Fluorinated aromatic compound

Abstract

Fluorinated aromatic compounds are provided. The present invention relates to aromatic isothiocyanates of formula U as defined in claim 1, to liquid crystalline media comprising one or more compounds of formula U, and to high frequency components, in particular microwave components for high frequency devices, comprising these media, such as devices for shifting the phase of microwaves, tunable filters, tunable material structures and electron beam steering antennas, e.g. phased array antennas. TIFF2022552279000286.tif46166

Description

Technical Field

[0001] The present invention relates to fluorinated aromatic compounds, liquid crystalline media containing the same, devices for shifting the phase of microwaves, tunable filters, tunable material structures, and high-frequency components including these media such as electronically beam-steered antennas (e.g., phased array antennas), in particular microwave components for high-frequency devices, and said devices.

Background Art

[0002] Liquid crystal media have been used for many years in electro-optical displays (liquid crystal displays: LCDs) for displaying information. However, in recent years, the use of liquid crystal media in components for microwave technology has also been proposed, for example, in German Patent Application No. 10 2004 029 429.1 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2005-120208 (Patent Document 2).

[0003] A. Gaebler, F. Goelden, S. Muller, A. Penirschke, and R. Jakoby, "Direct Simulation of Material Permittivites using an Eigen-Susceptibility Formulation of the Vector Variational Approach", 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463 - 467 (Non-Patent Document 1) describes the corresponding properties of the known liquid crystal mixture E7 (Merck, Germany).

[0004] German Patent Application No. 10 2004 029 429 (Patent Document 1) describes the use of liquid crystal media in microwave technology, especially in phase shifters. The liquid crystal media are discussed with respect to their properties in the corresponding frequency range, and liquid crystal media based mainly on mixtures of aromatic nitriles and isothiocyanates are shown.

[0005] European Patent Application Publication No. 2 982 730 (Patent Document 3) describes mixtures consisting entirely of isothiocyanate compounds.

[0006] Fluorine atoms are generally used in mesogenic compounds to introduce polarity. Especially in combination with terminal NCS groups, especially when the NCS group in the 1-position has two fluorine atoms in the ortho-position, the dipole of the whole molecule is the sum of the individual dipoles of the partial structures of the molecule, so that a high dielectric anisotropy value can be achieved. Since fluorine substitution often has a negative impact on the nematic phase properties of the compound, a balanced compromise regarding the number of fluorine atoms must be found.

[0007] The liquid crystal compositions available for use in microwave applications still have several drawbacks. There is a need to improve these media with respect to their general physical properties, storage stability, and stability under operation in devices. From the perspective of a large number of different parameters that need to be considered and improved for the development of liquid crystalline media for microwave applications, it is desirable to have a wider range of possible mixing components for the development of such liquid crystalline media.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Document

[0009]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0010] An object of the present invention is to provide a compound for use in a liquid crystal medium having improved properties related to applications in the microwave range of the electromagnetic spectrum.

Means for Solving the Problems

[0011] To solve the problems, compounds of formula U shown below and a liquid crystal medium containing the compounds are provided.

Modes for Carrying Out the Invention

[0012] The present invention relates to compounds of formula U.

[0013]

Chemical Formula

[0014] In the formula, R Urepresents H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, and in said group, one or more CH2 groups may be

Chemical formula

Chemical formula

[0015] The present invention further relates to a compound of formula UN.

[0016]

Chemical formula

[0017] In the formula, the groups and parameters have the meanings given above for formula U.

[0018] According to another aspect of the present invention, a method for synthesizing a compound of formula U from a compound of formula UN given below is provided.

[0019] The present invention further relates to a liquid crystal medium comprising a compound of formula U and to the use of a liquid crystal medium comprising a compound of formula U in components for high-frequency technology.

[0020] According to yet another further aspect of the present invention, components operable in the microwave range of the electromagnetic spectrum and devices comprising said components are provided. Preferred components are phase shifters, varactors, radio and radar antenna arrays, matching circuits and adaptive filters.

