Polymerizable compounds and the use thereof in liquid-crystal displays

Abstract

The present invention relates to polymerizable compounds, to processes and intermediates for the preparation thereof, and to the use thereof for optical, electro-optical and electronic purposes, in particular in liquid-crystal (LC) media and LC displays, especially in LC displays of the PS (polymer sustained) or PSA (polymer sustained alignment) type.

Claims

1. A compound of formula I ##STR00339## wherein G denotes -CM=CR.sup.cCO, COCR.sup.cCM-, CR.sup.cCM-CO or CO-CM=CR.sup.c M denotes X.sup.2-A.sup.4-(Z.sup.2-A.sup.3).sub.n2-R.sup.b, A.sup.1-4 each, independently of one another, and on each occurrence identically or differently, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which is optionally mono- or polysubstituted by L, and A.sup.2 and A.sup.4 may also denote a single bond, X.sup.1 and X.sup.2 each denote a single bond, Z.sup.1 and Z.sup.2 each denote a single bond, R.sup.a-c each, independently of one another, and on each occurrence identically or differently, denote P, P-Sp-, H, OH, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, SF.sub.5 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 may each be replaced, independently of one another, by C(R.sup.00)C(R.sup.00), CC, N(R.sup.00), O, S, CO, COO, OCO, OCOO 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 may be replaced by F, Cl, Br, I, CN or P-Sp-, wherein at least two of the radicals R.sup.a denote or contain a group P or P-Sp-, P denotes on each occurrence, identically or differently, a polymerisable group that is a vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane or epoxy group, Sp denotes on each occurrence, identically or differently, a spacer group or a single bond, R.sup.00 and R.sup.000 each, independently of one another, denote H or alkyl having 1 to 12 C atoms, L denotes on each occurrence, identically or differently, an unpolymerizable group that is F, Cl, CN, or straight-chain or branched C.sub.1-25-alkyl in which one or more non-adjacent CH.sub.2 groups optionally is replaced, independently of one another, by C(R.sup.00)C(R.sup.000), CC, N(R.sup.00), O, S, CO, COO, OCO, OCOO 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 may be replaced by F, Cl, Br, I or CN, n1 and n2 each, independently of one another, denote 0, 1, 2 or 3, n3 denotes 1, 2, 3 or 4, x denotes 2, 3 or 4, wherein at least one of (a) or (b) is satisfied: (a) at least one of n1 and n2 is different from 0, (b) at least one of A.sup.2 and A.sup.4 is not a single bond.

2. A compound of formula I according to claim 1 of sub-formulae: ##STR00340## ##STR00341##

3. The compound according to claim 2, wherein at least one of the aromatic, heteroaromatic, alicyclic or heterocyclic groups A.sup.1-4 is 1,4-phenylene or naphthalene-2,6-diyl, in which one or two CH groups are optionally replaced by N, and which are optionally mono- or polysubstituted by L.

4. The compound according to claim 2, wherein n1=n2=0, and one of A.sup.2 and A.sup.4 is a single bond and the other is 1,4-phenylene or naphthalene-2,6-diyl, in which one or two CH groups are optionally replaced by N, and which are optionally mono- or polysubstituted by L.

5. A compound of formula I according to claim 1 of the following sub-formulae: ##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346## ##STR00347## ##STR00348## in which Sp has one of the meanings given for Sp, and is identical to or different from Sp, R has one of the meanings indicated for R.sup.b which is different from H, P- and P-Sp-, and the phenylene and naphthalene groups are optionally substituted with one, two, three of four F atoms.

6. The compound according to claim 5, which is of one of the following formulae: I1a, I2a, I3a, I4a, I5a, I6a, I7a, I8a, 19a, I10a, I11a, I12a, I13a or I14a.

7. The compound according to claim 5, which is of one of the following formulae: I1b, I2b, I3b, I4b, I5b, I6b, I7b, I8b, I19b, I10b, I11b, I12b, I13b or I14b.

8. The compound according to claim 5, which is of one of the following formulae: I1c, I2c, I3c, I4c, I5c, I6c, I7c, I8c, 19c, I10c, I13c or I14c.

9. The compound according to claim 5, which is of one of the following formulae: I2d, I3d, I4d or I8d.

10. The compound according to claim 1, wherein the aromatic, heteroaromatic, alicyclic or heterocyclic groups A.sup.1-4 has 4 to 25 C atoms.

11. The compound according to claim 1, wherein at least one of the aromatic, heteroaromatic, alicyclic or heterocyclic groups A.sup.1-4 is 1,4-phenylene or naphthalene-2,6-diyl, in which one or two CH groups are optionally replaced by N, and which are optionally mono- or polysubstituted by L.

12. The compound according to claim 1, wherein n1=n2=0, and one of A.sup.2 and A.sup.4 is a single bond and the other is 1,4-phenylene or naphthalene-2,6-diyl, in which one or two CH groups are optionally replaced by N, and which are optionally mono- or polysubstituted by L.

13. A process for the preparation of a compound according to claim 1, in which R.sup.a and R.sup.b are each P-Sp, by esterification or etherification of a compound of formula I* ##STR00349## G denotes -CM=CR.sup.cCO, COCR.sup.cCM-, CR.sup.cCM-CO or CO-CM=CR.sup.c M denotes X.sup.2-A.sup.4-(Z.sup.2-A.sup.3).sub.n2-R.sup.b, A.sup.1-4 each, independently of one another, and on each occurrence identically or differently, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which is optionally mono- or polysubstituted by L, and A.sup.2 and A.sup.4 may also denote a single bond, X.sup.1 and X.sup.2 each denote a single bond, Z.sup.1 and Z.sup.2 each denote a single bond, R.sup.c each, independently of one another, and on each occurrence identically or differently, denote P, P-Sp-, H, OH, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, SF.sub.5 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 may each be replaced, independently of one another, by C(R.sup.00)C(R.sup.000), CC, N(R.sup.00), O, S, CO, COO, OCO, OCOO 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 may be replaced by F, Cl, Br, I, CN or P-Sp-, wherein at least two of the radicals R.sup.a denote or contain a group P or P-Sp-, P denotes on each occurrence, identically or differently, an acrylate or a methacrylate group, Sp denotes on each occurrence, identically or differently, a spacer group or a single bond, R.sup.00 and R.sup.000 each, independently of one another, denote H or alkyl having 1 to 12 C atoms, L denotes on each occurrence, identically or differently, P-Sp-, H, OH, CH.sub.2OH, halogen, SF.sub.5, NO.sub.2, a carbon group or hydrocarbon group, n1 and n2 each, independently of one another, denote 0, 1, 2 or 3, n3 denotes 1, 2, 3 or 4, x denotes 2, 3 or 4, wherein at least one of (a) or (b) is satisfied: (a) at least one of n1 and n2 is different from 0, (b) at least one of A.sup.2 and A.sup.4 is not a single bond, R.sup.a and R.sup.b denote -Sp-OSg, and Sg denotes an H atom or a protecting group, using, in case P is a methacrylate group, methacryloyl chloride or methacrylic anhydride or a methacrylic acid derivative in the presence of a base, or methacrylic acid in the presence of a dehydrating reagent, or in case P is an acrylate group, acryloyl chloride or acrylic anhydride or an acrylic acid derivative in the presence of a base, or acrylic acid in the presence of a dehydrating reagent.

14. The process according to claim 13, wherein the compound of the formula I* is ##STR00350## ##STR00351## ##STR00352## wherein each Sp independently has one of the meanings of Sp.

15. The process according to claim 13, wherein the aromatic, heteroaromatic, alicyclic or heterocyclic groups A.sup.1-4 has 4 to 25 C atoms.

16. A compound of the formula: ##STR00353## ##STR00354## ##STR00355## wherein Sg denotes an H atom or a protecting group, Sp each, denotes on each occurrence, identically or differently, a spacer group or a single bond, and Sp each, independently has one of the meanings of Sp, wherein in each compound one or more of the radicals Sp and Sp denote a single bond and one or more of the radicals Sp and Sp are not a single bond.

17. The compound according to claim 16, which is of one of the following formulae: I*1a, I*5a, I*6a, I*8b, I* 10a, I11*a or I12*a.

18. The compound according to claim 16, which is of one of the following formulae: I* 1b or I*6b.

19. The compound according to claim 16, which is of one of the following formulae: I*2a, I*3a, or I*4a.

20. The compound according to claim 16, which is of formula I13*a.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Above and below organic group denotes a carbon or hydrocarbon group.

(2) Carbon group denotes a mono- or polyvalent organic group containing at least one carbon atom, where this either contains no further atoms (such as, for example, CC) or optionally contains one or more further atoms, such as, for example, N, O, S, P, Si, Se, As, Te or Ge (for example carbonyl, etc.). The term hydrocarbon group denotes a carbon group which additionally contains one or more H atoms and optionally one or more heteroatoms, such as, for example, N, O, S, P, Si, Se, As, Te or Ge.

(3) Halogen denotes F, Cl, Br or I.

(4) Conjugated radical or conjugated group denotes a radical or group which contains principally sp.sup.2-hybridised (or possibly also sp-hybridised) carbon atoms, which may also be replaced by corresponding heteroatoms. In the simplest case, this means the alternating presence of double and single bonds. Principally in this connection means that naturally (non-randomly) occurring defects which result in conjugation interruptions do not devalue the term conjugated. Furthermore, the term conjugated is likewise used in this application text if, for example, arylamine units or certain heterocycles (i.e. conjugation via N, O, P or S atoms) are located in the radical or group.

(5) A carbon or hydrocarbon group can be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups. A carbon or hydrocarbon radical having more than 3 C atoms can be straight-chain, branched and/or cyclic and may also contain spiro links or condensed rings.

(6) The terms alkyl, aryl, heteroaryl, etc., also encompass polyvalent groups, for example alkylene, arylene, heteroarylene, etc.

(7) The term aryl denotes an aromatic carbon group or a group derived therefrom. The term heteroaryl denotes aryl as defined above, containing one or more heteroatoms.

(8) Preferred carbon and hydrocarbon groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18, C atoms, optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25, C atoms, or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having 6 to 40, preferably 6 to 25, C atoms.

(9) Further preferred carbon and hydrocarbon groups are C.sub.1-C.sub.40 alkyl, C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40 alkynyl, C.sub.3-C.sub.40 allyl, C.sub.4-C.sub.40 alkyldienyl, C.sub.4-C.sub.40 polyenyl, C.sub.6-C.sub.40 aryl, C.sub.6-C.sub.40 alkylaryl, C.sub.6-C.sub.40 arylalkyl, C.sub.6-C.sub.40 alkylaryloxy, C.sub.6-C.sub.40 arylalkyloxy, C.sub.2-C.sub.40 heteroaryl, C.sub.4-C.sub.40 cycloalkyl, C.sub.4-C.sub.40 cycloalkenyl, etc. Particular preference is given to C.sub.1-C.sub.22 alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.2-C.sub.22 alkynyl, C.sub.3-C.sub.22 allyl, C.sub.4-C.sub.22 alkyldienyl, C.sub.6-C.sub.12 aryl, C.sub.6-C.sub.20 arylalkyl and C.sub.2-C.sub.20 heteroaryl.

(10) Further preferred carbon and hydrocarbon groups are straight-chain, branched or cyclic alkyl radicals having 1 to 40, preferably 1 to 25, C atoms, which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN and in which one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by C(R.sup.x)C(R.sup.x), CC, N(R.sup.x), O, S, CO, COO, OCO, OCOO in such a way that 0 and/or S atoms are not linked directly to one another.

(11) R.sup.x preferably denotes H, halogen, a straight-chain, branched or cyclic alkyl chain having 1 to 25 C atoms, in which, in addition, one or more non-adjacent C atoms may be replaced by O, S, CO, COO, OCO, OCOO and in which one or more H atoms may be replaced by fluorine, an optionally substituted aryl or aryloxy group having 6 to 40 C atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms.

(12) Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, etc.

(13) Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclo-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, etc.

(14) Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, etc.

