crystalline component and a polymerizable or polymerized component comprising one or more polymerizable compounds of formula I, where the polymerized component is obtainable by polymerization of the polymerizable component,
R.sup.1-[A.sup.3Z.sup.3].sub.m-[A.sup.2].sub.k-[Z.sup.2].sub.n-A.sup.1-R.sub.a  (I) in which A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which is unsubstituted or mono- or polysubstituted by a group L or -Sp-P, L in each case, independently of one another, denotes H, F, Cl, 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 or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 25 C atoms, in which, in addition, one or more H atoms are each optionally replaced by F or Cl, P denotes a polymerizable group, Sp denotes a spacer group or a single bond, Z.sup.2 in each case, independently of one another, denotes —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)—, 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, n denotes 0 or 1, m denotes 0, 1, 2, 3, 4, 5 or 6, k 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, independently of one another, denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced by —O—, —S—, —CO—, —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, in addition, one or more H atoms are each optionally replaced by F or Cl, or a group -Sp-P, R.sup.a denotes an anchor group of the formula ##STR00557## p denotes 1 or 2, q denotes 2 or 3, B denotes a substituted or unsubstituted ring system or condensed ring system, Y, independently of one another, denotes —O—, —S—, —C(O)—, —C(O)O—, —OC(O)—, —NR.sup.11— or a single bond, o denotes 0 or 1, X.sup.1, independently of one another, denotes H, alkyl, fluoroalkyl, OH, NH.sub.2, NHR.sup.11, NR.sup.11.sub.2, OR.sup.11, C(O)OH, —CHO, where at least one group X.sup.1 denotes a radical selected from —OH, —NH.sub.2, NHR.sup.11, C(O)OH and —CHO, R.sup.11 denotes alkyl having 1 to 12 C atoms, Sp.sup.a, Sp.sup.c, Sp.sup.d each, independently of one another, denote a spacer group or a single bond, and Sp.sup.b denotes a tri- or tetravalent group, where the compound of formula I contains at least one polymerizable group P within at least one of the groups A.sup.1, A.sup.2, A.sup.3, Z.sup.2 and Z.sup.3, as are present.

2. The medium according to claim 1, wherein, in formula I, A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, where, in addition, one or more CH groups in these groups are each optionally replaced by N, cyclohexane-1,4-diyl, in which, in addition, 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, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl or octahydro-4,7-methanoindane-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, wherein each of these groups is unsubstituted or mono- or polysubstituted by a group L or -Sp-P.

3. The medium according to claim 1, wherein the compound of formula I is a compound of formula II, ##STR00558## in which R.sup.1, R.sup.a, A.sup.1, A.sup.2, A.sup.3, Z.sup.2, Z.sup.3, L, Sp, P, k, m and n independently are as defined in claim 1, p1, p2, p3 independently denote 0, 1, 2 or 3, and r1, r2, r3 independently denote 0, 1, 2 or 3, where the compound of the formula I1 contains at least one polymerizable group P within at least one of the groups A.sup.1, A.sup.2, A.sup.3, Z.sup.2 and Z.sup.3, as are present.

4. The medium according to claim 1, wherein the compound of formula I contains in total at least one polymerizable group -Sp-P on at least one of the groups A.sup.1, A.sup.2 and A.sup.3, as are present.

5. The medium according to claim 1, wherein said one or more polymerizable compounds of formula I are selected from compounds of formulae IA, IB, IC, ID and IE: ##STR00559## in which R.sup.1, R.sup.a, Z, Z.sup.3, L, Sp, P and n independently are as defined in claim 1, p1, p2, p3 independently denote 0, 1, 2 or 3, and r1, r2, r3 independently denote 0, 1, 2 or 3, where each of the compounds of formulae IA, IB, IC, ID and IE contains at least one polymerizable group P.

6. The medium according to claim 1, wherein, besides said one or more polymerizable compounds of formula I, the polymerizable or polymerized component of said medium further comprises one or more further polymerizable or further polymerized compounds, where the polymerized component is obtainable by polymerization of the polymerizable component.

7. The medium according to claim 1, wherein, besides said one or more compounds polymerizable of formula I, said medium further comprises one or more non-polymerizable compounds of formula I′,
R.sup.1-[A.sup.3-Z.sup.3].sub.m-[A.sup.2].sub.k-[Z.sup.2]-.sub.n-A.sup.1-R.sup.a  I′ in which m, k, n and the group R.sup.a are as defined for formula I, A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which is unsubstituted or mono- or polysubstituted by a group L, Z.sup.2 in each case, independently of one another, denotes —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—, or —(CR.sup.0R.sup.00).sub.n1—, 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—, or —(CR.sup.0R.sup.00).sub.n1—, n1 denotes 1, 2, 3 or 4, L in each case, independently of one another, denotes H, F, Cl, 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 or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms are each optionally replaced by F or Cl, 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, and R.sup.1, independently of one another, denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced by —O—, —S—, —CO—, —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, in addition, one or more H atoms are each optionally replaced by F or Cl.

8. The medium according to claim 7, wherein said one or more non-polymerizable compounds of formula I′ are selected from the following formulae: ##STR00560## in which R.sup.1, R.sup.a, Z.sup.2, Z.sup.3, L and n independently are as defined in claim 7, and r1, r2, r3 independently denote 0, 1, 2, 3 or 4.

9. The medium according to claim 1, wherein said one or more polymerizable compounds of formula I comprise one or more compounds selected from the following formulae: ##STR00561## ##STR00562## in which L, Sp, P, R.sup.a and Z.sup.2 independently are as defined in claim 1, Z.sup.3 denotes a single bond or —CH.sub.2CH.sub.2—, n denotes 0 or 1, p1, p2, p3 independently denote 0, 1, 2 or 3, r1, r2, r3 independently denote 0, 1, 2 or 3, and R.sup.1 denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced by —O—, —S—, —CO—, —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, in addition, one or more H atoms are each optionally replaced by F or Cl.

10. The medium according to claim 1, wherein group R.sup.a in formula I contains one, two or three OH groups.

11. The medium according to claim 1, wherein group R.sup.a denotes a group selected from ##STR00563## in which Sp.sup.a, Sp.sup.b, Sp.sup.c, p and X.sup.1 have the meaning as defined in claim 1.

12. The medium according to claim 1, wherein group R.sup.a denotes a group selected from the following part-formulae: ##STR00564## ##STR00565##

13. The medium according to claim 1, wherein, for the compound of the formula I, n=0.

14. The medium according to claim 1, wherein, for the compound of the formula I, P is vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane or epoxide.

15. The medium according to claim 1, wherein said medium comprises compounds of formula I in a concentration of less than 10% by weight.

16. The medium according to claim 1, wherein said medium comprises one or more polymerizable compounds of formula M or a (co)polymer comprising 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 the individual radicals have the following meanings: 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, denote a radical selected from the following groups: a) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene and 4,4′-bicyclohexylene, in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced by —O— or —S— and in which, in addition, one or more H atoms are each optionally replaced by a group L, or selected from ##STR00566## b) the group consisting of 1,4-phenylene and 1,3-phenylene, in which, in addition, one or two CH groups are each optionally replaced by N and in which, in addition, one or more H atoms are each optionally replaced by a group L or -Sp.sup.3-P, c) the group consisting of 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 and selenophene-2,5-diyl, each of which is unsubstituted or mono- or polysubstituted by a group L, d) the group consisting of saturated, partially unsaturated or fully unsaturated, and optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, one or more of said C atoms are each optionally replaced by heteroatoms, where, in addition, one or more H atoms in these radicals are each optionally replaced by a group L or -Sp.sup.3-P, and/or one or more double bonds are each optionally replaced by single bonds, and/or one or more CH groups are each optionally replaced by N, 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 straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 12 C atoms, M denotes —O—, —S—, —CH.sub.2—, —CHY.sup.1— or —CY.sup.1Y.sup.2—, Y.sup.1 and Y.sup.2 each, independently of one another, is alkyl having 1 to 12 C atoms, Cl or CN, W.sup.1, W.sup.2 each, independently of one another, denote —CH.sub.2CH.sub.2—, —CH═CH—, —CH.sub.2—O—, —O—CH.sub.2—, —C(R.sup.cR.sup.d)— or —O—, and 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 may 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, Cl, CN or straight-chain or branched alkyl having 1 to 25 C atoms, in which, in addition, 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 O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms are each optionally replaced by F, Cl, CN or P.sup.1-Sp.sup.1-, where the groups —OH, —NH.sub.2, —SH, —NHR, —C(O)OH and —CHO are not present in R.sup.aa, and R.sup.0, R.sup.00 each, independently of one another, denote H, F or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more H atoms are each optionally replaced by F.

17. The medium according to claim 16, wherein the polymerizable or polymerized component comprises 0.01 to 5% by weight of one or more compounds of the formula M.

18. The medium according to claim 7, wherein the polymerizable or polymerized component comprises 0.01 to 10% by weight of one or more non-polymerizable compounds of the formula I′.

19. The medium according to claim 1, wherein the polymerizable or polymerized component comprises one or more compounds selected from the compounds of the following formulae: ##STR00567## ##STR00568## ##STR00569## ##STR00570## ##STR00571## in which the individual radicals have the following meanings: P.sup.1, P.sup.2 and P.sup.3 each, independently of one another, denote a polymerizable group, Sp.sup.1, Sp.sup.2 and Sp.sup.3 each, independently of one another, denote a single bond or a spacer group, where, in addition, one or more of the radicals P.sup.1-Sp.sup.1-, P.sup.2-Sp.sup.2- and P.sup.3-Sp.sup.3- may denote a radical R.sup.aa, with the proviso that at least one of the radicals P.sup.1-Sp.sup.1-, P.sup.2-Sp.sup.2- and P.sup.3-Sp.sup.3- present does not denote R.sup.aa, R.sup.aa denotes H, F, Cl, CN or straight-chain or branched alkyl having 1 to 25 C atoms, in which, in addition, 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—, —N(R.sup.0)—, —O—, —S—, —CO—, —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, in addition, one or more H atoms are each optionally replaced by F, Cl, CN or P.sup.1-Sp.sup.1-, where —OH, —NH.sub.2, —SH, —NHR, —C(O)OH and —CHO are not present in the group R.sup.aa, R.sup.0, R.sup.00 each, independently of one another and on each occurrence identically or differently, denote H or alkyl having 1 to 12 C atoms, R.sup.y and R.sup.z each, independently of one another, denote H, F, CH.sub.3 or CF.sub.3, X.sup.1, X.sup.2 and X.sup.3 each, independently of one another, denote —CO—O—, O—CO— or a single bond, Z.sup.1 denotes —O—, —CO—, —C(R.sup.YR.sup.z)— or —CF.sub.2CF.sub.2—, Z.sup.2 and Z.sup.3 each, independently of one another, denote —CO—O—, —O—CO—, —CH.sub.2O—, —OCH.sub.2—, —CF.sub.2O—, —OCF.sub.2— or —(CH.sub.2).sub.n— where n is 2, 3 or 4, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF.sub.5 or straight-chain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 12 C atoms, L′ and L″ each, independently of one another, denote H, F or Cl, r denotes 0, 1, 2, 3 or 4, s denotes 0, 1, 2 or 3, t denotes 0, 1 or 2, and x denotes 0 or 1.

20. A liquid-crystal display comprising a liquid-crystal 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 a liquid-crystal medium according to claim 1 located between the substrates, where the compound of the formula I is suitable for effecting homeotropic alignment of the liquid-crystal medium with respect to the substrate surfaces.

21. The display according to claim 20, wherein the substrates have no alignment layers for homeotropic alignment.

22. The display according to claim 20, wherein the substrates have alignment layers on one or both sides.

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

24. The display according to claim 20, wherein said display is a VA-IPS display containing an LC medium having positive dielectric anisotropy and interdigital electrodes arranged on at least one substrate.

25. A process for the preparation of liquid-crystal medium, said process comprising mixing one or more compounds of the formula I according to claim 1 with a low-molecular-weight liquid-crystalline component, and one or more polymerizable compounds and/or any desired additives are optionally added.

26. A compound of formula I
R.sup.1-[A.sup.3-Z.sup.3].sub.m-[A.sup.2].sub.k-[Z.sup.2].sub.n-A.sup.1-R.sup.a  (I) in which A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which is unsubstituted or mono- or polysubstituted by a group L or -Sp-P, L in each case, independently of one another, denotes H, F, Cl, 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 or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 25 C atoms, in which, in addition, one or more H atoms are each optionally replaced by F or Cl, P denotes a polymerizable group, Sp denotes a spacer group or a single bond, Z.sup.2 in each case, independently of one another, denotes —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)—, 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, n denotes 0 or 1, m denotes 0, 1, 2, 3, 4, 5 or 6, k denotes 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, independently of one another, denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced by —O—, —S—, —CO—, —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, in addition, one or more H atoms are each optionally replaced by F or Cl, or a group -Sp-P, R.sup.a denotes an anchor group of the formula ##STR00572## p denotes 1 or 2, q denotes 2 or 3, B denotes a substituted or unsubstituted ring system or condensed ring system, Y, independently of one another, denotes —O—, —S—, —C(O)—, —C(O)O—, —OC(O)—, —NR.sup.11— or a single bond, o denotes 0 or 1, X.sup.1, independently of one another, denotes H, alkyl, fluoroalkyl, OH, NH.sub.2, NHR.sup.11, NR.sup.11.sub.2, OR.sup.aa, C(O)OH, —CHO, where at least one group X.sup.1 denotes a radical selected from —OH, —NH.sub.2, NHR.sup.11, C(O)OH and —CHO, R.sup.11 denotes alkyl having 1 to 12 C atoms, Sp.sup.a, Sp.sup.c, Sp.sup.d each, independently of one another, denote a spacer group or a single bond, and Sp.sup.b denotes a tri- or tetravalent group, where the compound of the formula I contains at least one polymerizable group P within at least one of the groups A.sup.1, A.sup.2, A.sup.3, Z.sup.2 and Z.sup.3, as are present.

