EP2297165A1

EP2297165A1 - Polymerizable chiral compounds containing 2,6-naphthyl- and isomannite units, and use thereof as chiral dopants

Info

Publication number: EP2297165A1
Application number: EP09765748A
Authority: EP
Inventors: Olivier Enger; Markus Hoffmann; Jochen Brill; Stephan Maurer; Bernd Ziegler
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-06-17
Filing date: 2009-06-04
Publication date: 2011-03-23
Also published as: TW201011035A; US20110092718A1; CN102066382A; WO2009153168A1; JP2011525482A; US8608977B2

Abstract

The present invention relates to compounds of the general formula (I) in which the variables have the following meaning: W is a grouping (Y^4-T^2-)_s(Y³-A^2-)_tY²-Z², Z¹, Z² are non-reactive radicals of reactive radicals for promoting polymerization independent of one another as defined more precisely in the description, A¹, A² are spacers independent of one another as defined more precisely in the description, Y¹ through Y⁵are linking units as defined more precisely in the description, Y⁶ is a single chemical bond or -CO-, T¹, T² are bivalent saturated or unsaturated, optionally substituted and optionally fused iso- or heterocyclic radicals independent of one another as defined more precisely in the description, Q indicates substituents as defined more precisely in the description, r, t are 0 or 1 independent of one another, s is 0, 1, 2 or 3 and q is 0, 1, 2, 3 or 4. The invention further relates to a fluid-crystalline composition that comprises at least one compound of the formula (I) and the use of the compounds of formula (I) as chiral dopants.

Description

Polymerizable chiral compounds containing 2,6-naphthyl and isomannitol units and their use as chiral dopants

description

The present invention relates to compounds of general formula I.

in which the variables have the following meaning:

W is a grouping (Y ⁴ -T ² -) _s (Y ³ -A ² -) _t Y ² -Z ² ,

Z ¹ , Z ² independently of one another are hydrogen, optionally substituted C 1 -C 20 -alkyl in which the carbon chain may be interrupted by oxygen atoms in ether function, sulfur atoms in thioether function or by nonadjacent imino or C 1 -C 4 -alkylimino groups, or reactive radicals, via which a polymerization can be brought about,

A ¹ , A ^{2 are,} independently of one another, spacers of 1 to 30 carbon atoms in which the carbon chain may be interrupted by oxygen atoms in ether function, sulfur atoms in thioether function or by nonadjacent imino or C 1 -C 4 -alkylimino groups,

Y ¹ , Y ² are each independently a single chemical bond, oxygen, sulfur, -CO-, -O-CO-, -CO-O-, -S-CO-, -CO-S-, -NR-CO- or - CO-NR-,

Y ³ for s> 0: irrespective of Y ¹ and Y ^{2 have} the abovementioned meaning or

-o-coo-, for s = 0: a single chemical bond or -CO-,

Y ^{4 is} a single chemical bond, oxygen, sulfur, -CO-, -O-CO-,

-CO-O-, -S-CO-, -CO-S-, -NR-CO- or -CO-NR-, with the proviso that Y ⁴ when bonded to the oxygen atom of the isomannitol unit is a single or chemical bond -CO- means Y ⁵ for r = 1: a single chemical bond, oxygen, sulfur, -CO-, -O-CO-, -CO-O-, -S-CO-, -CO-S-, -NR-CO- or - CO-NR-, for r = O: a single chemical bond or -CO-,

Y ^{6 is} a single chemical bond or CO-,

R is hydrogen or C 1 -C ₄ -alkyl,

T ¹ , T ² independently of one another divalent saturated or unsaturated, optionally substituted and optionally fused iso- or heterocyclic radicals,

Q is halogen, NO ₂ , NO, CN, CHO, L ¹ , CO-L ¹ , X ¹ -CO-L ¹ , X ¹ -SO-L ¹ ,

X ¹ -Sθ2-U, X ¹ -l_ ^{1 'CO-X} ¹ -L ^1', 0-C0-X ¹ -U ^', SO-X ¹ -L ^1', or SO ₂ -X ¹ -. ^{1 '} , where mean

L ¹ Ci-C ₂ O -alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ -alkyl kinyl, C ₆ -Cio-aryl, hetero- roaryl having 2 to 12 carbon atoms, C6-Cio-aryl-Ci -C _2θ alkyl,

C6-Cio-aryl-C ₂ -C _2O alkenyl, C6-Cio-aryl-C ₂ -C _2O alkynyl, heteroaryl-Ci-C ₂₀ alkyl, heteroaryl-Ci-C ₂₀ alkenyl, or heteroaryl- C 1 -C ₂₀ -alkynyl having in each case 2 to 12 carbon atoms in the heteroaryl radical, the C 1 -C ₂₀ -carbon chain being characterized by oxygen atoms in ether function, sulfur atoms in thioether function, nonadjacent imino, C 1 -C ₂₀ -alkylimino and / or or carbonyl groups and both the Cβ-Cio-aryl and the heteroaryl having one or more substituents selected from the group consisting of halogen, NO ₂ , NO, CN, CHO, L ² , CO-L ² , X ² -CO-L ² , X ² -SO-L ² , X ² -SO ₂ -L ² , X ² -

L ^{2 '} , CO-X ² -L ^2' , O-CO-X ² -L ^{2 '} , SO-X ² -L ^2' and SO ₂ -X ² -L ^{2 '} may be substituted,

L ^{1 'is} hydrogen or, independently of L ^1, the same meaning as L ¹ ,

L ² Ci-C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ -alkyl kinyl, C ₆ -Cio-aryl, heteroaryl having from 2 to 12 carbon atoms, C6-Cio-aryl-Ci-C _2θ alkyl, C6-Cio-aryl-C ₂ -C _2O alkenyl, C6-Cio-aryl-C ₂ -C _2O alkynyl, heteroaryl-Ci-C ₂₀ alkyl, heteroaryl-C ₂ -C ₂₀ - alkenyl or heteroaryl-C ₂ -

C ₂₀ -alkynyl having in each case 2 to 12 carbon atoms in the heteroaryl radical, L ^{2 'is} hydrogen or independently of L ² the same meaning as

L ²

and

X ¹ , X ² independently of one another oxygen, sulfur or NL ^{1 '} or NL ^2' ,

r, t are independently 0 or 1,

s 0, 1, 2 or 3,

wherein the respective variables T ² and Y ⁴ for the case s> 1 may be the same as or different from each other,

and

q is 0, 1, 2, 3 or 4.

Furthermore, the invention relates to a liquid-crystalline composition containing at least one compound of the invention, and the use of the inventive chiral compounds as dopants.

Numerous compounds do not go directly into the liquid, disordered state when heated from the crystalline state with defined local and remote order of the molecules, but go through a liquid-crystalline phase in which the molecules are mobile, but the molecular axes form an ordered structure. Elongated molecules often form nematic liquid-crystalline phases, which are characterized by an arrangement of long-range orientation by parallel arrangement of the longitudinal molecular axes. If such a nematic phase contains chiral compounds or chiral moieties, a chiral nematic or cholesteric phase can form, which is characterized by a helical superstructure.

Because of their remarkable optical properties, liquid crystalline materials, in particular nematic, chiral nematic or cholesteric materials, inter alia in optical or electro-optical applications of interest. Often, however, the temperature range in which the liquid crystalline phase occurs is outside the desired application temperature, or it extends only over a small temperature interval. Furthermore, chiral nematic phases are set Requires chiral compounds / dopants, which are as compatible as possible with the nematic host phase and cause an oversize large twist, ie have an oversized "Helical Twisting Power"("HTP").