(15) Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, etc.

(16) Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, etc.

(17) Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, etc.

(18) Aryl and heteroaryl groups can be monocyclic or polycyclic, i.e. they can contain one ring (such as, for example, phenyl) or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently bonded (such as, for example, biphenyl), or contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se.

(19) Particular preference is given to mono-, bi- or tricyclic aryl groups having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl groups having 5 to 25 ring atoms, which optionally contain fused rings and are optionally substituted. Preference is furthermore given to 5-, 6- or 7-membered aryl and heteroaryl groups, in which, in addition, one or more CH groups may be replaced by N, S or O in such a way that O atoms and/or S atoms are not linked directly to one another.

(20) Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1:3,1]terphenyl-2-yl, naphthyl, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, etc.

(21) Preferred heteroaryl groups are, for example, 5-membered rings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensed groups, such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]-thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations of these groups.

(22) The aryl and heteroaryl groups mentioned above and below may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.

(23) The (non-aromatic) alicyclic and heterocyclic groups encompass both saturated rings, i.e. those containing exclusively single bonds, and also partially unsaturated rings, i.e. those which may also contain multiple bonds. Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S and Se.

(24) The (non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e. contain only one ring (such as, for example, cyclohexane), or polycyclic, i.e. contain a plurality of rings (such as, for example, decahydronaphthalene or bicyclooctane). Particular preference is given to saturated groups. Preference is furthermore given to mono-, bi- or tricyclic groups having 5 to 25 ring atoms, which optionally contain fused rings and are optionally substituted. Preference is furthermore given to 5-, 6-, 7- or 8-membered carbocyclic groups, in which, in addition, one or more C atoms may be replaced by Si and/or one or more CH groups may be replaced by N and/or one or more non-adjacent CH.sub.2 groups may be replaced by O and/or S.

(25) Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered groups, such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered groups, such as cycloheptane, and fused groups, such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]-pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-methanoindane-2,5-diyl.

(26) Preferred substituents are, for example, solubility-promoting groups, such as alkyl or alkoxy, electron-withdrawing groups, such as fluorine, nitro or nitrile, or substituents for increasing the glass transition temperature (Tg) in the polymer, in particular bulky groups, such as, for example, t-butyl or optionally substituted aryl groups.

(27) Preferred substituents, also referred to as L above and below, are, for example, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, C(O)N(R.sup.x).sub.2, C(O)Y.sup.1, C(O)R.sup.x, N(R.sup.x).sub.2, in which R.sup.x has the meaning indicated above, and Y.sup.1 denotes halogen, optionally substituted silyl or aryl having 6 to 40, preferably 6 to 20, C atoms, and straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which one or more H atoms may optionally be replaced by F or Cl.

(28) Substituted silyl or aryl preferably means substituted by halogen, CN, R.sup.0, OR.sup.0, COR.sup.0, COOR.sup.0, OCOR.sup.0 or OCOOR.sup.0, in which R.sup.0 has the meaning indicated above.

(29) Particularly preferred substituents L are, for example, F, Cl, CN, NO.sub.2, CH.sub.3, C.sub.2H.sub.5, OCH.sub.3, OC.sub.2H.sub.5, COCH.sub.3, COC.sub.2H.sub.5, COOCH.sub.3, COOC.sub.2H.sub.5, CF.sub.3, OCF.sub.3, OCHF.sub.2, OC.sub.2F.sub.5, furthermore phenyl.

(30) ##STR00005##
is preferably

(31) ##STR00006##
in which L has one of the meanings indicated above.

(32) The polymerisable group P is a group which is suitable for a polymerisation reaction, such as, for example, free-radical or ionic chain polymerisation, polyaddition or polycondensation, or for a polymer-analogous reaction, for example addition or condensation onto a main polymer chain. Particular preference is given to groups for chain polymerisation, in particular those containing a CC double bond or CC triple bond, and groups which are suitable for polymerisation with ring opening, such as, for example, oxetane or epoxide groups.

(33) Preferred groups P are selected from the group consisting of CH.sub.2CW.sup.1COO, CH.sub.2CW.sup.1CO,

(34) ##STR00007##
CH.sub.2CW.sup.2(O).sub.k3, CW.sup.1CHCO(O).sub.k3, CW.sup.1CHCONH, CH.sub.2CW.sup.1CONH, CH.sub.3CHCHO, (CH.sub.2CH).sub.2CHOCO, (CH.sub.2CHCH.sub.2).sub.2CHOCO, (CH.sub.2CH).sub.2CHO, (CH.sub.2CHCH.sub.2).sub.2N, (CH.sub.2CHCH.sub.2).sub.2NCO, HOCW.sup.2W.sup.3, HSCW.sup.2W.sup.3, HW.sup.2N, HOCW.sup.2W.sup.3NH, CH.sub.2CW.sup.1CONH, CH.sub.2CH(COO).sub.k1-Phe-(O).sub.k2, CH.sub.2CH(CO).sub.k1-Phe-(O).sub.k2, Phe-CHCH, HOOC, OCN and W.sup.4W.sup.5W.sup.6Si, in which W.sup.1 denotes H, F, Cl, CN, CF.sub.3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH.sub.3, W.sup.2 and W.sup.3 each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, 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, which is optionally substituted by one or more radicals L as defined above which are other than P-Sp-, k.sub.1, k.sub.2 and k.sub.3 each, independently of one another, denote 0 or 1, k.sub.3 preferably denotes 1, and k.sub.4 denotes an integer from 1 to 10.

(35) Particularly preferred groups P are selected from the group consisting of CH.sub.2CW.sup.1COO, CH.sub.2CW.sup.1CO,

(36) ##STR00008##
CH.sub.2CW.sup.2O, CH.sub.2CW.sup.2, CW.sup.1CHCO(O).sub.k3, CW.sup.1CHCONH, CH.sub.2CW.sup.1CONH, (CH.sub.2CH).sub.2CHOCO, (CH.sub.2CHCH.sub.2).sub.2CHOCO, (CH.sub.2CH).sub.2CHO, (CH.sub.2CHCH.sub.2).sub.2N, (CH.sub.2CHCH.sub.2).sub.2NCO, CH.sub.2CW.sup.1CONH, CH.sub.2CH(COO).sub.k1-Phe-(O).sub.k2, CH.sub.2CH(CO).sub.k1-Phe-(O).sub.k2, Phe-CHCH and W.sup.4W.sup.5W.sup.6Si, in which W.sup.1 denotes H, F, Cl, CN, CF.sub.3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH.sub.3, W.sup.2 and W.sup.3 each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, 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.3 preferably denotes 1, and k.sub.4 denotes an integer from 1 to 10.

(37) Very particularly preferred groups P are selected from the group consisting of CH.sub.2CW.sup.1COO, in particular CH.sub.2CHCOO, CH.sub.2C(CH.sub.3)COO and CH.sub.2CFCOO, furthermore CH.sub.2CHO, (CH.sub.2CH).sub.2CHOCO, (CH.sub.2CH).sub.2CHO,

(38) ##STR00009##

(39) Further very particularly preferred groups P are selected from the group consisting of vinyl, vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide groups, and particularly preferably denote an acrylate or methacrylate group.

(40) Preferred spacer groups Sp other than a single bond are selected from the formula Sp-X, so that the radical P-Sp- conforms to the formula P-Sp-X, where Sp denotes alkylene having 1 to 20, preferably 1 to 12, C atoms, 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 may each be replaced, independently of one another, by O, S, NH, N(R.sup.0), Si(R.sup.00R.sup.000), CO, COO, OCO, OCOO, SCO, COS, N(R.sup.00)COO, OCON(R.sup.00), N(R.sup.00)CON(R.sup.00), CHCH or CC in such a way that O and/or S atoms are not linked directly to one another, X denotes O, S, CO, COO, OCO, OCOO, CON(R.sup.00), N(R.sup.00)CO, N(R.sup.00)CON(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, CHN, NCH, NN, CHCR.sup.0, CY.sup.2CY.sup.3, CC, CHCHCOO, OCOCHCH or a single bond, R.sup.00 and R.sup.000 each, independently of one another, denote H or alkyl having 1 to 12 C atoms, and Y.sup.2 and Y.sup.3 each, independently of one another, denote H, F, Cl or CN. X is preferably O, S, CO, COO, OCO, OCOO, CONR.sup.0, NR.sup.0CO, NR.sup.0CONR.sup.0 or a single bond.

(41) Typical spacer groups Sp are, for example, (CH.sub.2).sub.p1, (CH.sub.2CH.sub.2O).sub.q1CH.sub.2CH.sub.2, CH.sub.2CH.sub.2SCH.sub.2CH.sub.2, CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2 or (SiR.sup.00R.sup.000O).sub.p1, in which p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R.sup.00 and R.sup.000 have the meanings indicated above.

(42) Particularly preferred groups -Sp-X are (CH.sub.2).sub.p1, (CH.sub.2).sub.p1O, (CH.sub.2).sub.p1OCO, (CH.sub.2).sub.p1OCOO, in which p1 and q1 have the meanings indicated above.

(43) Particularly preferred groups Sp are, for example, in each case straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

(44) In a further preferred embodiment of the invention, R.sup.a and/or R.sup.b in formula I denote a radical containing two or more polymerisable groups (multifunctional polymerisable radicals). Suitable radicals of this type and polymerisable compounds containing them and the preparation thereof are described, for example, in U.S. Pat. No. 7,060,200 B1 or US 2006/0172090 A1. Particular preference is given to multifunctional polymerisable radicals selected from the following formulae:
X-alkyl-CHP.sup.1CH.sub.2CH.sub.2P.sup.2I*a
X-alkyl-C(CH.sub.2P.sup.1)(CH.sub.2P.sup.2)CH.sub.2P.sup.3I*b
X-alkyl-CHP.sup.1CHP.sup.2CH.sub.2P.sup.3I*c
X-alkyl-C(CH.sub.2P.sup.1)(CH.sub.2P.sup.2)C.sub.aaH.sub.2aa+1I*d
X-alkyl-CHP.sup.1CH.sub.2P.sup.2I*e
X-alkyl-CHP.sup.1P.sup.2I*f
X-alkyl-CP.sup.1P.sup.2-C.sub.aaH.sub.2aa+1I*g
X-alkyl-C(CH.sub.2P.sup.1)(CH.sub.2P.sup.2)CH.sub.2OCH.sub.2C(CH.sub.2P.sup.3)(CH.sub.2P.sup.4)CH.sub.2P.sup.5I*h
X-alkyl-CH((CH.sub.2).sub.aaP.sup.1)((CH.sub.2).sub.bbP.sup.2)I*i
X-alkyl-CHP.sup.1CHP.sup.2C.sub.aaH.sub.2aa+1I*k
X-alkyl-C(CH.sub.3)(CH.sub.2P.sup.1)(CH.sub.2P.sup.2)I*m
in which alkyl denotes a single bond or straight-chain or branched alkylene having 1 to 12 C atoms, in which one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by C(R.sup.00)C(R.sup.000), CC, N(R.sup.00), O, S, CO, COO, OCO, OCOO 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 may be replaced by F, Cl or CN, where R.sup.00 and R.sup.000 have the meanings indicated above, aa and bb each, independently of one another, denote 0, 1, 2, 3, 4, 5 or 6, X has one of the meanings indicated for X, and P.sup.1-5 each, independently of one another, have one of the meanings indicated for P.

(45) Formula I covers the following compounds

(46) ##STR00010##
wherein R.sup.a, R.sup.c, A.sup.1, A.sup.2, Z.sup.1, X.sup.1, M, n1 and x are as defined in formula I. Compounds of formula Ib and Ic are especially preferred.

(47) Particularly preferred compounds of the formula I and sub-formulae thereof indicated above and below are those which contain more than two, preferably three, four, five or six groups R.sup.a or R.sup.b which denote P or P-Sp-.

