TWI629282B - Polymerisable compounds and liquid-crystal media - Google Patents

Abstract

The present invention relates to a polymerizable compound of formula I

Wherein P, Sp, R ¹ , R ² , A ¹ , A ² , A ³ , Z ¹ , Z ³ , V, m, n, o, x and y have the meanings as indicated in the first embodiment; A liquid crystal medium comprising at least one compound of the formula I. These compounds are preferably sugar derivatives.

Description

Polymerizable compound and liquid crystal medium

The present invention relates to a polymerizable compound of the formula I, relating to a method for preparing the same, relating to its use as a component in a liquid crystal medium (LC medium), and to a photovoltaic display element containing such an LC medium. These compounds are preferably sugar derivatives.

The prior art discloses a medium for a display element operating in a liquid crystal blue phase (abbreviated as a blue phase) (WO 04/046805 A1, WO 2008/061606 A1).

The blue phase is usually observed when transitioning from a nematic state to an optically isotropic state. The medium in the liquid crystal blue phase can be blue (as suggested by the name) or colorless. To date, the aim has been to expand the temperature range of the blue phase from less than 1 degree to practical use (see H. Kikuchi et al., Nature Materials (2002), 1(1), 64-68; Kikuchi, H. Et al, Polymeric Materials Science and Engineering , (2003), 89, 90-91).

WO 2005/080529 A1 describes a polymer-stabilized blue phase comprising mono- and polyreactive monomers.

JP 2005 283 632 describes polymerizable compounds derived from carbohydrates which can be used for negative recording materials. Wherein the preparation process does not allow the preparation of the compounds of the invention in a manner suitable for use in LC media. This method does not produce a fully functionalized sugar derivative, whereas the OH functional group is in an open state. It shows the structures A and B:

WO 1994/014828 describes tetraacrylates derived from the so-called methyl glucitol-20 (MG-20, Glucam E-20). It has an average of about 20 ethoxylated units (ethylene glycol units) (including diol units in the ring) of methyl glucosides. Thus, in form, these materials are alkoxy polymers having a non-uniform composition. Its general structure is roughly described by the following formula:

For MG-20 (Glucam E-20), the sum of the parameters a, b, c and d is about 20, wherein the values of a, b, c and d may differ from each other. Since the composition of these materials is inconsistent and subject to change, the polymerizable compounds derived therefrom are not suitable for constructing a finely tuned polymerization network that stabilizes the blue phase. The use of such compounds by such complex structures does not achieve reproducible results as a blue phase. The purpose of WO 1994/014828 is to provide an ion conducting polymeric material for, for example, an electrolytic cell.

US 5,248, 747 and a similar publication (US Pat. No. 5,116,961), the disclosure of which is incorporated herein by reference in its entirety, in the use of the <RTI ID=0.0>0> Propylene fluorenyl-2,3,3',4,4'-penta-O-methylsucrose (D) was used as a crosslinking agent.

The synthesis of Compound D is described in US 5,302,676. During the synthesis, the structure is selected such that the secondary hydroxyl functional group of sucrose is methylated and the primary hydroxyl functional group is functionalized to methacrylate. The synthesis is a total of 4 steps.

In practice, the polymer stabilized blue phase described so far uses a single reactive non-liquid crystal monomer and a two reactive monomer (RM257) as monomers.

The present invention is based on the object of finding suitable monomers and corresponding polymers which stabilize the blue phase. The polymer is intended to have the following effects on the properties of the stabilized LC phase:

- widen the blue phase temperature range,

- Shorten response time,

- reduce the difference in clearing-points during aggregation,

- lowering the operating voltage (V _op ),

- reduce the variation of operating voltage with temperature,

- Reduce the transmission hysteresis of the groove when changing the operating voltage to achieve the defined shade of gray.

In addition, there is a need for a monomer material that has a good voltage holding ratio (VHR), has a high clearing point, and is stable upon exposure to light and temperature. Furthermore, good stability in LC materials or good compatibility with LC materials is essential to achieve a good distribution in the LC body.

In particular, it is an object of the present invention to provide improved reactive polymerizable compounds which are capable of stabilizing the blue phase and are suitable for the preparation of LC materials having improved properties.

This object is achieved according to the invention by a compound of the formula I.

Therefore, the present invention relates first to compounds of formula I

Wherein R ¹ and R ² represent

a) in each case, independently of each other, having from 1 to 15 C atoms of a halogenated or unsubstituted alkyl group, in addition, wherein one or more of the CH ₂ groups in such groups may be O The ways in which atoms are not directly connected to each other are each independently replaced by -C≡C-, -CH=CH-, -(CO)O-, -O(CO)-, -(CO)- or -O-,

b) group-Sp-P, or

c) F, Cl, H, Br, CN, SCN, NCS or SF ₅ , preferably a group from a) or b), A ² represents or A ¹ and A ³ are each represented independently of each other:

a) trans-1,4-cyclohexylene or cyclohexenylene, in addition, one or more of the non-adjacent CH ₂ groups may be replaced by -O- and/or -S- and wherein H may be substituted by F,

b) 1,4-phenylene, wherein one or two CH groups may be replaced by N and additionally, wherein one or more H atoms may be Br, Cl, F, CN, methyl, methoxy or mono- or Polyfluorinated methyl or methoxy substitution, or

c) Groups from the following groups: bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane- 2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3- Dibasic or hexahydropyridine-1,4-diyl,

One or more hydrogen atoms may be substituted by F, CN, SCN, SF ₅ , CH ₂ F, CHF ₂ , CF ₃ , OCH ₂ F, OCHF ₂ or OCF ₃ , and one or more double bonds may be replaced by a single bond. One or more CH groups may be replaced by N, M represents -O-, -S-, -CH ₂ -, -CHY- or -CYY ¹ -, and Y and Y ¹ represent Cl, F, CN, OCF ₃ or CF ₃ , Z ¹ , Z ^{3 are the} same or different and each independently represents a single bond, O, CH ₂ , OC(O)CH ₂ , —CH ₂ O—, —CH ₂ OCH ₂ —, —(CO)O -, -CF ₂ O-, -CH ₂ CH ₂ CF ₂ O-, -CF ₂ CF ₂ -, -CH ₂ CF ₂ -, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -CH= CH-, -CH=CF-, -CF=CF- or -C≡C-, wherein the asymmetric bridge can be oriented to both sides, and m represents 0, 1, 2, 3, 4, 5, 6, 7 Or 8, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1, 2 or 3, n, o means 0, 1, 2, 3, 4 or more, preferably 0, 1 2, 3 or 4, particularly preferably 0, 1, 2 or 3, x, y represents 0, 1, 2, 3 or 4, preferably 0, 1 or 2, wherein x + y 4, preferably 0, 1 or 2, particularly preferably 0 or 1, P represents a polymerizable group, Sp represents a spacer group or a single bond, and -Sp-P additionally represents a group R ¹ , wherein The number of the poly groups P is one or more. The compounds of the formula I according to the invention do not include the sugar derivatives A and B disclosed in the publication JP 2005 283 632, excluding methylglycol-20 tetraacrylate (i.e., the compound of formula C ), wherein a+b+ c+d represents an average of 20, preferably wherein a+b+c+d represents a natural number >10 and does not include a compound of formula D as described at the outset.

The use, method, medium and apparatus comprising a compound of formula I are not affected by this exception, i.e., they also include structures A , B , C and D.

The polymerizable group P is suitable for polymerization (for example, radical or ionic chain polymerization, addition polymerization or polycondensation) or a group suitable for the reaction of a polymer analog (for example, addition or condensation onto the polymer backbone). Particularly preferred are groups for chain polymerization (specifically, those containing a C=C double bond or a -C≡C-triplet), and groups suitable for ring opening polymerization (for example, propylene oxide or Epoxy group).

Preferred groups P are selected from the group consisting of CH ₂ =CW ¹ -COO-, CH ₂ =CW ¹ -CO-, , CH ₂ =CW ² -(O) _k3 -, CW ¹ =CH-CO-(O) _k3 -, CW ¹ =CH-CO-NH-, CH ₂ =CW ¹ -CO-NH-,CH ₃ - CH=CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH-CH ₂ ) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, (CH ₂ = CH-CH ₂ ) ₂ N-, (CH ₂ =CH-CH ₂ ) ₂ N-CO-, HO-CW ² W ³ -, HS-CW ² W ³ -, HW ² N-, HO-CW ² W ³ -NH-, CH ₂ =CW ¹ -CO-NH-,CH ₂ =CH-(COO) _k1 -Phe-(O) _k2 -,CH ₂ =CH-(CO) _k1 -Phe-(O) _k2 -, Phe-CH=CH-, HOOC-, OCN- and W ⁴ W ⁵ W ⁶ Si-, wherein W ¹ represents H, F, Cl, CN, CF ₃ , phenyl or has 1 to 5 C atoms An alkyl group (specifically H, F, Cl or CH ₃ ), each of W ² and W ³ independently representing H or an alkyl group having 1 to 5 C atoms (specifically H, methyl, B) Or a propyl group, W ⁴ , W ⁵ and W ⁶ each independently represent Cl, an oxaalkyl group having 1 to 5 C atoms or an oxacarbonylalkyl group, and W ⁷ and W ⁸ are each independently of each other. H, Cl or an alkyl group having 1 to 5 C atoms, Phe represents a 1,4-phenylene group (which is optionally substituted with one or more groups L as defined above), and k ₁ , k ₂ and k ₃ each independently represent 0 or 1, k ₃ Preferably, it is 1.

The preferred group P is CH ₂ =CW ¹ -COO-, specifically CH ₂ =CH-COO-, CH ₂ =C(CH ₃ )-COO- and CH ₂ =CF-COO-, further CH ₂ =CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-,

An excellent group P is a vinyloxy group, an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, an oxypropylene group and an epoxy group, specifically an acrylate group and a methyl group. Acrylate based.

Depending on the number of polymerizable groups per molecule, the monomers of the invention are suitable for forming polymers which are crosslinked to varying degrees. If it contains only one polymerizable group, it forms a polymer chain. At least in some cases, it preferably contains two or more polymerizable groups and functions as a crosslinking agent. The compounds of formula I preferably contain 2, 3, 4 or 5 polymerizable groups. It is particularly preferred to contain two or more polymerizable groups, specifically 4 or 5.

The term "spacer group" is also referred to above and hereinafter as "Sp", which is known to those skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 73(5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. Unless otherwise indicated, the terms "spacer group" above and below mean a flexible group in which a liquid crystal primary group and a polymerizable group are bonded to each other in a polymerizable liquid crystal or a liquid crystalline raw compound. .

Preferably, the spacer group Sp is selected from the group of Sp'-X such that the group P-Sp- conforms to the formula P-Sp'-X-, wherein Sp' represents from 1 to 24, preferably from 3 to 12 a C atom, particularly preferably an alkyl group of 4 to 12 C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, and additionally, one or more of which are not adjacent to the CH ₂ group Each of O and/or S atoms are independently connected to each other by -O-, -S-, -NH-, -NR ⁰ -, -SiR ⁰⁰ R ⁰⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR ⁰⁰ -CO-O-, -O-CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-NR ⁰⁰ -, -CH=CH- or -C≡C-substitution, wherein one or none of the CH ₂ groups are substituted, X represents -O-, -S-, -CO-, -COO-, -OCO-, -O -COO-, -CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-, -NR ⁰⁰ -CO-NR ⁰⁰ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, - N=CH-, -N=N-, -CH=CR ⁰ -, -CY ² =CY ³ -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or single bond , preferably a single bond, -O -, - OCO- or -OCH ₂ -, R ⁰⁰ and R ⁰⁰⁰ are each independently represents H or alkyl having 1-12 C atoms, and Y ² and Y ³ each independently represents H, F, Cl or CN another.

X is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ⁰ -CO-, -NR ⁰ -CO- NR ⁰ - or single button.

A typical spacer group Sp' is, for example, -(CH ₂ ) _p1 -, -(CH ₂ CH ₂ O) _p2 , -CH ₂ CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ CH ₂ -, - CH ₂ CH ₂ -NH-CH ₂ CH ₂ - or -(SiR ⁰⁰ R ⁰⁰⁰ -O) _p1 -, wherein p1 is an integer from 1 to 24, preferably 3, p2 is an integer from 1 to 6, and R ⁰⁰ and R ⁰⁰⁰ have the meanings indicated above.