If you want to fix the liquid crystalline order structures in the solid state, there are several possibilities. In addition to glassy solidification on cooling from the liquid-crystalline state, there is the possibility of incorporation into polymer networks or, in the case where the liquid-crystalline compounds and optionally dopants contain polymerizable groups, the polymerization of the liquid-crystalline compounds and optionally dopants themselves.

Furthermore, the highest possible birefringence of the liquid-crystalline materials is often desirable. From this aspect, liquid crystalline materials containing 2,6-naphthyl residues in particular appear to have high potential. However, suitable dopants must also be available for such liquid-crystalline materials in order, for example, to be able to set chiral nematic phases having a sufficient phase width in the desired case.

Polymerizable dopants which can contain or contain isomannitol radicals can be found, for example, in the publications WO 95/16007 A1, EP 0 750 029 A2 and DE 198 43 724 A1, but compounds according to the invention, as described in the beginning, are neither mentioned nor mentioned there suggested.

It is an object of the present invention to provide further chiral compounds with comparatively high HTP which are suitable for the preparation of liquid crystalline compositions and which furthermore form stable compositions in a wide mixing range of nematic host phase and chiral dopant and therefore do not tend to segregate or phase separate ,

Accordingly, the compounds of formula I described above were found.

For the variables Z ¹ and Z ² in formula I are in question as Ci-C2o-alkyl, whose d- C2o carbon chain may be interrupted by oxygen atoms in ether function, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- Butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, hept-3-yl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, Isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl (the above designations isooctyl, isononyl, isodecyl and isotridecyl are trivial terms and are derived from the alcohols obtained by the oxo synthesis - see Ullmanns Encyclopedia of the technical

Chemie, 4th Edition, Volume 7, pages 215 to 217, and Volume 11, pages 435 and 436), tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, Methoxymethyl, 2-ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxy-propyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2 or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 2- or 4-butoxy-butyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4, 8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 3,6,8-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl or 3,6,9,12-tetraoxatetradecyl; corresponding Ci-C2o-alkyl whose Ci-C2o carbon chain can be interrupted by sulfur atoms in thioether, non-adjacent imino, Ci-C2o-alkylimino and / or carbonyl groups, can formally from the previously exemplified oxygen-containing residues by replacing the Derive oxygen atoms with sulfur atoms, non-adjacent imino, Ci-C2o-alkylimino and / or carbonyl groups.

Suitable reactive radicals Z ¹ and Z ² , via which a polymerization can be brought about, are, for example

^ zN = C = S, ^ O-C = N, -C≡N, -COOH, -OH or -NH ₂ ,

wherein polymerization is to be understood as meaning all the construction reactions of polymers, that is to say addition polymerizations as chain reactions, addition polymerizations as step reactions and condensation polymerizations.

The variables R ^'of the reactive radicals shown above by way of example stand for hydrogen or C 1 -C ₄ -alkyl, ie methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl and can be identical or to be different.

Compounds with cyanate radicals can spontaneously trimerize to the corresponding cyanurates, those with cyano radicals, in particular with catalysis of acids, such as hydrochloric acid, or bases, to the corresponding triazines. Connections with Epoxide, thiirane, aziridine, isocyanate and isothiocyanate groups usually require further compounds with complementary reactive groups for the polymerization. Thus, for example, isocyanates can polymerize with alcohols to form urethanes and with amines to form urea derivatives. The same applies to thiiranes and aziridines. The complementary reactive groups may either be present in a second compound according to the invention which is mixed with the former, or they may be introduced into the polymerization mixture by auxiliary compounds containing two or more of these complementary groups. If these compounds contain in each case two of these reactive groups, linear polymers with a predominantly thermoplastic character are formed. If the compounds contain more than two reactive groups, crosslinked polymers are formed which are particularly stable mechanically. The maleimido group is particularly suitable for radical copolymerization with olefinic compounds such as styrene.

Preferred reactive radicals Z ¹ and Z ² in the compounds according to the invention are selected from the group consisting of

H ? ^Ha Cl

H ₂ C ^ ^C ^ - H ₂ C ^ ^C ^ 'HC ^ ^C ^' ^{HC≡C ~ CH} 2- ^{and (} Λ ^^ ^■

Particularly preferred reactive radicals Z ¹ and Z ² are

Preferred reactive groups Z ¹ -Y ¹ and Z ² -Y ² in the compounds according to the invention are selected from the group consisting of

COC,

Particularly preferred reactive groups Z ¹ -Y ¹ and Z ² -Y ² are in this case

H CH ₃

_HC ^ - ^{C ^} COC or ^ _coo _. In addition to hydrogen, the variable R appearing in the bridges Y ¹ to Y ^{5 is also} C ¹ -C ⁴ -alkyl, ie methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

Suitable spacers A ¹ and A ² are all groups known for this purpose. The spacers contain 1 to 30, preferably 3 to 12 carbon atoms and consist of predominantly linear aliphatic groups. They may be interrupted in the chain, for example, by non-adjacent oxygen or sulfur atoms or imino or C 1 -C ₄ -alkyl-imino groups, such as methylimino groups. Possible substituents for the spacer chain are fluorine, chlorine, bromine, cyano, methyl and ethyl.

Representative spacers A ¹ and A ² are, for example:

- (CH ₂ ) _P -, - (CH ₂ CH ₂ O) _m CH ₂ CH ₂ -, -CH ₂ CH ₂ SCH ₂ CH ₂ -, -CH ₂ CH ₂ NHCH ₂ CH ₂ -,

-CH ₂ -CH ₂ -N-CH ₂ -CH ₂ -, - (CH ₂ -CH-O-) _m CH ₂ -CH- or - (CH ₂ ) -CH-,

CH, CH ₃ CH. CH,

where m is 1 to 3 and p is 1 to 12.

The radicals T ¹ and T ² are divalent saturated or unsaturated iso- or heterocyclic radicals. These can not only consist of one, but also of several condensed rings. Thus, for example, divalent quinoline, decalin or naphthalene radicals may also be considered for T ¹ and T ² .

The radicals T ¹ and T ² in the compounds of the formula I are preferably divalent radicals selected from the group consisting of

where the radicals

irrespective of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I- with up to four (q being equal to 0, 1, 2, 3 or 4) identical or different substituents Q of the general definition given above, the rest

irrespective of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I- with up to three (q being 0, 1, 2 or 3) identical or different substituents Q of the general definition given above,

the rest

irrespective of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I- with up to two (q equals 0, 1 or 2) identical or different substituents Q of the general definition given above,

and

the rest

Irrespective of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I, it may be substituted by up to one (q equals 0 or 1) substituent Q of the general definition already given above.

In particular, the radicals T ¹ and T ² in the compounds of the formula I are divalent radicals selected from the group consisting of

where the radicals, independently of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I, have up to four (q equals 0, 1, 2, 3 or 4) identical or different substituents Q of the general definition already given above may be substituted.

Examples of the variables L ¹ and L ^{1 '} occurring in the definition of the variable Q in the meaning of a C 1 -C 20 -alkyl whose C 1 -C 20 carbon chain is represented by oxygen atoms in ether function, sulfur atoms in thioether function, nonadjacent imino, ci C2o-alkylimino and / or carbonyl groups may be interrupted, as well as for the variables L ² and L ^{2 '} in the meaning of a Ci-C2o-alkyl have already been listed by way of example in the variables Z ¹ and Z ² .