(48) Particularly preferred compounds of the formula I and sub-formulae thereof indicated above and below are those in which A.sup.1, A.sup.2, A.sup.3, A.sup.4 each, independently of one another, when being different from a single bond, denote 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, where one or more CH groups in these groups are optionally replaced by N, cyclohexane-1,4-diyl, in which, in addition, one or more non-adjacent CH.sub.2 groups are optionally replaced by 0 and/or S, 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, where all these groups are unsubstituted or mono- or polysubstituted by L, L denotes P, P-Sp-, OH, CH.sub.2OH, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, C(O)N(R.sup.x).sub.2, C(O)Y.sup.1, C(O)R.sup.x, N(R.sup.x).sub.2, optionally substituted silyl, optionally substituted aryl having 6 to 20 C atoms, straight-chain or branched alkyl or alkoxy having 1 to 25 C atoms, or straight-chain or branched alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 2 to 25 C atoms, in which, in addition, one or more H atoms in all these groups may be replaced by F, Cl, P or P-Sp-, Y.sup.1 denotes halogen, and R.sup.x denotes P, P-Sp-, 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 may be replaced by O, S, CO, COO, OCO, OCOO 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 may be replaced by F, Cl or P-Sp-.

(49) Further preferred compounds of the formula I and sub-formulae thereof indicated above and below are those in which x is 2 or 3, x is 2, R.sup.a and R.sup.b denote identical or different radicals P-Sp-, R.sup.a and R.sup.b denote identical or different radicals P-Sp- in which one or more radicals Sp denote a single bond, x is 2 or 3 and all radicals R.sup.a denote identical groups P-Sp-, R.sup.b denotes an unpolymerisable group, preferably selected from straight-chain or branched alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by C(R.sup.00)C(R.sup.000), CC, N(R.sup.00), O, S, CO, COO, OCO, OCOO 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 may be replaced by F, Cl, Br, I or CN, R.sup.b denotes P-Sp-, R.sup.b denotes P-Sp- wherein Sp denotes a single bond, R.sup.c denotes H, C.sub.1-8-alkyl or C.sub.1-8-alkoxy, preferably H, one or more of the radicals Sp denote a single bond, one or more of the radicals Sp denotes (CH.sub.2).sub.p1, (CH.sub.2).sub.p1O, (CH.sub.2).sub.p1OCO or (CH.sub.2).sub.p1OCOO, in which p1 denotes an integer from 1 to 12 and r1 denotes an integer from 1 to 8, L does not denote or contain a polymerisable group, A.sup.1 and A.sup.3 are selected from the group consisting of 1,4-phenylene and naphthalene-2,6-diyl, where, in addition, one or two CH groups in these rings are optionally replaced by N, and where these rings are optionally mono- or polysubstituted by L, as described above and below, A.sup.2 is a single bond, A.sup.4 is a single bond, A.sup.2 and A.sup.4, when being different from a single bond, are selected from the group consisting of 1,4-phenylene and naphthalene-2,6-diyl, where, in addition, one or two CH groups in these rings are optionally replaced by N, and where these rings are optionally mono- or polysubstituted by L, as described above and below, n1=n2=0, and one of A.sup.2 and A.sup.4 is a single bond and the other is not a single bond, and is preferably 1,4-phenylene or naphthalene-2,6-diyl, where, in addition, one or two CH groups in these rings are optionally replaced by N, and where these rings are optionally mono- or polysubstituted by L, as described above and below Z.sup.1 and Z.sup.2 are selected from the group consisting of O, COO, OCO, OCH.sub.2, CH.sub.2O, CF.sub.2O, OCF.sub.2, CH.sub.2CH.sub.2, CHCH, CFCF, CHCF, CFCH, CC, single bond, n1 is 0 or 1, preferably 0 and A.sup.2 is a single bond, n2 is 0 and A.sup.4 is a single bond, n2 is 0 and A.sup.4 is not a single bond, n2 is not 0 and is preferably 1 or 2, very preferably 1, and A.sup.4 is a single bond, X.sup.2-A.sup.4-(Z.sup.2-A.sup.3).sub.n2- does not denote COC.sub.6H.sub.4 (where C.sub.6H.sub.4 stands for 1,4-phenylene), X.sup.2-A.sup.4-(Z.sup.2-A.sup.3).sub.n2-R.sup.b does not denote COC.sub.6H.sub.5, L is an unpolymerisable group, preferably selected from F, Cl, CN and straight-chain or branched alkyl having 1 to 25, particularly preferably 1 to 10, C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by C(R.sup.00)C(R.sup.000), CC, N(R.sup.00), O, S, CO, COO, OCO, OCOO 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 may be replaced by F, Cl, Br, I or CN.

(50) Particularly preferred compounds of the formula I are selected from the group consisting of the following sub-formulae:

(51) ##STR00011## ##STR00012##
in which R.sup.a, R.sup.b, A.sup.1-4, Z.sup.1,2, X.sup.1,2, n1 and n2 each, independently of one another, have one of the meanings indicated in formula I or as indicated above and below.

(52) Especially preferred are compounds of formulae I1-I14, in which R.sup.a is P-Sp-, and P, Sp, R.sup.b, A.sup.1-4, Z.sup.1,2, X.sup.1,2, n1 and n2 each, independently of one another, have one of the meanings indicated in formula I or as indicated above and below.

(53) In case n1 or n2, respectively, is different from 0, the group -(A.sup.1-Z.sup.1).sub.n1-A.sup.2-X.sup.1 and X.sup.2-A.sup.4-(Z.sup.2-A.sup.2).sub.n2-, respectively, in the compounds of the formulae I and 11-114 preferably denotes 1,4-phenylene or naphthalene-2,6-diyl, where, in addition, one or two CH groups in these rings are optionally replaced by N, and where, in addition, these rings are optionally mono- or polysubstituted by L, as described above and below.

(54) Very preferred compounds of formulae I1 to I14 are those wherein n1 is 0 and A.sup.2 is a single bond.

(55) Further preferred compounds of formulae I1 to I14 are those wherein n2 is 1 and A.sup.4 is a single bond.

(56) Further preferred compounds of formulae I1 to I14 are those wherein R.sup.b denotes P-Sp-.

(57) Further preferred compounds of formulae I1 to I14 are those wherein R.sup.b denotes an unpolymerisable group, preferably selected from straight-chain or branched alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by C(R.sup.00)C(R.sup.000), CC, N(R.sup.00), O, S, CO, COO, OCO, OCOO 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 may be replaced by F, Cl, Br, I or CN.

(58) Very preferred compounds of formulae I1 to I14 are those wherein R.sup.a is P-Sp- and Sp is different from a single bond.

(59) Further preferred compounds of formulae I1 to I14 are those wherein R.sup.a is P-Sp- and one or both groups Sp denote a single bond.

(60) Further preferred compounds of formulae I1 to I14 are those wherein R.sup.b is P-Sp- and Sp denotes a single bond.

(61) Further preferred compounds of formulae I1 to I14 are those wherein R.sup.b is P-Sp- and Sp is different from a single bond.

(62) Very particularly preferred compounds of the formulae I1 to I14 are selected from the group consisting of the following sub-formulae:

(63) ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019##
in which P and Sp have one of the meanings indicated in formula I or above and below, Sp has one of the meanings given for Sp, and is identical to or different from Sp, and R has one of the meanings indicated for R.sup.b in formula I or above and below which is different from H, P and P-Sp-, and wherein the phenylene and naphthalene groups are optionally substituted with one, two, three of four F atoms.

(64) P in the compounds of the formulae I, I1 to I14 and I1a to I14c preferably denote an acrylate, fluoroacrylate or methacrylate group.

(65) Sp in the compounds of the formulae I, I1 to I14 and I1a to I14c preferably denote (CH.sub.2).sub.p1, O(CH.sub.2).sub.p1, (CH.sub.2).sub.p1O, OCO(CH.sub.2).sub.p1, (CH.sub.2).sub.p1OCO, OCOO(CH.sub.2).sub.p1 or (CH.sub.2).sub.p1OCOO, in which p1 denotes an integer from 1 to 12, preferably from 1 to 6, and r1 denotes an integer from 1 to 8, preferably 1, 2 or 3, where these groups are linked to P in such a way that 0 atoms are not linked directly to one another.

(66) Preference is given to compounds of the formulae I, I1 to I14 and I1a to I14c wherein P denotes an acrylate, fluoroacrylate or methacrylate group, and Sp denotes (CH.sub.2).sub.p1, O(CH.sub.2).sub.p1, (CH.sub.2).sub.p1O, OCO(CH.sub.2).sub.p1, (CH.sub.2).sub.p1OCO, OCOO(CH.sub.2).sub.p1 or (CH.sub.2).sub.p1OCOO, in which p1 denotes an integer from 1 to 12, preferably from 1 to 6, and r1 denotes an integer from 1 to 8, preferably 1, 2 or 3, where these groups are linked to P in such a way that O atoms are not linked directly to one another.

(67) Preference is furthermore given to compounds of the sub-formulae I1a-I14c in which one or more of the radicals Sp denote a single bond and one or more of the radicals Sp are not a single bond.

(68) Preference is furthermore given to compounds of the sub-formulae I1a-I14c in which one or more of the radicals Sp denote a single bond and one or more of the radicals Sp are not a single bond, and P denotes an acrylate, fluoroacrylate or methacrylate group.

(69) The invention furthermore relates to novel compounds of the formula I and sub-formulae I1 to I14 in which the individual radicals have the meaning indicated in formula I or as given above and below, and wherein

(70) a) X.sup.1 and/or X.sup.2 is a single bond, and/or

(71) b) one of n1 and n2 is different from 0 and/or

(72) c) one of A.sup.2 and A.sup.4 is not a single bond.

(73) Particular preference is given to novel compounds of the formula I and sub-formulae I1 to I14 as defined above, in which n2 is not 0 and preferably denotes 1 or 2.

(74) Particular preference is furthermore given to novel compounds selected from the sub-formulae I1a to I14c as defined above.

(75) The invention furthermore relates to novel intermediates for the preparation of compounds of the formula I, selected from the following formula:

(76) ##STR00020##
in which G, A.sup.1,2, Z.sup.1, X.sup.1, x and n1 have the meaning indicated in formula I or above and below, and the radicals R.sup.a and R.sup.b each, independently of one another, denote -Sp-OSg, where Sp has the meaning indicated in formula I or above and below, and Sg denotes an H atom or a protecting group, and wherein preferably
a) X.sup.1 and/or X.sup.2 is a single bond, and/or
b) one of n1 and n2 is different from 0 and/or
c) one of A.sup.2 and A.sup.4 is not a single bond.

(77) Suitable protecting groups Sg are known to the person skilled in the art. Preferred protecting groups are alkyl, acyl and alkyl- or arylsilyl groups, 2-tetrahydropyranyl or methoxymethyl.

(78) Particularly preferred intermediates are selected from the sub-formulae I1 to I14 as indicated above, where R.sup.a and R.sup.b are as defined in formula I*.

(79) Very particularly preferred intermediates are selected from the group consisting of the following sub-formulae:

(80) ##STR00021## ##STR00022## ##STR00023##
in which Sp and Sg have the meanings indicated above, and Sp has one of the meanings given for Sp, and is identical to or different from Sp. Sg particularly preferably denotes H. Particular preference is given to compounds of the formulae shown above in which one of the radicals Sp and Sp denotes (CH.sub.2).sub.p1 or a single bond and the other denotes a single bond, where p1 is as defined above.

(81) The compounds and intermediates of the formulae I and I* and sub-formulae thereof can be prepared analogously to processes known to the person skilled in the art and described in standard works of organic chemistry, such as, for example, in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart. For example, compounds of the formula I are synthesised by esterification or etherification of the intermediates of the formula I using corresponding acids, acid derivatives, or halogenated compounds containing a group P, such as, for example, (meth)acryloyl chloride or methacrylic anhydride in the presence of a base, or (meth)acrylic acid in the presence of a dehydrating reagent, such as, for example, DCC (dicyclohexylcarbodiimide).

(82) Particularly suitable and preferred processes for the preparation of compounds and intermediates of the formulae I and I* are depicted by way of example in the following schemes and preferably comprise one or more of the steps described below.