27. A compound according to claim 26, wherein m is 1.

28. A compound according to claim 26, wherein A.sup.1 and A.sup.2 independently denote 1,4-phenylene or cyclohexane-1,4-diyl, each of which is unsubstituted or mono- or polysubstituted by a group L or -Sp-P.

29. A method for effecting homeotropic alignment with respect to respect to a surface delimiting in a liquid-crystal medium, comprising adding to said medium one or more compounds according to claim 1.

30. A process for the production of a liquid-crystal display comprising a liquid-crystal 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 of 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, and polymerizing the polymerizable component(s), optionally with application of a voltage to the cell or under the action of an electric field.

31. The medium according to claim 16, wherein, in formula M, A.sup.1, A.sup.2 each, independently of one another, denote a radical selected from the following groups: a) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene and 4,4′-bicyclohexylene, in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced by —O— or —S— and in which, in addition, one or more H atoms are each optionally replaced by a group L, or selected from ##STR00573## b) the group consisting of 1,4-phenylene and 1,3-phenylene, in which, in addition, one or two CH groups are each optionally replaced by N and in which, in addition, one or more H atoms are each optionally replaced by a group L or -Sp.sup.3-P, c) the group consisting of 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 and selenophene-2,5-diyl, each of which is unsubstituted or mono- or polysubstituted by a group L, d) the group consisting of bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, ##STR00574## ##STR00575## where, in addition, one or more H atoms in these radicals are each optionally replaced by a group L or -Sp.sup.3-P, and/or one or more double bonds are each optionally replaced by single bonds, and/or one or more CH groups are each optionally replaced by N.

32. The medium according to claim 19, wherein, in formulae M43 to M84, P.sup.1, P.sup.2 and P.sup.3 each, independently of one another, denote an acrylate, meth-acrylate, fluoroacrylate, oxetane, vinyloxy or epoxide group, and Sp.sup.1, Sp.sup.2 and Sp.sup.3 each, independently of one another, denote a single bond or —(CH.sub.2).sub.p1—, —(CH.sub.2).sub.p1—O—, —(CH.sub.2).sub.p1—CO—O— or —(CH.sub.2).sub.p1—O—CO—O—, in which p1 is an integer from 1 to 12, and where the linking to the adjacent ring in the last-mentioned groups takes place via the O atom.

33. The medium according to claim 1, wherein A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, where, in addition, one or more CH groups in these groups are each optionally replaced by N, cyclohexane-1,4-diyl, in which, in addition, 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, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl or octahydro-4,7-methanoindane-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl (in particular gonane-3,17-diyl), where each of these groups is unsubstituted or mono- or polysubstituted by a group L or -Sp-P, L in each case, independently of one another, denotes H, F, Cl, Br, I, —CN, —NO.sub.2, —NCO, —NCS, —OCN, —SCN, —C(═O)N(R.sup.0).sub.2, —C(═O)R.sup.0, silyl, aryl having up to 20 C atoms, cycloalkyl having 3 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 25 C atoms, in which, in addition, one or more H atoms are each optionally replaced by F or Cl, P denotes a polymerizable group selected from CH.sub.2═CW.sup.1—CO—O—, ##STR00576## CH.sub.2═CW.sup.2—O—, CW.sup.1═CH—CO—(O).sub.k3—, (CH.sub.2═CH).sub.2CH—OCO—, (CH.sub.2═CH—CH.sub.2).sub.2CH—OCO—, (CH.sub.2═CH).sub.2CH—O—, (CH.sub.2═CH—CH.sub.2).sub.2N—, (CH.sub.2═CH—CH.sub.2).sub.2N—CO—, CH.sub.2═CW.sup.1—CO—NH—, CH.sub.2═CH—(COO).sub.k1-Phe-(O).sub.k2—, CH.sub.2═CH—(CO).sub.k1-Phe-(O).sub.k2—, Phe-CH═CH— and W.sup.4W.sup.5W.sup.6Si—, W.sup.1 denotes H, F, Cl, CN, CF.sub.3, phenyl or alkyl having 1 to 5 C atoms, W.sup.2 H or alkyl having 1 to 5 C atoms, W.sup.4, W.sup.5 and W.sup.6 each, independently of one another, denote Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W.sup.7 and W.sup.8 each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1,4-phenylene, k.sub.1, k.sub.2 and k.sub.3 each, independently of one another, denote 0 or 1, k.sub.4 denotes an integer from 1 to 10, Sp denotes single bond or Sp″-X″, Sp″ denotes alkylene having 1 to 20 which is optionally mono- or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced, independently of one another, by —O—, —S—, —Si(R.sup.00R.sup.000)—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —S—CO—, —CO—S—, —N(R.sup.00)—CO—O—, —O—CO—N(R.sup.00)—, —N(R.sup.00)—CO—N(R.sup.00)—, —CH═CH— or —C≡C— in such a way that O and/or S atoms are not linked directly to one another, X″ denotes —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —CO—N(R.sup.00)—, —N(R.sup.00)—CO—, —N(R.sup.00)—CO—N(R.sup.00)—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═N—, —N═CH—, —N═N—, —CH═CR.sup.0—, —CY.sup.2═CY.sup.3—, —C≡C—, —CH═CH—CO—O—, —O—CO—CH═CH— or a single bond, R.sup.0 in each case independently denotes H, F or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more H atoms are each optionally replaced by F, R.sup.00 in each case independently denotes alkyl having 1 to 12 C atoms, R.sup.000 in each case independently denotes H or alkyl having 1 to 12 C atoms, Y.sup.2 and Y.sup.3 each, independently of one another, denote H, F, Cl or CN, Z.sup.2 in each case, independently of one another, denotes —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)—, 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, n denotes 0 or 1, m denotes 0, 1, 2, 3, 4, 5 or 6, k denotes 0 or 1, R.sup.1 in each case, independently of one another, denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced by —O—, —S—, —CO—, —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, in addition, one or more H atoms are each optionally replaced by F or Cl, or a group -Sp-P, R.sup.a denotes an anchor group of the formulae ##STR00577## p denotes 1 or 2, Y in each case, independently of one another, denotes —O—, —S—, —C(O)—, —C(O)O—, —OC(O)—, —NR.sup.11— or a single bond, X.sup.1 in each case, independently of one another, denotes H, alkyl, fluoroalkyl, OH, NH.sub.2, NHR.sup.11, NR.sup.11.sub.2, OR.sup.1, C(O)OH, —CHO, where at least one group X.sup.1 denotes a radical selected from —OH, —NH.sub.2, NHR.sup.11, C(O)OH and —CHO, R.sup.11 denotes alkyl having 1 to 12 C atoms, Sp.sup.a denotes a single bond or a group selected from —CH.sub.2—, —CH.sub.2CH.sub.2—, —OCH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2—, —OCH.sub.2CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—, —OCH.sub.2CH.sub.2CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2—, and —OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2—, Sp.sup.b preferably denotes a trivalent group of the formula selected from CH, C(Me), C(CH.sub.2CH.sub.3) or N, or a tetravalent carbon atom, and Sp.sup.c and Sp.sup.d each independently denotes a single bond or a group selected from —CH.sub.2—, —CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—, and —CH.sub.2CH.sub.2OCH.sub.2CH.sub.2—.

34. The medium according to claim 1, wherein said one or more polymerizable compounds of formula I comprise one or more compounds selected from the following formulae: ##STR00578## ##STR00579## ##STR00580##

35. The medium according to claim 33, wherein A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote 1,4-phenylene or 1,4-cyclohexenylene, which in each case is unsubstituted or mono- or polysubstituted by a group L or -Sp-P.

36. The medium according to claim 1, wherein P is acrylate, methacrylate, or fluoroacrylate.

37. The medium according to claim 33, wherein, for the compound of the formula I, P is vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane or epoxide.

38. The medium according to claim 33, wherein P is acrylate, methacrylate, or fluoroacrylate.

Description

EXAMPLES

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

A) Synthesis Examples

Example 1

Synthesis of 2-methylacrylic acid 2-[2′-ethyl-4-(2-hydroxyethoxy)-4″-pentyl-[1,1′;4′,1″]terphenyl-3-yl]ethyl ester 1

(2) ##STR00340##

1) Synthesis of 4′-bromo-2′-ethylbiphenyl-4-ol A

(3) ##STR00341##

(4) 223 ml of water are added to 110.3 g (1.04 mol) of Na.sub.2CO.sub.3, and 154 g (0.49 mol) of 4-bromo-2-ethyl-1-iodobenzene, 75.1 g (0.54 mol) of 4-hydroxyphenylboronic acid and 850 ml of 1,4-dioxane are added, and the mixture is degassed. 14.5 g (19.8 mmol) of bis(1,1-diphenylphosphinoferrocene)-palladium(II) chloride are added, and the mixture is stirred at 80° C. for 18 h. When the reaction is complete (check by thin-layer chromatography with heptane/ethyl acetate 1:1), the reaction mixture is cooled to room temperature, diluted with water and methyl tert-butyl ether and acidified to pH 1-2 using 2 N HCl. The phases are separated, and the water phase is extracted with methyl tert-butyl ether, and the combined organic phases are dried over Na.sub.2SO.sub.4, filtered and evaporated in vacuo. The crude product obtained is filtered through silica gel with heptane/ethyl acetate (8:2), giving 96 g of the product A as a brown oil.

2) Synthesis of 2′-ethyl-4″-pentyl-[1,1′;4′,1″]terphenyl-4-ol B

(5) ##STR00342##

(6) 102 g (514 mmol) of 4-pentylphenylboronic acid and 135 g (467 mmol) of bromide A are dissolved in a mixture of 743 ml of toluene, 270 ml of ethanol and 350 ml of 2 N Na.sub.2CO.sub.2 and degassed. 8.1 g (7.0 mmol) of tetrakis-(triphenylphosphine)palladium are added, and the mixture is refluxed for 18 h. When the reaction is complete, the reaction mixture is cooled to room temperature, the water phase is separated off, the organic phase is washed with methyl tert-butyl ether (MTB ether), and the combined organic phases are dried over Na.sub.2SO.sub.4, filtered and evaporated in vacuo. The crude product is filtered through silica gel with dichloromethane, and the product fractions are recrystallized from heptane, giving 76.9 g of the product as colorless crystals.

(7) .sup.1H NMR (500 MHz, DMSO-d6)

(8) δ=0.89 ppm (t, 6.88 Hz, 3H, CH.sub.3), 1.08 (t, 7.51 Hz, 3H, CH.sub.3), 1.31 (m.sub.c, 4H, CH.sub.2), 1.61 (q, 7.58 Hz, 2H, CH.sub.2), 2.62 (q superimposed with t, 4H, benzylic CH.sub.2), 6.83 (d, 8.5 Hz, 2H, arom. H), 7.13 (d, 8.5 Hz, 2H, arom. H), 7.17 (d, 7.9 Hz, 1H, arom. H), 7.28 (d, 8.2 Hz, 2H, arom. H), 7.46 (dd, 7.93, 1.97 Hz, 1H, arom. H), 7.54 (d, 1.88 Hz, 1H, arom. H), 7.59 (d, 8.17 Hz, 2H, arom. H), 9.44 (s, 1H, arom. OH).

3) Synthesis of 3-bromo-2′-ethyl-4″-pentyl-[1,1′;4′,1″]terphenyl-4-ol C

(9) ##STR00343##

(10) 30.0 g (85.9 mmol) of alcohol B are dissolved in 1100 ml of dichloromethane and cooled to −48° C., and 5.28 ml (103 mmol) of bromine in 1100 ml of dichloromethane are slowly added at this temperature over the course of 40 min. The mixture is stirred at this temperature for a further 1 h and checked by thin-layer chromatography (toluene). The excess bromine is reduced using saturated NaHSO.sub.3 solution, and the phases are separated. The aqueous phase is extracted with dichloromethane, and the combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The crude product is filtered through silica gel with toluene, giving 35.3 g of the product as a white solid.

(11) .sup.1H NMR (500 MHz, CDCl.sub.3)

(12) δ=0.91 ppm (t, 6.99 Hz, 3H, CH.sub.3), 1.15 (t, 7.53 Hz, 3H, CH.sub.3), 1.36 (m.sub.c, 4H, CH.sub.2), 1.66 (m.sub.c, 2H, CH.sub.2), 2.65 (m.sub.c, 4H, benzylic CH.sub.2), 5.5 (s, 1H, arom. OH), 7.06 (d, 8.3 Hz, 1H, arom. H), 7.20 (dd, 8.28, 2.07 Hz superimposed with d 7.85 Hz, 2H, arom. H), 7.26 (d, 8.1 Hz, 2H, arom. H), 7.43 (dd, 7.87, 1.87 Hz, 2H, arom. H), 7.46 (d, 2.01 Hz, 1H, arom. H), 7.503 (d, 1.71 Hz, 1H, arom. H), 7.54 (d, 8.1 Hz, 2H, arom. H).