Examples of the variables L ¹ and L ^{1 '} occurring in the definition of the variable Q in the meaning of a C 2 -C 20 -alkenyl, whose C 2 -C 20 -carbon chain is represented by oxygen atoms in ether function, sulfur atoms in thioether function, non-adjacent imino, C 1 -C 20 -oxo Alkylimino and / or carbonyl groups may be interrupted, and for the variables L ² and L ^{2 '} in the meaning of a C2-C2o-alkenyl are in particular C 2 -C 20 -alk-1-enyl radicals. These residues can be derived from suitable residues previously exemplified by the variables Z ¹ and Z ² by formal replacement of two hydrogen atoms located on adjacent carbon atoms by another carbon-carbon bond.

Examples of the variables L ¹ and L ^{1 '} occurring in the definition of the variable Q in the meaning of a C 2 -C 20 -alkynyl, whose C 2 -C 20 -carbon chain is represented by oxygen atoms in ether function, sulfur atoms in thioether function, non-adjacent imino, C 1 -C 2 -oxyno Alkylimino and / or carbonyl groups may be interrupted, and for the variables L ² and L ^{2 '} in the meaning of a C2-C2o-alkynyl are in particular C 2 -C 20 -alk-1-ynyl radicals. These residues can be derived from suitable residues previously exemplified by the variables Z ¹ and Z ² by formal replacement of four hydrogen atoms located on adjacent carbon atoms by two more carbon-carbon bonds.

Examples of the variables L ¹ and L ^{1 '} occurring in the definition of the variable Q are the meaning of C6-Cio-aryl-C2-C2o-alkenyl, Cβ-Cio-aryl-C2-C2o-alkynyl, heteroaryl-C1-C2o-alkyl, heteroaryl-C2-C2o-alkenyl and heteroaryl-C2-C2o-alkynyl with in each case 2 to 12 carbon atoms in the heteroaryl radical, the C1-C20 carbon chain being characterized by oxygen atoms in ether function, sulfur atoms in thioether function, nonadjacent imino, C 1 -C 20 -alkylimino and / or carbonyl groups may be interrupted, and for the variables L ² and L ^{2 '} in the meaning of Cβ- Cio-aryl-Ci-C ₂ o-alkyl, C6-Cio-aryl-C ₂ -C ₂ o-alkenyl, C6-Cio -Aryl-C ₂ -C ₂ o-alkynyl, heteroaryl-Ci-C ₂ o-alkyl, heteroaryl-C ₂ -C ₂ o-alkenyl and heteroaryl-C ₂ -C ₂ o-alkynyl, each having 2 to 12 Carbon atoms in the heteroaryl radical are, in particular, those radicals which can be derived from the radicals exemplified above in the variables Z ¹ and Z ² by formal replacement of a terminal hydrogen atom by C 8 -do-Aryl or heteroaryl having 2 to 12 carbon atoms.

For the variables L ¹ and L ^{1 '} and L ² and L ^2' occurring in the definition of the variable Q, in particular phenyl and naphthyl are suitable as Cβ-C-io-Arv 1.

For the occurring in the definition of the variable Q variables L ¹ and L ^{1 '} and L ² and L ^2' are as heteroaryl having 2 to 12 carbon atoms such radicals in question, which, for example, of pyrrole, furan, thiophene, pyrazole, isoxazole, Isothiazole, imidazole, 1H-1, 2,3-triazole, 1H-1, 2,4-triazole, pyridine, pyrazine, pyridazine, 1H-azepine, 2H-azepine, oxazole, thiazole, 1, 2,3 -, 1, 2,4- or 1, 3,4-oxadiazole, 1, 2,3-, 1, 2,4- or 1, 3,4-thiadiazole and optionally the benzo or dibenzoanellierten rings, such as quinoline , Isoquinoline, indole, benzo [b] furan (coumarone), benzo [b] thiophene (thionaphthene), carbazole, dibenzofuran, dibenzo-thiophene, 1H-indazole, indoxazole, benzo [d] isothiazole, anthranil, benzimidazole, benzene oxazole, benzothiazole, cinnoline, phthalazine, quinazoline, quinoxaline or phenazine.

In the case of the variables L ¹ and L ^{1 '} occurring in the definition of the variable Q, the Cβ-Cio-aryl or heteroaryl having 2 to 12 carbon atoms with one or more substituents can be halogen, NO ₂ , NO, CN, CHO, L ² , CO-L ² , X ² -CO-L ² , X ² -SO-L ² , X ² -SO ₂ -L ² , X ² -L ^{2 '} , CO-X ² -L ^2' , O-CO -X ² -L ^{2 '} , SO-X ² -L ^2' and SO ₂ -X ² -L ^{2 '} .

In the definition of the variable Q occurring halogen means fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine.

The variables X ¹ and X ² occurring in the definition of the variable Q independently of one another denote oxygen, sulfur or NL ^{1 '} or NL ^2' .

Furthermore, preference is given to those compounds in which (Y ⁴ -T ² -) _s in the variable W of the formula I of a grouping of the formula Ia

(Y ⁴ -TH - Y ⁴ corresponds, in which mean:

Q ^' -independent of the specific choice of the substituents Q of the 2,6-

Naphthyl radical in formula I - identical or different substituents Q of the general definition already given above,

q ^'is 0, 1, 2, 3 or 4

and

s ^' values of 0, 1 or 2,

where the variables Y ⁴ and T ^{2 have the} same meaning as previously stated and for s ^' > 0 the variables Y ⁴ and for s ^' > 1 the variables T ² may be the same or different from each other.

In these preferred compounds, the variable W thus corresponds to the formula Ib shown below:

or the compounds according to the invention which are so preferred correspond to the formula Ic shown below:

where G ¹ and G ^{2 are} the moieties Z ¹ -Y ¹ -A ¹ -O-COO- or - (Y ³ -A ² -) _t Y ² -Z ² .

Particular preference is given to compounds of the formula I and the formula Ic shown above, taking into account the previous preferences, in which t assumes a value of 1 and Y ³ corresponds to a group -O-COO-.

Compounds of formula Ic taking into account the previous preference are:

in which G ¹ and G ² ^' groupings Z ¹ -Y ¹ -A ¹ -O-COO- or -OOC-OA ² - Y ² -Z ² , u and u ^' independently of one another represent values of O or 1, Ar independently of one another, optionally substituted with substituents Q substituted bivalent 1, 4-phenylene or divalent 2,6-naphthyl radical and Q and Q ^' and q and q ^{' plays} the role already mentioned

For example, here are the compounds

in which G ¹ and G ² Z ¹ -Y ¹ -A ¹ -O-COO- or -OOC-OA ² -Y ² -Z ² mean.

Further preferred compounds, taking into account the previous preferences, are characterized in that t assumes a value of 1 and the groups Z ¹ -Y ¹ -A ¹ - and -A ² -Y ² -Z ^{2 are} identical.

In particular, those compounds of the formulas I and Ic are preferred, taking into account the previous preferences, in which at least one of the radicals Z ¹ and Z ^{2 represents} a reactive radical. In this case, taking into account the previous preferences, preference is given to those compounds in which at least one of the reactive radicals Z ¹ and Z ²

especially

CH,

HI ³

^ C ^

H ₂ C "or H ₂ C" represents.

Furthermore, taking into account the previous preferences, preferred compounds in which Z ¹ -Y ¹ and Z ² - Y ^{2 are} identical reactive groups

COO, o or

^{^} O ^'o- ^{^} COO-

especially mean.

Taking into account the previous preferences, in particular the compounds

in which G ¹ and G ^{2 are} either both H ₂ C =CH-COO-A ¹ -O-COO- or -OOC-OA ² -OOC-CH =CH ₂ or H ₂ C =C (CH ₃ ) -COO-A ¹ -O-COO- or -OOC-OA ² -OOC-C (CH ₃ ) = CH ₂ .