(83) General access to coumarines is provided, for example, by condensation of salicylic aldehydes with phenylacetic acid derivatives in the sense of a Perkin reaction [cf. e.g. M. J. Matos et al., Bioorg. Med. Chem. Lett. 20 (2010) 5157-5160 and literature cited therein], or from salicylic aldehydes and benzonitriles (N. P. Buu-Ho, N. Hon, M. R. Khenissi, J. Chem. Soc. 1951, 2307) in accordance with scheme 1 for M=H (Formula 1). For substituents M other than H the aldehyde group is simply replaced by the corresponding ketone.

(84) ##STR00024##

(85) An alternative approach especially for non-aromatic acetic acid derivatives goes via a Wittig reaction as published by R. S. Mali, S. G. Tilve, S. N. Yeola, A. R. Manekar, Heterocycles (1987), 26(1), 121-7 (scheme 2).

(86) ##STR00025##

(87) Spacer groups can be introduced e.g. by Sonogashira coupling of hydroxy alkynes and subsequent hydrogenation either before or after the Perkin reaction (scheme 3 and 4).

(88) ##STR00026##

(89) ##STR00027##

(90) Introduction of a hydroxypropyl group by Stille coupling and subsequent hydroboration is described in B. S. Moon et al., Bioorg. Med. Chem. 2009, 17(9), 3479-3488. For a Heck reaction with allyl alcohol cf. R. A. Lerner et al., J. Am. Chem. Soc. 1996, 118, 11720-11724. Another general approach is given by in situ hydroboration of terminally unsaturated alcohols and Suzuki coupling as described e.g. in A. R. de Lera, Tetrahedron 2001, 57, 3125-3130. These reactions are exemplified by reactions to give the propyl homologue starting from a dibromosalicylic aldehyde (scheme 5) but are generally applicable to other isomers or congeners of salicylic aldehydes.

(91) ##STR00028##

(92) In the above scheme it can be advantageous to protect the salicylic aldehyde, esp. the aldehyde function, e.g. as an acetal. A method of protecting both the aldehyde and the hydroxyl group together is described in A. Hadfield, Synth. Comm. 1994, 24(7), 1025-1028 (Scheme 6).

(93) ##STR00029##

(94) Isoflavones are accessible by the method of R. J. Bass, Chem. Comm. 1976, 78, by treatment of benzyl aryl ketones with boron trifluoride etherate in the presence of mesyl chloride in dimethylformamide. The ketones themselves can be prepared in a simple manner by carbonylating Suzuki reaction by the method of A. Suzuki et al., J. Org. Chem. 1998, 63, 4762, as shown by way of example in scheme 7:

(95) ##STR00030##

(96) Alternatively, isoflavones can also be obtained by the method of K. M. Dawood, Tetrahedron 2007, 63, 9642, from chromanones via the corresponding bromoisoflavones by Suzuki reaction, as shown by way of example in scheme 8:

(97) ##STR00031##

(98) The flavones according to the invention are prepared, for example, by Baker-Venkataraman rearrangement (W. Baker, Nature 1952, 169, 706) or they can be prepared by the method of E. U. Mughal et al., Bioorg. Med. Chem. 2006, 14, 4704, from o-acylphenols by aldol condensation with aromatic aldehydes and subsequent oxidative cyclisation, as shown by way of example in Scheme 9:

(99) ##STR00032##

(100) For the production of PSA displays, the polymerisable compounds are polymerised or crosslinked (if one compound contains two or more polymerisable groups) by in-situ polymerisation in the LC medium between the substrates of the LC display with application of a voltage. The polymerisation can be carried out in one step. It is also possible firstly to carry out the polymerisation with application of a voltage in a first step in order to produce a pretilt angle, and subsequently, in a second polymerisation step without an applied voltage, to polymerise or crosslink the compounds which have not reacted in the first step (end curing).

(101) Suitable and preferred polymerisation methods are, for example, thermal or photopolymerisation, preferably photopolymerisation, in particular UV photopolymerisation. One or more initiators can optionally also be added here. Suitable conditions for the polymerisation and suitable types and amounts of initiators are known to the person skilled in the art and are described in the literature. Suitable for free-radical polymerisation are, for example, the commercially available photoinitiators Irgacure651, Irgacure184, Irgacure907, Irgacure369 or Darocure1173 (Ciba AG). If an initiator is employed, its proportion is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight.

(102) The polymerisable compounds according to the invention are also suitable for polymerisation without an initiator, which is accompanied by considerable advantages, such, for example, lower material costs and in particular less contamination of the LC medium by possible residual amounts of the initiator or degradation products thereof. The polymerisation can thus also be carried out without the addition of an initiator. In a preferred embodiment, the LC medium thus comprises no polymerisation initiator.

(103) The polymerisable component A) or the LC medium may also comprise one or more stabilisers in order to prevent undesired spontaneous polymerisation of the RMs, for example during storage or transport. Suitable types and amounts of stabilisers are known to the person skilled in the art and are described in the literature. Particularly suitable are, for example, the commercially available stabilisers from the Irganox series (Ciba AG), such as, for example, Irganox 1076. If stabilisers are employed, their proportion, based on the total amount of RMs or the polymerisable component A), is preferably 10-500,000 ppm, particularly preferably 50-50,000 ppm.

(104) The LC media according to the invention for use in PSA displays preferably comprise from >0 to <5% by weight, particularly preferably from >0 to <1% by weight, very particularly preferably from 0.01 to 0.5% by weight, of polymerisable compounds, in particular polymerisable compounds of the formulae indicated above.

(105) Particular preference is given to LC media comprising one, two or three polymerisable compounds according to the invention.

(106) Preference is furthermore given to LC media in which the polymerisable component (component A) comprises exclusively polymerisable compounds according to the invention.

(107) Preference is furthermore given to LC media in which component B) is an LC compound or an LC mixture which has a nematic liquid-crystal phase.

(108) Preference is furthermore given to achiral polymerisable compounds according to the invention and LC media in which the compounds of component A) and/or B) are selected exclusively from the group consisting of achiral compounds.

(109) Preference is furthermore given to LC media in which the polymerisable component or component A) comprises one or more polymerisable compounds according to the invention containing one polymerisable group (monoreactive) and one or more polymerisable compounds according to the invention containing two or more, preferably two, polymerisable groups (di- or multireactive).

(110) Preference is furthermore given to PSA displays and LC media in which the polymerisable component or component A) comprises exclusively polymerisable compounds according to the invention containing two polymerisable groups (direactive).

(111) The proportion of the polymerisable component or component A) in the LC media according to the invention is preferably from >0 to <5%, particularly preferably from >0 to <1%, very particularly preferably from 0.01 to 0.5%.

(112) The proportion of the liquid-crystalline component or component B) in the LC media according to the invention is preferably from 95 to <100%, particularly preferably from 99 to <100%.

(113) The polymerisable compounds according to the invention can be polymerised individually, but it is also possible to polymerise mixtures which comprise two or more polymerisable compounds according to the invention, or mixtures comprising one or more polymerisable compounds according to the invention and one or more further polymerisable compounds (comonomers), which are preferably mesogenic or liquid-crystalline. In the case of polymerisation of such mixtures, copolymers form. The invention furthermore relates to the polymerisable mixtures mentioned above and below. The polymerisable compounds and comonomers are mesogenic or non-mesogenic, preferably mesogenic or liquid-crystalline.

(114) Suitable and preferred mesogenic comonomers, particularly for use in PSA displays, are selected, for example, from the following formulae:

(115) ##STR00033## ##STR00034## ##STR00035##
in which the individual radicals have the following meanings: P.sup.1 and P.sup.2 each, independently of one another, denote a polymerisable group, preferably having one of the meanings indicated above and below for P, particularly preferably an acrylate, methacrylate, fluoroacrylate, oxetane, vinyl, vinyloxy or epoxide group, Sp.sup.1 and Sp.sup.2 each, independently of one another, denote a single bond or a spacer group, preferably having one of the meanings indicated above and below for Sp, and particularly preferably denote (CH.sub.2).sub.p1, (CH.sub.2).sub.p1O, (CH.sub.2).sub.p1COO or (CH.sub.2).sub.p1OCOO, 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, where, in addition, one or more of the radicals P.sup.1-Sp.sup.1- and P.sup.2Sp.sup.2- may denote R.sup.aa, with the proviso that at least one of the radicals P.sup.1-Sp.sup.1- and P.sup.2-Sp.sup.2- 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 may each be replaced, independently of one another, by C(R.sup.0)C(R.sup.00), CC, N(R.sup.0), O, S, CO, COO, OCO, OCOO 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 may be replaced by F, Cl, CN or P.sup.1Sp.sup.1-, particularly preferably straight-chain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms (where the alkenyl and alkynyl radicals have at least two C atoms and the branched radicals have at least three C atoms), R.sup.0, R.sup.00 each, independently of one another and identically or differently on each occurrence, 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, 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 COO, OCO, 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 or straight-chain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, preferably F, 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, x denotes 0 or 1.

(116) In the compounds of formulae M1 to M29

(117) ##STR00036##
is preferably

(118) ##STR00037##
wherein L on each occurrence, identically or differently, has one of the meanings given above or below, and is preferably F, Cl, CN, NO.sub.2, CH.sub.3, C.sub.2H.sub.5, C(CH.sub.3).sub.3, CH(CH.sub.3).sub.2, CH.sub.2CH(CH.sub.3)C.sub.2H.sub.5, OCH.sub.3, OC.sub.2H.sub.5, COCH.sub.3, COC.sub.2H.sub.5, COOCH.sub.3, COOC.sub.2H.sub.5, CF.sub.3, OCF.sub.3, OCHF.sub.2, OC.sub.2F.sub.5 or P-Sp-, very preferably F, Cl, CN, CH.sub.3, C.sub.2H.sub.5, OCH.sub.3, COCH.sub.3, OCF.sub.3 or P-Sp-, more preferably F, Cl, CH.sub.3, OCH.sub.3, COCH.sub.3 oder OCF.sub.3, especially F or CH.sub.3. Besides the polymerisable compounds described above, the LC media for use in the LC displays according to the invention comprise an LC mixture (host mixture) comprising one or more, preferably two or more, low-molecular-weight (i.e. monomeric or unpolymerised) compounds. The latter are stable or unreactive to a polymerisation reaction under the conditions used for polymerisation of the polymerisable compounds. In principle, any LC mixture which is suitable for use in conventional VA and OCB displays is suitable as host mixture. Suitable LC mixtures are known to the person skilled in the art and are described in the literature, for example mixtures in VA displays in EP 1 378 557 A1 and mixtures for OCB displays in EP 1 306 418 A1 and DE 102 24 046 A1.

(119) The polymerisable compounds of formula I are especially suitable for use in an LC host mixture that comprises one or more compounds having a terminal alkenyl group, where they show improved properties, like solubility, reactivity or capability of generating a tilt angle, compared to reactive mesogens known from prior art.

(120) In a first preferred embodiment the LC medium contains an LC host mixture based on compounds with negative dielectric anisotropy. Such LC media are especially suitable for use in PSA-VA displays. Particularly preferred embodiments of such an LC medium are those of sections a)-x) below: a) LC medium which comprises one or more compounds of the formulae CY and/or PY:

(121) ##STR00038## wherein a denotes 1 or 2, b denotes 0 or 1.

(122) ##STR00039##
denotes

(123) ##STR00040## R.sup.1 and R.sup.2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by O, CHCH, CO, OCO or COO in such a way that O atoms are not linked directly to one another, preferably alkyl or alkoxy having 1 to 6 C atoms, Z.sup.x and Z.sup.y each, independently of one another, denote CH.sub.2CH.sub.2, CHCH, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, COO, OCO, C.sub.2F.sub.4, CFCF, CHCHCH.sub.2O or a single bond, preferably a single bond, L.sup.1-4 each, independently of one another, denote F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, CHF.sub.2.