4) Synthesis of [2-(3-bromo-2′-ethyl-4″-pentyl-[1,1′;4′,1″]terphenyl-4-yloxy)-ethoxy]-tert-butyldimethylsilane D

(13) ##STR00344##

(14) 2.9 g (71.7 mmol) of NaH (60% suspension in paraffin oil) are initially introduced in 93 ml of dimethylformamide (DMF) and cooled to 2° C. with stirring, and a solution of alcohol C in DMF is slowly added at such a rate that the temperature does not exceed 12° C. When the addition is complete, the mixture is allowed to rise to room temperature (RT) and is stirred for a further 2 h (yellowish solution). 17.2 g (71.7 mmol) of (2-bromoethoxy)-tert-butyldimethylsilane, dissolved in DMF, are then slowly added, and the mixture is stirred at 50° C. for 18 h. The reaction solution is carefully added to ice-water and extracted with MTB ether. The combined organic phases are washed with water, dried over Na.sub.2SO.sub.4, filtered and evaporated in vacuo. The crude product obtained is filtered through silica gel with toluene, and the product fractions are evaporated in vacuo, giving 27.9 g of the desired product.

(15) MS (EI): 582.4 [M.sup.+]

(16) .sup.1H NMR (500 MHz, CDCl.sub.3)

(17) δ=0.00 ppm (s, 6H, Si—CH.sub.3), 0.78 (s, 12H, Si—C(CH.sub.3).sub.3), 1.01 (t, 7.52 Hz, CH.sub.3), 1.23 (m.sub.c, 4H, CH.sub.2), 1.52 (m.sub.c, 2H, CH.sub.2), 2.51 (m.sub.c, 4H, benzylic CH.sub.2), 3.91 (t, 5.24 Hz, 2H, CH.sub.2O), 4.02 (t, 5.24 Hz, 2H CH.sub.2O), 6.84 (d, 8.45 Hz, 1H, arom. H), 7.08 (dd, 8.37, 2.33 Hz superimposed with d 7.66 Hz, 2H, arom. H), 7.12 (d, 8.2 Hz, 2H, arom. H), 7.29 (dd, 7.86, 1.9 Hz, 2H, arom. H) 7.36 (d, 1.79 Hz, 1H, arom. H), 7.41 (d, 8.12 Hz superimposed with d, 2.15 Hz, 3H, arom. H).

5) Synthesis of 2-{4-[2-(tert-butyldimethylsilanyloxy)ethoxy]-2′-ethyl-4′-pentyl-[1,1′;4′,1″]terphenyl-3-yl}ethanol E

(18) ##STR00345##

(19) 8.5 g (14 mmol) of bromide D are dissolved in 41 ml of tetrahydrofuran (THF) and cooled to −78° C., and 10.6 ml (17 mmol) of butyllithium (1.6 molar solution in THF) are slowly added. 6.23 ml (16 mmol) of ethylene oxide (2.5-3.3 molar in THF) are subsequently added, and the mixture is stirred for a further 30 min. 2.13 ml (17 mmol) of boron trifluoride/diethyl ether complex in 10 ml of cooled THF are then slowly added at −78° C. (exothermic), and the mixture is stirred at this temperature for 2 h. The reaction solution is subsequently allowed to warm to room temperature (RT) over the course of 2 h and is poured into ice-water. The mixture is extracted with MTB ether, and the organic phase is dried over Na.sub.2SO.sub.4, filtered and evaporated in vacuo. The crude product obtained is purified over silica gel with heptane/ethyl acetate (H/EA) 9:1 and subsequently with H/EA (4:1), and the product fractions are evaporated in vacuo, giving 3.61 g of the product as an oil.

(20) MS (EI): 546.4 [M.sup.+]

(21) .sup.1H NMR (500 MHz, CDCl.sub.3)

(22) δ=0.00 ppm (s, 6H, Si—CH.sub.3), 0.81 (s, 12H, Si—C(CH.sub.3).sub.3), 1.03 (t, 7.53 Hz, CH.sub.3), 1.24 (m.sub.c, 4H, CH.sub.2), 1.54 (m.sub.c, 2H, CH.sub.2), 1.73 (t, 6.25 Hz, 1H, OH), 2.54 (m.sub.e, 4H, benzylic CH.sub.2), 2.85 (t, 6.3 Hz, 2H, CH.sub.2—O), 3.76 (q, 6.15 Hz, 2H, CH2-OH) 3.88 (t, 5.18 Hz, 2H, CH.sub.2O), 3.99 (t, 5.18 Hz, 2H CH.sub.2O), 6.81 (d, 8.26 Hz, 1H, arom. H), 7.01-7.08 (m 2H, arom. H), 7.10-7.16 (d superimposed with singlet, 3H, arom. H), 7.30 (dd, 7.86, 1.92 Hz, 2H, arom. H), 7.38 (d, 1.8 Hz, 1H, arom. H), 7.42 (d, 8.14, 2H, arom. H).

6) Synthesis of 2-methylacrylic acid 2-{4-[2-(tert-butyldimethylsilanyloxy)-ethoxy]-2′-ethyl-4″-pentyl-[1,1′;4′,1″]terphenyl-3-yl}ethyl ester F

(23) ##STR00346##

(24) 8.50 g (15.5 mmol) of alcohol E, 1.84 ml (21.8 mmol) of methacrylic acid and 0.19 g (1.55 mmol) of 4-(dimethylamino)pyridine are dissolved in 100 ml of dichloromethane and cooled to 5° C. 3.37 g (21.8 mmol) of 4-N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride, dissolved in 40 ml of dichloromethane, are slowly added, and the mixture is stirred at room temperature for 72 h. The reaction mixture is diluted with dichloromethane and filtered through silica gel, and the product fractions are evaporated in vacuo at max. 30° C., giving 7.5 g of the product as a clear oil.

(25) MS (EI): 614.5 [M.sup.+]

(26) .sup.1H NMR (500 MHz, CDCl.sub.3)

(27) δ=0.00 ppm (s, 6H, Si—CH.sub.3), 0.81 (s, 12H, Si—C(CH.sub.3).sub.3), 1.02 (t, 7.49 Hz, CH.sub.3), 1.24 (m.sub.c, 4H, CH.sub.2), 1.55 (m.sub.c, 2H, CH.sub.2), 1.79 (s, 3H, CH.sub.3), 2.53 (m.sub.c, 4H, benzylic CH.sub.2), 2.95 (t, 6.89 Hz, 2H, CH.sub.2—O), 3.89 (t, 5.11 Hz, 2H, CH.sub.2O), 3.99 (t, 5.14 Hz, 2H CH.sub.2O), 4.28 (t, 6.94, 2H, CH.sub.2—O), 5.39 (s, 1H, olefin. H), 5.95, (s, 1H, olefin. H), 6.8 (d, 8.24 Hz, 1H, arom. H), 7.03-7.06 (m 2H, arom. H), 7.10 (d, 7.86 Hz, 1H, arom. H), 7.14 (d, 8.76 Hz, 2H, arom. H), 7.30 (dd, 7.86, 1.82 Hz, 2H, arom. H), 7.38 (d, 1.63 Hz, 1H, arom. H), 7.43 (d, 8.07, 2H, arom. H).

7) Synthesis of 2-methylacrylic acid 2-[2′-ethyl-4-(2-hydroxyethoxy)-4″-pentyl-[1,1′;4′,1″]terphenyl-3-yl]ethyl ester G

(28) ##STR00347##

(29) 7.60 g (12.2 mmol) of compound F are dissolved in 150 ml of THF and cooled to 2° C. 7.01 ml (14.0 mmol) of HCl (2 N) are then slowly added, and the mixture is stirred at 2-4° C. for 1 h. The reaction solution is subsequently allowed to warm to RT over the course of 3 h and is carefully adjusted to pH 7 using NaHCO.sub.3 solution. The mixture is extracted with MTB ether, and the organic phases are dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The crude product is purified on silica gel with heptane/ethyl acetate (1:1), and the product fractions are combined and recrystallized twice from acetonitrile (1:4) at −20° C. The product obtained is dried at 60° C. in a bulb-tube distillation apparatus (removal of acetonitrile), giving 3.2 g of the product as a white solid.

(30) Phases: Tg −16 C 58 I

(31) MS (EI) 500.3 [M.sup.+]

(32) .sup.1H NMR (500 MHz, CDCl.sub.3)

(33) δ=0.91 ppm (t, 6.88 Hz, CH.sub.3), 1.14 (t, 7.52 Hz, 3H, CH.sub.3), 1.37 (m.sub.c, 4H, CH.sub.2), 1.67 (m, 2H, CH.sub.2), 1.04 (s, 3H, CH.sub.3), 2.65 (m.sub.c, 4H, benzylic CH.sub.2), 3.04 (t, 7.74 Hz, 2H, CH.sub.2—O), 3.19 (t, 6.81 Hz, 1H, OH), 4.03 (m.sub.c, 2H, CH.sub.2O), 4.15 (t, 4.02 Hz, 2H CH.sub.2O), 4.42 (t, 7.5 Hz, 2H, CH.sub.2—O), 5.56 (s, 1H, olefin. H), 6.12, (s, 1H, olefin. H), 6.91 (d, 8.32 Hz, 1H, arom. H), 7.30-7.13 (m 5H (superimposed with CHCl.sub.3), arom. H), 7.42 (dd, 7.87, 1.91 Hz, 1H, arom. H), 7.506 (d, 1.76 Hz, 1H, arom. H), 7.54 (d, 8.15 Hz, 2H, arom. H).

Example 2

Synthesis of 2-methylacrylic acid 2′-ethyl-4″-(2-hydroxyethyl)-6″-(2-methylacryloyloxy)-4-pentyl-[1,1′;4′,1″]terphenyl-3″-yl ester 2

(34) ##STR00348##

1) Synthesis of 4-bromo-2-ethyl-4′-pentylbiphenyl A2

(35) ##STR00349##

(36) 45.0 g (234 mmol) of 4-pentylphenylboronic acid, 70.0 g (225 mmol) of 4-bromo-2-ethyl-1-iodobenzene are dissolved in a mixture of 300 ml of toluene, 200 ml of ethanol and 200 ml of Na.sub.2CO.sub.3 solution (2 molar) and blanketed with argon. 8.00 g (6.92 mmol) of tetrakis(triphenylphosphine)palladium(0) are subsequently added, and the reaction mixture is refluxed for 18 h. When the reaction is complete, the mixture is allowed to cool to room temperature, and water is added, the phases are separated, the organic phase is washed with water and dried over Na.sub.2SO.sub.4, filtered and evaporated in vacuo. The crude product (orange oil) is filtered through silica gel with heptane, giving 56.2 g of the product as a colorless oil.

(37) .sup.1H NMR (500 MHz, CDCl.sub.3)

(38) δ=0.91 ppm (t, 6.97 Hz. 3H, CH.sub.3), 1.09 (t, 7.58 Hz, 3H. CH.sub.3), 1.36 (m.sub.c, 4H, CH.sub.2), 1.66, (m.sub.c, 2H, CH.sub.2), 2.56 (q, 7.55 Hz, 2H, benz. CH.sub.2), 2.64 (dd, 7.71 Hz, 2H, benz. CH.sub.2), 7.05 (d, 8.15 Hz, 1H, arom. H), 7.16 (d, 8.21 Hz, 2H, arom. H), 7.21 (d, 8.14 Hz, 2H, arom. H), 7.3 (dd, 8.14, 2.12 Hz, 1H, arom. H), 7.42 (d, 1H, 2.08 Hz, 1H, benz. H), 7.24 (d, 8.2 Hz, 2H, arom. H), 7.27 (d, 8.2 Hz, 2H, arom. H), 7.35 (dd, 7.87, 1.71 Hz, 1H, arom. H), 7.42 (d, 1.53 Hz, 1H, arom. H).

2) Synthesis of 2-ethyl-4′-pentylbiphenyl-4-boronic acid B2

(39) ##STR00350##

(40) 65.0 g (196 mmol) of bromide A2 are dissolved in 475 ml of tetrahydrofuran (THF) and cooled to −78° C., and 128.8 ml (206 mmol, 1.6 molar in n-hexane) of n-butyllithium are added dropwise. The reaction mixture is stirred at −78° C. for a further 60 min, and 24.5 ml (216 mmol) of trimethyl borate are added dropwise at this temperature. The mixture is stirred at this temperature for a further one hour, then allowed to thaw slowly to 0° C. and carefully rendered acidic using 2 N hydrochloric acid at 0° C., stirred briefly, and the phases are separated. The aqueous phase is extracted with MTB ether, and the combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. The crude product is filtered through silica gel firstly by means of dichloromethane and then with MTB ether and evaporated in vacuo, giving 43.7 g of the product as a smectic solid.