[0021] Preferred embodiments of the present invention are the subject of the independent claims or are apparent from the present specification.

[0022] Surprisingly, by using a compound of formula U in a liquid crystal medium, it has been found that it is possible to achieve a liquid crystal medium having excellent stability, high dielectric anisotropy, suitably fast switching times, a suitable nematic phase range, high tunability and low dielectric losses. In particular, the use of a compound of formula U enables a liquid crystal medium with reduced dielectric losses with little or no adverse effect on other relevant parameters such as the nematic phase range, dielectric anisotropy or tunability.

[0023] The medium according to the present invention is distinguished by a high clearing temperature, a wide nematic phase range and excellent low-temperature stability (LTS). As a result, devices comprising the medium are operable under extreme temperature conditions.

[0024] The medium is further distinguished by a high value of dielectric permittivity anisotropy and a low rotational viscosity. As a result, the threshold voltage, i.e. the lowest voltage at which the device can be switched, is very low. Low operating voltages and low threshold voltages are desirable in order to realize devices with improved switching characteristics and high energy efficiency. The low rotational viscosity enables fast switching of the devices according to the present invention.

[0025] These properties make the medium particularly suitable for use in high-frequency technology and components and devices for applications in the microwave range, in particular devices for shifting the phase of microwaves, tunable filters, tunable material structures and electron beam steering antennas (such as phased array antennas).

[0026] As used herein, "high-frequency technology" shall mean electromagnetic wave applications having frequencies in the range of 1 MHz to 1 THz, preferably 1 GHz to 500 GHz, more preferably 2 GHz to 300 GHz, and particularly preferably about 5 GHz to 150 GHz.

[0027] As used herein, halogen is F, Cl, Br or I, preferably F or Cl, and particularly preferably F.

[0028] As used herein, alkyl is linear or branched or cyclic and has 1 to 15 C atoms, preferably linear and, unless otherwise indicated, has 1, 2, 3, 4, 5, 6 or 7 C atoms, and thus is preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl.

[0029] As used herein, branched alkyl is preferably isopropyl, s-butyl, isobutyl, isopentyl, 2-methylhexyl or 2-ethylhexyl.

[0030] As used herein, cyclic alkyl shall mean linear or branched alkyl or alkenyl having up to 12 C atoms, preferably alkyl having 1 to 7 C atoms, provided that the group CH2 is replaced by a carbocyclic ring having 3 to 5 C atoms and is very preferably selected from the group consisting of cyclopropylalkyl, cyclobutylalkyl, cyclopentylalkyl and cyclopentenylalkyl.

[0031] In this specification, the alkoxy group is linear or branched and contains 1 to 15 carbon atoms. It is preferably linear and, unless otherwise indicated, has 1, 2, 3, 4, 5, 6 or 7 carbon atoms, and is thus preferably methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy or n-heptoxy.

[0032] In this specification, the alkenyl group is preferably an alkenyl group having 2 to 15 carbon atoms, the group is linear or branched and contains at least one C-C double bond. It is preferably linear and has 2 to 7 carbon atoms. Thus, it is preferably vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl. When two carbon atoms of the C-C double bond are substituted, the alkenyl group may be in the form of E and / or Z isomers (trans / cis). Generally, each E isomer is preferred. Among the alkenyl groups, prop-2-enyl, but-2- and -3-enyl and pent-3- and -4-enyl are particularly preferred.

[0033] In this specification, alkynyl is understood to mean an alkynyl group having 2 to 15 carbon atoms, the group is linear or branched and contains at least one C-C triple bond. 1- and 2-propynyl and 1-, 2- and 3-butynyl are preferred.

[0034] R F When represents a halogenated alkyl, alkoxy, alkenyl or alkenyloxy, it may be branched or unbranched. Preferably, it is unbranched and is monofluorinated, polyfluorinated or perfluorinated, more preferably perfluorinated, and has 1, 2, 3, 4, 5, 6 or 7 carbon atoms, or in the case of alkenyl, 2, 3, 4, 5, 6 or 7 carbon atoms.