Another object of the present invention is a liquid crystalline composition containing at least one compound of formula I and the preferences described above.

In this case, the liquid-crystalline composition according to the invention can essentially either be non-polymerisable or polymerizable.

A polymerizable or non-polymerizable liquid-crystalline composition according to the invention is quite generally not only to be understood as a composition whose one or more components already possess per se (in the temperature range of interest) liquid-crystalline properties, but rather is also to be understood as such a composition, the first by mixing the ingredients or only by admixing the compounds of the invention has liquid crystalline behavior (eg, lyotropic systems). Furthermore, the compounds of the formula I according to the invention and their preferred embodiments may themselves already have liquid-crystalline behavior, but they need not necessarily possess this property.

A non-polymerizable composition according to the invention is in particular a composition which under normal polymerization conditions is not capable of forming self-supporting polymerization or condensation products. This composition can be prepared, for example, by mixing suitable, commercially available liquid-crystalline materials, as used, for example, for active LC layers in display technology, with one or more of the compounds of the formula I according to the invention or their preferred embodiments. If it is the latter are compounds containing one or two reactive radicals Z ¹ and Z ^2, so these are present in the inventive compositions in such a concentration that these TION or to generate corresponding tightly crosslinked self-supporting polymerization condensation products insufficiently is.

A polymerizable composition according to the invention is in particular a composition in which at least one of the components is capable of forming polymerization or condensation products under customary polymerization conditions and which is polymerizable as such and can be polymerized or condensed to form self-supporting products.

Depending on the number of reactive radicals in the components of the polymerizable liquid-crystalline composition, the desired degree of polymerization, crosslinking and / or condensation after polymerization or

Set condensation. This composition can be readily prepared by mixing suitable materials with one or more of the compounds of the present invention, which materials themselves may be polymerizable or nonpolymerizable, liquid crystalline, or even liquid crystalline.

Suitable polymerisable, liquid-crystalline materials are compounds which are described, for example, in WO publications 95/22586 A1, 95/24454 A1, 95/24455 A1, 96/04351 A1, 96/24647 A1, 97/00600 A2, 97/34862 A1, 98/47979 A1 and 2006/120220 A1, as well as the documents EP 1 134 270 A1 and DE 198 35 730 A1 and essentially correspond to the schematic structure PYAYMYAYP, wherein the variables P, Y and A have similar meanings as the variables Z ¹ and Z ² , Y ¹ , Y ² , Y ³ and A ¹ and A ² in formula I, M denotes a mesogenic unit and the linking group Y linked to the mesogenic moiety M is represented by the group -O-COO- in Formula I of the present application is substantiated.

The reactive compounds which are listed in DE 100 25 782 A1 as constituent B) of the liquid-crystalline compositions described therein can be added to the liquid-crystalline composition according to the invention as further monomers. These usually cost-effective compounds themselves usually show no liquid-crystalline behavior, but their admixture opens up the

Possibility to reduce the proportion of costly components in the composition according to the invention without noticeable their liquid-crystalline behavior influence. In addition, properties of the composition, such as degree of crosslinking, viscosity, elasticity, etc., can be adjusted with the aid of such reactive monomers. The choice of suitable reactive monomers is readily accomplished by those skilled in the art, optionally after preliminary testing. It should be noted here that such reactive compounds can also act as (auxiliary) compounds in the sense discussed above.

By mixing nematic and inventive compounds, a chiral nematic or cholesteric composition according to the invention is obtained, which possesses special optical properties, such as, for example, angle-dependent color effects, reflection in the IR or UV wavelength range of the spectral range, etc.

The liquid-crystalline composition according to the invention may contain further additives. As such, suitable photoinitiators, diluents, thickeners, defoamers and deaerators, lubricants and flow control agents, thermosetting or radiation-curing aids, substrate wetting aids, wetting and dispersing aids, water repellents, adhesion promoters and auxiliaries for improving the scratch resistance, dyes and pigments and additives selected from the group of light, heat and / or oxidation stabilizers. The chemical-physical nature of these additives is discussed in detail in document WO 00/47694 A1.

By oligomerization or polymerization of a polymerizable liquid-crystalline composition according to the invention, it is possible to prepare oligomers or polymers, which in particular in the form of a film, i. a self-supporting layer of uniform thickness can be obtained. This film can be located on a substrate which is such that by suitable measures an easy detachment and transfer to another substrate for permanent whereabouts is possible. Such a film is useful, for example, in the field of film coating and laminating.

Furthermore, such films - adapted in their properties to the appropriate purpose - in various areas. For example, they can be used in optical information display devices. Such devices include video or overhead projectors, electrophoretic displays, traffic displays, LCDs for use in computer monitors, televisions, screens in printers or kitchen appliances, and billboards, lights, and billboards, as well as mobile screens such as mobile phones. Screens in cell phones, laptops, digital cameras, vehicles, and destination displays on buses and trains. You can in these devices in a variety of

Function may be included, for example as a color filter or films for the production of wavelength-selective or broadband polarized light. Furthermore, substrates can be printed or coated by means of the polymerizable liquid-crystalline composition according to the invention by applying this composition to the substrate and then polymerizing.

With regard to the procedure for printing or coating substrates with liquid-crystalline materials, reference should be made to the document WO 96/02597 A2. Moreover, a polymerized layer produced by means of such a method and partially or completely covering the original substrate surface is also to be understood as a substrate, so that the

Production of multi-printed and / or coated substrates is possible.

It should be noted further here that under "printing" usually the incomplete covering of the substrate surface, by "coating" the complete covering of the substrate surface is understood.

In addition to paper and cardboard products, for example, for carrier bags, magazines, brochures, gift packaging and packaging materials for consumer, luxury and deluxe goods, as well as films, such as decorative and non-decorative packaging purposes, as well as textiles of any kind and leather in question come as substrates , Furthermore come as substrates and those for the production of banknotes, securities, tickets u.a. used materials.

However, other substrates are also consumer electronics, such as music cassettes (MCs), SVHS and VHS cassettes, mini-discs (MDs), compact discs (CDs), digital versatile discs (DVDs) and the corresponding playback and / or or recorders, televisions, radios, telephones / cell phones, computer equipment, etc., and leisure, sports, household and play goods, such as bicycles, children's vehicles, skis, snowboards and surfboards, inline skaters and Roll and ice skates and household appliances. In addition, such substrates include, for example, writing utensils and spectacle frames.

However, other substrates are also very different films which are used in optical or electro-optical components or in their manufacture. Such films consist for example of polyvinyl alcohol (PVA), triacetyl cellulose (TAC), polyimide (PI), polyvinyl cinnamate (PVC) or polyolefins, such as polynorbornene, and may, for example, (broadband) polarizers, light-guiding elements for backlighting in LCDs (so-called " light guides "), films for the distribution of light (so-called" BEFs ", ie brightness enhancement films) and films for the production of polarized light in LCDs (so-called" DBEFs ", ie" dual-brightness enhancement films "). Other substrates in this context, however, can also be certain assemblies of the LCDs, such as glass or polymer discs, which optionally still have a transparent conductive coating, for example, indium tin oxide (ITO) possess.

Light guides or BEFs can be produced, for example, by coating a suitable substrate using a polymerizable, chiral nematic composition according to the invention and its subsequent polymerization. In this case, the coating process can be repeated more or less frequently with compositions of the same or different composition according to the invention in order to produce corresponding optical components, such as retardation films, (broadband) polarizers and optical filters. This makes it possible to produce a correspondingly more compact design of the optical components in LCDs.