3) Synthesis of 2-(4-bromo-2,5-dimethoxyphenyl)ethanol C2

(41) ##STR00351##

(42) 10.0 g (33.8 mmol) of 1,4-dibromo-2,5-dimethoxybenzene are dissolved in 300 ml of THF and cooled to −78° C., and 23.0 ml (36.8 mmol, 1.6 molar in n-hexane) of n-butyllithium are added dropwise, and the mixture is stirred for a further 5 min. 1.70 g (38.6 mmol) of ethylene oxide in 20 ml of THF cooled to 2° C. are then allowed to run into the reaction mixture. 5.00 ml (39.8 mmol) of boron trifluoride/diethyl ether complex are then carefully added dropwise at −78° C., and stirring is continued at this temperature for a further 15 min. After checking the reaction by means of thin-layer chromatography, the reaction is quenched with 5.0 ml of isopropanol while cold, allowed to thaw to 0° C., water and MTB ether are carefully added, and stirring is continued. The phases are separated, the water phase is extracted with MTB ether, the organic phases are combined, washed with saturated sodium chloride solution and dried over sodium sulfate and evaporated in vacuo. The crude product is filtered through silica gel with dichloromethane/MTB ether (9:1), giving 5.8 g of the product as a slightly yellow oil.

4) Synthesis of 2-(2′-ethyl-2″,5″-dimethoxy-4-pentyl[1,1′;4′,1″]terphenyl-4″)-ethanol D2

(43) ##STR00352##

(44) 23.0 g (25% by weight in toluene, 19.4 mmol) of alcohol C2 and 5.70 g (18.7 mmol, 85%) of B2 are dissolved in a mixture of 200 ml of toluene, 100 ml of ethanol and 40 ml (1 mol/l, 40 mmol) of Na.sub.2CO.sub.3 and degassed by passing in argon. 100 mg (0.87 mmol) of tetrakis(triphenylphosphine)palladium(O) are then added, and the mixture is refluxed for 60 min. The mixture is cooled to room temperature, and water is added. The phases are separated, the organic phase is washed with water, dried over sodium sulfate, filtered and evaporated in vacuo. The crude product is filtered through silica gel with a mixture of dichloromethane and MTB ether (95:5) and evaporated in vacuo, giving 6.0 g of the product as a pale-brown oil.

(45) .sup.1H NMR (500 MHz, DMSO-d.sub.6)

(46) δ=0.89 ppm (t, 6.8 Hz, 3H, CH.sub.3), 1.06 (t, 7.54 Hz, 3H, CH.sub.3), 1.33 (m.sub.c, 4H, CH.sub.2), 1.63 (quin., 7.51 Hz, 2H, CH.sub.2), 2.67-2.54 (m, 4H, benz. CH.sub.2), 2.77 (t, 7.25 Hz, 2H, benz. CH.sub.2), 3.60 (dt, 7.21, 5.49 Hz, 2H, CH.sub.2CH.sub.2OH), 3.72 (s, 3H, OCH.sub.3), 3.79 (s, 3H, OCH.sub.3), 4.62 (t, 5.36 Hz, 1H, OH), 6.90 (s, 1H, arom. H), 6.95 (s, 1H, arom. H), 7.15 (d, 7.86 Hz, 1H, arom. H).

5) Synthesis of 2′-ethyl-4″-(2-hydroxyethyl)-4-pentyl-[1,1′;4′,1″]terphenyl-2″,5″-diol E2

(47) ##STR00353##

(48) 4.70 g (10.9 mmol) of alcohol D2 are dissolved in 50 ml of dichloromethane and cooled to −28° C. 2.3 ml (24.2 mmol) of boron tribromide are carefully added, and the mixture is stirred at −25° C. for 3 h. When the reaction is complete, the reaction mixture is added to ice-water with stirring and carefully neutralized using 2 N sodium hydroxide solution. The phases are separated, the water phase is extracted with dichloromethane, and the combined organic phases are washed with water and dried over sodium sulfate, filtered and evaporated. The crude product (orange oil) is filtered through silica gel firstly with dichloromethane and MTB ether (9:1) and then with (3:1), and the product fractions are evaporated in vacuo. The product formed is recrystallized from toluene at 5° C., giving 1.7 g of the product as colorless crystals.

(49) .sup.1H NMR (500 MHz, DMSO-d.sub.6)

(50) δ=0.89 ppm (t, 6.83 Hz, 3H, CH.sub.3), 1.07 (t, 7.55 Hz, 3H, CH.sub.3), 1.34 (m.sub.c, 4H, CH.sub.2), 1.64 (quin., 7.3 Hz, 2H, CH.sub.2), 2.71-2.55 (m, 6H, benz. CH.sub.2), 3.58 (dt, 7.0, 5.01 Hz, 2H, CH.sub.2CH.sub.2OH), 4.70, (t, 5.07 Hz, CH.sub.2OH), 6.68 (s, 1H, arom. H), 6.74 (s, 1H, arom. H), 7.15 (d, 7.89 Hz, arom. H), 7.25 (d, 8.26 Hz, 2H, arom. H), 7.28 (d, 8.26 Hz, 2H, arom. H), 7.37 (dd, 7.9, 1.8 Hz, 1H, arom. H), 7.43 (d, 1.60 Hz, 1H, arom. H), 8.67 (s, 2H, arom. OH).

6) Synthesis of 4″-[2-(tert-butyldimethylsilanyloxy)ethyl]-2′-ethyl-4-pentyl-[1,1′;4′,1″]terphenyl-2″,5″-diol F2

(51) ##STR00354##

(52) 1.20 g (2.96 mmol) of alcohol E2 and 0.214 ml (3.23 mmol) of imidazole are dissolved in 9.0 ml of THF and cooled to 2° C., and 490 mg (3.25 mmol) of tert-butylchlorodimethylsilane, dissolved in 4 ml of THF, are subsequently added dropwise over the course of 30 min, and the mixture is stirred at this temperature for 60 min. Ammonium chloride solution is added to the reaction mixture, which is then extracted with MTB ether. The organic phase is separated off and dried over sodium sulfate, filtered and evaporated in vacuo, giving an orange oil, which is filtered through silica gel with toluene and toluene and ethyl acetate (98:2), giving 1.0 g of the product as a yellow oil.

(53) .sup.1H NMR (500 MHz, CDCl.sub.3)

(54) δ=0.00 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.82 (s, 12H, SiC(CH.sub.3).sub.3), 1.02 (t, 7.56 Hz, 3H, CH.sub.3), 1.26 (m.sub.c, 4H, CH.sub.2), 1.57 (m.sub.c, 2H, CH.sub.2), 2.55 (m.sub.c, 4H, benz. CH), 2.78 (t, 4.98 Hz, 2H, CH.sub.2CH.sub.2OSi), 3.85 (t, 5.1 Hz, 2H, CH.sub.2OSi), 4.82 (s, 1H, arom. OH), 6.59 (s, 1H, arom. H), 6.79 (s, 1H, arom. H) 7.13 (2×d(superimposed) 4H, arom. H), 7.18 (d, 7.78 Hz, 1H, arom. H), 7.21 (dd, 7.78, 1.7 Hz, 1H, arom. H), 7.29, (d, 1.4 Hz, 1H, arom. H), 7.82 (s, 1H, arom. OH).

7) Synthesis of 2-methylacrylic acid 4″-[2-(tert-butyldimethylsilanyloxy)ethyl]-2′-ethyl-6″-(2-methylacryloyloxy)-4-pentyl-[1,1′;4′,1″]terphenyl-3″-ylester G2

(55) ##STR00355##

(56) 2.30 g (4.43 mmol) of phenol F2, 1.0 ml (11.8 mmol) of methacrylic acid and 30.0 mg (0.25 mmol) of 4-(dimethylamino)pyridine are dissolved in 25 ml of dichloromethane and cooled to 1° C. 1.80 g (11.6 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC), dissolved in 20 ml of dichloromethane, are then added dropwise at 1-4° C., and the mixture is subsequently stirred at room temperature (RT) for 18 h. 0.4 ml of methacrylic acid and 0.6 g of EDC are subsequently again added at RT, and the mixture is stirred at RT for a further 18 h. The reaction solution is then filtered directly through a 100 ml silica-gel frit with dichloromethane and evaporated in vacuo, giving 3.3 g of the yellow crude product as a partially crystalline solid, which is dissolved in 10 ml of heptane/ethyl acetate (EA) (95:5), and undissolved constituents are filtered off. The mixture is subsequently filtered through 120 g of silica gel with heptane/EA (95:5), giving 2.4 g of the product as a yellow oil.

(57) .sup.1H NMR (500 MHz, CDCl.sub.3)

(58) δ=0.00 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.86 (s, 12H, SiC(CH.sub.3).sub.3), 1.06 (t, 7.55 Hz, 3H, CH.sub.3), 1.35 (m.sub.c, 4H, CH.sub.2), 1.65 (m.sub.c, 2H, CH.sub.2), 1.93 (s, 3H, CH.sub.3), 2.07 (s, 3H, CH.sub.3), 2.58 (q, 7.52, 2H, benz. CH.sub.2), 2.63 (t, 7.91, 2H, benz. CH.sub.2), 2.78 (t, 7.23 Hz, 2H, CH.sub.2CH.sub.2OSi), 3.79 (t, 7.26 Hz, 2H, CH.sub.2OSi), 5.62 (s, 1H, olefin. H), 5.77 (s, 1H, olefin. H), 6.18 (s, 1H, olefin. H), 6.37 (s, 1H, olefin. H), 7.12 (s, 1H, arom. H), 7.16 (d, 7.86 Hz, 1H, arom. H), 7.18 (s, 1H, arom. H), 7.19, (s, 4H, arom. H), 7.24 (dd, (superimposed with CHCl.sub.3, 1H, arom. H), 7.32, (d, 1.39 Hz, 1H, arom. H).

Synthesis of 2-methylacrylic acid 2′-ethyl-4″-(2-hydroxyethyl)-6″-(2-methylacryloyloxy)-4-pentyl-[1,1′;4′,1″]terphenyl-3″-yl ester 2

(59) ##STR00356##

(60) 2.20 g (3.36 mmol) of compound G2 are dissolved in 50 ml of THF and cooled to 2° C. 2.00 ml (4.00 mmol) of hydrochloric acid (2N) are then slowly added dropwise, and the mixture is stirred at up to room temperature (RT) for 3 h. The mixture is then neutralized using sodium hydrogencarbonate solution with cooling, and water and MTB ether are added. The phases are separated, and the water phase is subsequently extracted with MTB ether. The combined organic phases are washed with water, dried over sodium sulfate, filtered and evaporated in vacuo, giving the crude product as a yellow oil, which is filtered through 200 g of silica gel with dichloromethane/MTB ether (98:2). The product obtained (colorless oil) is evaporated in vacuo and then dried at 60° C. and 0.09 mbar until solvent no longer escapes, giving the product (700 mg) as a colorless, viscous resin.

(61) .sup.1H NMR (500 MHz, CDCl.sub.3)

(62) δ=0.92 (t, 6.63 Hz, 3H, CH.sub.3), 1.08 (t, 7.54 Hz, 3H, CH.sub.3), 1.37 (m.sub.c, 4H, CH.sub.2), 1.67 (m.sub.c, 3H, CH.sub.2, OH), 1.94 (s, 3H, CH.sub.3), 2.09 (s, 3H, CH.sub.3), 2.60 (q, 7.53 Hz, 2H, benz. CH.sub.2), 2.70 (t, 7.9 Hz, 2H, benz. H), 2.85, (t, 6.4 Hz, 2H, CH.sub.2CH.sub.2OH), 3.87 (q., 6.24 Hz, 2H, CH.sub.2OH), 5.66 (s, 1H, olefin. H), 5.79 (s, 1H, olefin. H), 6.21 (s, 1H, olefin. H), 6.39 (s, 1H, olefin. H), 7.17 (s, 1H, arom. H), 7.19 (d, 7.87 Hz, 1H, arom. H), 7.21, 7.22 (2×S (superimposed) 5H, arom. H), 7.26 (dd (superimposed with CHCl.sub.3), 1H, arom. H), 7.33 (d, 1.59 Hz, 1H, arom. H).

Example 3

Synthesis of 2-{5-[2-ethyl-4-(4-pentylphenyl)phenyl]-2-[4-hydroxy-3-(hydroxymethyl)butoxy]phenyl}ethyl 2-methylprop-2-enoate 4

(63) ##STR00357##

1) Synthesis of 4′-bromo-2′-ethylbiphenyl-4-ol A

(64) ##STR00358##

(65) 223 ml of water are added to 110.3 g (1.04 mol) of Na.sub.2CO.sub.3, and 154 g (0.49 mol) of 4-bromo-2-ethyl-1-iodobenzene, 75.1 g (0.54 mol) of 4-hydroxy-phenolboronic acid and 850 ml of 1,4-dioxane are added, and the mixture is degassed. 14.5 g (19.8 mmol) of bis(1,1-diphenylphosphinoferrocene)palladium(II) chloride are added, and the mixture is stirred at 80° C. for 18 h. When the reaction is complete (check by thin-layer chromatography with heptane/ethyl acetate 1:1), the reaction mixture is cooled to room temperature, diluted with water and methyl tert-butyl ether and acidified to pH 1-2 using 2 N HCl. The phases are separated, and the water phase is extracted with methyl tert-butyl ether, and the combined organic phases are dried over Na.sub.2SO.sub.4, filtered and evaporated in vacuo. The crude product obtained is filtered through silica gel with heptane/ethyl acetate (8:2), giving 96 g of the product A as a brown oil.