[0035] RP is preferably CN, NCS, Cl, F, -(CH2) n -CH=CF2, -(CH2) n -CH=CHF, -(CH2) n -CH=Cl2, -C n F 2n+1 , -(CF2) n -CF2H, -(CH2) n -CF3, -(CH2) n -CHF2, -(CH2) n CH2F, -CH=CF2, -O(CH2) n -CH=CF2, -O(CH2) n CHCl2, -OC n F 2n+1 , -O(CF2) n -CF2H, -O(CH2) n CF3, -O(CH2) n -CHF2, -O(CF) n CH2F, -OCF=CF2, -SC n F 2n+1 , -S(CF) n -CF3, where n is an integer from 0 to 7.

[0036] The compounds of general formula U can be prepared by methods known per se described in the literature (for example, standard works such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart) under the exact reaction conditions suitable for said reaction. Here, modifications which are known per se but not mentioned in more detail herein can be used.

[0037] It is also possible to form in situ by not isolating the starting material from the reaction mixture and immediately converting it further to the compounds of general formula U.

[0038] The preferred synthetic routes leading to the compounds according to the invention are illustrated in the scheme below and further explained by the examples.

[0039] A preferred intermediate is 5-bromo-1,3-difluoro-2-alkylbenzene, which can be reacted to give a compound of general formula UN by a cross-coupling reaction generally known as, for example, the Suzuki, Stille, Sonogashira reaction, etc. Preferred routes are illustrated in Schemes 1 and 2, provided that the groups and parameters have the meaning defined in claim 1.

[0040]

Chem.

[0041]

Chem.

[0042] Preferred reagents for the process according to the invention (Scheme 3) for converting a compound of formula UN into a compound of formula U are carbon disulfide, thiophosgene, thiocarbonyldiimidazole, di-2-pyridylthiocarbonate, bis(dimethylthiocarbamoyl)disulfide, dimethylthiocarbamoyl chloride and phenylchlorothiobromate, very preferably thiophosgene.

[0043]

Chem.

[0044] The reactions described should be considered as illustrative only. A person skilled in the art can carry out the corresponding modifications of the described syntheses and also follow other suitable synthetic routes to obtain a compound of formula U.

[0045] The compound of formula U is preferably

[0046]

Chem.

Chem.

[0047] In a preferred embodiment of the present invention, the compound of formula U is selected from the compounds of formulae U-1 to U-20, very preferably the compounds of formulae U-1 to U-13

[0048] [Chemical formula]

[0049] [Chemical formula]

[0050] [Chemical formula]

[0051] [Chemical formula]

[0052] wherein the groups occurring have the meanings given above for formula U and its sub-formulae preferably R U represents an alkyl having 1 to 7 C atoms, and Y 1 , Y 2 , Y 3 and Y 4represents H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, which may be the same or different, and more preferably Y 1 and Y 2 each independently represents H or F, particularly H, and Y 3 and Y 4 very preferably represents H, and L 1 and L 2 each independently represents very preferably H, F, methyl or ethyl, particularly H

[0053] According to one aspect of the present invention, R U is H, alkyl or alkoxy having 1 to 12 carbon atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 carbon atoms, preferably alkyl having 1 to 12 carbon atoms, and one or more CH2 groups in the group may be replaced by

Chemical formula

[0054] According to another aspect of the present invention, a compound of formula U is provided, wherein R U represents R P provided that R P is halogen, CN, NCS, R F R F -O- or R F -S-, provided that R F represents alkyl fluoride or alkenyl fluoride having up to 9 carbon atoms, preferably CF3 or OCF3

[0055] In a preferred embodiment of the present invention, the medium contains one or more compounds selected from the group of compounds of formula I, II and III

[0056]