Another object of the present invention is the use of the liquid-crystalline composition of the invention or the oligomer or polymer of the invention for the production of optical components. As such, e.g. LCDs and their components, such as (broadband) polarizers, optical filters, delay films (so-called "retardation films") and BEFs call.

With regard to the preparation of such components based on polymerizable liquid-crystalline materials, reference should be made, for example, to the document WO 00/37585 A1.

With regard to the use of a polymerizable chiral nematic composition according to the invention for the production of (broadband) polarizers, reference may be made analogously to, for example, US Pat. Nos. 6,421,107, 6,417,902, 6,061,108, 6,099,758, 6,016,177, 5,948,831 and 5,793,456 , US 5,691,789 and US 5,506,704.

However, the liquid-crystalline composition according to the invention can also be used as a disperse liquid-crystalline phase in so-called "polymer-dispersed liquid crystals" ("PDLCs"). Such PDLCs may in principle have either an isotropic polymer matrix and both a macroscopic-isotropic and anisotropic disperse liquid-crystalline phase or an anisotropic polymer matrix and both a macroscopic isotropic and anisotropic disperse liquid crystalline phase, the macroscopic isotropic phase being from the statistical distribution of microscopic anisotropic domains results.

In general, the preparation of such PDLCs is based on a (generally optically anisotropic) polymer film in which the liquid-crystalline phase is in the form of very fine inclusions, usually in the micrometer or submicron size range, uniformly dispersed. By stretching the polymer film, an anisotropic optical behavior is imposed on both the polymer matrix and the dispersed phase. If polymerizable liquid-crystalline compositions according to the invention are used, the anisotropic state of the dispersed phase can be freezed by polymerization, thus achieving, for example, significantly better temperature (change) resistance. The polymer matrix used here is usually polyvinyl alcohol.

Furthermore, a polymerizable chiral nematic composition according to the invention can also be used, for example, for the production of optical components, as described in US Pat. No. 5,235,443 and US Pat. No. 5,050,966.

Other possible substrates are also found in the construction sector surfaces such as building walls or windows. In the latter case, in addition to a decorative and a functional effect may be desired. It is thus possible to produce multiple layers on the window material whose individual layers have different chemical-physical properties. If, for example, using a chiral compound according to the invention and a corresponding compound with opposite optical rotation individual layers of polymerized liquid crystalline compositions with opposite twist, or with the addition of different concentrations of inventive chiral compound individual layers of the polymerized liquid crystalline composition same direction of rotation but each different pitch and thus applied different reflection properties, so specific specific wavelengths or wavelength ranges of the light spectrum can be reflected. As a result, for example, an IR or UV-reflective window coating is possible.

Thus, the polymerizable, liquid-crystalline composition according to the invention or the oligomers or polymers optionally obtainable therefrom can be used for the production of heat-insulating coatings comprising one or more cholesteric layers which are above 750 nm in the infrared wavelength range, in particular in the wavelength range from 751 nm to about 2000 nm at least 40%, in particular at least 45% of the incident radiation reflect.

With regard to this aspect of the polymerizable, liquid-crystalline composition according to the invention, especially with regard to thermal insulation coatings, reference should also be made to document WO 99/19267 A1. The liquid-crystalline composition according to the invention can furthermore also be used as a liquid-crystalline colorant or for the preparation of liquid-crystalline colorants. Use as a colorant is possible if the composition already possesses color by itself. This color may be based on interference effects of the present chiral nematic phase and / or on the absorption effects of dyes and / or pigments. Furthermore, the composition, irrespective of whether it has or does not have color, can also be used to prepare colorants. With regard to the production of liquid-crystalline colorants and their use for printing or coating substrates, reference is made by analogy to the document WO 96/02597 A2.

The composition according to the invention can furthermore be used in the preparation of dispersions and emulsions which are preferably based on water. For the preparation of such dispersions and emulsions using liquid-crystalline materials, reference may be made to WO-documents 96/02597 A2 and US Pat

98/47979 A1. These dispersions and emulsions can also be used for printing and coating substrates, as already exemplified above.

Furthermore, the composition according to the invention can also find use in the production of pigments. The preparation of such pigments is known and described for example in detail in document WO 99/1 1733 A1. In addition, however, pigments which are pre-adjusted in shape and size can also be produced using printing techniques or with the aid of nets in the interstices of which the polymerizable composition is located. The following

Polymerization or condensation of the liquid crystal composition is followed by the removal or dissolution from the substrate or from the network. These procedures are described in detail in WO publications 96/02597 A1, 97/27251 A1, 97/27252 A1 and EP 0 931 1 10 A1.

These pigments may be single-layered or multi-layered. The latter pigments can usually only be produced if coating processes are used in which successive layers are produced one above the other and finally subjected to mechanical comminution.

For the above-described use of the liquid-crystalline composition according to the invention as a liquid-crystalline colorant or for the preparation of liquid-crystalline colorants, in the preparation of dispersions and emulsions and in the preparation of pigments, use is preferably made of a polymerizable composition. Examples:

1) Synthesis building blocks:

1.1) The preparation of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid

followed according to WO 2006/120220 A1 (page 30, "A").

1.2) Preparation of compound (1)

175.4 g (1, 2 mol) of isomannitol and 138.1 g (1, 0 mol) of 4-hydroxybenzoic acid were submitted together with 8.2 g (0.04 mol) of p-toluenesulfonic monohydrate in 500 ml_ XyIoI and to 140 ⁰ C heated. From this mixture, the resulting water of reaction was removed. Subsequently, the XyIoI was removed from the reaction mixture by slow addition of 1 L of water / methanol 1: 1. In this case, about 320 ml of water / methanol mixture were also removed. After complete elimination, another 1000 ml of water were added and stirred at room temperature overnight. From the reaction solution, a brown precipitate precipitated, which contained the compound (2) shown below as a by-product and was sucked off. The desired product was in the filtrate, which was concentrated and allowed to stand overnight. It precipitated a yellowish precipitate, which was filtered off, dissolved in hot water, filtered through silica gel and dried overnight at 60 ⁰ C in vacuo. 68.3 g of the above compound (1) were obtained.

1.3) Preparation of compound (2)

131, 5 g (0.9 mol) isomannitol and 273.5 g (1, 98 mol) 4-hydroxybenzoic acid were charged into 400 g toluene and heated to 85 ⁰ C. At this temperature, 3.9 g (0.039 mol) of sulfuric acid 98% was added. It was then heated to reflux and the resulting water of reaction was removed. After circling, 10.2 g of sodium carbonate, dissolved in 162 ml_ water, added and stirred for 10 min. The solvent was then exchanged for the water by slowly adding 400 ml of hot water. After the complete replacement, 400 ml of n-propanol was starting at 90 ⁰ C, was added. Thereafter, the batch cooled to room temperature. From the reaction solution precipitated out sandy precipitate. This was filtered off, washed with 300 ml_ water and dried. 201.5 g (58%) of the above compound (2) were obtained.

1.4) Preparation of the compound (3)

Compound (3) was prepared analogously to compound (1). However, instead of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid was used.