2) Synthesis of 2′-ethyl-4″-pentyl-[1,1′;4′,1″]terphenyl-4-ol B

(66) ##STR00359##

(67) 102 g (514 mmol) of 4-pentyl-1-benzeneboronic acid and 135 g (467 mmol) of bromide A are dissolved in a mixture of 743 ml of toluene, 270 ml of ethanol and 350 ml of 2 N Na.sub.2CO.sub.2 and degassed. 8.1 g (7.0 mmol) of tetrakis-(triphenylphosphine)palladium are added, and the mixture is refluxed for 18 h. When the reaction is complete, the reaction mixture is cooled to room temperature, the water phase is separated off, the organic phase is washed with methyl tert-butyl ether (MTB ether), and the combined organic phases are dried over Na.sub.2SO.sub.4, filtered and evaporated in vacuo. The crude product is filtered through silica gel with dichloromethane, and the product fractions are recrystallized from heptane, giving 76.9 g of the product as colorless crystals.

(68) .sup.1H NMR (500 MHz, DMSO-d.sub.6)

(69) δ=0.89 ppm (t, 6.88 Hz, 3H, CH.sub.3), 1.08 (t, 7.51 Hz, 3H, CH.sub.3), 1.31 (m.sub.c, 4H, CH.sub.2), 1.61 (q, 7.58 Hz, 2H, CH.sub.2), 2.62 (q. superimposed with t, 4H, benzylic CH.sub.2), 6.83 (d, 8.5 Hz, 2H, arom. H), 7.13 (d, 8.5 Hz, 2H, arom. H), 7.17 (d, 7.9 Hz, 1H, arom. H), 7.28 (d, 8.2 Hz, 2H, arom. H), 7.46 (dd, 7.93, 1.97 Hz, 1H, arom. H), 7.54 (d, 1.88 Hz, 1H, arom. H), 7.59 (d, 8.17 Hz, 2H, arom. H), 9.44 (s, 1H, arom. OH).

3) Synthesis of 3-bromo-2′-ethyl-4″-pentyl-[1,1′;4′,1″]terphenyl-4-ol C

(70) ##STR00360##

(71) 30.0 g (85.9 mmol) of alcohol B are dissolved in 1100 ml of dichloromethane and cooled to −48° C., and 5.28 ml (103 mmol) of bromine in 1100 ml of dichloromethane are slowly added at this temperature over the course of 40 min. The mixture is stirred at this temperature for a further 1 h and checked by thin-layer chromatography (toluene). The excess bromine is reduced using saturated NaHSO.sub.3 solution, and the phases are separated. The aqueous phase is extracted with dichloromethane, and the combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated in vacuo. The crude product is filtered through silica gel with toluene, giving 35.3 g of the product as a white solid.

(72) .sup.1H NMR (500 MHz, CDCl.sub.3)

(73) δ=0.91 ppm (t, 6.99 Hz, 3H, CH.sub.3), 1.15 (t, 7.53 Hz, 3H, CH.sub.3), 1.36 (m.sub.c, 4H, CH.sub.2), 1.66 (m.sub.c, 2H, CH.sub.2), 2.65 (m.sub.c, 4H, benzylic CH.sub.2), 5.5 (s, 1H, arom. OH), 7.06 (d, 8.3 Hz, 1H, arom. H), 7.20 (dd, 8.28, 2.07 Hz superimposed with d 7.85 Hz, 2H, arom. H), 7.26 (d, 8.1 Hz, 2H, arom. H), 7.43 (dd, 7.87, 1.87 Hz, 2H, arom. H), 7.46 (d, 2.01 Hz, 1H, arom. H), 7.503 (d, 1.71 Hz, 1H, arom. H), 7.54 (d, 8.1 Hz, 2H, arom. H).

4) Synthesis of 6-(2-{2-bromo-4-[2-ethyl-4-(4-pentylphenyl)phenyl]phenoxy}-ethyl)-2,2,3,3,9,9,10,10-octamethyl-4,8-dioxa-3,9-disilaundecane D

(74) ##STR00361##

(75) 10.0 g (24.0 mmol) of bromide C, 8.64 g (25.0 mmol) of 4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)oxy]methyl}butan-1-ol K and 7.03 g (26.81 mmol) of triphenylphosphine are dissolved in 76.5 ml of tetrahydrofuran (THF). 5.46 ml (27.9 mmol) of diisopropyl azodicarboxylate are then added dropwise to the reaction solution at room temperature (RT). The clear and slightly yellow reaction solution formed is stirred at RT for 20 h. The reaction mixture is then evaporated in vacuo and filtered through silica gel with heptane/dichloromethane, giving 17.45 g of the desired product.

(76) .sup.1H NMR (500 MHz, CDCl.sub.3)

(77) δ=0.00 ppm (s, 12H Si(CH.sub.3).sub.2), 0.854 (m.sub.c, 21H, 2×Si(C(CH.sub.3).sub.3), CH.sub.3), 1.09 (t, 7.5 Hz, 3H, CH.sub.3), 1.31 (m.sub.c, 4H), 1.61 (m.sub.c, 2H, CH.sub.2), 1.83 (q, 6.58 Hz, 2H, benz. CH.sub.2), 1.91 (sept., 5.64 Hz, 1H, CH.sub.2CH.sub.1(CH.sub.2OTBDMS).sub.2), 2.59 (m.sub.c, 4H, 2×CH.sub.2), 3.62 (m.sub.c, 4H, CH.sub.2OTBDMS), 4.12 (t, 6.49 Hz, OCH.sub.2), 6.87 (d, 8.43 Hz, 1H, arom. H), 7.15 (dd.sub.(superimposed), 7.83, 2.54 Hz, 1H, arom. H), 7.16 (d, 7.83 Hz, 1H, arom. H), 7.21 (d, 7.25 Hz, 2H, arom. H), 7.37 (dd, 7.86, 1.84 Hz, 1H, arom. H), 7.44 (d, 1.68 Hz, 1H, arom. H), 7.47 (d.sub.(superimposed), 1.90 Hz, 1H, arom. H), 7.49 (d.sub.(superimposed), 8.22 Hz, 2H, arom. H).

5) Synthesis of 2-(2-{4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)-oxy]methyl}butoxy}-5-[2-ethyl-4-(4-pentylphenyl)phenyl]phenyl)ethanol E

(78) ##STR00362##

(79) 17.5 g (23.0 mmol) of bromide D are dissolved in 65.0 ml of tetrahydrofuran (THF) and cooled to −70° C., and 17.1 ml (27.0 mmol) of butyllithium (1.6 M solution in hexane) are added dropwise at this temperature. A solution of 8.70 ml (25.0 mmol) of ethylene oxide in 10.0 ml of cooled (−25° C.) THF is then added rapidly. The reaction mixture is stirred at −70° C. for 45 minutes, and a solution of 3.45 ml (27.0 mmol) of boron trifluoride in THF at −25° C. is subsequently carefully added dropwise. The reaction mixture is then stirred at −70° C. for 3 h, diluted with 20 ml of MTB ether and allowed to come to room temperature over the course of 2 h. It is then carefully poured into ice-water and extracted with MTB ether. The combined org. phases are washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. The crude product obtained is filtered through silica gel with heptane/ethyl acetate (9:1, then 4:1), and the product fractions are evaporated in vacuo, giving 7.5 g of the product having a purity of 99.4% according to HPLC.

6) Synthesis of 2-(2-{4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)-oxy]methyl}butoxy}-5-[2-ethyl-4-(4-pentylphenyl)phenyl]phenyl)ethyl 2-methylprop-2-enoate F

(80) ##STR00363##

(81) 17.2 g (24.0 mmol) of alcohol E, 4.50 ml (53.1 mmol) of methacrylic acid (stabilized) and 0.33 g (2.71 mmol) of 4-(dimethylamino)pyridine are dissolved in 150 ml of dichloromethane (DCM) at room temperature and cooled to 2° C. 9.20 ml (53.3 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide as a solution in 50 ml of dichloromethane are then added dropwise at 2-5° C., and the mixture is stirred at room temperature for 20 h. The reaction solution is then filtered directly through silica gel with DCM, giving 15.5 g of the product having a purity of 99.6% (HPLC).

7) Synthesis of 2-{5-[2-ethyl-4-(4-pentylphenyl)phenyl]-2-[4-hydroxy-3-(hydroxymethyl)butoxy]phenyl}ethyl 2-methylprop-2-enoate G

(82) ##STR00364##

(83) 15.5 g (19.6 mmol) of ester F are dissolved in 225 ml of tetrahydrofuran (THF) and cooled to 2° C., and 23.5 ml (47.0 mmol) of HCl (2 mol/l) are slowly added dropwise. The reaction mixture is subsequently stirred at room temperature for a further 3 h and carefully neutralized using saturated sodium hydrogencarbonate solution. The reaction product is extracted with MTB ether, and the combined organic phases are washed with water and dried over sodium sulfate, filtered and evaporated at 30° C. in vacuo. The crude product is filtered through silica gel with heptane/ethyl acetate (2:1, 1:1 and finally with 1:2), and the product fractions are evaporated at 30° C. in vacuo, giving 10.9 g of a colorless solid, which is dissolved in 200 ml of pentane and 105 ml of MTB ether under reflux and is subsequently crystallized using acetone/dry ice. Drying at room temperature in vacuo gives 9.0 g of the desired product as a colorless solid having a purity of 99.8% (HPLC).

(84) Phase Behavior

(85) Tg=−18° C./C (melting point)=72° C./l (isotropic)

(86) .sup.1H NMR (500 MHz, CDCl.sub.3)

(87) δ=0.95 ppm (t, 6.9 Hz, 3H, CH.sub.3), 1.17 (t, 7.56 Hz, 3H, CH3), 1.39 (m.sub.c, 4H), 1.70 (quin. 7.33 Hz, 2H, CH.sub.2), 1.92 (q, 6.35 Hz, 2H, benz. CH.sub.2), 1.95 (s, 3H, CH.sub.3), 2.17 (m.sub.c, 1H,), 2.48 (s.sub.(broad)q, 2H, 2×OH), 2.68 (m.sub.c, 4H), 3.08 (t, 7.25 Hz, 2H), 3.82 (dd, 10.69, 6.84 Hz 2H CH.sub.2HOCH.sub.a2CH), 3.93 (dd, 10.77, 3.99 Hz, 2H, HOCH.sub.b2CH), 4.15 (t, 5.95 Hz, 2H, CH.sub.2), 4.44 (t, 7.26 Hz, 2H, CH.sub.2), 5.57 (s, 1H,), 6.11 (s, 1H), 6.93 (d, 8.27 Hz, 1H, arom. H), 7.19 (d, 2.05 Hz, 1H, arom. H), 7.21 (dd, 8.23, 2.28 Hz, 1H, arom. H), 7.29 (d, 7.98 Hz, 2H, arom. H) 7.45, (dd, 8.07, 2.02 Hz, 1H, arom. H), 7.53 (d, 1.68 Hz, 1H, arom. H), 7.58 (8.09 Hz, 2H, arom. H).

8) Synthesis of 1,3-diethyl 2-[2-(benzyloxy)ethyl]propanedioate H

(88) ##STR00365##

(89) 240.0 ml (0.628 mol) of sodium methoxide (20% solution in ethanol) are initially introduced in 300 ml of ethanol and heated to 81° C. 180.0 ml (1.180 mol) of diethyl malonate are then added rapidly over the course of 10 minutes (min.), and immediately thereafter 100.0 g (0.451 mol) of 2-bromoethoxy-methylbenzene are added over the course of 15 min. The reaction mixture is stirred under reflux for 4 h, subsequently cooled to room temperature (RT) and poured into a mixture of ice-water and MTB ether. The mixture is carefully adjusted to pH 4 to 5 using 25% hydrochloric acid, and the organic phase is separated off. The water phase is extracted a number of times with MTB ether. The combined organic phases are washed with water and dried over sodium sulfate, filtered and evaporated, giving 223.6 g of an orange liquid, from which the excess diethyl malonate is separated off by distillation at a bath temperature of 100-150° C. (top temperature 70-77° C.) and a vacuum of 5 mbar. The crude product obtained (133.2 g of orange liquid) is filtered through 2 l of silica gel with dichloromethane/MTB ether (8:2), giving the product as a yellow liquid.

9) Synthesis of 2-[2-(benzyloxy)ethyl]propane-1,3-diol I

(90) ##STR00366##

(91) 170.0 ml (340 mmol) of lithium aluminum hydride solution (2 molar in THF) are initially introduced, and a solution of 66.5 g (225.9 mmol) of ester H in 350.0 ml of tetrahydrofuran (THF) is added with cooling (up to a maximum reaction temperature of 50° C.). The reaction mixture is subsequently stirred at 66° C. for 5 h. The reaction mixture is cooled to room temperature (RT), and 100 ml of ethyl acetate are carefully added dropwise. 20 ml of water and a hot solution of 27.8 ml (377.4 mmol) of sodium carbonate decahydrate (Emprove®) in 30 ml of water are then carefully added, and the mixture is stirred for 15 min. The colorless precipitate is filtered off with suction and washed with copious THF. The filtrate is evaporated, giving 45.4 g of the product as a colorless, slightly cloudy oil, which is filtered through 1.2 liters of silica gel with ethyl acetate (EA) and EA/methanol (95:5 and 9:1). The product fractions are evaporated, giving 23.8 g of the product as a colorless oil.