(124) Preferably, both L.sup.1 and L.sup.2 denote F or one of L.sup.1 and L.sup.2 denotes F and the other denotes Cl, or both L.sup.3 and L.sup.4 denote F or one of L.sup.3 and L.sup.4 denotes F and the other denotes Cl.

(125) The compounds of the formula CY are preferably selected from the group consisting of the following sub-formulae:

(126) ##STR00041## ##STR00042## ##STR00043## ##STR00044## in which a denotes 1 or 2, alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, and (O) denotes an oxygen atom or a single bond. Alkenyl preferably denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2.

(127) The compounds of the formula PY are preferably selected from the group consisting of the following sub-formulae:

(128) ##STR00045## ##STR00046## ##STR00047## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, and (O) denotes an oxygen atom or a single bond. Alkenyl preferably denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. b) LC medium which additionally comprises one or more compounds of the following formula:

(129) ##STR00048## in which the individual radicals have the following meanings:

(130) ##STR00049##
denotes

(131) ##STR00050##

(132) ##STR00051##
denotes

(133) ##STR00052## R.sup.3 and R.sup.4 each, independently of one another, denote alkyl having 1 to 12 C atoms, in which, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by O, CHCH, CO, OCO or COO in such a way that O atoms are not linked directly to one another, Z.sup.y denotes CH.sub.2CH.sub.2, CHCH, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, COO, OCO, C.sub.2F.sub.4, CFCF, CHCHCH.sub.2O or a single bond, preferably a single bond.

(134) The compounds of the formula ZK are preferably selected from the group consisting of the following sub-formulae:

(135) ##STR00053##
in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl preferably denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. c) LC medium which additionally comprises one or more compounds of the following formula:

(136) ##STR00054## in which the individual radicals on each occurrence, identically or differently, have the following meanings: R.sup.5 and R.sup.6 each, independently of one another, have one of the meanings indicated above for R.sup.1,

(137) ##STR00055##
denotes

(138) ##STR00056##

(139) ##STR00057##
denotes

(140) ##STR00058##
and e denotes 1 or 2.

(141) The compounds of the formula DK are preferably selected from the group consisting of the following sub-formulae:

(142) ##STR00059## ##STR00060## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and alkenyl* preferably denote CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. d) LC medium which additionally comprises one or more compounds of the following formula:

(143) ##STR00061## in which the individual radicals have the following meanings:

(144) ##STR00062##
denotes

(145) ##STR00063## f denotes 0 or 1, R.sup.1 and R.sup.2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by O, CHCH, CO, OCO or COO in such a way that O atoms are not linked directly to one another, Z.sup.x and Z.sup.y each, independently of one another, denote CH.sub.2CH.sub.2, CHCH, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, COO, OCO, C.sub.2F.sub.4, CFCF, CHCHCH.sub.2O or a single bond, preferably a single bond, L.sup.1 and L.sup.2 each, independently of one another, denote F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, CHF.sub.2.

(146) Preferably, both radicals L.sup.1 and L.sup.2 denote F or one of the radicals L.sup.1 and L.sup.2 denotes F and the other denotes Cl.

(147) The compounds of the formula LY are preferably selected from the group consisting of the following sub-formulae:

(148) ##STR00064## ##STR00065## ##STR00066## in which R.sup.1 has the meaning indicated above, alkyl denotes a straight-chain alkyl radical having 1-6 C atoms, (O) denotes an oxygen atom or a single bond, and v denotes an integer from 1 to 6. R.sup.1 preferably denotes straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms, in particular CH.sub.3, C.sub.2H.sub.5, n-C.sub.3H.sub.7, n-C.sub.4H.sub.9, n-C.sub.5H.sub.11, CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. e) LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:

(149) ##STR00067## in which alkyl denotes C.sub.1-6-alkyl, L.sup.x denotes H or F, and X denotes F, Cl, OCF.sub.3, OCHF.sub.2 or OCHCF.sub.2. Particular preference is given to compounds of the formula G1 in which X denotes F. f) LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:

(150) ##STR00068## ##STR00069## in which R.sup.5 has one of the meanings indicated above for R.sup.1, alkyl denotes C.sub.1-6-alkyl, d denotes 0 or 1, and z and m each, independently of one another, denote an integer from 1 to 6. R.sup.5 in these compounds is particularly preferably C.sub.1-6-alkyl or -alkoxy or C.sub.2-6-alkenyl, d is preferably 1. The LC medium according to the invention preferably comprises one or more compounds of the above-mentioned formulae in amounts of 5% by weight. g) LC medium which additionally comprises one or more biphenyl compounds selected from the group consisting of the following formulae:

(151) ##STR00070## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and alkenyl* preferably denote CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2.

(152) The proportion of the biphenyls of the formulae B1 to B3 in the LC mixture is preferably at least 3% by weight, in particular 5% by weight.

(153) The compounds of the formula B2 are particularly preferred.

(154) The compounds of the formulae B1 to B3 are preferably selected from the group consisting of the following sub-formulae:

(155) ##STR00071## in which alkyl* denotes an alkyl radical having 1-6 C atoms. The medium according to the invention particularly preferably comprises one or more compounds of the formulae B1a and/or B2c. h) LC medium which additionally comprises one or more terphenyl compounds of the following formula:

(156) ##STR00072## in which R.sup.5 and R.sup.6 each, independently of one another, have one of the meanings indicated above for R.sup.1, and

(157) ##STR00073## each, independently of one another, denote

(158) ##STR00074## in which L.sup.5 denotes F or Cl, preferably F, and L.sup.6 denotes F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F or CHF.sub.2, preferably F.

(159) The compounds of the formula T are preferably selected from the group consisting of the following sub-formulae:

(160) ##STR00075## ##STR00076## ##STR00077## in which R denotes a straight-chain alkyl or alkoxy radical having 1-7 C atoms, R* denotes a straight-chain alkenyl radical having 2-7 C atoms, (O) denotes an oxygen atom or a single bond, and m denotes an integer from 1 to 6. R* preferably denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2.

(161) R preferably denotes methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy or pentoxy.

(162) The LC medium according to the invention preferably comprises the terphenyls of the formula T and the preferred sub-formulae thereof in an amount of 0.5-30% by weight, in particular 1-20% by weight.

(163) Particular preference is given to compounds of the formulae T1, T2, T3 and T21. In these compounds, R preferably denotes alkyl, furthermore alkoxy, each having 1-5 C atoms.

(164) The terphenyls are preferably employed in mixtures according to the invention if the n value of the mixture is to be 0.1. Preferred mixtures comprise 2-20% by weight of one or more terphenyl compounds of the formula T, preferably selected from the group of compounds T1 to T22. i) LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:

(165) ##STR00078## in which R.sup.1 and R.sup.2 have the meanings indicated above and preferably each, independently of one another, denote straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms.

(166) Preferred media comprise one or more compounds selected from the formulae O1, O3 and O4. k) LC medium which additionally comprises one or more compounds of the following formula:

(167) ##STR00079## in which

(168) ##STR00080##
denotes

(169) ##STR00081##

(170) R.sup.9 denotes H, CH.sub.3, C.sub.2H.sub.5 or n-C.sub.3H.sub.7, (F) denotes an optional fluorine substituent, and q denotes 1, 2 or 3, and R.sup.7 has one of the meanings indicated for R.sup.1, preferably in amounts of >3% by weight, in particular 5% by weight and very particularly preferably 5-30% by weight.

(171) Particularly preferred compounds of the formula FI are selected from the group consisting of the following sub-formulae:

(172) ##STR00082## in which R.sup.7 preferably denotes straight-chain alkyl, and R.sup.9 denotes CH.sub.3, C.sub.2H.sub.5 or n-C.sub.3H.sub.7. Particular preference is given to the compounds of the formulae FI1, FI2 and FI3. m) LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:

(173) ##STR00083## in which R.sup.8 has the meaning indicated for R.sup.1, and alkyl denotes a straight-chain alkyl radical having 1-6 C atoms. n) LC medium which additionally comprises one or more compounds which contain a tetrahydronaphthyl or naphthyl unit, such as, for example, the compounds selected from the group consisting of the following formulae:

(174) ##STR00084## ##STR00085## in which R.sup.10 and R.sup.11 each, independently of one another, have one of the meanings indicated for R.sup.1, preferably denote straight-chain alkyl or alkoxy having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms, and Z.sup.1 and Z.sup.2 each, independently of one another, denote C.sub.2H.sub.4, CHCH, (CH.sub.2).sub.4, (CH.sub.2).sub.3O, O(CH.sub.2).sub.3, CHCHCH.sub.2CH.sub.2, CH.sub.2CH.sub.2CHCH, CH.sub.2O, OCH.sub.2, COO, OCO, C.sub.2F.sub.4, CFCF, CFCH, CHCF, CH.sub.2 or a single bond. o) LC medium which additionally comprises one or more difluoro-dibenzochromans and/or chromans of the following formulae:

(175) ##STR00086## in which R.sup.11 and R.sup.12 each, independently of one another, have the meanings indicated above, ring M is trans-1,4-cyclohexylene or 1,4-phenylene, Z.sup.m C.sub.2H.sub.4, CH.sub.2O, OCH.sub.2, COO or OCO, c is 0 or 1, preferably in amounts of 3 to 20% by weight, in particular in amounts of 3 to 15% by weight.

(176) Particularly preferred compounds of the formulae BC, CR and RC are selected from the group consisting of the following sub-formulae:

(177) ##STR00087## ##STR00088## ##STR00089## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, (O) denotes an oxygen atom or a single bond, c is 1 or 2, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and alkenyl* preferably denote CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2.

(178) Very particular preference is given to mixtures comprising one, two or three compounds of the formula BC-2. p) LC medium which additionally comprises one or more fluorinated phenanthrenes and/or dibenzofurans of the following formulae:

(179) ##STR00090## in which R.sup.11 and R.sup.12 each, independently of one another, have the meanings indicated above, b denotes 0 or 1, L denotes F, and r denotes 1, 2 or 3.

(180) Particularly preferred compounds of the formulae PH and BF are selected from the group consisting of the following sub-formulae:

(181) ##STR00091## in which R and R each, independently of one another, denote a straight-chain alkyl or alkoxy radical having 1-7 C atoms. q) LC medium which, apart from the polymerisable compounds according to the invention, in particular of the formula I or sub-formulae thereof and the comonomers, comprises no compounds which contain a terminal vinyloxy group (OCHCH.sub.2). r) LC medium which comprises 1 to 5, preferably 1, 2 or 3, polymerisable compounds, preferably selected from polymerisable compounds according to the invention, in particular of the formula I or sub-formulae thereof. s) LC medium in which the proportion of polymerisable compounds, in particular of the formula I or sub-formulae thereof, in the mixture as a whole is 0.05 to 5%, preferably 0.1 to 1%. t) LC medium which comprises 1 to 8, preferably 1 to 5, compounds of the formulae CY1, CY2, PY1 and/or PY2. The proportion of these compounds in the mixture as a whole is preferably 5 to 60%, particularly preferably 10 to 35%. The content of these individual compounds is preferably in each case 2 to 20%. u) LC medium which comprises 1 to 8, preferably 1 to 5, compounds of the formulae CY9, CY10, PY9 and/or PY10. The proportion of these compounds in the mixture as a whole is preferably 5 to 60%, particularly preferably 10 to 35%. The content of these individual compounds is preferably in each case 2 to 20%. v) LC medium which comprises 1 to 10, preferably 1 to 8, compounds of the formula ZK, in particular compounds of the formulae ZK1, ZK2 and/or ZK6. The proportion of these compounds in the mixture as a whole is preferably 3 to 25%, particularly preferably 5 to 45%. The content of these individual compounds is preferably in each case 2 to 20%. w) LC medium in which the proportion of compounds of the formulae CY, PY and ZK in the mixture as a whole is greater than 70%, preferably greater than 80%. x) LC medium in which the LC host mixture contains one or more compounds containing an alkenyl group, preferably selected from the group consisting of formula CY, PY and LY, wherein one or both of R.sup.1 and R.sup.2 denote straight-chain alkenyl having 2-6 C atoms, formula ZK and DK, wherein one or both of, R.sup.3 and R.sup.4 denote straight-chain alkenyl having 2-6 C atoms, and formula B2 and B3, very preferably selected from formulae CY15, CY16, CY34, CY32, PY15, PY16, ZK3, ZK4, DK3, DK6, B2 and B3, most preferably selected from formulae ZK3, ZK4, B2 and B3. The concentration of these compounds in the LC host mixture is preferably from 2 to 70%, very preferably from 3 to 55%. y) PSA-VA display in which the pretilt angle is preferably 85, particularly preferably 80.