1.5) Preparation of the compound (4)

7.3 g (50 mmol) of isomannitol and 18.5 g (1 10 mmol) of 4-hydroxy-3-methoxybenzoic acid were initially charged in 90 g of toluene and heated to 100 ^° C. At this temperature, 0.12 ml_ sulfuric acid conc. added. It was then heated to reflux and the resulting water of reaction was removed. After the azeotropic distillation 45 ml of methanol were metered in at 125 ⁰ C and stirred for 10 min. Thereafter, 0.57 g of sodium carbonate, dissolved in 9.1 ml of water, dissolved and stirred for 30 min. Thereafter, 33 ml of methanol and 50 ml of water were added again and stirred again for 30 min. The reaction solution was heated again to 65 ⁰ C and filtered through silica gel. The filtrate was mixed with 4 g of activated charcoal, refluxed for one hour and filtered while hot. The filtrate was concentrated, precipitated with 200 ml of water and stirred overnight. The product was filtered off with suction and, after drying overnight in vacuo, 5.7 g (26%) of the desired compound were obtained.

1.6) Preparation of compound (5)

44.7 g (0.3 mol) and 130.8 isomannitol g (0.66 mol) of 4-hydroxy-3,5-dimethoxybenzoe- acid (syringic acid) were introduced into 536.7 g xylene and heated to 100 ⁰ C. , At this temperature, 0.73 ml of sulfuric acid were concentrated. added. It was then heated to reflux and the resulting water of reaction was removed. After azeotropically 5 ml_ of methanol at 125 ⁰ C 271, metered and stirred for 10 min. Thereafter, 3.4 g of sodium carbonate, in 54.3 ml_ water, were metered in dissolved and stirred for 30 min. Subsequently, 149.3 g of methanol and 299 ml_ of water were added and again stirred for 30 min. Then the batch stood overnight at room temperature. It turned off product. This was sucked off. The

Nutschgut was dissolved at 65 ⁰ C in 1000 ml of methanol and filtered through silica gel. The filtrate was treated with 4 g of activated carbon, refluxed for two hours and filtered while hot. Precipitation precipitated from the filtrate. This was filtered off with suction and after drying under reduced pressure gave 54.5 g (36%) of the desired compound.

1.7) Preparation of the compound (6)

(6)

7.4 g (20 mmol) of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid were stirred for one hour in 30 ml of oxalyl chloride with addition of 7 mg of kerobit BHT and 4 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 40 ml_ ethylene glycol dimethyl ether and at 0-5 ⁰ C to a Solution consisting of 37.6 g (200 mmol) of 6-hydroxy-2-naphthoic acid, 8.6 g (66 mmol) of N, N-dimethylcyclohexylamine and 250 ml of N, N-dimethylacetamide added dropwise. It was stirred for one hour at 0-5 ⁰ C and over the weekend at room temperature. The batch was then precipitated to 1 L of water. The resulting precipitate was stirred in 250 ml of methanol, filtered off with suction and dried. This gave 6.7 g (62%) of the desired compound.

2) Compounds of the invention

HTP values were determined by the method of Cano on the basis of mixtures of the compounds according to the invention with the nematic compound of the formula shown below:

(For preparation, see WO 97/00600 A2, pages 29/30, Example 6).

2.1) Preparation of the compound

12.2 g (33 mmol) of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid were stirred for one hour in 75 ml of oxalyl chloride with the addition of 10 mg of Kerobit BHT and 5 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 65 ml of ethylene glycol dimethyl ether and at 0-5 ⁰ C to a solution consisting of 2.2 g (15 mmol) isomannitol, 9.0 g (71 mmol) of N, N-dimethylcyclohexylamine and 50 mL N Added dropwise N-dimethylacetamide and then stirred at 0-5 ⁰ C for 30 min. Then, the reaction mixture was stirred at 40 ^° C. for 3 hours. Overnight the batch cooled to room temperature. The next morning was concentrated to 400 g of ice / water and 15 mL hydrochloric acid. like, stirred for 3 hours and then sucked off. The resulting filter cake was stirred in 400 ml of methanol, stirred for 4 hours and then purified by column chromatography (SiÜ2, petroleum ether / ethyl acetate 1: 1). This gave 0.9 g (<10%) of the desired compound.

2.2) Preparation of the compound

21, 0 g (57 mmol) of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid and 21 mg of 4-methoxyphenol were placed in 31, 5 mg of ethylene glycol dimethyl ether and dissolved at 45 ⁰ C. Then 0.14 g of DMF was added and at a maximum temperature of 50 ⁰ C, 7.6 g (59 mmol) of oxalyl chloride were added dropwise. After a stirring time of 2 hours at 45-50 ⁰ C, the acid chloride prepared at 0-2 ⁰ C to a solution consisting of 9.7 g (25 mmol) of the compound (2), 2 mg of 4-hydroxy-2,2 , 6,6-Tetra- methylpiperidin-1-oxyl (hydroxy-TEMPO) and 15.2 g (119 mmol) of N, N-dimethylcyclohexylamine in 31, 5 g of N, N-dimethylacetamide was added dropwise. It was stirred for one hour at 0 ⁰ C, then heated to 40 ⁰ C and stirred at this temperature for three hours. After cooling to room temperature, 1 1, 8 ml_ (74 mmol) hydrochloric acid 20% and 150 ml_ methanol were added and stirred for 4 hours. The precipitated product was filtered off with suction, washed with 100 ml of water and dried. This gave 24.5 g (92%) of the desired product. HTP = 34 μm ^-1

2.3) Preparation of a mixture of the compounds

A mixture of 13.8 g (37 mmol) of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid and 1.18 g (37 mmol) of 4- (4-acryloyloxybutyloxycarbonyloxy) benzoic acid (prepared according to WO 97 / 00600 A2) were stirred for one hour in 160 ml of oxalyl chloride with addition of 24 mg of kerobit BHT and 1 l of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 100 mL of methylene chloride and treated at 0-5 ⁰ C to a solution consisting of 4.7 g (32 mmol) isomannitol, 19 g (150 mmol) N, N-dimethylcyclohexylamine and 100 ml of methylene chloride dropwise. The mixture was stirred for 30 min at 0-5 ⁰ C and overnight at room temperature. Then, the reaction mixture was stirred at 40 ^° C. for 5 hours. After cooling to room temperature, the solution was washed first with acidic water (pH 3) and then with water. The organic phase was dried over sodium sulfate and partially concentrated. The remaining concentrated solution was precipitated with 100 ml of methanol and stirred overnight. The product obtained was filtered off with suction, then stirred again in 150 ml of methanol / water 1: 1 and then filtered. The

Nutschgut was dissolved in 100 mL of methylene chloride, treated with 10 g of silica gel and filtered after a short stirring. The filtrate was concentrated by half, precipitated with 150 ml of n-hexane and stirred overnight. The product was filtered off with suction and dried overnight at 40 ^° C. in vacuo. 3.4 g (14%) of the desired compounds were obtained.