(92) .sup.1H NMR (500 MHz, CDCl.sub.3)

(93) δ=1.74 ppm (q, 6.38 Hz, 2H CH.sub.2CH.sub.2CH.sub.1), 1.91 (sept., 5.17 Hz, 1H, CH.sub.2CH.sub.1(CH.sub.2OTBDMS).sub.2), 2.46 (s.sub.(broad), 1H, 2×OH), 3.61 (t, 5.77 Hz, 2H, CH.sub.2OCH.sub.2CH.sub.2), 3.72 (dd, 10.9, 5.86 Hz, 2H, 3.76 CH.sub.1CH.sub.2OTBDMS), (dd, 4.71, 10.9 Hz, 2H, CH.sub.1CH.sub.2OTBDMS), 4.55 (s, 2H, CH.sub.2-benzyl.), 7.41-7.30 (m, 5H, arom. H).

10) Synthesis of 6-[2-(benzyloxy)ethyl]-2,2,3,3,9,9,10,10-octamethyl-4,8-dioxa-3,9-disilaundecane J

(94) ##STR00367##

(95) 53.7 g (255.39 mmol) of diol I and 3.0 g (24.56 mmol) of 4-(dimethylamino)-pyridine are dissolved in 600 ml of dichloromethane and cooled to 5° C. 110.0 ml (0.79 mmol) of triethylamine are then added, and a solution of 100.0 g (0.66 mol) of tert-butyldimethylchlorosilane in 400 ml of dichloromethane (DCM) is subsequently added dropwise at 2-7° C., and the mixture is stirred at room temperature for 20 h. The ammonium salts which have precipitated out are filtered off with suction, washed with DCM, and the organic phase is washed with saturated sodium chloride solution and water, dried over sodium sulfate, filtered and evaporated, giving the crude product (130.1 g) as an orange oil, which is filtered through 2 l of silica gel with toluene, giving, after evaporation of the product fractions, 113.2 g of the product as a slightly yellow oil.

11) Synthesis of 4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)-oxy]methyl}butan-1-ol

(96) ##STR00368##

(97) 60.0 g (110.8 mmol) of J are dissolved in 600 ml of ethyl acetate, 30.0 g of Pd/C (basic, 50% of water) are added, and the starting material is debenzylated for 24 h under a hydrogen atmosphere (1 bar, 50° C.). The reaction mixture (50% of product) is filtered off with suction and debenzylated again for a further 40 h using 15.0 g of Pd/C (basic, 50% of water) under a hydrogen atmosphere (1 bar, 50° C.). The reaction mixture is filtered at room temperature and evaporated, giving the crude product (50.0 g) as a colorless oil, which is filtered through 1 l of silica gel with pentane/MTB ether (9:1 to 7:3), giving 41.6 g of the product as a colorless oil.

(98) .sup.1H NMR (500 MHz, CDCl.sub.3)

(99) δ=0.00 ppm (2, 12H, 2×Si(CH.sub.3).sub.2), 0.83 (s, 18H, 2×Si(C(CH.sub.3).sub.3), 1.53 (q, 6.21 Hz, 2H, CH.sub.2CH.sub.2CH.sub.1), 1.74 (sept. 6.08 Hz, 1H, CH.sub.2CH.sub.1(CH.sub.2OTBDMS).sub.2), 3.16 (s.sub.(broad), 1H, OH), 3.47 (dd, 10.02, 6.26 Hz, 2H, CH.sub.1CH.sub.2OTBDMS), 3.57 (dd, 10.02, 5.72, 2H, CH.sub.1CH.sub.2OTBDMS), 3.62 (q (broad), 5.37 Hz, 2H CH.sub.2OH).

Example 4

Synthesis of 3-{5-[2-ethyl-4-(4-pentylphenyl)phenyl]-2-(3-hydroxypropoxy)-3-{3-[(2-methylprop-2-enoyl)oxy]propyl}phenyl}propyl 2-methylprop-2-enoate 13

(100) ##STR00369##

1) Synthesis of 2,6-dibromo-4-[2-ethyl-4-(4-pentylphenyl)phenyl]phenol A13

(101) ##STR00370##

(102) 20.6 g (59.80 mmol) of 2′-ethyl-4″-pentyl-[1,1′;4′,1″]terphenyl-4-ol B are initially introduced in 150 ml of dichloromethane (DCM), and 1.50 ml (10.67 mmol) of diisopropylamine are added dropwise. The reaction solution is cooled to −5° C. using a dry ice/acetone bath, and a solution of 21.6 g (121.4 mmol) of N-bromosuccinimide in 300 ml of DCM is subsequently added dropwise. The reaction solution is stirred at room temperature (RT) for 18 h and acidified using 2 M HCl, water is added, and the phases are separated. The aqueous phase is extracted with DCM, dried over sodium sulfate, filtered and evaporated in vacuo. The crude product is filtered through 600 g of silica gel with toluene/heptane (1:1+1% of triethylamine). The product fractions are combined and, after evaporation, recrystallized from heptane at −30° C., giving the product as a viscous oil in a yield of 15.1 g and a purity of 99.1% (gas chromatography).

2) Synthesis of tert-butyl(2,6-dibromo-4-[2-ethyl-4-(4-pentylphenyl)phenyl]-phenoxy)dimethylsilane B13

(103) ##STR00371##

(104) 10.6 g (20.32 mmol) of bromide A13 are initially introduced in 150 ml of dichloromethane (DCM), 2.90 g (42.6 mmol) of imidazole are added, and the mixture is stirred at room temperature (RT) for 30 min. A solution of 4.00 g (26.54 mmol) of tert-butyldimethylchlorosilane in 20 ml of DCM is then added dropwise, and the mixture is stirred at RT for a further 18 h. The reaction mixture is evaporated in vacuo and dissolved in ethyl acetate (EA), water is added, and, after stirring, the phases are separated. The aqueous phase is extracted with EA, and the combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate and evaporated in vacuo. The crude product obtained is filtered through 400 ml of silica gel with heptane, and the product fractions are combined and evaporated in vacuo, giving 6.6 g of the product as a colorless oil.

(105) MS (EI): 616.3 [M.sup.+]

(106) .sup.1H NMR (500 MHz, CDCl.sub.3)

(107) δ=0.38 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.88 (t, 6.6 Hz, 3H, CH.sub.3), 1.06 (s, 9H, Si(C(CH.sub.3).sub.3)), 1.13 (t, 8.06 Hz, 3H, CH.sub.3), 1.38-1.27 (m, 4H, CH.sub.2), 1.63 (quin., 7.7 Hz, 2H, CH.sub.2), 2.66-2.59 (m, 4H, CH.sub.2), 7.17 (d, 7.15 Hz, 1H, arom. H), 7.23 (d, 7.62 Hz, 2H, arom. H), 7.39 (dd, 7.86, 1.89 Hz, 1H, arom. H), 7.44 (s, 2H, arom. H), 7.462 (d, 1.75 Hz, 1H, arom. H), 7.50 (d, 8.13 Hz, 2H, arom. H).

3) Synthesis of 4-[2-ethyl-4-(4-pentylphenyl)phenyl]-2,6-bis(3-hydroxypropyl)-phenol C13

(108) ##STR00372##

(109) 2.90 g (27.4 mmol) of sodium carbonate, 100.0 mg (0.56 mmol) of palladium-(II) chloride and 180.0 mg (0.39 mmol) of 2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl are initially introduced in 30 ml of water, and a solution of 15.6 g (25.9 mmol) of bromide B13 and 4.10 g (28.9 mmol) of 2-butoxy-1,2-oxaborolane in 135 ml of tetrahydrofuran (THF) is added. 120 μl (0.87 mmol) of triethylamine are added, the mixture is degassed with nitrogen for 20 minutes (min.) and subsequently stirred under reflux for 18 h. The reaction mixture is cooled to room temperature, and water and MTB ether are added. After the reaction solution has been stirred, the phases are separated, the aqueous phase is extracted with MTB ether, and the combined organic phases are washed with saturated sodium chloride solution, dried using sodium sulfate, filtered and evaporated in vacuo. The crude product is filtered through 350 ml of silica gel with toluene/ethyl acetate (1:1), and the product fractions are combined and evaporated in vacuo.

(110) .sup.1H NMR (500 MHz, DMSO-d.sub.6)

(111) δ=0.89 ppm (t, 7.08 Hz, 3H, CH.sub.3), 1.05 (t, 7.92 Hz, 3H, CH.sub.3), 1.33 (m.sub.c, 4H, CH.sub.2), 1.62 (quint, 7.29 Hz, 2H, CH.sub.2), 1.73 (quint, 6.73 Hz, 2H, CH.sub.2), 2.69-2.58 (m, 8H, benzyl-CH.sub.2), 3.45 (q, 6.42 Hz, 4H, CH.sub.2), 4.52 (t, 5.04 Hz, 2H, OH), 6.89 (s, 2H, arom. H), 7.2 (d, 7.9 Hz, 1H, arom. H), 7.29 (d, 8.98 Hz, 2H, arom. H), 7.46 (dd, 7.92, 1.90 Hz, 1H, arom. H), 7.54 (d, 1.78 Hz, 1H, arom. H), 7.59 (d, 8.12 Hz, 2H, arom. H), 8.25 (s, 1H, arom. OH).

4) Synthesis of 3-(2-{3-[(tert-butyldimethylsilyl)oxy]propoxy}-5-[2-ethyl-4-(4-pentylphenyl)phenyl]-3-(3-hydroxypropyl)phenyl)propan-1-ol D13

(112) ##STR00373##

(113) 2.9 g (6.0 mmol) of trisalcohol C13, 2.40 g (9.0 mmol) of (3-bromopropoxy)-(tert-butyl)dimethylsilane and 1.70 g (12.3 mmol) of potassium carbonate are added to 20 ml of N,N-dimethylformamide, and the mixture is stirred at 80° C. for 6 h. The reaction mixture is cooled to room temperature, water and MTB ether are added, and, after stirring, the phases are separated. The aqueous phase is extracted with MTB ether, and the combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated in vacuo. The crude product obtained is filtered through 50 ml of silica gel with toluene/ethyl acetate (4:1), and the product fractions are combined and evaporated in vacuo.

(114) .sup.1H NMR (500 MHz, CDCl.sub.3)

(115) δ=0.00 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.81 (s, 9H, Si(C(CH.sub.3).sub.3)), 1.03 (t, 6.6 Hz, 3H, CH.sub.3), 1.30-1.19 (m, 4H, CH.sub.2), 1.58-1.49 (m, 2H, CH.sub.2), 1.67 (quint., 5.5 Hz, 4H, CH.sub.2), 1.88 (quint., 6.23 Hz, 2H, CH.sub.2), 2.61-2.50 (m, 8H, CH.sub.2), 3.37 (q, 6.41 Hz, 4H, CH.sub.2), 3.76 (t, 6.2 Hz, 2H, CH.sub.2), 3.79 (t, 5.69 Hz, 2H, CH.sub.2), 4.33 (t, 5.5 Hz, 2H, OH), 6.92 (s, 2H, arom. H), 7.14 (d, 7.89 Hz, 1H, arom. H), 7.21 (d, 8.26 Hz, 2H, arom. H), 7.39 (dd, 7.93, 1.76 Hz, 1H, arom. H), 7.48 (d, 1.64 Hz, 1H, arom. H), 7.52 (d, 8.08 Hz, 2H, arom. H).

5) Synthesis of 3-(2-{3-[(tert-butyldimethylsilyl)oxy]propoxy}-5-[2-ethyl-4-(4-pentylphenyl)phenyl]-3-{3-[(2-methylprop-2-enoyl)oxy]propyl}phenyl)propyl 2-methylprop-2-enoate E13

(116) ##STR00374##

(117) 2.5 g (4.0 mmol) of bisalcohol 013, 1.40 ml (16.5 mmol) of methacrylic acid (stabilized using hydroquinone monomethyl ether) and 55.0 mg (0.45 mmol) of 4-(dimethylamino)pyridine are dissolved in 25 ml of dichloromethane (DCM) and cooled to 2° C. A solution of 2.48 ml (16.52 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide in 25 ml of DCM is then added dropwise at 2-5° C., and the mixture is stirred for a further 18 h. The reaction mixture is filtered directly through 100 ml of silica gel with DCM, and the product fractions are combined. The crude product obtained is filtered through 200 ml of silica gel and 20 ml of basic aluminum oxide with DCM/heptane (4:1), and the product fractions are evaporated in vacuo.

6) Synthesis of 3-{5-[2-ethyl-4-(4-pentylphenyl)phenyl]-2-(3-hydroxypropoxy)-3-{3-[(2-methylprop-2-enoyl)oxy]propyl}phenyl}propyl 2-methylprop-2-enoate 13

(118) ##STR00375##

(119) 3.1 g (4.0 mmol) of ester E13 are initially introduced in 40 ml of tetrahydrofuran (THF) and cooled to 2° C. 2.40 ml (4.80 mmol) of hydrochloric acid (2 N) are then added slowly, and the mixture is subsequently stirred at room temperature (RT) for 4 h. When the reaction is complete, the reaction mixture is carefully neutralized using sodium hydrogencarbonate, MTB ether is added, and the mixture is stirred. The organic phase is separated off, the water phase is extracted with MTB ether, and the organic phases are combined, washed with water, dried over sodium sulfate, filtered and evaporated at a maximum of 30° C. in vacuo. The crude product obtained (viscous oil) is filtered through 150 ml of silica gel with heptane/ethyl acetate (2:1), and the product fractions are evaporated at a maximum of 30° C. in vacuo. The product obtained (highly viscous oil) is dried at room temperature in an oil-pump vacuum (10.sup.−2 mbar) for 72 h.