(182) In a second preferred embodiment the LC medium contains an LC host mixture based on compounds with positive dielectric anisotropy. Such LC media are especially suitable for use in PSA-OCB-, PSA-TN-, PSA-Posi-VA-, PSA-IPS- oder PSA-FFS-displays.

(183) Particularly preferred is an LC medium of this second preferred embodiment, which contains one or more compounds selected from the group consisting of compounds of formula AA and BB

(184) ##STR00092##
and optionally contains, in addition to the compounds of formula AA and/or BB, one or more compounds of formula CC

(185) ##STR00093##
in which the individual radicals have the following meanings:

(186) ##STR00094##
each, independently of one another, and on each occurrence, identically or differently

(187) ##STR00095##
each, independently of one another, and on each occurrence, identically or differently

(188) ##STR00096## R.sup.21, R.sup.31, R.sup.41, R.sup.42 each, independently of one another, alkyl, alkoxy, oxaalkyl or fluoroalkyl having 1 to 9 C atoms or alkenyl having 2 to 9 C atoms, X.sup.0 F, Cl, halogenated alkyl or alkoxy having 1 to 6 C atoms or halogenated alkenyl or alkenyloxy having 2 to 6 C atoms, Z.sup.31 CH.sub.2CH.sub.2, CF.sub.2CF.sub.2, COO, trans-CHCH, trans-CFCF, CH.sub.2O or a single bond, preferably CH.sub.2CH.sub.2, COO, trans-CHCH or a single bond, particularly preferably COO, trans-CHCH or a single bond, Z.sup.41, Z.sup.42 CH.sub.2CH.sub.2, COO, trans-CHCH, trans-CFCF, CH.sub.2O, CF.sub.2O, CC or a single bond, preferably a single bond, L.sup.21, L.sup.22, L.sup.31, L.sup.32 H or F, g 1, 2 or 3, h 0, 1, 2 or 3. X.sup.0 is preferably F, Cl, CF.sub.3, CHF.sub.2, OCF.sub.3, OCHF.sub.2, OCFHCF.sub.3, OCFHCHF.sub.2, OCFHCHF.sub.2, OCF.sub.2CH.sub.3, OCF.sub.2CHF.sub.2, OCF.sub.2CHF.sub.2, OCF.sub.2CF.sub.2CHF.sub.2, OCF.sub.2CF.sub.2CHF.sub.2, OCFHCF.sub.2CF.sub.3, OCFHCF.sub.2CHF.sub.2, OCF.sub.2CF.sub.2CF.sub.3, OCF.sub.2CF.sub.2CClF.sub.2, OCClFCF.sub.2CF.sub.3 or CHCF.sub.2, very preferably F or OCF.sub.3

(189) The compounds of formula AA are preferably selected from the group consisting of the following formulae:

(190) ##STR00097##
in which A.sup.21, R.sup.21, X.sup.0, L.sup.21 and L.sup.22 have the meanings given in formula AA, L.sup.23 and L.sup.24 each, independently of one another, are H or F, and X.sup.0 is preferably F. Particularly preferred are compounds of formulae AA1 and AA2.

(191) Particularly preferred compounds of formula AA1 are selected from the group consisting of the following subformulae

(192) ##STR00098##
in which R.sup.0 has one of the meanings given for R.sup.21 in formula AA1, X.sup.0, L.sup.21 and L.sup.22 have the meaning given in formula AA1, L.sup.23, L.sup.24, L.sup.25 and L.sup.26 are each, independently of one another, H or F, and X.sup.0 is preferably F.

(193) Very particularly preferred compounds of formula AA1 are selected from the group consisting of the following subformulae:

(194) ##STR00099##

(195) In which R.sup.0 has the meaning given for R.sup.21 in formula AA1.

(196) Very preferred compounds of formula AA2 are selected from the group consisting of the following subformulae

(197) ##STR00100## ##STR00101##
in which R.sup.0 has the meaning given for R.sup.21 in formula AA1, X.sup.0, L.sup.21 and L.sup.22 have the meaning given in formula AA, L.sup.23, L.sup.24, L.sup.25 and L.sup.26 each, independently of one another, are H or F, and X.sup.0 is preferably F.

(198) Very particularly preferred compounds of formula AA2 are selected from the group consisting of the following subformulae

(199) ##STR00102## ##STR00103##
in which R.sup.0 has the meaning given for R.sup.21 in formula AA1.

(200) Particularly preferred compounds of formula AA3 are selected from the group consisting of the following subformulae

(201) ##STR00104##
in which R.sup.0 has the meaning given for R.sup.21 in formula AA1, X.sup.0, L.sup.21 and L.sup.22 have the meaning given in formula AA3, and X.sup.0 is preferably F.

(202) Particularly preferred compounds of formula AA4 are selected from the group consisting of the following subformulae

(203) ##STR00105##
in which R.sup.0 has the meaning given for R.sup.21 in formula AA1.

(204) The compounds of formula BB are preferably selected from the group consisting of the following formulae:

(205) ##STR00106##
in which A.sup.31, A.sup.32, R.sup.31, X.sup.0, L.sup.31 and L.sup.32 have the meanings given in formula BB, and X.sup.0 is preferably F. Particularly preferred are compounds of formulae BB1 and BB2.

(206) Particularly preferred compounds of formula BB1 are selected from the group consisting of the following subformulae

(207) ##STR00107##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB1, X.sup.0, L.sup.31 and L.sup.32 have the meaning given in formula BB1, and X.sup.0 is preferably F.

(208) Very particularly preferred compounds of formula BB1a are selected from the group consisting of the following subformulae

(209) ##STR00108##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB1.

(210) Very particularly preferred compounds of formula BB1 b are selected from the group consisting of the following subformulae

(211) ##STR00109##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB1.

(212) Particularly preferred compounds of formula BB2 are selected from the group consisting of the following subformulae

(213) ##STR00110## ##STR00111##
in which R.sup.0 has one of the meanings given for R.sup.21 in formula BB2, X.sup.0, L.sup.31 and L.sup.32 have the meaning given in formula BB2, L.sup.33, L.sup.34, L.sup.35 and L.sup.36 are each, independently of one another, H or F, and X.sup.0 is preferably F.

(214) Very particularly preferred compounds of formula BB2 are selected from the group consisting of the following subformulae:

(215) ##STR00112##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(216) Very particularly preferred compounds of formula BB2b are selected from the group consisting of the following subformulae

(217) ##STR00113##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(218) Very particularly preferred compounds of formula BB2c are selected from the group consisting of the following subformulae

(219) ##STR00114##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(220) Very particularly preferred compounds of formula BB2d and BB2e are selected from the group consisting of the following subformulae

(221) ##STR00115##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(222) Very particularly preferred compounds of formula BB2f are selected from the group consisting of the following subformulae

(223) ##STR00116##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(224) Very particularly preferred compounds of formula BB2g are selected from the group consisting of the following subformulae

(225) ##STR00117##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(226) Very particularly preferred compounds of formula BB2h are selected from the group consisting of the following subformulae

(227) ##STR00118##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(228) Very particularly preferred compounds of formula BB2i are selected from the group consisting of the following subformulae

(229) ##STR00119##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(230) Very particularly preferred compounds of formula BB2k are selected from the group consisting of the following subformulae

(231) ##STR00120##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(232) Alternatively to, or in addition to, the compounds of formula BB1 and/or BB2 the LC media may also comprise one or more compounds of formula BB3 as defined above.

(233) Particularly preferred compounds of formula BB3 are selected from the group consisting of the following subformulae

(234) ##STR00121##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB3.

(235) Preferably the LC media according to this second preferred embodiment comprise, in addition to the compounds of formula AA and/or BB, one or more dielectrically neutral compounds having a dielectric anisotropy in the range from 1.5 to +3, preferably selected from the group of compounds of formula CC as defined above.

(236) Particularly preferred compounds of formula CC are selected from the group consisting of the following subformulae

(237) ##STR00122## ##STR00123##

(238) In which R.sup.41 and R.sup.42 have the meanings given in formula CC, and preferably denote each, independently of one another, alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy with 1 to 7 C atoms, or alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl with 2 to 7 C atoms, and L.sup.4 is H or F.

(239) Preferably the LC media according to this second preferred embodiment comprise, in addition or alternatively to the dielectrically neutral compounds of formula CC, one or more dielectrically neutral compounds having a dielectric anisotropy in the range from 1.5 to +3, selected from the group of compounds of formula DD.

(240) ##STR00124##

(241) In which A.sup.41, A.sup.42, Z.sup.41, Z.sup.42, R.sup.41, R.sup.42 and h have the meanings given in formula CC.

(242) Particularly preferred compounds of formula DD are selected from the group consisting of the following subformulae

(243) ##STR00125##
in which R.sup.41 and R.sup.42 have the meanings given in formula DD and R.sup.41 preferably denotes alkyl bedeutet, and in formula DD1 R.sup.42 preferably denotes alkenyl, particularly preferably vorzugsweise (CH.sub.2).sub.2CHCHCH.sub.3, and in formula DD2 R.sup.42 preferably denotes alkyl, (CH.sub.2).sub.2CHCH.sub.2 or (CH.sub.2).sub.2CHCHCH.sub.3.

(244) The compounds of formula AA and BB are preferably used in the LC medium according to the invention in a concentration from 2% to 60%, more preferably from 3% to 35%, and very particularly preferably from 4% to 30% in the mixture as a whole.

(245) The compounds of formula CC and DD are preferably used in the LC medium according to the invention in a concentration from 2% to 70%, more preferably from 5% to 65%, even more preferably from 10% to 60%, and very particularly preferably from 10%, preferably 15%, to 55% in the mixture as a whole.

(246) The combination of compounds of the preferred embodiments a)-y) mentioned above with the polymerised compounds described above causes low threshold voltages, low rotational viscosities and very good low-temperature stabilities in the LC media according to the invention at the same time as constantly high clearing points and high HR values, and allows the rapid establishment of a particularly low pretilt angle in PSA displays. In particular, the LC media exhibit significantly shortened response times, in particular also the grey-shade response times, in PSA displays compared with the media from the prior art.

(247) The liquid-crystal mixture preferably has a nematic phase range of at least 80 K, particularly preferably at least 100 K, and a rotational viscosity of not greater than 250 mPa.Math.s, preferably not greater than 200 mPa.Math.s, at 20 C.

(248) In the VA-type displays according to the invention, the molecules in the layer of the LC medium in the switched-off state are aligned perpendicular to the electrode surfaces (homeotropically) or have a a tilted homeotropic alignment. On application of an electrical voltage to the electrodes, a realignment of the LC molecules takes place with the longitudinal molecular axes parallel to the electrode surfaces.

(249) LC media according to the invention based on compounds with negative dielectric anisotropy according to the first preferred embodiment, in particular for use in displays of the PSA-VA type, have a negative dielectric anisotropy , preferably from 0.5 to 10, in particular from 2.5 to 7.5, at 20 C. and 1 kHz.

(250) The birefringence n in LC media according to the invention for use in displays of the PSA-VA type is preferably below 0.16, particularly preferably from 0.06 to 0.14, very particularly preferably from 0.07 to 0.12.

(251) In the OCB-type displays according to the invention, the molecules in the layer of the LC medium have a bend alignment. On application of an electrical voltage, a realignment of the LC molecules takes place with the longitudinal molecular axes perpendicular to the electrode surfaces.