Chemical formula

[0057] wherein R 1 represents a non-fluorinated alkyl or non-fluorinated alkoxy having H, 1 to 17 C atoms, preferably 3 to 10 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15 C atoms, preferably 3 to 10 C atoms, preferably a non-fluorinated alkyl or non-fluorinated alkenyl, and in said group one or more CH2 groups may be

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0058] R 2 represents a non-fluorinated alkyl or non-fluorinated alkoxy having H, 1 to 17, preferably 3 to 10 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably a non-fluorinated alkyl or non-fluorinated alkenyl, and in said group one or more CH2 groups may be

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0059] R 3 represents a non-fluorinated alkyl or non-fluorinated alkoxy having H, 1 to 17, preferably 3 to 10 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably a non-fluorinated alkyl or non-fluorinated alkenyl, and in said group one or more CH2 groups may be

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0060] In the compounds of Formulas I, II and III, R L preferably represents H. In another preferred embodiment, in the compounds of Formulas I, II and III, one or two groups R L , preferably one group R L is different from H.

[0061] In a preferred embodiment of the present invention, the compound of Formula I is selected from the group of compounds of Formulas I-1 to I-5.

[0062] [Chem.]

[0063] wherein, L 1 , L 2 and L 3 each occurrence represents the same or different H or F, and the other groups have the respective meanings shown above in Formula I, preferably R 1 represents non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms.

[0064] The medium preferably contains one or more compounds of formula I-1, preferably selected preferably from the group of compounds of formulae I-1a to I-1d, preferably the compound of formula I-1b.

[0065]

Chemical formula

[0066] In the formula, R 1 has the meaning shown above for formula I and preferably represents a non-fluorinated alkyl having 1 to 7 C atoms or a non-fluorinated alkenyl having 2 to 7 C atoms.

[0067] The medium preferably contains one or more compounds of formula I-2, preferably selected preferably from the group of compounds of formulae I-2a to I-2e, preferably the compound of formula I-2c.

[0068]

Chemical formula

[0069] In the formula, R 1 has the meaning shown above for formula I and preferably represents a non-fluorinated alkyl having 1 to 7 C atoms or a non-fluorinated alkenyl having 2 to 7 C atoms.

[0070] The medium preferably contains one or more compounds of formula I-3, preferably selected preferably from the group of compounds of formulae I-3a to I-3d, preferably the compound of formula I-3b.

[0071]

Chemical formula

[0072] In the formula, R 1 has the meaning shown above for formula I and preferably represents a non-fluorinated alkyl having 1 to 7 C atoms or a non-fluorinated alkenyl having 2 to 7 C atoms.

[0073] The medium preferably contains one or more compounds of formula I-4, preferably selected from the group of compounds of formula I-4a to I-4e, preferably the compound of formula I-4b.

[0074]

Chemical formula

[0075] In the formula, R 1 has the meaning shown above in formula I and preferably represents non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms.

[0076] The medium preferably contains one or more compounds of formula I-5, preferably selected from the group of compounds of formula I-5a to I-5d, preferably the compound of formula I-5b.

[0077]

Chemical formula

[0078] In the formula, R 1 has the meaning shown above in formula I and preferably represents non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms.

[0079] The medium preferably contains one or more compounds of formula II, preferably selected from the group of compounds of formula II-1 to II-3, preferably selected from the group of compounds of formula II-1 and II-2.

[0080]

Chemical formula

[0081] In the formula, the groups that appear have the meanings given above in formula II, and preferably R 2represents a non-fluorinated alkyl or alkoxy having H, 1 to 7 C atoms or a non-fluorinated alkenyl having 2 to 7 C atoms, and [Chemical formula] represents, On the other hand, independently, [Chemical formula] preferably [Chemical formula] most preferably [Chemical formula] represents, and preferably, R 2 is C n H 2n+1 or CH2=CH-(CH2) Z represents, and n represents an integer within the range of 1 to 15, preferably within the range of 1 to 7 and particularly preferably within the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0082] The compound of formula II-1 is preferably selected from the group of compounds of formula II-1a to II-1e.