The preferred group -X-Sp'-system -(CH ₂ ) _p1 -, -O-(CH ₂ ) _p1 -, -OCO-(CH ₂ ) _p1 -, -OCOO-(CH ₂ ) _p1 -, Wherein p1 is as defined above.

In each case, the preferred group Sp' is, for example, a straight-chain ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a decyl group, a decyl group, Stretching, stretching, undecyl, dodecyl, octadecyl, ethyl ethoxy, methyl, methyleneoxy, butyl, ethylthio, ethyl, ethyl N-methylimido group exoethyl, 1-methylalkylene, vinyl, propylene and butylene. Sp' is particularly preferably an alkylene group as defined above having 4 to 12 C atoms in the case where the group X represents a single bond or 3 to 12 in the case where the group X does not represent a single bond C atoms.

If A ¹ and A ³ occur more than once (for x or y > 1), they can have different meanings. The same applies to the groups Z ¹ , Z ³ and -Sp-P. The groups -Sp-P are preferably identical to each other.

The groups R ¹ and R ² preferably independently of each other represent a group P-Sp-, H, an alkyl group having 1 to 10 C atoms, an alkoxy group or an alkoxymethyl group.

The compounds of the invention are especially suitable as a polymerizable component in liquid crystal media. The polymer satisfies in every respect the requirements for the purpose of stabilizing the liquid crystal phase, in particular the blue phase. A significant reduction in operating voltage was observed compared to conventional systems. At the same time, the tendency to form a transmission hysteresis (gray value) is reduced, which depends on (increasing or decreasing) the operating voltage. In addition, for PSA-VA type displays (refer to JP 10-036847 A, EP 1170626 A2, US 6861107, US 7169449, US 2004/0191428, US 2006/0066793) and other PSA ("Polymer Stabilized Alignment") displays. The amount of the compound which is a polymerizable component in the mixture is preferably <1%. Additionally, in many cases it can be prepared simply from commercially available sugar compounds.

A particularly preferred compound of formula I is derived from a carbohydrate or a substance also known as a sugar. The terms carbohydrate and sugar are well known to those skilled in the art. It is a product of oxidation of a polyol, that is, a hydroxy aldehyde (aldose) or a hydroxy ketone (ketose) and a compound derived therefrom and a condensate thereof.

A preferred type I compound is derived from a monosaccharide (simple sugar) having five (pentose sugars such as xylose) or six carbon atoms (hexoses such as glucose). It is capable of ring closure. The equilibrium of this reaction is usually on one side of the cyclic hemiacetal. The open-chain form in solution or solid is usually negligible. Here, the sugar may be in the form of a furanose (5-membered ring) or a pumose (6-membered ring). In addition, a new solid center is formed when the ring is closed. The alpha and beta anomers can be distinguished by looking at the position of the OH group.

For example, the enantiomeric forms of glucose are represented by the prefixes D and L. In fact, D-glucose is exclusively present. L-glucose can only be obtained synthetically.

Only the main form of sugar is represented by its name below. For example, D-glucose is actually exclusively present in the form of a pumose. The following D-glucose is therefore expressed as:

The wavy wedge bond at the anomeric center indicates that it is or may be a mixture of alpha and beta anomers. For more information on monosaccharides see [ Mongosaccharides : Their Chemistry and their roles in natural products . P. Collins and R. Ferrier 1995 John Wiley & Sons , Chichester.].

Particularly preferred compounds of the invention are derived from, for example, the following sugars:

The preferred starting materials for the synthesis of Compound I of the present invention are not limited to naturally occurring carbohydrates. The sugars, enantiomers, derivatives or chemically modified compounds which can be obtained synthetically are also preferred starting materials for the compounds of the formula I according to the invention. Thus, in a broad sense, polyhydroxypyran and polyhydroxyfuran are preferred starting materials for the compound I of the invention.

In a preferred embodiment of the invention, both x and y represent zero, as shown in formula IA:

Wherein R ¹ , R ² , Sp, P, m and A ² are as defined above.

The above and below groups [P-Sp-] may be in the position of any H atom present, that is, directly adjacent to R ¹ or R ² .

A preferred embodiment of the IA structure is shown in sub-forms IA-1 through IA-32 below, in which a planar representation is selected. All possible stereoisomers (enantiomers and diastereomers, reference to the above sugar structure) are therefore included. For the purposes of the present invention, all possible stereoisomers resulting from the sugar structures disclosed above are preferred. These may be in stereoisomeric pure form or in the form of a mixture of stereoisomers.

Wherein R ^{1 '} to R ^{5 '} have the meanings indicated for R ¹ , but R ^{1 '-5' is} preferably hydrogen, a straight or linear alkyl group having 1 to 12 C atoms, an alkenyl group, Alkoxy or alkoxymethyl, more preferably hydrogen or alkoxy, and wherein X ¹ to X ⁵ are as defined above for X, and Sp ¹ to Sp ⁵ are as defined above for Sp', and P ¹ to P ⁵ is as defined in P above.

Among them, a compound containing a tetrahydropyran ring (IA1-IA19) is particularly preferable. Among them, those having more than two polymerizable groups are preferred (IA1-IA10).

In still another preferred embodiment of the invention, x+y>0. Here, the polyfunctionalized ring A ² from formula I is preferably substituted by a liquid crystal original group of the formula:

Here, the group preferably has the following meanings:

Wherein Z ⁴ is one of the meanings of Z ¹ /Z ³ .

Above and below Group

Preferably, it represents a group selected from the group consisting of:

The liquid crystal primordial group is preferably attached to the (poly)hydroxypiperan unit via a bridge. Due to the particular reactivity, it is preferred here to carry out the attachment via the CH ₂ OH functional group of the hexose and/or via the OH functional group on the terminal isomerization center. Here, glucose is used as an example to mark these locations:

尤佳的桥键 Z ¹ , Z ³ series (for example) single bond,

and

More preferably, one of the parameters x or y is equal to zero. The preferred structure IB obtained therefrom is shown below in sub-forms IB-1 to IB-5, wherein a planar representation is selected. All possible stereoisomers (enantiomers and diastereomers, reference to the above sugar structure) are therefore included. For the purposes of the present invention, all possible stereoisomers resulting from the sugar structures disclosed above are preferred. These may be in stereoisomeric pure form or in the form of a mixture of stereoisomers.

Further, Sp ^1-5 -P ^1-5 in Formula IB may be replaced by R ^{1 '-5'} one or more times. This is preferably suitable for P ⁵ -Sp ⁵ - and/or P ¹ -Sp ¹ -. Here, R ^{1 '-5'} has the meaning given for R ¹ , but R ^{1 '-5' is} preferably hydrogen, a straight or linear alkyl group having 1 to 12 C atoms, alkene Alkyl, alkoxy or alkoxymethyl, more preferably hydrogen or alkoxy.

Wherein R ¹ , A ¹ , Z ¹ , X ^1-5 , Sp ^1-5 , P ^1-5 and x are as defined above.

Especially preferred are IB-1 and IB-5 compounds.

A particularly preferred structure I (wherein both x and y are not zero) is shown below in sub-forms IC-1 to IC-3. Select the plane representation here. For the purposes of the present invention, however, all possible stereoisomers (enantiomers and diastereomers) which result from the position of the substituent on the ring are preferred. These may be in stereoisomeric pure form or in the form of a mixture of stereoisomers. Further, Sp ^1-5 -P ^1-5 in the formula IC may be replaced by R ^{1 '-5'} one or more times. This is preferably suitable for P ⁵ -Sp ⁵ - and/or P ¹ -Sp ¹ -. Here, R ^{1 '-5'} has the meaning given for R ^1,2 , but R ^{1 '-5' is} preferably hydrogen, a straight or linear alkyl group having 1 to 12 C atoms. Alkenyl, alkoxy or alkoxymethyl, more preferably hydrogen or alkoxy.

Wherein R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , X ^1-5 , Sp ^1-5 , P ^1-5 , x and y are as defined above.

An excellent compound is an IC-1 type compound.

Simple sugars can be linked together via a glycosidic bond by a condensation reaction to give a disaccharide or polysaccharide.

Preferred compounds of formula I are also derived from disaccharides (disaccharides such as rock sugar or lactose).

Particularly preferred compounds of the invention are derived, for example, from maltose, cellobiose, isomaltose, isomaltulose, gentiobiose, trehalose, sucrose, lactose, lauryl disaccharide.

The choice of preferred disaccharides for the synthesis of Compound I of the present invention is not limited to naturally occurring compounds. Syntheticly obtained enantiomers, derivatives or chemically modified compounds are also preferred starting materials for the compounds of formula I of the invention.

A subtype of a particularly good compound derived from maltose.

A subform of a particularly preferred compound derived from sucrose.

The selected synthetic method is illustrated by an example starting from the preferred monosaccharide. In particular, the synthetic method refers to D-(+)-xylose (1) , L-(+)-arabinose (35) , deoxy-D-ribose (16) , D-(+)-glucose by way of example. (70) and D-(+)-galactose (116) are described. These are intended to illustrate, not limit, the invention. Those skilled in the art will be able to readily apply the method to other starting materials.

Further, in particular, a type I compound containing a particularly preferred acrylate type polymerizable group will be discussed herein, wherein the polymerizable group P generally represents CH ₂ =CW ¹ -COO-, wherein the W ¹ system As defined above for Formula I. These excellent include acrylate groups (CH ₂ =CH-COO-) and methacrylate groups (CH ₂ =C(CH ₃ )-COO-).

The hydroxy functional group of the carbohydrate is critical for the construction of the spacer group, which means that -O- is pre-specified as part of the spacer group -Sp'-X-. These compounds are especially preferred.

In a preferred method, the spacer group Sp'-X (which is equal to -OC(O)-(CH ₂ ) _p1 -) is constructed by esterification using ω-bromoalkanoic acid 2 . Here and below the position ω means that the substituent (here bromine) is at the end of the chain, such as, for example, in 5-bromovaleric acid = 5-bromopentanoic acid . The resulting compound 3 can then be converted to a type I polymerizable compound by reaction with acrylic acid 4 (R = H or Me is preferred) (e.g., compound 5 in reaction Figure 1 ).

Reaction Figure 1: Sp=-O-C(O)-(CH ₂ ) _P1 - Synthesis of Compound I (especially = 5), taking D-(+)-xylose (1) as an example. In this figure, W ¹ =R. R is preferably H or CH ₃ .

For the synthesis of intermediate 3 , ω-bromoalkylphosphonium chloride 6 can also be used. Such compounds can be obtained from carboxylic acid 2 , for example by reaction with sulfinium chloride.

Reaction Figure 2: Synthesis of Intermediate 3 using ω-bromoalkylphosphonium chloride 6

Other preferred compounds are those in which Sp'-X=-O-(CH ₂ ) _p1 - wherein the parameter p1 is preferably greater than 2.

A method for obtaining a particularly preferred compound (where p1 = 3) is shown in Reaction Scheme 3 , and still taking the reaction of D-(+)-xylose (1) as an example.

Reaction Figure 3: Sp=-O-(CH ₂ ) ₃ - Synthesis of Compound I (especially = 11), taking the reaction of D-(+)-xylose (1) as an example. In this figure, W ¹ =R. R is preferably H or CH ₃ .

First, alkylation/allylation of sugar 1 is carried out using allyl bromide (7) [A. Leydet et al., J. Med . Chem . 1997 , 40, 350-356]. Allyl bromide (7) is a sufficiently strong alkylating agent which also allows efficient and complete alkylation of the secondary alcohol functionality. Other alkylating agents (e.g., alkyl bromides or alkyl tosylates) generally do not have sufficient reactivity to adequately react with the free sugars.

A hydroboration/oxidation reaction is then carried out to construct a 1,3-propanediol spacer group to give compound 9 . Compound 9 is then esterified (Method A) or (Method B) using acrylonitrile or acrylic acid to provide compound 11 . For the purposes of the present invention, other preferred starting materials can be carried out in a similar manner.