(120) Melting point: highly viscous oil at room temperature.

(121) Tg (glass transition temperature) −39° C.

(122) MS (EI): 654.5 [M.sup.+]

(123) .sup.1H NMR (500 MHz, CDCl.sub.3)

(124) δ=0.94 ppm (t, 7.02 Hz, 3H, CH.sub.3), 1.18 (t, 7.56 Hz, 3H, CH.sub.3), 1.44-1.36 (m, 4H, CH.sub.2), 1.57 (s.sub.(broad), 1H, OH), 1.69 (quint., 8.25 Hz, 2H, CH.sub.2), 1.98 (s, 6H, CH.sub.3), 2.14-2.04 (m, 6H, CH.sub.2), 2.67 (q, 7.49 Hz, 4H, CH.sub.2), 2.81 (t, 7.72 Hz, 4H, CH.sub.2), 3.97 (t.sub.(broad), 5.77 Hz, 2H, CH.sub.2), 4.03 (t, 5.94 Hz, 2H, CH.sub.2), 4.26 (t, 6.47 Hz, 4H, CH.sub.2), 5.58 (t, 1.58 Hz, 1H), 6.13 (s, 1H), 7.06 (s, 2H, arom. H), 7.26 (d, 7.87 Hz, 1H, arom. H), 7.29 (d, 2H, arom. H), 7.46 (dd, 7.87, 1.9 Hz, 1H, arom. H), 7.53 (d, 1.78 Hz, 1H, arom. H), 7.57 (d, 8.12 Hz, 2H, arom. H).

Examples 5 to 165

(125) The following compounds are prepared analogously to Examples 1 to 3 and Schemes 1 to 3.

(126) TABLE-US-00008 Example Structure  5.  6.  7.  8.  9. 0  10.  11.  12.  13.  14.  15.  16.  17.  18.  19. 0  20.  21.  22.  23.  24.  25.  26.  27.  28.  29. 00  30. 01  31. 02  32. 03  33. 04  34. 05  35. 06  36. 07  37. 08  38. 09  39. 0  40.  41.  42.  43.  44.  45.  46.  47.  48.  49. 0  50.  51.  52.  53.  54.  55.  56.  57.  58.  59. 0  60.  61.  62.  63.  64.  65.  66.  67.  68.  69. 0  70.  71.  72.  73.  74.  75.  76.  77.  78.  79. 0  80.  81.  82.  83.  84.  85.  86.  87.  88.  89. 0  90.  91.  92.  93.  94.  95.  96.  97.  98.  99. 0 100. 101. 102. 103. 104. 105. 106. 107. 108. 109. 0 110. 111. 112. 113. 114. 115. 116. 117. 118. 119. 0 120. 121. 122. 123. 124. 125. 126. 127. 128. 129. 00 130. 01 131. 02 132. 03 133. 04 134. 05 135. 06 136. 07 137. 08 138. 09 139. 0 140. 141. 142. 143. 144. 145. 146. 147. 148. 149. 0 150. 151. 152. 153. 154. 155. 156. 157. 158. 159. 0 160. 161. 162. 163. 164. 165.

B) Mixture Examples

(127) 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.

(128) TABLE-US-00009 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 CCH-34  9.25% K.sub.1 [pN, 20° C.]: 13.1 CCH-23 24.50% K.sub.3 [pN, 20° C.]: 13.3 PYP-2-3  8.75% γ.sub.1 [mPa .Math. s, 20° C.]: 113 PCH-3O1  7.00% V.sub.0 [20° C., V]: 2.22

(129) TABLE-US-00010 H2: 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 [pN, 20° C.]: 15.1 CCH-34  9.00% K.sub.3 [pN, 20° C.]: 14.6 CCH-35  6.00% γ.sub.1 [mPa .Math. s, 20° C.]: 140 PCH-53 10.00% V.sub.0 [20° C., V]: 2.23 CCH-3O1  6.00% CCH-3O3  9.00%

(130) TABLE-US-00011 H3: Nematic host mixture (Δε < 0) CC-3-V1  9.00% Clearing point [° C.]: 74.7 CCH-23 18.00% Δn [589 nm, 20° C.]: 0.098 CCH-34  3.00% Δε [1 kHz, 20° C.]: −3.4 CCH-35  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 [pN, 20° C.]: 14.9 CPY-2-O2 8.00% K.sub.3 [pN, 20° C.]: 15.9 CPY-3-O2 11.00% γ.sub.1 [mPa .Math. s, 20° C.]: 108 CY-3-O2 15.50% V.sub.0 [20° C., V]: 2.28 PY-3-O2 11.50%

(131) TABLE-US-00012 H4: 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 [pN, 20° C.]: 12.2 CY-3-O4  4.50% K.sub.3 [pN, 20° C.]: 13.4 PYP-2-4  5.50% γ.sub.1 [mPa .Math. s, 20° C.]: 92 PPGU-3-F  1.00% V.sub.0 [20° C., V]: 2.28

(132) TABLE-US-00013 H5: Nematic host mixture (Δε < 0) CCH-23 20.00% Clearing point [° C.]: 74.8 CCH-3O1  6.00% Δn [589 nm, 20° C.]: 0.105 CCH-34  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 [pN, 20° C.]: 12.7 CPY-3-O2 11.00% K.sub.3 [pN, 20° C.]: 13.6 CY-3-O2 14.00% γ.sub.1 [mPa .Math. s, 20° C.]: 120 CY-3-O4  4.00% V.sub.0 [20° C., V]: 2.16 PCH-3O1  4.00% PYP-2-3  9.00%

(133) TABLE-US-00014 H6: 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 CCPC-33  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 [pN, 20° C.]: 16.8 CLY-3-O2  3.50% K.sub.3 [pN, 20° C.]: 17.3 CLY-3-O3  2.00% γ.sub.1 [mP .Math. s, 20° C.]: 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%

(134) TABLE-US-00015 H7: 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 CCH-34  9.00% K.sub.1 [pN, 20° C.]: 12.9 CCH-23 22.00% K.sub.3 [pN, 20° C.]: 13.0 PYP-2-3  7.00% γ.sub.1 [mPa .Math. s, 20° C.]: 115 PYP-2-4  7.50% V.sub.0 [20° C., V]: 2.20 PCH-3O1  7.00%

(135) TABLE-US-00016 H8: 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 [pN, 20° C.]: 12.9 CC-3-V1 10.00% K.sub.3 [pN, 20° C.]: 15.7 PYP-2-3 12.50% γ.sub.1 [mPa .Math. s, 20° C.]: 97 PPGU-3-F  0.50% V.sub.0 [20° C., V]: 2.42

(136) TABLE-US-00017 H9: Nematic host mixture (Δε < 0) CCH-35 9.50% Clearing point [° C.]: 79.1 CCH-5O1 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 [pN, 20° C.]: 14.6 CPY-2-O2 12.00% K.sub.3 [pN, 20° C.]: 14.5 CY-3-O4 9.00% γ.sub.1 [mPa .Math. s, 20° C.]: 178 CY-5-O4 11.00% V.sub.0 [20° C., V]: 2.12 PCH-53 13.50%

(137) TABLE-US-00018 H10: Nematic host mixture (Δε < 0) BCH-32 4.00% Clearing point [° C.]: 74.8 CC-3-V1 8.00% Δn [589 nm, 20° C.]: 0.106 CCH-23 13.00% Δε [1 kHz, 20° C.]: −3.5 CCH-34 7.00% ε.sub.∥ [1 kHz, 20° C.]: 3.6 CCH-35 7.00% ε.sub.⊥ [1 kHz, 20° C.]: 7.1 CCY-3-O2 13.00% K.sub.1 [pN, 20° C.]: 14.8 CPY-2-O2 7.00% K.sub.3 [pN, 20° C.]: 15.8 CPY-3-O2 12.00% γ.sub.1 [mPa .Math. s, 20° C.]: 115 CY-3-O2 12.00% V.sub.0 [20° C., V]: 2.23 PCH-3O1 2.00% PY-3-O2 15.00%

(138) TABLE-US-00019 H11: 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 [pN, 20° C.]: 14.9 CPY-3-O2 10.00% K.sub.3 [pN, 20° C.]: 15.9 PYP-2-3 7.00% γ.sub.1 [mPa .Math. s, 20° C.]: 222 CC-3-V1 7.00% V.sub.0 [20° C., V]: 1.91 CC-5-V 10.00% CCPC-33 2.00% CCPC-35 2.00%

(139) TABLE-US-00020 H12: 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 [pN, 20° C.]: 14.7 CCY-2-1 8.00% K.sub.3 [pN, 20° C.]: 16.0 CCY-3-1 7.00% γ.sub.1 [mPa .Math. s, 20° C.]: 250 CPY-3-O2 9.00% V.sub.0 [20° C., V]: 1.90 CPY-3-O2 9.00% BCH-32 6.00% PCH-53 10.00%

(140) TABLE-US-00021 H13: Nematic host mixture (Δε < 0) CC-3-V1 10.25% Clearing point [° C.]: 74.7 CCH-23 18.50% Δn [589 nm, 20° C.]: 0.103 CCH-35 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 [pN, 20° C.]: 15.4 CPY-2-O2 6.00% K.sub.3 [pN, 20° C.]: 16.8 CPY-3-O2 9.75% γ.sub.1 [mPa .Math. s, 20° C.]: 104 CY-3-O2 11.50% V.sub.0 [20° C., V]: 2.46 PP-1-2V1 3.75% PY-3-O2 13.00%

(141) TABLE-US-00022 H14: 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 CCH-35 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 [pN, 20° C.]: 15.3 PY-3-O2 14.00% K.sub.3 [pN, 20° C.]: 16.2 PY-4-O2 9.00% γ.sub.1 [mPa .Math. s, 20° C.]: 88 PYP-2-4 0.50% V.sub.0 [20° C., V]: 2.44

(142) TABLE-US-00023 H15: Nematic host mixture (Δε > 0) CC-4-V 10.00% Clearing point [° C.]: 77.0 CC-5-V 13.50% Δn [589 nm, 20° C.]: 0.113 PGU-3-F 6.50% Δε [1 kHz, 20° C.]: 19.2 ACQU-2-F 10.00% ε.sub.∥ [1 kHz, 20° C.]: 23.8 ACQU-3-F 12.00% ε.sub.⊥ [1 kHz, 20° C.]: 4.6 PUQU-3-F 11.00% K.sub.1 [pN, 20° C.]: 11.5 CCP-V-1 12.00% K.sub.3 [pN, 20° C.]: 11.1 APUQU-2-F 6.00% γ.sub.1 [mPa .Math. s, 20° C.]: 122 APUQU-3-F 7.00% V.sub.0 [20° C., V]: 0.81 PGUQU-3-F 8.00% CPGU-3-OT 4.00%

(143) TABLE-US-00024 H16: Nematic host mixture (Δε > 0) PGU-2-F 3.50% Clearing point [° C.]: 77.0 PGU-3-F 7.00% Δn [589 nm, 20° C.]: 0.105 CC-3-V1 15.00% Δε [1 kHz, 20° C.]: 7.2 CC-4-V 18.00% ε.sub.∥ [1 kHz, 20° C.]: 10.3 CC-5-V 20.00% ε.sub.⊥ [1 kHz, 20° C.]: 3.1 CCP-V-1 6.00% K.sub.1 [pN, 20° C.]: 15.3 APUQU-3-F 15.00% K.sub.3 [pN, 20° C.]: 13.5 PUQU-3-F 5.50% γ.sub.1 [mPa .Math. s, 20° C.]: 63 PGP-2-4 3.00% V.sub.0 [20° C., V]: 1.53 BCH-32 7.00%

(144) TABLE-US-00025 H17: Nematic host mixture (Δε > 0) APUQU-2-F 6.00% Clearing point [° C.]: 74.0 APUQU-3-F 12.00% Δn [589 nm, 20° C.]: 0.120 PUQU-3-F 18.00% Δε [1 kHz, 20° C.]: 17.4 CPGU-3-OT 9.00% ε.sub.∥ [1 kHz, 20° C.]: 22.0 CCGU-3-F 3.00% ε.sub.⊥ [1 kHz, 20° C.]: 4.5 BCH-3F•F•F 14.00% K.sub.1 [pN, 20° C.]: 10.1 CCQU-3-F 10.00% K.sub.3 [pN, 20° C.]: 10.8 CC-3-V 25.00% γ.sub.1 [mPa .Math. s, 20° C.]: 111 PGP-2-2V 3.00% V.sub.0 [20° C., V]: 0.80

(145) TABLE-US-00026 H18: Nematic host mixture (Δε > 0) PUQU-3-F 15.00% Clearing point [° C.]: 74.3 APUQU-2-F 5.00% Δn [589 nm, 20° C.]: 0.120 APUQU-3-F 12.00% Δε [1 kHz, 20° C.]: 14.9 CCQU-3-F 11.00% ε.sub.∥ [1 kHz, 20° C.]: 19.1 CCQU-5-F 1.50% ε.sub.⊥ [1 kHz, 20° C.]: 4.3 CPGU-3-OT 5.00% K.sub.1 [pN, 20° C.]: 11.2 CCP-3OCF3 4.50% K.sub.3 [pN, 20° C.]: 10.8 CGU-3-F 10.00% γ.sub.1 [mPa .Math. s, 20° C.]: 98 PGP-2-3 1.50% V.sub.0 [20° C., V]: 0.91 PGP-2-2V 8.00% CC-3-V 26.50%