(252) LC media according to the invention for use in displays of the PSA-OCB type are preferably those based on compounds with positive dielectric anisotropy according to the second preferred embodiment, and preferably have a positive dielectric anisotropy c from +4 to +17 at 20 C. and 1 kHz. The birefringence n in LC media according to the invention for use in displays of the PSA-OCB type is preferably from 0.14 to 0.22, particularly preferably from 0.16 to 0.22.

(253) LC media according to the invention, based on compounds with positive dielectric anisotropy according to the second preferred embodiment, for use in displays of the PSA-TN-, PSA-posi-VA-, PSA-IPS- oder PSA-FFS-type, preferably have a positive dielectric anisotropy from +2 to +30, particularly preferably from +3 to +20, at 20 C. and 1 kHz.

(254) The birefringence n in LC media according to the invention for use in displays of the PSA-TN-, PSA-posi-VA-, PSA-IPS- oder PSA-FFS-type is preferably from 0.07 to 0.15, particularly preferably from 0.08 to 0.13.

(255) The LC media according to the invention may also comprise further additives which are known to the person skilled in the art and are described in the literature, such as, for example, polymerisation initiators, inhibitors, stabilisers, surface-active substances or chiral dopants. These may be polymerisable or non-polymerisable. Polymerisable additives are accordingly ascribed to the polymerisable component or component A). Non-polymerisable additives are accordingly ascribed to the non-polymerisable component or component B).

(256) In a preferred embodiment the LC media contain one or more chiral dopants, preferably in a concentration from 0.01 to 1%, very preferably from 0.05 to 0.5%. The chiral dopants are preferably selected from the group consisting of compounds from Table B below, very preferably from the group consisting of R- or S-1011, R- or S-2011, R- or S-3011, R- or S4011, and R- or S-5011.

(257) In another preferred embodiment the LC media contain a racemate of one or more chiral dopants, which are preferably selected from the chiral dopants mentioned in the previous paragraph.

(258) Furthermore, it is possible to add to the LC media, for example, 0 to 15% by weight of pleochroic dyes, furthermore nanoparticles, conductive salts, preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutylammonium tetraphenylborate or complex salts of crown ethers (cf., for example, Haller et al., Mol. Cryst. Liq. Cryst. 24, 249-258 (1973)), for improving the conductivity, or substances for modifying the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases. Substances of this type are described, for example, in DE-A 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430 and 28 53 728.

(259) The individual components of the preferred embodiments a)-z) of the LC media according to the invention are either known or methods for the preparation thereof can readily be derived from the prior art by the person skilled in the relevant art, since they are based on standard methods described in the literature. Corresponding compounds of the formula CY are described, for example, in EP-A-0 364 538. Corresponding compounds of the formula ZK are described, for example, in DE-A-26 36 684 and DE-A-33 21 373.

(260) The LC media which can be used in accordance with the invention are prepared in a manner conventional per se, for example by mixing one or more of the above-mentioned compounds with one or more polymerisable compounds as defined above, and optionally with further liquid-crystalline compounds and/or additives. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after thorough mixing. The invention furthermore relates to the process for the preparation of the LC media according to the invention.

(261) It goes without saying to the person skilled in the art that the LC media according to the invention may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.

(262) The structure of the LC displays according to the invention corresponds to the usual geometry for PSA displays, as described in the prior art cited at the outset. Geometries without protrusions are preferred, in particular those in which, in addition, the electrode on the colour filter side is unstructured and only the electrode on the TFT side has slots. Particularly suitable and preferred electrode structures for PSA-VA displays are described, for example, in US 2006/0066793 A1.

(263) The following examples explain the present invention without restricting it. However, they show the person skilled in the art preferred mixture concepts with compounds preferably to be employed and the respective concentrations thereof and combinations thereof with one another. In addition, the examples illustrate which properties and property combinations are accessible.

(264) The following abbreviations are used:

(265) (n, m, z: in each case, independently of one another, 1, 2, 3, 4, 5 or 6)

(266) TABLE-US-00001 TABLE A 0 0 0 0 0 0 0

(267) In a preferred embodiment of the present invention, the LC media according to the invention comprise one or more compounds selected from the group consisting of compounds from Table A.

(268) TABLE-US-00002 TABLE B 00 01 02 03 04 05 06 07 08 09 0

(269) Table B shows possible chiral dopants which can be added to the LC media according to the invention.

(270) The LC media preferably comprise 0 to 10% by weight, in particular 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight, of dopants. The LC media preferably comprise one or more dopants selected from the group consisting of compounds from Table B.

(271) TABLE-US-00003 TABLE C 0 0 0

(272) Table C shows possible stabilisers which can be added to the LC media according to the invention.

(273) (n here denotes an integer from 1 to 12, preferably 1, 2, 3, 4, 5, 6, 7 or 8, terminal methyl groups are not shown).

(274) The LC media preferably comprise 0 to 10% by weight, in particular 1 ppm to 5% by weight, particularly preferably 1 ppm to 1% by weight, of stabilisers. The LC media preferably comprise one or more stabilisers selected from the group consisting of compounds from Table C.

(275) TABLE-US-00004 TABLE D RM-1 RM-2 0 RM-3 RM-4 RM-5 RM-6 RM-7 RM-8 RM-9 RM-10 RM-11 RM-12 0 RM-13 RM-14 RM-15 RM-16 RM-17 RM-18 RM-19 RM-20 RM-21 RM-22 0 RM-23 RM-24 RM-25 RM-26 RM-27 RM-28 RM-29 RM-30 RM-31 RM-32 0 RM-33 RM-34 RM-35 RM-36 RM-37 RM-38 RM-39 RM-40 RM-41 RM-42 0 RM-43 RM-44 RM-45 RM-46 RM-47 RM-48 RM-49 RM-50 RM-51 RM-52 00 RM-53 01 RM-54 02 RM-55 03 RM-56 04 RM-57 05 RM-58 06 RM-59 07 RM-60 08 RM-61 09 RM-62 0 RM-63 RM-64 RM-65 RM-66 RM-67 RM-68 RM-69 RM-70 RM-71 RM-72 0 RM-73 RM-74

(276) Table D shows illustrative compounds which can be used in the LC media in accordance with the present invention, preferably as reactive mesogenic compounds.

(277) In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds from Table D.

(278) In addition, the following abbreviations and symbols are used: V.sub.0 threshold voltage, capacitive [V] at 20 C., n.sub.e extraordinary refractive index at 20 C. and 589 nm, n.sub.o ordinary refractive index at 20 C. and 589 nm, n optical anisotropy at 20 C. and 589 nm, .sub. dielectric permittivity perpendicular to the director at 20 C. and 1 kHz, dielectric permittivity parallel to the director at 20 C. and 1 kHz, dielectric anisotropy at 20 C. and 1 kHz, cl.p., T(N,I) clearing point [ C.], .sub.1 rotational viscosity at 20 C. [mPa.Math.s], K.sub.1 elastic constant, splay deformation at 20 C. [pN], K.sub.2 elastic constant, twist deformation at 20 C. [pN], K.sub.3 elastic constant, bend deformation at 20 C. [pN].

(279) Unless explicitly noted otherwise, all concentrations in the present application are quoted in percent by weight and relate to the corresponding mixture as a whole, comprising all solid or liquid-crystalline components, without solvents.

(280) Unless explicitly noted otherwise, all temperature values indicated in the present application, such as, for example, for the melting point T(C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I), are quoted in degrees Celsius ( C.). M.p. denotes melting point, cl.p.=clearing point. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between these symbols represent the transition temperatures.

(281) All physical properties are and have been determined in accordance with Merck Liquid Crystals, Physical Properties of Liquid Crystals, Status November 1997, Merck KGaA, Germany, and apply for a temperature of 20 C., and n is determined at 589 nm and at 1 kHz, unless explicitly indicated otherwise in each case.

(282) The term threshold voltage for the present invention relates to the capacitive threshold (V.sub.0), also known as the Freedericks threshold, unless explicitly indicated otherwise. In the examples, the optical threshold may also, as generally usual, be quoted for 10% relative contrast (V.sub.10).

(283) Unless stated otherwise, the process of polymerizing the polymerisable compounds in the PSA displays as described above and below is carried out at a temperature where the LC medium exhibits a liquid crystal phase, preferably a nematic phase, and most preferably is carried out at room temperature.

(284) The display used for measurement of the capacitive threshold voltage consists of two plane-parallel glass outer plates at a separation of 20 m, each of which has on the inside an electrode layer and an unrubbed polyimide alignment layer on top, which effect a homeotropic edge alignment of the liquid-crystal molecules.

(285) The display or test cell used for measurement of the tilt angles consists of two plane-parallel glass outer plates at a separation of 4 m, each of which has on the inside an electrode layer and a polyimide alignment layer on top, where the two polyimide layers are rubbed antiparallel to one another and effect a homeotropic edge alignment of the liquid-crystal molecules.

(286) The polymerisable compounds are polymerised in the display or test cell by irradiation with UVA light of defined intensity for a prespecified time, with a voltage simultaneously being applied to the display (usually 10 V to 30 V alternating current, 1 kHz). In the examples, unless indicated otherwise, a metal halide lamp and an intensity of 100 mW/cm.sup.2 is used for polymerisation. The intensity is measured using a standard UVA meter (Hoenle UV-meter high end with UVA sensor).

(287) The tilt angle is determined by crystal rotation experiment (Autronic-Melchers TBA-105). A low value (i.e. a large deviation from the 90 angle) corresponds to a large tilt here.

(288) The VHR value is measured as follows: 0.3% of a polymerisable monomeric compound is added to the LC host mixture, and the resultant mixture is introduced into VA-VHR test cells (not rubbed, VA-polyimide alignment layer, LC-layer thickness d6 m). The HR value is determined after 5 min at 100 C. before and after UV exposure at 1 V, 60 Hz, 64 s pulse (measuring instrument: Autronic-Melchers VHRM-105).

Example 1

2-Methylacrylic acid-4-{8-[4-(2-methyl-acryloyloxy)-butyl]-3-[4-(2-methyl-acryloyloxy)-phenyl]-2-oxo-2H-chromen-6-yl}-butyl ester (1)

(289) ##STR00322##

1.1 6,8-Dibromo-3-(4-methoxy-phenyl)-chromen-2-one

(290) ##STR00323##

(291) 3,5-Dibromo-2-hydroxybenzaldehyd (30.0 g, 107 mmol) [CAS-Nr. 90-59-5] and 4-methoxyphenylacetic acid (35.7 g, 166 mmol) are heated in 51 ml acetic anhydride and 60 ml triethylamine overnight at reflux. The reaction mixture is cooled down to 80 C. and poured onto 1000 ml 2 M sodium hydroxide under stirring. After 5 min the precipitated product is filtered by vacuum, washed with water and digested two times with 100 ml ethanol. 6,8-Dibromo-3-(4-methoxy-phenyl)-chromen-2-one is obtained as a yellow solid.

(292) .sup.1H-NMR (300 MHz, CDCl.sub.3)

(293) =3.86 (s, 3H, OCH.sub.3), 6.98 (AB-m.sub.c, therein: J=8.9 Hz, 2H, Ph-H), 7.66 (AB-m.sub.c, therein: J=8.9 Hz, 2H, Ph-H), 7.60 (d, J=2.2, Hz, 1H, ArH), 7.62 (s, 1H, ArH), 7.84 (d, J=2.2 Hz, 1H, ArH).