Allally propylated compound8Or an analog is also used to obtain a glycol-containing spacer group (Sp'-X'=O(CH)₂)₂A suitable starting material for the compound of -). For this purpose, the double bond is cleaved by means of ozonolysis and the resulting aldehyde is obtained.12Restore to13. However, in order to obtain a production-acceptable yield, it seems that the ozonide formed in the initial stage of ozonolysis (not shown) is directly reduced to an alcohol using sodium borohydride on alumina.13More favorable [M. Dubber, T. Lindhorst,Carbohydr.Res. 1998, 310, 35-41].

Reaction Figure 4: Sp=-O-(CH ₂ ) ₂ - Synthesis of Compound I (especially = 14), taking the reaction of D-(+)-xylose (1) as an example. In this figure, W ¹ =R. R is preferably H or CH ₃ .

The free OH group of the 1,n-diol spacer group can also be converted to the corresponding bromide 15 . These compounds are also useful as intermediates for the synthesis of Compound I.

Reaction Scheme 5: Synthesis of alkyl bromide 15 as a synthetic intermediate of Compound I. An example of the synthesis of a material obtained from D-(+)-xylose (1).

An alkyl bromide of the formula 15 or a similar compound (refer to the reaction scheme of Figure 6 , a reaction example of deoxy-D-ribose ( 16 )) can be reacted with a carbon-containing nucleophile (for example, an 18-type alkyl-Grignard reagent) to obtain A compound of Sp'-X=-O-(CH ₂ ) ₃ (CH ₂ ) _p1 -. This is shown in Reaction Scheme 6 , taking the reaction of 2-deoxy-D-ribose ( 16 ) as an example. The synthesis of bromide 17 was carried out as described above. The 17 and 18 type alkyl-Grignard reagents (PG = protecting group) are then reacted. Removal of the alcohol protecting group provides the alcohol 20 . The hydroxy functional group can then be reacted with an acrylic acid (derivative) to give compound 21 .

Reaction Figure 6: Sp=-O-(CH ₂ ) ₃ (CH ₂ ) _P1 - Synthesis of Compound I (especially = 21), taking the reaction of 2-deoxy-D-ribose (16) as an example. In this figure, W ¹ =R. R is preferably H or CH ₃ .

It is of course also possible to convert the OH group of the compound (for example compound 9 ) to another suitable leaving group. In addition to bromide, it is especially preferred to be iodide, chloride, tosylate, mesylate or triflate (not shown in each case).

The substrate obtained by ozonolysis of the O-allylation compound (refer to Reaction Scheme 4 or Reaction Scheme 7 ) is suitable, for example, with a type 24 reagent (PG = protecting group, preferably a germyl protecting group) The Wittig reaction of the group) produces a compound containing an alkenyl spacer group (for example, 27 in the reaction scheme 7 ).

Reaction Figure 7: Sp=-O-(CH ₂ )C=C-(CH) ₂ ) _P1 - Synthesis of Compound I (especially = 27), taking the reaction of 2-deoxy-D-ribose (16) as an example. In this figure, W ¹ =R. R is preferably H or CH ₃ .

The 28 type Wittig reagent is especially suitable if the compound containing an alkyl spacer group is prepared from an aldehyde (e.g., 23 ). The product of the Wittig reaction is subjected to hydrogenation, during which the benzyl protecting group dissociates and the double bond is hydrogenated. This method is listed in Reaction Scheme 8 .

Reaction Figure 8: Sp=-O-(CH ₂ ) ₃ (CH ₂ ) _P1 - Synthesis of Compound I (especially = 21), taking the reaction of 2-deoxy-D-ribose (16) as an example. In this figure, W ¹ =R. R is preferably H or CH ₃ .

In general, the synthesis of intermediates (e.g., 20 and 26 ) does not necessarily require the use of a protecting group. [HO-(CH ₂ ) _p1 -CH ₂ PPh ₃ ] ⁺ Br ^- type Wittig reagent (not shown) can also be used. Other preferred reagents for the synthesis of Compound I of Sp = -(CH ₂ )-C=C-(CH ₂ ) _p1 - or Sp = -(CH ₂ ) ₃ (CH ₂ ) _p1 - are bromoalkyl-Wittig Salt 30 . The Wittig reaction of an aldehyde (e.g., 12 ) gives compound 31 which can then be converted, for example, to the compound I wherein Sp = -(CH ₂ )-C ⁼ C-(CH ₂ ) _p1 - using the acrylic acid 6 in the presence of a base. (Refer to Example 32 in Reaction Scheme 9 ).

Reaction Figure 9: Sp=-(CH ₂ )-C=C-(CH ₂ ) _P1 The synthesis of the compound I (especially = 32) is exemplified by the reaction using the aldehyde 12 of the bromoalkyl-Wittig salt 30. In this figure, W ¹ =R. R is preferably H or CH ₃ .

To obtain Compound I of Sp = -(CH ₂ ) ₃ (CH ₂ ) _p1 - in this manner (refer to Compound 34 in Reaction Scheme 10 ), Intermediate 31 was subjected to hydrogenation. The resulting compound 33 was then reacted with acrylic acid 4 .

Reaction Scheme 10: Synthesis of Sp=-(CH from Intermediate 31) ₂ ) ₃ (CH ₂ ) _P1 - Compound I. In this figure, W ¹ =R. R is preferably H or CH ₃ .

In general, the free sugar alkylation reaction using a protected bromoalkanol 36 (or iodide, tosylate or triflate) is also suitable for the synthesis of HO-(CH ₂ ) _p1 - A particularly preferred spacer group for the OH group (see Figure 11 for the reaction ).

Reaction Figure 11: Sp=-O-(CH ₂ ) _P1 - Synthesis of Compound I (especially = 39), taking the reaction of L-(+)-arabinose (35) as an example. In this figure, W ¹ =R. R is preferably H or CH ₃ .

However, this alkylated form is generally not unsuitable (in particular) for the sufficient alkylation of the secondary OH groups of the carbohydrate. In addition, the degree of difficulty increases with the number of secondary OH groups to be alkylated. For certain applications, such as the alkylation of 4,6-O-ethylidene-α-D-glucopyranose as described in the prior art (JP 2005 283 632), different alkylated structural units are obtained. The mixture is sufficient. However, for the applications described herein for LC display applications, it is desirable to be able to prepare individual compounds of high purity to prepare well-defined mixtures. The method described above does not seem to be suitable for this purpose. Specifically, in a reaction medium (solvent such as dichloromethane, ether, ethyl acetate, toluene, etc.) commonly used in organic reactions, the presence of a plurality of OH groups in the "free" sugar generally hinders sufficient synthesis treatment. Ability. Thus, one of the methods of sugar chemistry is first to protect, and in many cases to protect all OH groups first (see also the deoxygenation reaction at the terminal isomerization center, reaction Figure 30 ).

One way to achieve better reactivity with an alkylating agent such as an alkyl bromide is to use a glycoside (e.g., an alkyl glycoside, such as compound 40 ) as a co-reactant. These compounds are sufficiently reactive. The thorough alkylation of alkyl glycosides using alkyl bromides has been described in the following literature: [a) J. Slawomir, Bull. Pol. Ac. Sci. 1988 , 36, 327-332. b) R. Nouguier, C Medani, Tetrahedron Lett. 1987 , 28, 319-320.c) M. Goebel, I. Ugi, Synthesis 1991 , 1095-1098]. The term glycoside is generally applied to compounds having a substituent with a non-free hydroxy function at the anomeric center. Alkyl glycosides are readily obtained by reacting a sugar with an alcohol in the presence of an acid. This is a acetalization reaction. A variety of simple glycosides are commercially available from the market.

Reaction Scheme 12: Synthesis of methyl glycoside 40 and reaction with a type 36 protected bromoalkanol, taking L-(+)-arabinose (35) as an example. W ¹ =R. R is preferably H or CH ₃ .

The methyl glycoside 40 is then alkylated here using a protected bromoalkanol 36 (PG = protecting group) and sodium hydride (as a base). The methyl glycoside 41 can then be cleaved again using acid catalysis. Subsequently, the remaining OH functional groups still have protected spacer groups. This process can be carried out using the compound 43 in an acetalization reaction, or can be carried out using the compound 36a in the form of an alkylation reaction. Other spacer groups can be attached here except in the usual position. Thus, for example, groups having different spacer group lengths q1 can be attached. Q1 represents an integer between 1 and 24, preferably between 1 and 12. After deprotection, esterification can be carried out to give a preferred acrylate.

The reaction sequence can be further simplified (refer to Reaction Scheme 13). Thus, for example, a spacer group having a protecting group can be introduced in the first step.

Reaction Scheme 13: Synthesis of glycoside 44 and reaction with a type 36 protected bromoalkanol, taking L-(+)-arabinose (35) as an example. W ¹ =R. R is preferably H or CH ₃ .

Other preferred functionalizations and further functionalized co-reactants which can be subjected to acetalization at the anomeric center are shown in Figure 14 .

Reaction Figure 14: Synthesis of various glycosides 46, 48, 50, taking D-(+)-xylose (1) as an example

Reaction with ω-bromoalkanol 45

Reaction with ω-hydroxyalkyl acrylate 47

Reaction with 1,ω-diol 49

Preferred are also compounds in which other groups R ₁ -[A ₁ -Z ₁ ] _x - are present in the terminal isomerization center. More preferably, it is an alkyl group and a liquid crystal original group. For example, the connection is made via a bridge key (refer to the reaction diagram 15 ).

Reaction Figure 15: Synthesis of various glycosides, such as compounds 52 and 54, with L-(+)-arabinose (35) as an example; variable groups as defined above, or in Z ¹ Or Z ³ Connected to ring A via a bridge ² In the case of Z ¹ Or Z ³ Together with this bridge key has Z ^1-5 One of the definitions .

Example A: Reaction with alcohol 51

Example B: Reaction with alcohol 53

Therefore, a more preferred co-reactant is alkyl alcohol 55 or 55a , cyclohexyl alcohol 58 , cyclohexylmethanol 60 , phenol 62 and benzyl alcohol 64 (see reaction scheme 16 ), and carboxylic acid (not shown here). .

Reaction Figure 16: Synthesis of various Eugenosides 56, 57, 59, 61, 63, 65, taking L-(+)-arabinose (35) as an example. W ¹ =R. R is preferably H or CH ₃ .

Example A: Reaction with alkyl alcohol 55

Example B: Reaction with alkyl alcohol 55a

Example C: Reaction of 58 with cyclohexanol

Example D: Reaction with cyclohexylmethanol 60

Example E: Reaction with phenol 62

Example F: Reaction with benzyl alcohol 64

Above and below Group

Preferably, it represents a group selected from the group consisting of:

Compounds 56, 57, 59, 61, 63 and 65 or compounds obtained from other sugars can then be suitably functionalized (see, for example, the method of Reaction Figures 1-13), for example as shown in Reaction Scheme 17.

Reaction Figure 17: Substituent R on the terminal isomerization center ₁ -[A ₁ -Z ₁ ] _x - Synthesis of Compound I (especially = 67 and 69). W ¹ =R. R is preferably H or CH ₃ See Figure 15 for the definition of the group.

Example A: Reaction with ω-bromoalkanoic acid 2

Example B: Allylation, borohydride pathway

The sugars contain hydroxyl functional groups having different reactivity. Hexoses (e.g., D-(+)-glucose (70) ) contain three alcohol groups having different reactivity (see Figure 1 ) - a primary hydroxyl functional group, a secondary hydroxyl functional group, and an anomeric hydroxy functional group. The specific reactivity of the terminal isomerization centers has been discussed above.

Figure 1: Different hydroxy functional groups in sugar, here D-(+)-glucose (70) as an example

In general, all of the reactions given above can be carried out using D-(+)-glucose (70) and other hexoses, and the corresponding compound I can be obtained in this manner. Still illustrated by the two examples in Figure 18 of the reaction .

Reaction Scheme 18: D-(+)-glucose (70) reaction gives examples of Compound I (especially = 71 and 72). W ¹ =R. R is preferably H or CH ₃ .

Example A: Complete reaction with ω-bromoanthracene chloride 6

Example B: 1,3-diol spacer groups on all sides are allyylated

The different reactivity of the hydroxyl functional groups can also be utilized here again to introduce different spacer groups (chain length, type), in particular if a protecting group is used. It is illustrated by the example in the reaction diagram of FIG .