(146) TABLE-US-00027 H19: Nematic host mixture (Δε > 0) CCQU-3-F 9.00% Clearing point [° C.]: 94.5 CCQU-5-F 9.00% Δn [589 nm, 20° C.]: 0.121 PUQU-3-F 16.00% Δε [1 kHz, 20° C.]: 20.4 APUQU-2-F 8.00% ε.sub.∥ [1 kHz, 20° C.]: 24.7 APUQU-3-F 9.00% ε.sub.⊥ [1 kHz, 20° C.]: 4.3 PGUQU-3-F 8.00% K.sub.1 [pN, 20° C.]: 12.1 CPGU-3-OT 7.00% K.sub.3 [pN, 20° C.]: 13.9 CC-4-V 18.00% γ.sub.1 [mPa .Math. s, 20° C.]: 163 CC-5-V 5.00% V.sub.0 [20° C., V]: 0.81 CCP-V-1 6.00% CCPC-33 3.00% PPGU-3-F 2.00%

(147) TABLE-US-00028 H20: Nematic host mixture (Δε > 0) CC-3-V 28.50% Clearing point [° C.]: 85.6 CCP-V1 3.00% Δn [589 nm, 20° C.]: 0.121 CCPC-33 2.00% Δε [1 kHz, 20° C.]: 19.5 PGU-2-F 4.00% ε.sub.∥ [1 kHz, 20° C.]: 23.8 CCQU-3-F 8.00% ε.sub.⊥ [1 kHz, 20° C.]: 4.3 CCQU-5-F 6.00% K.sub.1 [pN, 20° C.]: 11.6 CCGU-3-F 3.00% K.sub.3 [pN, 20° C.]: 12.7 PUQU-2-F 2.00% γ.sub.1 [mPa .Math. s, 20° C.]: 126 PUQU-3-F 10.00% V.sub.0 [20° C., V]: 0.81 APUQU-2-F 6.00% APUQU-3-F 9.00% PGUQU-3-F 5.00% PGUQU-4-F 5.00% PGUQU-5-F 4.00% CPGU-3-OT 4.00% PPGU-3-F 0.50%

(148) The following polymerizable self-alignment additives are used:

(149) TABLE-US-00029 Polymerizable self- Structure alignment Where appropriate phase behavior (T.sub.g: glass transition temperature, additive No. C: crystalline, I: isotropic phase), transition temperatures in ° C.  1  2  3  4 0  5  6  7  8  9 10 11 12 13 14 0 15 16 17 18 19

(150) The following polymerizable compound is used:

(151) ##STR00556##

Mixture Example 1

(152) Polymerizable self-alignment additive 1 (2.0% by weight) is added to a nematic LC medium H1 of the VA type (Δ∈<0), and the mixture is homogenized.

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

(154) The mixture formed is introduced into a test cell (without polyimide alignment layer, layer thickness d≈4.0 μm, ITO coating on both sides, structured ITO for multidomain switching, without passivation layer). The LC medium has a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cell formed can be switched reversibly by application of a voltage.

(155) VA alignment layers which are used for PM-VA, PVA, MVA and analogous technologies are no longer necessary with the use of additives such as polymerizable self-alignment additive 1.

Mixture Example 2

(156) Polymerizable self-alignment additive 1 (2.0% by weight) is added to a nematic LC medium H15 of the VA-IPS type (Δ∈>0), and the mixture is homogenized.

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

(158) The mixture formed is introduced into a test cell (without polyimide alignment layer, layer thickness d≈4 μm, ITO interdigital electrodes arranged on one substrate surface, glass on the opposite substrate surface, without passivation layer). The LC medium has a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA-IPS cell formed can be switched reversibly by application of a voltage.

(159) VA alignment layers which are used for VA-IPS, HT-VA and analogous technologies are no longer necessary with the use of additives such as polymerizable self-alignment additive 1.

Mixture Examples 3-20

(160) Polymerizable self-alignment additives 2-19 (% by weight in accordance with Table 5) are added to a nematic LC medium H1 (Δ∈<0) analogously to Mixture Example 1, and the mixture is homogenized. The mixtures formed are introduced into test cells without pre-alignment layer. The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cells formed can be switched reversibly by application of a voltage.

Mixture Examples 21-33

(161) Polymerizable self-alignment additives 2-4, 7, 10, 12-19 (% by weight in accordance with Table 5) are added to a nematic LC medium H15 (Δ∈>0) analogously to Mixture Example 2, and the mixture is homogenized. The mixtures formed are introduced into test cells without pre-alignment layer. The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA-IPS cells formed can be switched reversibly by application of a voltage.

Mixture Examples 34-98

(162) Polymerizable self-alignment additives 1, 4, 13, 18 and 19 (% by weight in accordance with Table 5) are added to nematic LC media H2-H14 (Δ∈<0) analogously to Mixture Example 1, and the mixture is homogenized. The mixtures formed are introduced into test cells without pre-alignment layer (cf. Mixture Example 1). The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cells formed can be switched reversibly by application of a voltage.

Mixture Examples 99-123

(163) Polymerizable self-alignment additives 1, 4, 13, 18 and 19 (% by weight in accordance with Table 5) are added to nematic LC media H16-H20 (Δ∈>0) analogously to Mixture Example 2, and the mixture is homogenized. The mixtures formed are introduced into test cells without pre-alignment layer. The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA-IPS cells formed can be switched reversibly by application of a voltage.

Mixture Examples 1a, 3a-5a, 8a, 11a, 13a-19a (polymerization of Mixture Examples 1, 3-5, 8, 11, 13-19)

(164) In each case, a polymerizable self-alignment additive 1, 2-4, 7, 10, 12-18 (% by weight in accordance with Table 5) is added to a nematic LC medium H1 (Δ∈<0), and the mixture is homogenized.

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

(166) The mixtures formed are introduced into test cells (without polyimide alignment layer, layer thickness d≈4.0 μm, ITO coating on both sides (structured ITO for multidomain switching), without passivation layer). The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cell formed can be switched reversibly by application of a voltage.

(167) While applying a voltage greater than the optical threshold voltage (for example 14 Vpp), the VA cells are irradiated for 12 min with UV light having an intensity of 100 mW/cm.sup.2 at 20° C. with a 340 nm band-pass filter. This causes polymerization of the polymerizable compounds. The homeotropic alignment is thus additionally stabilized, a ‘pre-tilt’ is established, and a polymer layer forms (Table 1). The PSA-VA cells obtained can be switched reversibly up to the clearing point on application of a voltage. The response times are shortened compared with the unpolymerized cell. The threshold voltages (V.sub.10) change (Table 2). Depending on the chemical structure of the polymerizable component, the VHR (voltage holding ratio) can be improved slightly (Table 3).

(168) The polymerization can also be carried out without application of a voltage. The homeotropic alignment is thus additionally stabilized and a polymer layer forms without a ‘pre-tilt’ being established. The polymer layer acts as protective layer and improves the long-term stability of the PSA-VA cell.

(169) VA alignment layers which are used for PSA, PS-VA and analogous technologies are no longer necessary with the use of additives such as the polymerizable self-alignment additives 1-4.

Mixture Examples 1 b, 3b-5b, 8b, 11 b, 13b-19b (Polymer Stabilization of Mixture Examples 1a, 3a-5a, 8a, 11a, 13a-19a)

(170) A polymerizable compound (RM-1, 0.3% by weight) and a polymerizable self-alignment additive 1, 2-4, 7, 10, 12-18 (% by weight in accordance with Table 5) are added to a nematic LC medium H1 (Δ∈<0), and the mixture is homogenized.

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

(172) The mixtures formed are introduced into test cells (without polyimide alignment layer, layer thickness d≈4.0 μm, ITO coating on both sides (structured ITO for multidomain switching), without passivation layer). The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cell formed can be switched reversibly by application of a voltage.

(173) While applying a voltage greater than the optical threshold voltage (for example 14 Vpp), the VA cells are irradiated for 12 min with UV light having an intensity of 100 mW/cm.sup.2 at 20° C. with a 340 nm band-pass filter. This causes polymerization of the polymerizable compounds. The homeotropic alignment is thus additionally stabilized, a ‘pre-tilt’ is established, and a polymer layer forms (Table 1). The PSA-VA cells obtained can be switched reversibly up to the clearing point on application of a voltage. The response times are shortened compared with the unpolymerized cell. The threshold voltages (V.sub.10) change (Table 2). Depending on the chemical structure of the polymerizable components, the VHR (voltage holding ratio) can be improved slightly (Table 4).

(174) The polymerization can also be carried out without application of a voltage. The homeotropic alignment is thus additionally stabilized and a polymer layer forms without a ‘pre-tilt’ being established. The polymer layer acts as protective layer and improves the long-term stability of the PSA-VA cell.

(175) VA alignment layers which are used for PSA, PS-VA and analogous technologies are no longer necessary with the use of additives such as the polymerizable self-alignment additives 1-4.

(176) TABLE-US-00030 TABLE 1 Layer thickness d and roughness R.sub.a of the polymer layer formed after UV irradiation. Host H1 in combination with polymerizable self- alignment additive (PSAA). Test cell of the PSA type. Polymerization conditions: 0 Vpp, 15 min, 100 mW/cm.sup.2, 340 nm band-pass filter, 40° C.. Cell preparation for AFM measurements: the cells are rinsed with cyclohexane after the irradiation, the cell substrates are separated from one another and used for the measurements (Park or Veeco, room temperature). Mixture Further Example PSAA polym. comp. R.sub.a/nm d/nm 1a 1 1.4 12 3a 2 3.6 20 5a 4 2.2 — 6a 5 2.5 46 1b 1 RM-1 2.2 33 6b 5 RM-1 1.4 52

(177) TABLE-US-00031 TABLE 2 Response times and threshold voltages V.sub.10 of VA and PSA cells. Host H1 in combination with polymerizable self-alignment additive (PSAA). Polymerization conditions: UV-1 (340 nm band- pass filter, 20° C., 14 Vpp, 2 min, 50 mW/cm.sup.2); UV-2 (340 nm band-pass filter, 20° C., 0 Vpp, 10 min, 100 mW/cm.sup.2). Further UV Response Mixture polym. irradiation Cell time/ms Example PSAA comp. UV-1 + -2 type V.sub.10/V 0 V.fwdarw.5 V 1 1 No VA 2.50 32 3 2 No VA 2.43 35 4 3 No VA 2.45 33 5 4 No VA 2.51 31 7 6 No VA 2.47 34 8 7 No VA 2.48 31 10 9 No VA 2.42 34 13 12 No VA 2.48 28 14 13 No VA 2.48 34 15 14 No VA 2.50 28 17 16 No VA 2.51 28 19 18 No VA 2.49 31  1a 1 Yes PSA 2.58 23  3a 2 Yes PSA 1.57 20  4a 3 Yes PSA 2.53 16  5a 4 Yes PSA 2.47 27  8a 7 Yes PSA 2.53 16 14a 13 Yes PSA 2.53 29  1b 1 RM-1 Yes PSA 2.64 19  3b 2 RM-1 Yes PSA — —  4b 3 RM-1 Yes PSA 2.60 17  5b 4 RM-1 Yes PSA 2.57 29 14b 13 RM-1 Yes PSA 2.58 26

(178) TABLE-US-00032 TABLE 3 VHR (voltage holding ratio, 60 Hz, 100° C., 5 min) before and after heating (2 h, 120° C.). Host mixture H1 in combination with polymerizable self-alignment additive (PSAA). VHR/% Mixture UV Before After Example PSAA irradiation Cell type heating heating H1 — No 99.0 99.3 1 1 No VA 98.6 98.6 3 2 No VA 97.9 96.0 4 3 No VA 97.4 98.3 5 4 No VA 96.4 — 8 7 No VA 96.7 — 13 12 No VA 96.4 96.9 14 13 No VA 96.4 92.0 15 14 No VA 97.2 94.8 17 16 No VA 97.7 97.8 19 18 No VA 97.6 97.8

(179) TABLE-US-00033 TABLE 4 VHR (voltage holding ratio, 6 Hz, 100° C., 5 min) before and after UV irradiation. Host mixture H1 in combination with polymerizable self-alignment additive (PSAA). Polymerization conditions: UV-1 (340 nm band-pass filter, 20° C., 0 Vpp, 2 min, 50 mW/cm.sup.2); UV-2 (340 nm band-pass filter, 20° C., 0 Vpp, 10 min, 100 mW/cm.sup.2). Further UV Mixture polym. irradiation Before After Example PSAA comp. UV-1 + -2 Cell type UV UV H1 — Yes 94.1 93.1 H1 — RM-1 Yes 93.1 94.7 1a 1 Yes PSA 92.5 85.9 3a 2 Yes PSA 89.6 92.8 1b 1 RM-1 Yes PSA 92.6 89.9 3b 2 RM-1 Yes PSA 90.6 97.4 5b 4 RM-1 Yes PSA 91.3 93.2

(180) TABLE-US-00034 TABLE 5 % by weight for Mixture Examples 1-123 PSAA % by wt. 1 2.0 2 2.0 3 2.0 4 0.3 5 4.0 6 3.0 7 2.5 8 3.0 9 3.0 10 2.5 11 3.0 12 2.0 13 1.5 14 0.3 15 0.3 16 0.3 17 0.5 18 0.5 19 3.0