1.2. 6,8-Bis-(4-hydroxy-but-1-ynyl)-3-(4-methoxy-phenyl)-chromen-2-one

(294) ##STR00324##

(295) 6,8-Dibromo-3-(4-methoxy-phenyl)-chromen-2-one (30.8 g, 75.1 mmol), copper(I)iodide (1.50 g, 7.88 mmol) and bis(acetonitril)palladium(II) chloride (5.00 g, 7.12 mmol) are dissolved in 300 ml DMF and 50 ml diisopropylamin at 70 C., and a solution of butyne-1-ol (20.0 g, 285 mmol) in 50 ml DMF is added dropwise within 30 min. The reaction mixture is stirred overnight at 80 C., then poured onto 300 ml water and acidified with 2 N hydrochloric acid. The precipitated product is filtered by vacuum, then filtered through silica gel with THF/toluene (4:1) and addition of a small amount of ethanol, and the crude product is recrystallized from toluene. 6,8-Bis-(4-hydroxy-but-1-ynyl)-3-(4-methoxy-phenyl)-chromen-2-one is obtained as light brown solid, which is pure enough to be used as starting material for the next step.

1.3 6,8-Bis-(4-hydroxy-butyl)-3-(4-methoxy-phenyl)-chromen-2-one

(296) ##STR00325##

(297) 6,8-Bis-(4-hydroxy-but-1-ynyl)-3-(4-methoxy-phenyl)-chromen-2-one is hydrogenated in THF on Pd/activated charcoal until the reaction is completed. The catalyst is filtered off, the solvent removed in vacuo and the crude product is filtered through silica gel with THF/toluene (3:2) and recrystallized from toluene. 6,8-Bis-(4-hydroxy-butyl)-3-(4-methoxy-phenyl)-chromen-2-one is obtained as a colourless solid.

(298) .sup.1H-NMR (300 MHz, CDCl.sub.3)

(299) =1.47 (s, br., 1H, OH), 1.55-1.86 ppm (m, 8H, CH.sub.2), 2.68 (t, J=7.4 Hz, 2H, ArCH.sub.2), 2.89 (t, J=7.3 Hz, 2H, ArCH.sub.2), 3.69 (m.sub.c, 4 H, CH.sub.2O) 3.85 (s, 3H, OCH.sub.3), 6.97 (AB-m.sub.c, therein: J=8.9 Hz, 2H, Ph-H), 7.17 (dd, J=2.0 Hz, J=9.9 Hz, 2H, ArH), 7.67 (AB-m.sub.c, therein: J=8.9 Hz, 2H, Ph-H), 7.70 (s, br., 1H, ArH).

1.4 6,8-Bis-(4-hydroxy-butyl)-3-(4-hydroxy-phenyl)-chromen-2-one

(300) ##STR00326##

(301) 6,8-Bis-(4-hydroxy-butyl)-3-(4-methoxy-phenyl)-chromen-2-one (14.3 g, 36.0 mmol) is dissolved in 270 ml dichloromethane and a solution of boron tribromide (12 ml, 126 mmol) in 30 ml dichloromethane is added under ice-cooling. The cooling is removed and the reaction mixture is stirred overnight at room temp. The solution is poured onto ice/water, acidified with 2 N hydrochloric acid, and extracted three times with ethyl acetate. The combined organic layers are washed with water and dried over sodium sulfate. The solvent is removed in vacuo and the residue is filtered through silica gel with toluene/THF (7:3). 6,8-Bis-(4-hydroxy-butyl)-3-(4-hydroxy-phenyl)-chromen-2-one is obtained as a viscous oil.

1.5 2-Methyl-acrylic acid-4-{8-[4-(2-methyl-acryloyloxy)-butyl]-3-[4-(2-methyl-acryloyloxy)-phenyl]-2-oxo-2H-chromen-6-yl}-butyl ester

(302) ##STR00327##

(303) 6,8-Bis-(4-hydroxy-butyl)-3-(4-hydroxy-phenyl)-chromen-2-one (10.1 g, 25.1 mmol) is suspended in 230 ml dichloromethane, methacrylic acid (8.5 g, 99.0 mmol) and DMAP (0.5 g) are added, and then a solution of 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimid (15.0 g, 96.6 mmol) in 20 ml dichloromethane is added under ice-cooling. After 1 h the cooling is removed and the reaction mixture is stirred overnight at room temp. The solvent is removed in vacuo and the residue is purified by column chromatography on silica with dichloromethane/ethyl acetate (95:5) as eluent. 2-Methyl-acrylic acid-4-{8-[4-(2-methyl-acryloyloxy)-butyl]-3-[4-(2-methyl-acryloyloxy)-phenyl]-2-oxo-2H-chromen-6-yl}-butyl ester is obtained as a colourless oil.

(304) .sup.1H-NMR (300 MHz, CDCl.sub.3)

(305) =1.70-1.85 ppm (m, 8H, CH.sub.2), 1.94 (m.sub.c, 6 H, 2 Me), 2.08 (m.sub.c, 3 H, Me), 2.70 (m.sub.c, 2 H, ArCH.sub.2), 2.92 (m.sub.c, 2 H, ArCH.sub.z), 4.20 (m.sub.e, CH.sub.2O), 5.55 (m.sub.c, 2 H, 2 CHHC(Me)COO), 5.78 (m.sub.c, 1 H, CHHC(Me)COO), 6.10 (m.sub.c, m.sub.c, 2 H, 2 CHHC(Me)COO), 6.37 (m.sub.c, 1 H, CHHC(Me)COO), 7.15-7.24 (m, 3H, ArH), 7.71-7.80 (m, 4H, ArH).

Example 2

2-Methyl-acrylic acid-3-{3-[4-(2-methyl-acryloyloxy)-phenyl]-6-[3-(2-methyl-acryloyloxy)-propyl]-2-oxo-2H-chromen-8-yl}-propyl ester (2)

(306) ##STR00328##

(307) In analogy to example 1,2-methyl-acrylic acid-3-{3-[4-(2-methyl-acryloyloxy)-phenyl]-6-[3-(2-methyl-acryloyloxy)-propyl]-2-oxo-2H-chromen-8-yl}-propyl ester (2) is obtained from 3-(4-Hydroxy-phenyl)-6,8-bis-(3-hydroxy-propyl)-chromen-2-one as colourless crystals with a melting point of 49 C.

Example 3

2-Methylacrylic acid-2-{6-[2-(2-methyl-acryloyloxy)-ethyl]-3-[4-(2-methyl-acryloyloxy)-phenyl]-2-oxo-2H-chromen-8-yl}-ethyl ester (3)

(308) ##STR00329##

(309) In analogy to example 1,2-methyl-acrylic acid-2-{6-[2-(2-methyl-acryloyloxy)-ethyl]-3-[4-(2-methyl-acryloyloxy)-phenyl]-2-oxo-2H-chromen-8-yl}-ethyl ester is obtained from 3-(4-hydroxy-phenyl)-6,8-bis-(2-hydroxyethyl)-chromen-2-one as colourless crystals.

Example 4

2-Methylacrylic acid-4-{6,7-bis-[3-(2-methyl-acryloyloxy)-butyl]-2-oxo-2H-chromen-3-yl}-phenyl ester (4)

(310) ##STR00330##

(311) In analogy to the synthesis sequence as described in example 1,2-methyl-acrylic acid 4-{6,7-bis-[3-(2-methyl-acryloyloxy)-butyl]-2-oxo-2H-chromen-3-yl}-phenyl ester is obtained from 5-bromo-4-chlor-2-hydroxybenzaldehyde [CAS-No. 876492-31-8] as a colourless oil.

Example 5

2-Methyl-acrylic acid-4-{5,7-bis-[3-(2-methyl-acryloyloxy)-butyl]-2-oxo-2H-chromen-3-yl}-phenyl ester (5)

(312) ##STR00331##

(313) In analogy to the synthesis sequence as described in Example 1,2-methyl-acrylic acid-4-{5,7-bis-[3-(2-methyl-acryloyloxy)-butyl]-2-oxo-2H-chromen-3-yl}-phenyl ester is obtained from 2,4-dibromo-6-hydroxybenzaldehyde [CAS-No. 73289-92-6] as a colourless oil.

Example 6

2-Methyl-acrylic acid-4-{7,8-bis-[3-(2-methyl-acryloyloxy)-butyl]-2-oxo-2H-chromen-3-yl}-phenyl ester (6)

(314) ##STR00332##

(315) In analogy to the synthesis sequence as described in Example 1,2-methyl-acrylic acid-4-{7,8-bis-[3-(2-methyl-acryloyloxy)-butyl]-2-oxo-2H-chromen-3-yl}-phenyl ester is obtained from 3,4-dibromo-2-hydroxybenzaldehyde [CAS-No. 51042-20-7] as a colourless oil.

(316) The following compounds are obtained in analogy to the synthesis described in Example 1:

(317) ##STR00333## ##STR00334## ##STR00335## ##STR00336##

Mixture Example A

(318) The nematic LC mixture N1 is formulated as follows.

(319) TABLE-US-00005 CY-3-O2 18.00% cl.p. +74.5 CPY-2-O2 10.00% n 0.1021 CPY-3-O2 10.00% 3.1 CCY-3-O2 9.00% .sub. 3.5 CCY-4-O2 4.00% K.sub.3/K.sub.1 1.16 CC-3-V 40.00% .sub. 86 PYP-2-3 9.00% V.sub.0 2.29

(320) For each measured sample, the polymerisable monomeric compound (1) or (2) from Example 1 or 2, respectively (hereinafter referred to as monomer M1 or M2, see below), is added to the LC mixture N1 at a concentration of 0.3% by weight. Each resultant polymerisable mixture is inserted into a VA e/o test cell (rubbed antiparallel, VA-polyimide alignment layer, LC-layer thickness d4 m). The cells are irradiated with UV light having an intensity of 100 mW/cm.sup.2 for the time indicated with application of a voltage of 24 V (alternating current), causing polymerisation of the monomeric compound. The tilt angle is determined before and after UV irradiation by a crystal rotation experiment (Autronic-Melchers TBA-105).

(321) ##STR00337##

(322) In order to determine the polymerisation rate, the residual content of unpolymerised RM (in % by weight) in the test cells is measured by HPLC after various exposure times. For this purpose each mixture is polymerised in the test cell under the stated conditions. The mixture is then rinsed out of the test cell using MEK (methyl ethyl ketone) and measured.

(323) In addition, the VHR values of the polymerisable LC mixtures comprising N1 and monomer M1 or M2, respectively, are before and after UV exposure are measured as described above.

(324) For comparative purposes, the experiments as described above are also carried out with monomer C1 of prior art.

(325) ##STR00338##

(326) The tilt-angle results for monomers M1, M2 and C1 in N1 are shown in Table 1. The residual concentrations of monomer M1, M2 and C1 in N1 after different exposure times are shown in Table 2. The VHR values of mixtures containing N1 together with M1, M2 or C1 are shown in Table 3.

(327) TABLE-US-00006 TABLE 1 (t = exposure time) C1 M1 M2 t/s Tilt angle/ 0 88.8 89.0 89.2 30 82.2 82.1 60 77.5 76.1 120 77.2 74.3 73.5 240 72.1 71.2 71.8 360 70.3 71.4 70.5

(328) TABLE-US-00007 TABLE 2 (t = exposure time) C1 M1 M2 t/s RM concentration/% 0 0.300 0.300 0.300 20 0.164 0.138 40 0.0375 0.027 60 0.035 0.015 90 0.061 0.008 120 0.1105 0.009 0.0055 180 0 360 0.067

(329) TABLE-US-00008 TABLE 3 (t = exposure time) C1 M1 M2 t/s VHR/% 0 98.50 98.20 97.93 30 96.99 96.34 60 96.57 95.96 90 96.03 120 94.20 95.60 95.56 180 95.14 300 94.14 93.87 600 81.16 91.79 91.85 900 73.87 89.37 87.80

(330) As can be seen from Table 1, a small tilt angle after polymerisation is achieved more quickly in PSA displays containing monomers M1 and M2 according to the invention, compared to PSA displays containing the monomer Cl from prior art.

(331) As can be seen from Table 2, significantly more rapid and complete polymerisation is achieved in PSA displays containing the monomers M1 and M2 according to the invention, compared to PSA displays containing the monomer Cl from prior art.

(332) As can be seen from Table 3, the VHR values of monomers M1 and M2 according to the invention in LC mixture N1 after UV exposure are significantly higher than the VHR values of monomer Cl in N1.