The anomeric center may be protected as an alkyl glycoside as described above, or may be introduced directly into a desired spacer or precursor (compound 73 , q1 is between 1 and 24, preferably between 1 and 12) Integer). The introduction of a trityl protecting group gives compound 74 the difference between the primary and secondary OH groups. The secondary OH group can then be esterified, for example, using a bromoalkanoic acid. The trityl protecting group in 75 is then removed and a suitable group can be attached to the primary OH group. The esterification is again selected here, in which case ω-bromo alkanoic acid 2a having a different chain length s1 is used. S1 is an integer between 1 and 24, preferably between 1 and 12. Finally, all of the polymerizable groups are introduced by reaction with acrylic acid 4 to give compound 77 .

Reaction Figure 19: Protecting group strategy for D-(+)-glucose (70) reaction. W ¹ =R. R is preferably H or CH ₃ .

Those skilled in the art will be able to combine or add the starting materials, reagents and methods shown in a suitable manner and thereby obtain a variety of possible Type I compounds.

The primary OH group is also preferably attached to other groups R ₁ -[A ₁ -Z ₁ ] _x - or R ₂ -[A ₃ -Z ₃ ] _y - (preferably alkyl and liquid crystal original groups) position. For this purpose, for example, tetrabenzyl ether 80 can be used. It is obtained from D-(+)-glucose (70). First, the C6-OH group is protected as a trityl ether and then the other positions are benzylated. After removing the trityl group, 80 was obtained (refer to Reaction Scheme 20 ).

Reaction Scheme 20: Synthesis of a preferred intermediate for C6-OH group derivatization/functionalization, taking D-(+)-glucose (70) reaction as an example

In the simplest case, the functionalization is carried out by alkylating the primary OH group with an alkyl halide (eg iodide 81 ), tosylate or triflate ( Refer to the example in Reaction Scheme 21 ). The benzyl group is then cleaved and the remaining OH functional groups of compound 83 are converted accordingly.

Reaction Figure 21: Functionalization of C6-OH by alkylation (better reaction Examples of the order); see Figure 15 for the definition of the group.

Here and hereinafter the groups X ¹¹ to X ⁵⁵ together with the adjacent group -O- are taken from the meaning of the definition of the group X or X ¹ to X ⁵ . Thus, the -OX ¹¹ - moiety corresponds to, for example, the group -X- in formula I or X ¹ in formulas IA to IC.

A further preferred reaction esterifies the C6-OH functional group with a carboxylic acid 85 (see Reaction Scheme 22 ).

Reaction Scheme 22: Functionalization of C6-OH by esterification (examples of preferred reaction sequences); see Figure 15 for definition of groups.

Mitsunobu esterification can also be carried out using a suitable alcohol 99 (for example, but specifically phenol 89 ) (see Reaction Scheme 23 ). After removal of the benzyl protecting group, intermediate 91 is obtained which can then be converted to the type 92 compound.

Reaction Scheme 23: Functionalization of C6-OH by esterification (examples of preferred reaction sequences).

In addition, the C6-hydroxy group can be converted to a good leaving group (e.g., bromide or tosylate). Further, a nucleophilic reagent (preferably using a carbon-containing nucleophile (for example, Grignard reagent 94 ) and an oxygen-containing nucleophile (for example, a phenol 89 , an alcohol 99 or a carboxylic acid 85 ) may be further used, such as 93 or 98 . The compound is converted to other preferred intermediates 96 , 91 , 100 and 87 .

Reaction Scheme 24: Conversion of a C6-hydroxy group to a leaving group (here a tosylate or bromide) and reaction with a nucleophile; the definition of the group is shown in Figure 15.

A: Synthesis of tosylate 93 and reaction with Grignard reagent 94

B: Synthesis of bromide 98 and reaction with phenol 89

C: Reaction of bromide 98 with alcohol 99

D: Reaction of bromide 98 with carboxylic acid 85

Oxide 80 (e.g. Swern oxidation) to give the aldehyde 102. It is a better substrate for the Wittig reaction (see Figure 25 ) or for the addition reaction. Wittig reaction to give the compound C- bridge containing -C =, in the subsequent hydrogenation -C = C- bridge bonds may be converted to -CH ₂ -CH ₂ - bridge. In this way, a simple alkyl group can also be introduced.

Reaction Scheme 25: Synthesis of aldehyde 102 and reaction with reagent 103 (Wittig reaction); for the definition of the group, see Reaction Scheme 15.

If the target is to obtain a compound containing a double bond, then other protecting groups must be used.

Reaction Scheme 26: Synthesis of aldehyde 108 and conversion to a compound I containing a -C=C-bridge by Wittig reaction (especially = 12); for the definition of the group, see Figure 15.

If intended to obtain the compound containing an ester bond, the carboxylic acid 113 (see FIG. 27 reactions). These carboxylic acids can be obtained from the oxidation of compound 80 by TEMPO. Esterification using alcohol 99 gives compound 114 . After removal of the benzyl group, the spacer group and the polymerizable group can be attached again.

Reaction Scheme 27: Synthesis of Carboxylic Acid 113 and esterification using alcohol/phenol 99. The synthesis of compound I (especially = 115) containing an ester bridge at C6; see Figure 15 for the definition of the group.

Wherein the group R ¹ -[A ¹ -Z ¹ ] _x - or R ² -[A ³ -Z ³ ] _y - is a compound I which is introduced at an anomeric center or via a OH group Especially good compound.

However, a compound having a group R ¹ -[A ¹ -Z ¹ ] _x - or R ² -[A ³ -Z ³ ] _y - attached at a different position of the sugar skeleton is also a preferred compound (see, for example, a substructure) IB and IC ). For its synthesis, it is necessary in some cases to distinguish between the three different secondary OH functional groups present. For this purpose, a wide variety of methods from sugar chemistry can be employed by those skilled in the art. One possibility, in which a cyclic acetal is used, is shown below, taking the reaction of D-(+)-galactose (116) as an example. It is first converted to, for example, the corresponding methyl glycoside 117 . The OH groups in the C4 and C5 groups may be selectively protected in the form of an acetonide (compound 118 ). The primary and secondary OH groups are then distinguished again using a trityl protecting group. The remaining OH groups in compound 119 are then suitably derivatized. The protecting group can then be removed to give 121 . Deprotection can also be performed sequentially to attach different spacer groups. For the sake of brevity, this possibility is not shown here. Functionalization can then be carried out, for example, using the methods indicated above to give polymerizable compound 122 or 123 .

Reaction Figure 28: Substituent R on the sugar skeleton C6 ¹ -[A ¹ -Z ¹ ] _x -or R ² -[A ³ -Z ³ ] _y - Synthesis of Compound I (especially = 122 or 123), taking D-(+)-galactose (116) as an example

In addition, adjacent OH groups can be converted to epoxides. A nucleophile can be used to open the ring. This also makes it possible to distinguish between two secondary OH groups and has indicated a further possibility of forming a CC bond in the sense of S _N 2 reaction. An example is shown in Reaction Scheme 29 . Here, the benzal acetal 124 formed from the methyl glycoside of D-(+)-glucose is converted to the epoxide 125 . The ring is then opened, for example, using Grignard reagent 126 . The OH groups in 127 can then be suitably functionalized in each case after dissociation.

Reaction Figure 29: Synthesis and reaction of epoxide 125

Also preferred are compounds wherein the group R ¹ -[A ¹ -Z ¹ ] _x - on the terminal anomeric center represents hydrogen. These compounds are also obtainable from the deoxygenation reaction of sugars by an anomeric center. Deoxygenation is usually carried out by means of free radicals, for example using tin hydride. One possible reaction sequence is shown in Reaction Scheme 30 , taking the reaction of L-(+)-arabinose (35) as an example. First, all the OH groups acylated, by reaction with PBr ₃ and brominated anomeric center. The resulting compound 128 was then deoxygenated using tributyltin hydride. After hydrolysis of the ester group, suitable unit 129 is obtained for the synthesis of compound I (= 130 in reaction diagram 30 ). Of course, the deoxygenation reaction can also be carried out in a similar manner in other synthetic steps.

Reaction Figure 30: Deoxygenation of an anomeric center, taking L-(+)-arabinose (35) as an example

A further preferred form of functionalization of the anomeric center is fluorination. This enables, for example, even better compatibility with conventional highly fluorinated LC materials. The glycosyl fluoride can also be obtained from an acetate (for example) by reaction with an HF/pyridine complex (see Reaction Scheme 31 ).

Reaction Figure 31: Synthesis of glycosyl fluoride 132, taking L-(+)-arabinose (35) as an example

A further preferred reaction is the Wittig-Horner-Emmons reaction at the anomeric center with a stable ylide. In this way, a C-glycoside (e.g., 134 ) can be obtained from which a spacer group can be constructed. An example is shown in Reaction Scheme 32 .

Reaction Figure 32: Wittig-Horner-Emmons reaction at the endo-isomerization center.

Other preferred spacer groups and their synthesis will be discussed again herein. The above examples have shown that a compound containing an extended OH group of the formula -Sp"-OH or a -Sp"-Br- unit (wherein Sp" is in each case represented by two or more C atoms An analogous bromide-based important intermediate (eg, compound 9 , 15 ) of the oxacycloalkenyl chain. It can bond other groups.

The compound (for example, 9 ) can be, for example, sequentially reacted with ω-bromoalkanoic acid 2 or ω-bromoalkyl fluorenyl chloride 6 (refer to Reaction Scheme 33 ).

Reaction Scheme 33: Synthesis example of relatively complex spacer groups. Synthesis of Compound 136. W ¹ =R. R is preferably H or CH ₃ .

Relatively complex spacer groups can be constructed or the chain can be extended in this manner or in a similar manner. Here, those skilled in the art should be able to combine suitable methods with each other. These also include the alkylation reaction using alpha-bromomethyl acetate 137 and the reaction of bromide with, for example, (poly)ethylidene glycol 141 .

Hydrolysis of the product 137 using an alpha-bromomethyl acetate alkylation reaction can be carried out, and the acrylate group can be directly attached via esterification, for example, using (2-hydroxyalkylalkyl) acrylate 47 .

The product reacted with (poly)ethyl 141 can be directly converted to an acrylate.

Reaction Scheme 34: Synthesis of relatively complex spacer groups. Synthesis of compounds 140 and 143. W ¹ =R. R is preferably H or CH ₃ .

The alkylation reaction of α-bromomethyl acetate 137 and subsequent reaction were carried out.

Reaction with ethylene glycol 141 .

The alkylation reaction using alpha-bromomethyl acetate 137 is also suitable, for example, for attachment of a preferred spacer group Sp'X=OCH ₂ C(O)O(CH) on all sides starting from a glycoside (e.g., 144 ). ₂ ) ₂ - (Refer to Figure 35 ).

Reaction Figure 35: where Sp'X=OCH ₂ C(O)O(CH ₂ ) ₂ - Synthesis of Compound I (especially = 147). An example of the reaction of methyl glycoside 144. W ¹ =R. R is preferably H or CH ₃ .

Accordingly, the invention is generally further directed to a process for the preparation of a compound of formula I as defined for a compound by means of a monosaccharide or a disaccharide (specifically the sugars mentioned or depicted above) and derivatives thereof Derived to implement.

The invention further relates to the use of the compounds of the formula I in liquid-crystalline media, in particular as polymers in such media. These compounds can also be used as polymers for stabilizing the liquid crystal phase, specifically the blue phase. Such uses are well known to us and are set forth in the Examples section of the cited documents and blue phase examples. In general, the medium polymerizes at a temperature at the blue phase. This greatly broadens the range of stability of this phase.

Preferably, the liquid crystal medium is characterized in that it is at least 15 ° C to 30 ° C (preferably 10 ° C to 40 ° C, particularly preferably 0 ° C to 50 ° C, and preferably -10 ° C to 60 ° C after stabilizing the blue phase by polymerization). ) has a blue phase within the range.

The invention likewise relates to a liquid-crystalline medium comprising a polymer or comprising at least one non-polymeric monomer of the formula I or both, the polymer comprising at least one monomer component of the formula I.

Particularly preferred media of the invention are those mentioned below: the medium comprises one or more monoreactive monomers or polymers constructed from one or more monoreactive monomers and optionally other monomers. The proportion of the monoreactive monomer is preferably from 1% to 15%, particularly preferably from 2% to 12%. Preferred single-reacting single systems have those of formula I* (as indicated below), with individual groups being particularly preferred for the preferred embodiment of formula I* and only the group Ra is polymerizable. More preferred are compounds of the formula I* wherein n = 1 and B ¹ /B ² represents cyclohexane-1,4-diyl or 1,4-phenylene.