2.4) Preparation of the compound

17.0 g (46 mmol) of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid were stirred for one hour in 65 ml of oxalyl chloride with addition of 15 mg of hydroxy TEMPO and 9 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 90 mL of methylene chloride and added at 0-5 ⁰ C to a solution consisting of 5.3 g (20 mmol) of the compound (1), 11, 7 g (90 mmol)

N, N-dimethylcyclohexylamine and 90 mL of methylene chloride are added dropwise. The mixture was stirred for 30 min at 0-5 ⁰ C and overnight at room temperature. Then, the reaction mixture was stirred at 40 ^° C. for 6.5 hours. After cooling to room temperature, the solution was washed first with 200 mL of acidic water (pH 3) and then with 200 mL of water. The organic phase was dried over sodium sulfate and filtered. The filtrate crystallized by addition of 300 mL of methanol. It was stirred overnight and vacuumed the next morning. For cleaning was the filter cake was dissolved in methylene chloride, filtered through silica gel and then concentrated. The remaining residue was mixed with a little n-hexane, precipitated with methanol and stirred overnight. The product obtained was filtered off with suction and dried overnight at 40 ^° C. under reduced pressure. 0.7 g (4%) of the desired compound were obtained. HTP = 35 μm ^-1

2.5) Preparation of the compound

The synthesis was carried out in two stages:

Step 1 :

4.8 g (15 mmol) of 4 (4-acryloyloxybutyloxycarbonyloxy) benzoic acid were stirred for one hour in 35 ml of oxalyl chloride with the addition of 5 mg of hydroxy TEMPO and 3 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 45 ml of methylene chloride and treated at 0-5 ⁰ C to a solution consisting of 4.4 g (17 mmol) of the compound (1), 6.4 g (50 mmol) N, N-dimethylcyclohexylamine and 45 ml_ Dropped methylene chloride and then stirred at 0-5 ⁰ C for 1.5 hours. The reaction was washed first with 125 ml of slightly acidic water (pH 5) and then with 125 ml of water. The organic phase was dried over sodium sulfate and filtered through silica gel. The filtrate was transferred to a flask and cooled again to 0-5 ⁰ C.

Level 2:

7.4 g (20 mmol) of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid were stirred for one hour in 30 ml of oxalyl chloride with the addition of 7 mg of hydroxy TEMPO and 4 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 40 ml of methylene chloride and treated at 0-5 ⁰ C for already manufactured filtrate prepared from Step 1, added with 9.0 g (70 mmol) N, N-dimethylcyclohexylamine, dropwise. It was stirred for one hour at 0-5 ⁰ C and stirred overnight at room temperature. The reaction was washed first with 125 ml of slightly acidic water (pH 5) and then with 125 ml of water. The organic phase was dried over sodium sulfate and filtered through silica gel. The filtrate was precipitated with 100 ml of methanol. The product obtained was filtered off with suction and dried. 1.4 g (10%) of the desired compound were obtained. HTP = 32 μm ^-1 2.6) Preparation of a mixture of the compounds

17.0 g (46 mmol) of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid were stirred for one hour in 90 ml of oxalyl chloride with the addition of 20 mg of Kerobit BHT and 9 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 90 ml of methylene chloride and treated at 0-5 ⁰ C to a solution consisting of 3.9 g (10 mmol) of the compound (2), 2.7 g (10 mmol) of the compound (1), 11, 5 g (90 mmol) of N, N-dimethylcyclohexylamine and 90 ml of methylene chloride are added dropwise and then stirred for 30 min at 0-5 ⁰ C and overnight at room temperature. Then the reaction mixture was stirred for 5 hours at 40 ⁰ C., then filtered through silica gel and precipitated with 450 ml of methanol. The batch stirred over the weekend at room temperature. The product obtained was filtered off with suction. Purification was carried out by dissolving in 100 ml of methylene chloride and reprecipitating with 200 ml of methanol. After two hours, the product was filtered off, then stirred again in water and sucked off again. After drying at 40 ^° C. in vacuo, overnight, 9.1 g of the desired mixture were obtained. HTP = 30 μm ^-1

2.7) Preparation of the compound

The synthesis was carried out in two stages:

Step 1 :

2.9 g (9 mmol) of 4- (4-acryloyloxybutyloxycarbonyloxy) benzoic acid were stirred for one hour in 20 ml of oxalyl chloride with addition of 3 mg of kerobit BHT and 2 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 26 ml of methylene chloride and at 0-5 ⁰ C to a solution consisting of 3.2 g (10 mmol) of the compound (3), added dropwise 3.7 g (29 mmol) of N, N-dimethylcyclohexylamine and 26 ml of methylene chloride and then stirred at 0-5 ⁰ C for 2 hours.

Level 2:

5.8 g (18 mmol) of 4 (4-acryloyloxybutyloxycarbonyloxy) benzoic acid were stirred for one hour in 40 ml of oxalyl chloride with addition of 6 mg of kerobit BHT and 4 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 52 ml of methylene chloride and treated at 0-5 ⁰ C to the already prepared solution from Step 1, added with 7.7 g (60 mmol) N, N-dimethylcyclohexylamine, dropwise. It was stirred for one hour at 0-5 ⁰ C and overnight at room temperature. It was then heated to 40 ⁰ C and stirred at this temperature for 5 hours. Subsequently, it was washed first with 250 ml of slightly acidic water (pH 5) and then with 250 ml of water. The organic phase was dried over sodium sulfate and filtered through silica gel. The filtrate was partially concentrated and then precipitated with 150 mL of methanol. The product was stirred at room temperature for one hour, then was filtered off with suction and dried. This gave 1.8 g (9%) of the desired compound. HTP = 31 μm ^-1

2.8) Preparation of the compound

1 1, 1 g (31 mmol) of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid were stirred with the addition of 150 mg of hydroxy-TEMPO and 5 drops of DMF in 45 mL of oxalyl chloride for one hour. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 45 ml of methylene chloride and at 0-5 ⁰ C to a solution consisting of 6.5 g (15 mmol) of the compound (4), 4.9 g (39 mmol) of N, N-dimethylcyclohexylamine and 45 mL Methylene chloride added dropwise. It was stirred for two hours at 0-5 ⁰ C and then stirred at room temperature overnight. Then the

Reaction mixture for 6 hours at 40 ⁰ C and stirred over the weekend at room temperature. Now, the solution was washed first with 500 mL of acidic water (pH 3) and then with 500 mL of water. The organic phase was dried over 30 g of sodium sulfate and filtered. The filtrate was concentrated by column chromatography (SiO 2; toluene / ethyl acetate 3: 1).

2.9) Preparation of the compound

17.1 g (48 mmol) of 6- (4-acryloyloxy-butoxycarbonyloxy) -2-naphthoic acid were stirred for one hour in 65 ml of oxalyl chloride with addition of 200 mg of hydroxy TEMPO and 8 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was dissolved in 70 ml_ methylene chloride and added at 0-5 ⁰ C to a solution consisting of 10.0 g (20 mmol) of the compound (5), 7.7 g (61 mmol) of N, N-dimethylcyclohexylamine and 70 ml_ Methylene chloride added dropwise. It was 2 hours at 0-5 ⁰ C and stirred overnight at room temperature. Then, the reaction mixture was stirred at 40 ^° C. for 6 hours. After cooling to room temperature, the solution was washed first with 500 mL of acidic water (pH 3) and then with 500 mL of water. The organic phase was dried over sodium sulfate and concentrated. The product was purified by column chromatography (SiO 2, petroleum ether / ethyl acetate 1: 2 to petroleum ether / ethyl acetate 2: 1). 1.0 g (4%) of the desired compound was obtained. HTP = 19 μm ^-1

2.10) Preparation of the compound

5.3 g (10 mmol) of compound (6) were stirred for one hour in 45 ml of oxalyl chloride with the addition of 4 mg of kerobit BHT and 4 drops of DMF. Subsequently, the excess oxalyl chloride was distilled off. The residue was placed in 180 mL of methylene chloride and treated at 0-5 ⁰ C to a solution consisting of 0.63 g (4.3 mmol) isomannitol, 4.2 g (33 mmol) of N, N-dimethylcyclohexylamine and 20 mL of methylene chloride , The mixture was stirred for 30 min at 0-5 ⁰ C and over the weekend at room temperature. Then, the reaction mixture was stirred at 40 ^° C. for 5.5 hours. After cooling to room temperature, the solution was washed first with 200 mL of acidic water (pH 3) and then with 200 mL of water. The organic phase was dried over sodium sulfate, filtered and largely concentrated. The remaining solution was precipitated with 200 ml of methanol / water 1: 1, filtered off with suction and dried. This gave 1, 3 g (26%) of the desired compound.