In addition to the single reactive monomers mentioned above, the medium comprises one or more compounds useful as crosslinkers, the compounds being distinguished by a plurality of reactive groups. These include compounds of formula I.

The medium comprises one or more di-reactive monomers or a polymer constructed from one or more di-reactive monomers and optionally other monomers. The proportion of the two reactive monomers is preferably from 0% to 9%, particularly preferably from 0% to 5%. In a preferred embodiment, the direactive monomer is partially or completely replaced by a compound of formula I of the invention containing three or more reactive groups.

The sum of the mono- and di-reactive monomers is preferably from 3% to 17%, particularly preferably from 6 to 14%.

It is also possible to use three reactive or polyreactive (>3) monomers. In some or all cases, a tri-reactive or polyreactive (>3) monomer is preferred to be a compound of formula I.

The ratio of monoreactive monomer to crosslinker is preferably between 3:1 and 1:1. This ratio depends on the number of reactive groups of the crosslinking agent involved. In the case of using a four-reactive cross-linking agent, the ratio is particularly preferably between 3:1 and 2:1, and in the case of using a two-reactive cross-linking agent, the ratio is particularly preferably between 1.5:1 and 1. Between:1.

The monoreactive monomer has, for example, the structure R ^a -Sp-P of the following formula, wherein P represents a polymerizable group, Sp represents a spacer group or a single bond, and R ^a represents an organic group having at least 3 C atoms Group.

The group R ^a may be a so-called liquid crystal primordial group, which usually contains one or more rings, or a simple, usually chain-like, non-liquid crystal primordial group.

The non-liquid crystal primordial group is preferably a linear or branched alkyl group having 1 to 30 C atoms, and further, one or more of the non-contiguous CH ₂ groups may be directly connected to each other by O and/or S atoms. The manners are each independently of each other via -C(R ⁰ )=C(R ⁰⁰ )-, -C≡C-, -N(R ⁰⁰ )-, -O-, -S-, -CO-, -CO- O-, -O-CO-, -O-CO-O- is substituted, and in addition, one or more H atoms may be replaced by F, Cl, Br, I or CN.

The preferred meanings of P and Sp correspond to the meanings indicated below for formula I*.

Preferred liquid crystal monomers having one, two or more polymerizable groups are characterized by Formula I*

R ^a -B ¹ -(Z ^b -B ² ) _m -R ^b I*

Wherein individual groups have the following meanings: R ^a and R ^b each independently represent P, P-Sp-, H, halogen, SF ₅ , NO ₂ , carbon or hydrocarbyl, wherein such radicals R ^a and R ^b At least one of or represents a group P or P-Sp-, each occurrence of P is the same or different and represents a polymerizable group, each occurrence of Sp is the same or different and represents a spacer group or a single bond, B ¹ And B ² each independently represent an aromatic, heteroaromatic, alicyclic or heterocyclic group preferably having 4 to 25 ring atoms, which may also contain a fused ring and which may also be monosubstituted by L Or polysubstituted, L represents P-Sp-, H, OH, CH ₂ OH, halogen, SF ₅ , NO ₂ , carbon or hydrocarbyl, and Z ^b is the same or different at each occurrence and represents -O-, -S- , -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O- , -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -(CH ₂ ) _n1 -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -(CF ₂ ) _n1 -, -CH= CH-, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, CR ⁰ R ⁰⁰ or a single bond, and R ⁰ and R ⁰⁰ each independently represent H Or an alkyl group having 1 to 12 C atoms, m Indicates 0, 1, 2, 3 or 4, and n1 represents 1, 2, 3 or 4.

Preferably, the compound of formula I* is one in which one or more of the groups represents the following meaning: R ^a and R ^b each independently represent P, P-Sp-, H, F, Cl, Br. , I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, SF ₅ or a linear or branched alkyl group having 1 to 25 C atoms, in addition, one or more The non-adjacent CH ₂ groups may be independently from each other by the manner in which O and/or S atoms are not directly connected to each other by -C(R ⁰ )=C(R ⁰⁰ )-, -C≡C-, -N(R ⁰⁰ ). -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- instead, and additionally, one or more of the H atoms may be F, Cl, Br, I, CN, P or P-Sp-substitution, wherein at least one of the groups R ^a and R ^b represents or contains a group P or P-Sp-, and B ¹ and B ² each independently represent 1, 4 - phenyl, naphthalene-1,4-diyl, naphthalene-2,6-diyl, phenanthrene-2,7-diyl, indole-2,7-diyl, indole-2,7-diyl, Coumarin, flavonoids (in addition, wherein one or more of the CH groups may be replaced by N), cyclohexane-1,4-diyl (in addition, one or more of which are not adjacent to the CH ₂ group) Group can be replaced by O and / or S), 1,4-cyclohexenyl, bicyclo [1.1.1] pentane-1 ,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, hexahydropyridine-1,4-diyl, dehydrogenated Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indoline-2,5-diyl or octahydro-4,7-methylene Hydroquinone-2,5-diyl, wherein all such groups may be unsubstituted or mono- or polysubstituted by L, and L represents P, P-Sp-, OH, CH ₂ OH, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)N(R ^x ) ₂ , -C(=O)Y ¹ , -C(=O)R ^x , -N(R ^x ) ₂ , optionally substituted methylidene, optionally substituted aryl having 6 to 20 C atoms, or linear or having 1 to 25 C atoms Branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, in addition, one or more of the H atoms may be F, Cl, P or P-Sp - Substituting, P and Sp have the meanings given above, Y ¹ represents halogen, R ^x represents P, P-Sp-, H, halogen, linear, branched or 1 to 25 C atoms cyclic alkyl groups (in addition, one or more non-adjacent CH ₂ groups may be O and / or S atoms are not directly connected with each other The formula is replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and additionally, one or more of the H atoms may be F, Cl, P or P-Sp-substituted), optionally substituted aryl or aryloxy having 6 to 40 C atoms, or optionally substituted heteroaryl having 2 to 40 C atoms or Heteroaryloxy, and/or m represents 0, 1 or 2.

The term "carbon-based" means a monovalent or polyvalent organic radical containing at least one carbon atom, wherein it is free of other atoms (eg, -C≡C-) or optionally one or more other atoms (eg, N, O, S, P, Si, Se, As, Te or Ge) (for example, carbonyl, etc.). The term "hydrocarbyl" refers to a carbon radical that additionally contains one or more H atoms and optionally one or more heteroatoms (eg, N, O, S, P, Si, Se, As, Te, or Ge).

"Halogen" means F, Cl, Br or I, preferably F or Cl.

The carbyl or hydrocarbyl group can be a saturated or unsaturated group. The unsaturated group is, for example, an aryl group, an alkenyl group or an alkynyl group. The carbon group or hydrocarbon group having 3 or more C atoms may be linear, branched, and/or cyclic and may also contain a spiro bond or a fused ring.

The terms "alkyl", "aryl", "heteroaryl" and the like also encompass polyvalent groups such as alkyl, aryl, heteroaryl and the like.

The term "aryl" means an aromatic carbon group or a group derived therefrom. The term "heteroaryl" means an "aryl" group as defined above containing one or more heteroatoms.

Preferred carbon-based and hydrocarbon-based alkyl, alkenyl, alkynyl, alkoxy groups having from 1 to 40, preferably from 1 to 25, particularly preferably from 1 to 18, C atoms, optionally substituted Alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy; optionally substituted aryl and aryloxy having 6 to 40, preferably 6 to 25, C atoms And optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, aryl having 6 to 40, preferably 6 to 25, C atoms Alkylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy.

Other preferred group of carbon and hydrocarbon-based radical C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₃ -C ₄₀ allyl group, C ₄ -C ₄₀ alkyl di Alkenyl, C ₄ -C ₄₀ polyalkenyl, C ₆ -C ₄₀ aryl, C ₆ -C ₄₀ alkylaryl, C ₆ -C ₄₀ arylalkyl, C ₆ -C ₄₀ alkylaryloxy A C ₆ -C ₄₀ arylalkyloxy group, a C ₂ -C ₄₀ heteroaryl group, a C ₄ -C ₄₀ cycloalkyl group, a C ₄ -C ₄₀ cycloalkenyl group or the like. Particularly preferred are C ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl, C ₂ -C ₂₂ alkynyl, C ₃ -C ₂₂ allyl, C ₄ -C ₂₂ alkyldienyl, C ₆ -C ₁₂ aryl, C ₆ -C ₂₀ arylalkyl and C ₂ -C ₂₀ heteroaryl.

Other preferred carbon-based and hydrocarbon groups are linear, branched or cyclic alkyl groups having from 1 to 40, preferably from 1 to 25, C atoms which are unsubstituted or substituted by F, Cl, Br, I or CN is mono- or poly-substituted, and one or more of the non-adjacent CH ₂ groups may be independently from each other independently by -C(R ^x )=C(R ^x ) in such a manner that O and/or S atoms are not directly connected to each other. )-, -C≡C-, -N(R ^x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-.

R ^x preferably denotes H, halogen, a linear, branched or cyclic alkyl chain having from 1 to 25 C atoms, and additionally, one or more of the non-adjacent C atoms may be -O-, -S- , -CO-, -CO-O-, -O-CO-, -O-CO-O-, and wherein one or more of the H atoms may be replaced by fluorine; having from 6 to 40 C atoms as appropriate a substituted aryl or aryloxy group; or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms.

Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy , third butoxy, 2-methylbutoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy Base, n-dodecyloxy and the like.

Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, 2-methylbutyl, n-pentyl , second amyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-decyl, n-decyl, n-undecane Base, n-dodecyl, dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, and the like.

Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, ring Octenyl and the like.

Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy , third butoxy, 2-methylbutoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy Base, n-dodecyloxy and the like.

Preferred amine groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

The aryl and heteroaryl groups may be monocyclic or polycyclic, that is, they may contain one ring (eg, phenyl) or two or more rings, which may also be fused (eg, naphthyl) or co- Valence linkage (eg, biphenyl), or a combination of fused and linked rings. The heteroaryl group contains one or more heteroatoms, preferably selected from the group consisting of O, N, S and Se.

Particularly preferred are monocyclic, bicyclic or tricyclic aryl groups having 6 to 25 C atoms, and monocyclic, bicyclic or tricyclic heteroaryl groups having 2 to 25 C atoms, which are optionally contained A fused ring and replaced as appropriate. Further preferred are 5-, 6- or 7-membered aryl and heteroaryl groups, in addition, one or more of the CH groups may be N, S or may be independently bonded to each other by O atoms and/or S atoms. O replacement.

Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1':3',1"]triphenyl-2'-yl, naphthyl, anthracenyl, binaphthyl , phenanthryl, fluorenyl, indanyl, decyl, fluorenyl, tetraphenyl, pentacene, benzindenyl, anthracenyl, fluorenyl, indenyl, stilbene Wait.

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; - Member 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 a condensed group such as anthracene, isoindole, pyridazine, oxazole, benzimidazole, benzene And triazole, anthracene, naphthimidazole, phenamimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthraquinone, phenanthroxazole, different Oxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline , benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzoxazine, benzopyrimidine, quinoxaline, phenazine, Pyridine, azacarbazole, benzoporphyrin, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene , benzothiadiazole thiophene, or a combination of such groups. Heteroaryl groups can also be substituted with alkyl, alkoxy, thioalkyl, fluoro, fluoroalkyl or other aryl or heteroaryl groups.

(Non-aromatic) alicyclic and heterocyclic groups include both saturated rings (ie, those which exclusively contain a single bond) and partially unsaturated rings (ie, those which may also contain multiple bonds). The heterocycle contains one or more heteroatoms, preferably selected from the group consisting of Si, O, N, S and Se.

The (non-aromatic) alicyclic and heterocyclic groups may be monocyclic (ie, containing only one ring (eg, cyclohexane)) or polycyclic (ie, containing a plurality of rings (eg, decalin or bicyclic) Octane)). Particularly preferred are saturated groups. Preferred are further monocyclic, bicyclic or tricyclic groups having from 3 to 25 C atoms, optionally containing a fused ring and optionally substituted. More preferably a 5-, 6-, 7- or 8-membered carbocyclic group, in which 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 ₂ groups may be replaced by -O- and/or -S-.

Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups such as cyclopentane, tetrahydrofuran, tetrahydrothiophene, pyrrolidine; 6-member groups such as cyclohexane, cyclohexene, tetrahydrogen Piperane, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, hexahydropyridine; a 7-member group such as cycloheptane; and a condensed group such as tetralin , decalin, indoline, 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-methyleneindoline-2,5-diyl.

Preferred substituents are, for example, groups which promote dissolution (for example alkyl or alkoxy groups), electron withdrawing groups (for example, fluorine, nitro or nitriles), or for increasing the glass transition temperature of polymers (Tg) a group, in particular a bulky group (for example, a tert-butyl group or an optionally substituted aryl group).

Preferred substituents (also referred to above as "L") are, for example, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C (=O)N(R ^x ) ₂ , -C(=O)Y ¹ , -C(=O)R ^x , -N(R ^x ) ₂ , where R ^x has the meaning indicated above, and Y ¹ represents a halogen, optionally substituted methylidene or an aryl group having 6 to 40, preferably 6 to 20 C atoms, and a linear or branched alkane having 1 to 25 C atoms. Alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein one or more H atoms may be replaced by F or Cl, as appropriate.

"Substituted carboxyalkyl or aryl" preferably means halogen, -CN, R ⁰ , -OR ⁰ , -CO-R ⁰ , -CO-OR ⁰ , -O-CO-R ⁰ or -O. -CO-OR ⁰ substitution, wherein R ⁰ has the meaning indicated above.

Further preferred substituents L are, for example, F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , further a phenyl group. Preferred or Where L has one of the meanings indicated above.

The polymerizable group P is suitable for polymerization (for example, radical or ionic chain polymerization, addition polymerization or polycondensation) or a group suitable for the reaction of a polymer analog (for example, addition or condensation onto the polymer backbone). Particularly preferred are groups for chain polymerization (specifically, those containing C=C double bonds or C≡C triple bonds), and groups suitable for ring opening polymerization (for example, propylene oxide or epoxy) Compound group).

Preferred groups P are as defined above for Formula I.

Preferably, the spacer group Sp is selected from the group consisting of the formula Sp'-X- as set forth above for Formula I.

In still another preferred embodiment of the present invention, P-Sp- represents a group (polyfunctional polymerizable group) containing two or more polymerizable groups. Suitable groups of this type, and polymerizable compounds containing the same, and their preparation are described, for example, in US 7,060,200 B1 or US 2006/0172090 A1. Particularly preferred are selected from the following polyfunctional polymerizable groups P-Sp-:

-X-alkyl-CHP ¹ -CH ₂ -CH ₂ P ² I*a

-X-alkyl-C(CH ₂ P ¹ )(CH ₂ P ² )-CH ₂ P ³ I*b

-X-alkyl-CHP ¹ CHP ² -CH ₂ P ³ I*c

-X-alkyl-C(CH ₂ P ¹ )(CH ₂ P ² )-C _aa H _2aa+1 I*d

-X-alkyl-CHP ¹ -CH ₂ P ² I*e

-X-alkyl-CHP ¹ P ² I*f

-X-alkyl-CP ¹ P ² -C _aa H _2aa+1 I*g

-X-Alkyl-C(CH ₂ P ¹ )(CH ₂ P ² )-CH ₂ OCH ₂ -C(CH ₂ P ³ )(CH ₂ P ⁴ )CH ₂ P ⁵ I*h

-X-alkyl-CH((CH ₂ ) _aa P ¹ )((CH ₂ ) _bb P ² ) I*i

-X-alkyl-CHP ¹ CHP ² -C _aa H _2aa+1 I*k

-X-alkyl-C(CH ₃ )(CH ₂ P ¹ )(CH ₂ P ² ) I*m

Wherein alkyl represents a single bond or a straight or branched alkyl group having from 1 to 12 C atoms, wherein one or more of the non-adjacent CH ₂ groups may be such that O and/or S atoms are not directly bonded to each other. Each independently of -C(R ⁰⁰ )=C(R ⁰⁰⁰ )-, -C≡C-, -N(R ⁰⁰ )-, -O-, -S-, -CO-, -CO-O- , -O-CO-, -O-CO-O- is substituted, and additionally, one or more of the H atoms may be replaced by F, Cl or CN, wherein R ⁰⁰ and R ⁰⁰⁰ have the meanings indicated above, aa and bb Each independently represents 0, ¹ , 2, 3, 4, 5 or 6, and P ^1-5 each have one of the meanings indicated for P independently of each other.

The polymerizable compound and RM can be prepared in a manner similar to that known to those skilled in the art and described in standard work on organic chemistry, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag , Stuttgart. Other synthetic methods are given in the documents cited above and below. In the simplest case, such RM is used, for example, by the use of a corresponding acid, acid derivative or halogenated compound containing a group P in the presence of a dehydrating reagent such as DCC (dicyclohexylcarbodiimide). (for example, (meth)acrylofluorene or (meth)acrylic acid) esterified or etherified 2,6-dihydroxynaphthalene or 4,4'-dihydroxybiphenyl to be synthesized.

As a further component, the liquid crystal medium preferably comprises a non-polymerizable compound which supports the liquid crystal phase, which is also referred to as a host mixture. The proportion is usually from 50% by weight to 95% by weight, preferably from 80% by weight to 90% by weight. In the case of a polymer-stabilized blue phase, the non-polymerizable moiety preferably comprises a compound selected from Table A (see the Examples section). This portion preferably consists of 50% by weight or more of these compounds, and is preferably 80% by weight or more.

The liquid crystal medium having a blue phase of the present invention preferably has positive dielectric anisotropy. It can be constructed in such a manner as to have extremely high dielectric anisotropy and high optical anisotropy values.

Other preferred compounds of the invention for liquid crystal media are selected from the group consisting of the compounds of formula II and III:

Wherein R ¹ independently of each other represents an unsubstituted alkyl group having from 1 to 15 C atoms, and wherein one or more of the CH ₂ groups in the group may not directly be mutually O atoms The manner of connection is independent of each other by -C≡C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO) -, -(CO)- or -O-, preferably a linear alkyl group having 2 to 7 C atoms, and A ² and A ³ are independently represented

Z ² and Z ³ independently of each other represent a single bond, CF ₂ O, CH ₂ CH ₂ , CF ₂ CH ₂ , CF ₂ CF ₂ , CFHCFH, CFHCH ₂ , (CO)O, CH ₂ O, C=C, CH =CH, CF=CH, CF=CF, wherein an asymmetric linking member (eg CF ₂ O) can be oriented in two possible directions, X ¹ representing F, Cl, CN, or having 1 to 3 C atoms An alkyl group, an alkenyl group, an alkenyloxy group, an alkyl alkoxy group or an alkoxy group which is mono- or polysubstituted by F, and L ¹ to L ⁴ represents H or F.

The liquid crystal medium preferably comprises between 20% and 40% by weight of a compound of formula II. If a compound of formula III is present, it is preferably used up to 20% by weight. If other compounds are present, they are selected from other compounds having high dielectric anisotropy, high optical anisotropy and preferably having a high clearing point.

Preferred compounds of formula II are those of formula IIa:

Wherein R ¹ and L ¹ are as defined for formula II.

Preferred compounds of formula III are those of formula IIIa or IIIb:

Wherein R ¹ is as defined for formula III.

LC media which can be used in accordance with the invention are prepared in a manner which is customary per se, for example by the addition of one or more of the above-mentioned compounds with one or more polymerizable compounds as defined above, and optionally The liquid crystal compound and/or the additive are mixed. In general, it is advantageous to dissolve a desired amount of the component in a small amount in a component constituting the main portion at a high temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and after thorough mixing, remove the solvent by, for example, distillation. The invention further relates to a process for preparing an LC medium of the invention.

It will be apparent to those skilled in the art that the LC media of the present invention may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.

For the purposes of the present invention, the terms alkyl, alkenyl and the like are defined as follows: The term "alkyl" embraces straight-chain and branched alkyl groups having from 1 to 9 carbon atoms, in particular straight-chain methyl groups. , ethyl, propyl, butyl, pentyl, hexyl and heptyl. A group having 2 to 5 carbon atoms is usually preferred.

The term "alkenyl" encompasses straight-chain and branched alkenyl groups having up to 9 carbon atoms, in particular straight-chain groups. More preferably, the alkenyl group is a C ₂ -C ₇ -1E-alkenyl group, a C ₄ -C ₇ -3E-alkenyl group, a C ₅ -C ₇ -4-alkenyl group, a C ₆ -C ₇ -5-alkenyl group, and C ₇ -6-alkenyl, in particular C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -3E-alkenyl and C ₅ -C ₇ --4-alkenyl. Examples of preferred alkenyl groups are ethenyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like . Groups having up to 5 carbon atoms are generally preferred.

The term "fluoroalkyl" as used in this application encompasses a straight-chain group containing at least one fluorine atom (preferably terminal fluorine), namely fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl. Base, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other locations of fluorine are not excluded.

The term "haloalkyl" preferably encompasses mono- or polyfluorinated and/or chlorinated groups. Includes perfluorinated groups. More preferred are fluorinated alkyl groups, specifically CF ₃ , CH ₂ CF ₃ , CH ₂ CHF ₂ , CHF ₂ , CH ₂ F, CHFCF ₃ and CF ₂ CHFCF ₃ .

The term "alkylene" encompasses straight-chain and branched alkanediyl groups having from 1 to 12 carbon atoms, in particular straight-chain groups methylene, ethyl, propyl, butyl and extens Amyl. Groups having 2 to 8 carbon atoms are generally preferred.

Other combinations of embodiments and variations of the invention may be derived from the scope of the invention as claimed.

Abbreviations used: DCC bicyclohexylcarbodiimide, DMAP 4-(dimethylamino)pyridine, 9-BBN 9-borobicyclo[3.3.1]decane, MTBE methyl tert-butyl ether, DMSO dimethyl hydrazine.

Each phase code: C: crystal; N: nematic; BP: blue phase; Tg: glass transition temperature; I: isotropic.

Instance Example 1: 5-(2-Methylpropenylmethoxy)pentanoic acid (3R,4S,5R)-4,5,6-indole-[5-(2-methylpropenyloxy)pentanyl Vinyl]tetrahydropyran-3-yl ester

The compound of the present invention 5-(2-methylpropenyloxy)pentanoic acid (3R,4S,5R)-4,5,6-indole-[5-(2-methylpropenyloxy)pentanyl The benzyloxy]tetrahydropyran-3-yl ester was synthesized as described below.

1.1 Use of bromopentanoate to D-(+)-xylose: 5-bromopentanoic acid (3R,4S,5R)-4,5,6-indole-(5-bromopentenyloxy)tetrahydroperoxide Preparation of m--3-yl ester

First, 20.0 g (0.13 mol) of D-(+)-xylose was introduced into 1500 ml of dichloromethane together with 120.0 g (0.67 mol) of 5-bromopentanoic acid and 1.0 g (8.19 mmol) of DMAP. A solution of 140.0 g (0.68 mol) DCC in 500 ml of dichloromethane was added and the mixture was stirred at room temperature for 72 h. 50.0 g (0.40 mol) of oxalic acid was added, and after 1 h, the insoluble matter was filtered off. The filtrate was concentrated to dryness and purified by column chromatography on the residue (SiO _2, dichloromethane: 3: MTBE = 97).

1.2 5-(2-Methylacryloyloxy)pentanoic acid (3R,4S,5R)-4,5,6-indole-[5-(2-methylpropenyloxy)pentenyloxy Preparation of tetrahydropyran-3-yl ester

3.5 g (4.36 mmol) of 5-bromopentanoic acid (3R,4S,5R)-4,5,6-indole-(5-bromopentenyloxy)tetrahydropyridinium in 50 ml of DMSO at 50 °C The m--3-yl ester was stirred with 4.4 ml (52.0 mmol) of methacrylic acid and 8.44 g (61.1 mmol) of potassium carbonate. The suspension was diluted with MTBE and washed with water. The aqueous phase was extracted with MTBE and the combined organic phases were washed with saturated sodium chloride. The solution was dried over sodium sulfate and concentrated to dryness. By column chromatography (SiO _2, dichloromethane: MTBE = 95: 5) and the residue was purified to give a colorless oil of 5- (2-Bing Xixi yloxy) valeric acid (3R, 4S, 5R -4,5,6-indole-[5-(2-methylpropenyloxy)pentenyloxy]tetrahydropyran-3-yl ester (α:β 88:12).