Claims

claims

1 . Compounds of the general formula I

in which the variables have the following meaning:

W is a grouping (Y ⁴ -T ² -) _s (Y ³ -A ² -) _t Y ² -Z ² ,

Z ¹ , Z ² independently of one another are hydrogen, optionally substituted C 1 -C 20 -alkyl in which the carbon chain can be interrupted by oxygen atoms in ether function, sulfur atoms in thioether function or by nonadjacent imino or C 1 -C 4 -alkylimino groups, or reactive radicals, via which a polymerization can be brought about,

Y ¹ , Y ^{2 are} independently a single chemical bond, oxygen,

Sulfur, -CO-, -O-CO-, -CO-O-, -S-CO-, -CO-S-, -NR-CO- or -CO-NR-,

-o-coo-, for s = 0: a single chemical bond or -CO-,

Y ^{4 is} a single chemical bond, oxygen, sulfur, -CO-, -O-

CO-, -CO-O-, -S-CO-, -CO-S-, -NR-CO- or -CO-NR-, with the proviso that Y ⁴ is bonded to the oxygen atom of the isomannitol

Unit means a single chemical bond or -CO-,

Y ⁵ for r = 1: a single chemical bond, oxygen, sulfur, -CO-, -O-CO-, -CO-O-, -S-CO-, -CO-S-, -NR-CO- or -CO-NR-, for r = O: a single chemical bond or CO-,

Y ^{6 is} a single chemical bond or CO-,

R is hydrogen or C 1 -C ₄ -alkyl,

Q is halogen, NO _2, NO, CN, CHO, L ^1, CO-L ^1, X ¹ -CO-L ^1, X ¹ -SO-L ^1, X ¹ -Sθ2-U, X ¹ -U ^', C0 -X ¹ -U ^', 0-C0-X ¹ ^-U', SO-X ¹ -U ^'or

Sθ2-X ¹ -L ^{1 '} , where mean

L ¹ Ci-C ₂ -alkyl, C ₂ -C ₂ -alkenyl, C ₂ -C ₂₀ -alkyl kinyl, C ₆ -Cio-aryl, hetero- aryl having 2 to 12 carbon atoms, C6-Cio-aryl Ci-C _2θ alkyl, Cβ- Cio-aryl-C ₂ -C _2O alkenyl, C6-Cio-aryl-C ₂ -C _2O -alkynyl, heteroaryl,

C 1 -C ₂₀ -alkyl, heteroaryl-C 1 -C ₂₀ -alkenyl or heteroaryl-C 1 -C ₂₀ -alkynyl having in each case 2 to 12 carbon atoms in the heteroaryl radical, the C 1 -C ₂₀ -carbon chain being characterized by oxygen atoms in ether function, sulfur atoms in Thioether function, non-adjacent imino, C 1 -C ₂₀ -alkylimino and / or carbonyl groups, and both the C 6 -C 10 -aryl and the heteroaryl having one or more substituents selected from the group consisting of halogen, NO ₂ , NO, CN, CHO, L ² , CO-L ² , X ² -CO-L ² , X ² -SO-L ² , X ² -SO ₂ -L ² , X ² -L ^{2 '} , CO-X ² L ^{2 '} , O-CO-X ² -L ^2' , SO-X ² -L ^{2 '} and SO ₂ -X ² -L ^2' may be substituted,

L ^{1 'is} hydrogen or, independently of L ^1, the same meaning as L ¹ ,

L ² Ci-C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ -alkyl kinyl, C ₆ -Cio-aryl, heteroaryl having from 2 to 12 carbon atoms, C6-Cio-aryl-Ci-C _2θ alkyl, Cβ- Cio-aryl-C ₂ -C _2O alkenyl, C6-Cio-aryl-C ₂ -C _2O alkynyl, heteroaryl Ci-C ₂₀ alkyl, heteroaryl-C ₂ -C ₂₀ alkenyl or Heteroaryl-C ₂ -C ₂₀ -alkynyl having in each case 2 to 12 carbon atoms in the heteroaryl radical,

L ^{2 'is} hydrogen or independently of L ² the same meaning as L ² and

r, t are independently 0 or 1,

0, 1, 2 or 3,

and

q is 0, 1, 2, 3 or 4.

2. Compounds according to claim 1, in which the variables T ¹ and T ^{2 are} independently

where the radicals

Irrespective of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I of claim 1, up to four (q = 0, 1, 2, 3 or 4) are identical. or different substituents Q of the general definition according to claim 1,

the rest

Irrespective of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I of claim 1 with up to three (q being 0, 1, 2 or 3) identical or different substituents Q of the general definition according to claim 1 .

the rest

irrespective of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I of claim 1 with up to two (q equals 0, 1 or 2) identical or different substituents Q of the general definition according to claim 1,

and

the rest

irrespective of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I of claim 1 with up to one (q equals 0 or 1) substituents tuenten Q the general definition according to claim 1 may be substituted.

3. Compounds according to claim 1, in which the variables T ¹ and T ² independently of one another

the radicals, independently of the particular choice of the substituents Q of the 2,6-naphthyl radical in formula I of claim 1, having up to four (q equals 0, 1, 2, 3 or 4) identical or different substituents Q of the general definition can be substituted according to claim 1.

Compounds according to one or more of claims 1 to 3, in which (Y ⁴ - T ² -) s in the variable W of the formula I of a grouping of the formula Ia

corresponds, in which mean:

Q ^' independently of the specific choice of the substituents Q of the 2,6-naphthyl radical in formula I of claim 1, identical or different substituents of the general definition Q according to claim 1,

0, 1, 2, 3 or 4

and

s ^' values of 0, 1 or 2,

where the variables Y ⁴ and T ^{2 have the} same meaning as in the preceding claims and for s ^' > 0 the variables Y ⁴ and for s ^' > 1 the variables T ² may be the same or different from each other.

5. Compounds according to one or more of claims 1 to 4, in which t is 1 and Y ³ corresponds to a group -O-COO-.

6. Compounds according to one or more of claims 1 to 5, in which at least one of the radicals Z ¹ and Z ^{2 represents} a reactive radical.

7. Compounds according to one or more of claims 1 to 5, in which at least one of the radicals Z ¹ and Z ^{2 is} a reactive radical

represents.

8. Compounds according to one or more of claims 1 to 5, in which at least one of the radicals Z ¹ and Z ^{2 is} a reactive radical

H ? ^H3

H ₂ C ^ ^ or _H g> ^

represents.

9. Compounds according to one or more of claims 1 to 5, in which t is 1 and the groups Z ¹ -Y ¹ -A ¹ - and -A ² -Y ² -Z ^{2 are the} same.

10. Compounds according to one or more of claims 1 to 5 and 9, in which Z ¹ -Y ¹ and Z ² - Y ^{2 are} identical reactive groups

Cl Cl

I i

H, C * ^{C ^} ° ^~ - H _Q C ^ ^{C ^ C00 ~} , HC≡C-CH ₂ -O-, HC = C-CH _r COO-,

o- or

^* O ^' o- coo-

mean.

1 1. Compounds according to one or more of claims 1 to 5 and 9, in which Z ¹ -Y ¹ and Z ² - Y ² identical reactive groups

H CH ₃

_HC ^ - ^{C ^} _COO or _HC ^ C _COO _

mean.

12. A liquid-crystalline composition containing at least one compound of the formula I according to one or more of claims 1 to 11.

13. Use of the compounds of the formula I according to one or more of claims 1 to 1 1 as chiral dopants.