Phase sequence: Tg-62 I

¹ H-NMR (300 MHz, CHCl ₃ ): δ = 6.29 (d, 1H, J = 3.7 Hz, H _- pyranyl), 6.11-6.07 (m, 4H, H _acrylate ), 5.57-5.54 (m, 4H, H _acrylate ), 5.47 (t, 1H, J = 9.8 Hz, H _- pyranyl), 5.10-5.02 (m, 2H, H _- pyranyl), 4.20 - 4.10 (m, 8 H, 4 x CH ₂ OC(O)), 3.94 (dd, 1H, J = 11.3 Hz, J = 5.9 Hz, H _-pyranyl ), 3.69 (t, 1H, J = 11.3 Hz, H _- pyranyl), 2.52-2.23 ( m, 8H, 4 x OC(O) CH ₂ ), 1.95-1.93 (m, 12H, 4 x C Me = CH ₂ ), 1.79-1.63 (m, 16H, H _aliphatic ).

(The data indicated is for the major anomers)

MS (EI) : m/e (%) = 822 (1, M ⁺ ), 69 (100).

Example 2: 5-Phenyl decyloxypentanoic acid (3R,4S,5R)-4,5,6-indole-(5-propenylfluorenylpentyloxy)tetrahydropyran-3-yl ester

The present invention is a compound 5-propenyl methoxy valeric acid (3R, 4S, 5R)-4,5,6-indole-(5-propenyl methoxy-pentenyloxy)tetrahydropyran-3- The base ester is synthesized as described below.

2.1 5-Acryl-mercaptooxyvaleric acid (3R,4S,5R)-4,5,6-indole-(5-propenyloxypentenyloxy)tetrahydropyran-3-yl ester preparation

17.0 g (17.3 mmol) of 5-bromopentanoic acid (3R,4S,5R)-4,5,6-indole-(5-bromopentenyloxy)tetrahydropyridinium in 500 ml of DMSO at 50 °C The m--3-yl ester was stirred with 14.3 ml (0.21 mol) of acrylic acid and 33.5 g (0.24 mol) of potassium carbonate. The suspension was diluted with MTBE and washed with water. The aqueous phase was extracted with MTBE and the combined organic phases were washed with saturated sodium chloride. The solution was dried over sodium sulfate and concentrated to dryness. By column chromatography (SiO _2, dichloromethane: MTBE = 95: 5 and SiO _2, pentane: MTBE = 6: 4) The residue was purified to give a colorless oil Bing Xixi 5- yloxy acid (3R,4S,5R)-4,5,6-indole-(5-propenyloxypentenyloxy)tetrahydropyran-3-yl ester (a: β 92:8).

Phase sequence: Tg-57 I

¹ H-NMR (300 MHz, CHCl ₃ ): δ = 6.40 (dm, 4H, J = 17.4 Hz, H _acrylate ), 6.29 (d, 1H, J = 3.8 Hz, H _-pyranyl ), 6.17-6.06 (m, 4H, H _acrylate ), 5.83 (dm, 4H, J = 10.4 Hz, H _acrylate ), 5.47 (t, 1H, J = 9.8 Hz, H _-pyranyl ), 5.10-5.00 (m, 2H) , H _-pyranyl ), 4.22-4.10 (m, 8 H, 4 × CH ₂ OC(O)), 3.94 (dd, 1H, J = 11.3 Hz, J = 5.9 Hz, H _-pyranyl ), 3.70 ( t, 1H, J = 11.3 Hz, H _- pyranyl), 2.52-2.24 (m, 8H, 4 x OC(O) CH ₂ ), 1.79-1.63 (m, 16H, H _aliphatic ).

(The data indicated is for the major anomers)

Example 3: 5-(Phenylmercaptooxypentanoic acid (3R,4S)-4,6-bis-(5-propenylfluorenylpentyloxy)tetrahydropyran-3-yl ester

The compound of the present invention 5-propenyl methoxy valeric acid (3R, 4S)-4,6-bis-(5-propenyl fluorenylpentenyloxy) tetrahydropyran-3-yl ester is as follows The synthesis.

3.1 Use of bromopentanoate to decolorize 2-deoxy-D-ribose: 5-bromopentanoic acid (3R,4S)-4,6-bis-(5-bromopentenyloxy)tetrahydropyran-3-yl Preparation of ester

First, 15.0 g (0.11 mol) of 2-deoxy-D-ribose was introduced into 2000 ml of dichloromethane together with 80.0 g (0.44 mol) of 5-bromopentanoic acid and 1.0 g (8.19 mmol) of DMAP. A solution of 100.0 g (0.48 mol) DCC in 500 ml of dichloromethane was added and the mixture was stirred at room temperature for 48 h. An additional 20.0 g (0.11 mol) of 5-bromopentanoic acid was added and the mixture was stirred again for 72 h. 50.0 g (0.40 mol) of oxalic acid was added, and after 1 h, the insoluble matter was filtered off. The filtrate was concentrated to dryness and by column chromatography (SiO _2, dichloromethane: MTBE = 97: 3 and Al ₂ O _3, dichloromethane: MTBE = 97: 3) and the residue was purified to give a colorless oil (5R,4S)-4,6-bis-(5-bromopentenyloxy)tetrahydropyran-3-yl ester of 5-bromopentanoic acid.

3.2 Preparation of 5-propenyldecyloxypentanoic acid (3R,4S)-4,6-bis-(5-propenylfluorenylpentyloxy)tetrahydropyran-3-yl ester

15.0 g (24.1 mmol) of 5-propenyl decyloxypentanoic acid (3R,4S)-4,6-bis-(5-acrylenyloxypentanyloxy) in 500 ml DMSO at 50 °C Tetrahydropyran-3-yl ester was stirred with 15.0 ml (0.22 mol) of acrylic acid and 37.0 g (0.27 mol) of potassium carbonate for 24 h. The suspension was diluted with MTBE and washed with water. The aqueous phase was extracted with MTBE and the combined organic phases were washed with saturated sodium chloride. The solution was dried over sodium sulfate and concentrated to dryness. The residue was purified by column was chromatographed _{(SiO 2 / Al 2 O 3} , dichloromethane: MTBE = 95: 5 and SiO _2, dichloromethane: MTBE = 9: 1), to give a colorless oil propylene 5- Mercaptooxyvaleric acid (3R,4S)-4,6-bis-(5-propenylfluorenylpentenyloxy)tetrahydropyran-3-yl ester (α:β 99:1).

Phase sequence: Tg-57 I

¹ H-NMR (400 MHz, CHCl ₃ ): δ = 6.41 (dd, 3H, J = 17.2 Hz, J = 1.6 Hz, H _acrylate ), 6.30-6.27 (m, 1H, H _- pyranyl), 6.12 (ddd, 3H, J = 17.2 Hz, J = 10.4 Hz, J = 1.6 Hz, H _acrylate ), 5.83 (dd, 3H, J = 10.4 Hz, J = 1.6 Hz, H _acrylate ), 5.36-5.30 ( m,1H,H _-Pyloryl ), 5.24 (s (wide), 1H, H _- pyranyl), 4.23-4.14 (m, 6H, 3 × CH ₂ OC(O)), 4.01 (dd, 1H, J =13.0 Hz, J=1.6 Hz, H _-pyridyl ), 3.86 (dd, 1H, J = 13.0 Hz, J = 2.6 Hz, H _-pyranyl ), 2.48-2.40 (m, 4H, H _aliphatic ), 2.36-2.29 (m, 2H, H _aliphatic ), 2.28-2.20 (m, 1H, H _-pyranyl ), 1.92 (dm, 1H, J = 13.0 Hz, H _-pyranyl ), 1.80-1.67 (m, 12H, H _aliphatic ).

Example 4: 2-(3R,4S,5S)-4,5,6-indole-(2-methylpropenyloxy)tetrahydropyran-3-yl 2-methacrylate

The compound of the invention 2-(3R,4S,5S)-4,5,6-indole-(2-methylpropenyloxy)tetrahydropyran-3-yl ester is synthesized as described below .

First, 5.0 g (33.3 mmol) of L-(+)-arabinose was introduced into 300 ml of THF together with 34.0 ml (0.4 mol) of methacrylic acid and 0.2 g (1.6 mmol) of DMAP. A solution of 82.5 g (0.40 mol) DCC in 200 ml of THF was added and the mixture was stirred at room temperature for 20 h. 25.2 g (0.2 mol) of oxalic acid was added, and after 1 h, insoluble material was filtered off. The filtrate was concentrated to dryness and by column chromatography (SiO _2, dichloromethane) to give the residue, to give a mixture of isomers as a base end (α: β = 3: 1 ) in the form of methyl methacrylate (3R,4S,5S)-4,5,6-indole-(2-methylpropenyloxy)tetrahydropyran-3-yl ester.

Phase sequence: Tg-21 I

^{The 1} H- and ¹³ C-NMR spectrum data were consistent with the structure.

MS (EI) : m / e (%) = 422 (1, M ⁺ ), 337 (28, [MH ₂ C=CH(CH ₃ ) -COO] ⁺ ), 41 (100).

Example 5: 2-{(3S,4R,5R)-2,3,5-indole-[3-(2-methylpropenyloxy)propoxy]tetrahydropyran- 2-methacrylate 4-yloxy}propyl ester

The compound of the present invention 2-{(3S,4R,5R)-2,3,5-indole-[3-(2-methylpropenyloxy)propoxy]tetrahydropyran- The 4-yloxy}propyl ester was synthesized as described below.

5.1 L-(+)-Allylation of arabinose

100.0 g (2.50 mol) of NaH (60% suspension in mineral oil) was washed with pentane and suspended in 1700 ml of DMF. 62.5 g (0.42 mol) of L-(+)-arabinose was metered in and the batch was stirred for 1 h in an ultrasonic bath. The mixture was then stirred at room temperature for 1 h. A solution of 220 ml (2.54 mol) of allyl bromide in 300 ml of DMF was slowly metered at a rate such that the internal temperature did not exceed 27 ° C while cooling in countercurrent. When the addition was completed, the mixture was stirred for 22 h.

Ethanol was added to the batch and the batch was then added to ice water. The mixture was extracted several times with MTBE and the combined organic phases were washed with a sodium chloride solution. The solution was dried over sodium sulfate and concentrated to dryness. The crude product was purified by column chromatography (SiO ₂ , CH ₂ Cl ₂ → MTBE).

5.2 Boron Hydrogenation / Oxidation

First, 15.0 g (48.3 mmol) of (3S,4R,5R)-2,3,4,5-tetraallyloxytetrahydropyran was introduced into THF, and 900 ml (0.45 mol) of 9-BBN was added. The 0.5 M solution in THF) and the batch was refluxed for 5 h. After cooling, the mixture was hydrolyzed with water and 40 ml of 50% NaOH was added. 130 ml (1.49 mol) of 30% H ₂ O _{2 was} added dropwise and the mixture was stirred for 19 h. Add 50 g of potassium carbonate and gently pour out the organic phase. The solution was treated with a solution of ammonium ferrous sulfate (II) and dried over sodium sulfate. After removal of the solvent by column chromatography (SiO _2, MTBE → methanol) to give the remaining crude product was obtained as a colorless oil 3 - [(3S, 4R, 5R) -3,4,5- three - ( 3-hydroxypropoxy)tetrahydropyran-2-yloxy]propan-1-ol.

5.3 Esterification using methacrylic acid

First, 8.0 g (20.9 mmol) of 3-[(3S,4R,5R)-3,4,5-indole-(3-hydroxypropoxy)tetrahydropyran-2-yloxy]propan-1- The alcohol was introduced into 200 ml of THF along with 21.3 ml (0.25 mol) of methacrylic acid and 0.2 g (1.6 mmol) of DMAP. A solution of 50.0 g (0.24 mol) DCC in 100 ml THF was added and the mixture was stirred at room temperature for 22 h. Dioxalic acid was added and the insoluble material was filtered off after 1 h. The filtrate was concentrated to dryness, and the residue was purified by chromatography to afford 2-[(3S,4R,5R) 2- methacrylic acid as a mixture of anomers (α:β=95:5) -2,3,5-indole-[3-(2-methylpropenyloxy)propoxy]tetrahydropyran-4-yloxy}propyl ester.

^{The 1} H- and ¹³ C-NMR spectrum data were consistent with the structure.

MS (EI) : m/e (%) = 654 (1, M ⁺ ), 325 (5), 127 (100).

Example 6-9:

Example Compounds 6-9 were obtained analogously to Example 1 from the corresponding sugars and reacted with bromopentanoic acid and methacrylic acid. In each case, the spectral data (NMR, MS) were consistent with the structure.

Use case

The following abbreviations are used to describe the components of the liquid crystal basic mixture (main body):

Use the following monomers:

RM220 has a phase sequence C 82.5 N 97 I.

RM257 has a phase sequence of C 66 N 127 I.

The following additives were used: (DP: palmitic dopant, IN: polymerization initiator)

Aggregation description

The phase properties of the medium were determined in a test cell having a thickness of about 10 microns and an area of 2 x 2.5 cm prior to sample polymerization. The tank is filled with capillary action at a temperature of 75 °C. The measurement was carried out under a polarizing microscope with a hot stage at a temperature of 1 ° C/min.

The polymerization of the medium is carried out by using a UV lamp (H) having an effective power of about 1.5 mW/cm ² . Nle, Bluepoint 2.1, 365 nm interference filter) was irradiated for 180 seconds. The polymerization is carried out directly in the photoelectric test cell. The polymerization is initially carried out at a temperature such that the medium is at a blue phase I (BP-I). The polymerization is carried out in a plurality of sub-steps which gradually reach a complete polymerization. The temperature range of the blue phase typically changes during the polymerization. Thus, between each substep, the temperature can be varied to keep the medium in the blue phase. In practice, this can be carried out by observing the sample under a polarizing microscope about 5 s or more after each irradiation operation. If the sample becomes dark, the indication is converted to an isotropic phase. Accordingly, the temperature of the next substep can be lowered. The overall irradiation time to achieve maximum stability at the indicated irradiation power is typically 180 s. Other polymerizations can be performed according to the optimal irradiation/temperature program. Alternatively, the polymerization can also be carried out in a single irradiation step, in particular if a broad blue phase is present even before polymerization.

Photoelectric characterization

After the blue phase was subjected to the above polymerization and stabilized, the phase width of the blue phase was measured. Photoelectric characterization is then carried out at different temperatures, which may be in this range and may also be outside this range as desired.

The test slot used has an interdigital electrode mounted on the surface of one of the grooves. The slot gap, electrode spacing and electrode width are typically each 10 microns. This uniform size is hereinafter referred to as the gap width. The area covered by the electrodes is about 0.4 cm ² . The test slot does not have an alignment layer. For photoelectron characterization, the grooves were placed between crossed polarizing filters with the electrodes longitudinally at an angle of 45 to the axis of the polarizing filter. Measurements were performed at appropriate angles with respect to the plane of the grooves using DMS301 (Autronic-Melchers) or on polarized microscopes with high sensitivity cameras. In the no voltage state, the configuration produces a substantially black image (defined as a transmission of 0%).

First, the characteristic operating voltage is measured on the test slot and then the response time is measured. The operating voltage is applied to the slot electrode in the form of a rectangular voltage having alternating signs (frequency of 100 Hz) and variable amplitude, as described below.

The transmittance in the no-voltage state was set to 0%. The transmittance is measured while increasing the operating voltage. The characteristic quality of the operating voltage V ₁₀₀ is defined by a maximum of about 100% intensity. Also, the characteristic voltage V ₁₀ was measured at a maximum transmittance of 10%. These values are determined at different temperatures in the blue phase range.

At the lower end of the blue phase temperature range, a relatively high characteristic operating voltage V _{100 is} observed. At the upper end of the temperature range (close to the clearing point), the value of V ₁₀₀ is greatly increased. In the region of minimum operating voltage, V ₁₀₀ typically only slowly increases with temperature. This temperature range is referred to as the available flat temperature range (FR), which is defined by T ₁ and T ₂ . The width of the "flat range" (FR) is (T ₂ -T ₁ ) and is called the flat range width (WFR). The exact values of T ₁ and T ₂ are determined by the intersection of the tangent of the flat curve portion FR in the V ₁₀₀ /temperature map and the tangent of the adjacent steep curve portion.

In the second part of the measurement, the response time (τ _on , τ _off ) is determined during the switching. The response time τ _{on is} defined as the time it takes to reach 90% intensity after applying a voltage at the V ₁₀₀ level at the selected temperature. The response time τ _{off is} defined as the time it takes for the maximum intensity from V ₁₀₀ to begin to fall by 90% after the voltage is reduced to 0 V. The response time is also measured at different temperatures in the blue phase range.

As a further characterization, the transmittance is measured for operating voltages that vary continuously between 0 V and V ₁₀₀ at temperatures in the FR range. The hysteresis can be obtained by comparing the curves of increasing and decreasing the operating voltage. The difference between the transmittances at 0.5‧V ₁₀₀ and the difference between the voltages at 50% transmittance are, for example, characteristic hysteresis values and are referred to as ΔT ₅₀ and ΔV _{50 , respectively} .

Application example M1 (for comparison), M2, M3 (for comparison), M4

The following polymerizable media have the following composition:

The media are characterized as described prior to polymerization. The RM component was then polymerized by performing a single irradiation (180 s) in the blue phase and the resulting medium was characterized again.

Compared to the media M1 and M3 (excluding RM-1), the inventive media M2 and M4 which have been polymerized with RM-1 exhibit a significant reduction in operating voltage (V ₁₀ , V ₁₀₀ ) and hysteresis (ΔV ₅₀ ). Mixtures M3 and M4 differ from mixtures M1 and M2 by an increase in the proportion of palmitic dopants, which means that in contrast to M1/M2, M3/M4 forms an invisible blue phase (wavelength shifted to the UV region). Examples M3 and M4 show that hysteresis and operating voltage are reduced due to the interpretive content for the invisible blue phase.

Claims (11)

a compound of formula IA Wherein R ¹ and R ² represent a) in each case, independently of each other, a halogenated or unsubstituted alkyl group having from 1 to 15 C atoms, in addition, one or more of such groups The CH ₂ groups may be independently of each other by -C≡C-, -CH=CH-, -(CO)O-, -O(CO)-, -(CO)- in such a manner that the O atoms are not directly connected to each other. Or -O-substitution, b) group-Sp-P, or c) F, Cl, H, Br, CN, SCN, NCS or SF ₅ , A ² represents or m represents 1, 2 or 3, and P is, in each case, independently of one another selected from the group consisting of acrylate groups and methacrylate groups, and Sp in each case independently represents a single bond or is selected from the group of Sp'-X, In order for the group P-Sp- to conform to the formula P-Sp'-X-, wherein Sp' represents an alkylene group having from 1 to 24 C atoms, which is optionally via F, Cl, Br, I or CN - Or polysubstituted, and additionally, one or more of the non-adjacent CH ₂ groups are each independently -O-, -S-, -NH-, -NR in such a manner that O and/or S atoms are not directly connected to each other ⁰ -, -SiR ⁰⁰ R ⁰⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR ⁰⁰ -CO-O-, - O-CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-NR ⁰⁰ -, -CH=CH- or -C≡C- instead, X means -O-, -S-, -CO-, -COO-, - OCO-, -O-COO-, -CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-, -NR ⁰⁰ -CO-NR ⁰⁰ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, - CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH =N-, -N=CH-, -N=N-, -CH=CR ⁰ -, -CY ² =CY ³ -, -C≡C-, -CH=CH-COO-, -OCO-CH= CH- or a single bond, R ⁰⁰ and R ⁰⁰⁰ are each independently of one another denote H or with 1 to 12 C atoms in the alkyl group, Y ² and Y ³ are each independently H, F, Cl or CN, and also addition -Sp-P together represent the group R ^1, wherein the polymerizable group P The amount is one or more, wherein the compound of the formula IA is selected from the group consisting of the compounds of the formulae IA-1 to IA-32: Wherein R ^{1 '} to R ^{5 '} are as defined above for R ¹ , X ¹ to X ⁵ are as defined above for X, and Sp ¹ to Sp ⁵ are as defined above for Sp′, and P ¹ to P ⁵ are as defined above for P, and do not include compounds of formulas A , B , C and D Where a+b+c+d represents a natural number >10 The compound of claim 1, characterized in that the number and position of the ring A ² and its substituent correspond to a sugar selected from the group consisting of ribose, deoxyribose, arabinose, xylose, lyxose, ribulose, wood Keto, glucose, allose, altrose, mannose, gulose, idose, galactose, talose, fructose, fucose or rhamnose. A compound according to claim 1 or 2, characterized in that R ¹ and/or R ² represents a P-Sp- group, H, an alkoxy group having 1 to 10 C atoms or an alkoxymethyl group. A compound according to claim 1 or 2, characterized in that the number of polymerizable groups is 2, 3, 4 or 5. A process for the preparation of a compound of formula IA according to any one of claims 1 to 4 which is carried out by the derivatization of a monosaccharide. A liquid crystal medium characterized by comprising one or more compounds of the formula IA Wherein R ¹ and R ² represent a) in each case, independently of each other, a halogenated or unsubstituted alkyl group having from 1 to 15 C atoms, in addition, one or more of such groups The CH ₂ groups may each independently pass through -C≡C-, -CH=CH-, -(CO)O-, -O(CO)-, -(CO)- in such a manner that the O atoms are not directly connected to each other. Or -O-substitution, b) group -Sp-P, c) F, Cl, H, Br, CN, SCN, NCS or SF ₅ , A ² represents or m represents 1, 2 or 3, and P is, in each case, independently of one another selected from the group consisting of acrylate groups and methacrylate groups, and Sp in each case independently represents a single bond or is selected from the group of Sp'-X, In order for the group P-Sp- to conform to the formula P-Sp'-X-, wherein Sp' represents an alkylene group having from 1 to 24 C atoms, which is optionally via F, Cl, Br, I or CN - Or polysubstituted, and additionally, one or more of the non-adjacent CH ₂ groups are each independently -O-, -S-, -NH-, -NR in such a manner that O and/or S atoms are not directly connected to each other ⁰ -, -SiR ⁰⁰ R ⁰⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR ⁰⁰ -CO-O-,- O-CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-NR ⁰⁰ -, -CH=CH- or -C≡C- instead, X means -O-, -S-, -CO-, -COO-, - OCO-, -O-COO-, -CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-, -NR ⁰⁰ -CO-NR ⁰⁰ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, - CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH =N-, -N=CH-, -N=N-, -CH=CR ⁰ -, -CY ² =CY ³ -, -C≡C-, -CH=CH-COO-, -OCO-CH= CH- or a single bond, R ⁰⁰ and R ⁰⁰⁰ each independently represent H or An alkyl group having 1 to 12 C atoms, each of Y ² and Y ³ independently representing H, F, Cl or CN, and -Sp-P additionally together represent a group R ¹ wherein the compound of the formula IA Is selected from the group consisting of compounds of formula IA-1 to IA-32: Wherein R ^{1 '} to R ^{5 '} are as defined above for R ¹ , X ¹ to X ⁵ are as defined above for X, and Sp ¹ to Sp ⁵ are as defined above for Sp′, and P ¹ to P ⁵ are as defined above for P; or a polymer comprising one or more compounds of the formula IA. The liquid crystal medium of claim 6, characterized in that it is stabilized by polymerization After the blue phase, it has the blue phase at least in the range of 20 ° C to 25 ° C. A method of making a photovoltaic device comprising a medium stabilized by a liquid crystal polymer, characterized in that a liquid crystal medium comprising one or more compounds of the formula IA of claim 6 is polymerized. A use of one or more compounds of the formula IA as set forth in claim 6 as a component or polymer component in a liquid crystal medium. A use of the liquid crystal medium of claim 6 or 7 for photovoltaic applications. An optoelectronic liquid crystal display comprising the liquid crystal medium of claim 6 or 7.