[0083] [Chemical formula]

[0084] In the formula, R 2 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and n independently of each other represents an integer within the range of 1 to 15, preferably within the range of 1 to 7 and particularly preferably within the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0085] The compound of formula II-2 is preferably selected from the group of compounds of formula II-2a and II-2b.

[0086]

Chemical formula

[0087] wherein R 2 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, n represents an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0088] The compound of formula II-3 is preferably selected from the group of compounds of formula II-3a to II-3d.

[0089]

Chemical formula

[0090] wherein R 2 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, n represents an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0091] The compound of formula III is preferably selected from the group of compounds of formulae III-1 to III-6, more preferably from the group of compounds of formulae III-1, III-2, III-3 and III-4, and particularly preferably from the group of compounds of formula III-1.

[0092]

Chemical formula

[0093] wherein Z 31 and Z 32 are each independently trans-CH=CH- or trans-CF=CF-, preferably trans-CH=CH-, or in formula III-6, one of Z 31 and Z 32 may represent -C≡C-, and the other group has the meaning given above in formula III, and preferably R 3 is non-fluorinated alkyl or alkoxy having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms, and

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0094] The compound of formula III-1 is preferably selected from the group of compounds of formulae III-1a to III-1l, more preferably from the group of compounds of formulae III-1a, III-1b, III-1g and III-1h, and particularly preferably from the group of compounds of formulae III-1b, III-1f, III-1g and III-1i.

[0095]

Chemical formula

[0096]

Chemical formula

[0097]

Chemical formula

[0098] In the formula, R 3 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, n represents an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0099] The compound of formula III-2 is preferably a compound of formulae III-2a to III-2l, very preferably III-2b and / or III-2j.

[0100]

Chemical formula

[0101]

Chemical formula

[0102] wherein R 3 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, n represents an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0103] The compound of formula III-5 is preferably selected from the compounds of formula III-5a.

[0104]

Chemical formula

[0105] R 3 has the meaning shown above in formula III-5, preferably C n H 2n+1 represents, wherein n represents an integer in the range of 1 to 7, preferably in the range of 1 to 5.

[0106] In a preferred embodiment, the medium according to the invention comprises one or more compounds selected from the group of compounds of formulae IIA-1-1 to IIA-1-12, very preferably IIA-1-1 or IIA-1-2.

[0107]

Chem.

[0108]

Chem.

[0109] In the formula, R 1 represents alkyl or alkenyl having up to 7 C atoms, preferably ethyl, n-propyl, n-butyl or n-pentyl, n-hexyl, R L represents, in each occurrence, the same or different alkyl or alkenyl having 1 to 5 C atoms or cycloalkyl or cycloalkenyl having 3 to 6 C atoms each, preferably methyl, ethyl, n-propyl, n-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopenta-1-enyl, very preferably ethyl, and the compound of formula II-1 are excluded.

[0110] In addition, the liquid crystal medium according to the invention in a certain embodiment, which may be the same as or different from the previous preferred embodiments, preferably contains one or more compounds of formula IV.

[0111]

Chem.

[0112] In the formula,

Chem.

Chem.

Chem.

[0113] In a preferred embodiment of the present application, the liquid crystal medium additionally contains one or more compounds selected from the group of compounds of formulas V, VI, VII, VIII and IX.

[0114]

Chemical formula

[0115] wherein L 51 represents R 51 or X 51 and L 52 represents R 52 or X 52 and R 51 and R 52are, independently of one another, a non-fluorinated alkyl or non-fluorinated alkoxy having H, 1 to 17, preferably 3 to 10 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably an alkyl or non-fluorinated alkenyl, X 51 and X 52 are, independently of one another, H, F, Cl, -CN, -NCS, -SF5, a fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or a fluorinated alkenyl, fluorinated alkenyloxy or fluorinated alkoxyalkyl having 2 to 7 C atoms, preferably a fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and [Chemical formula] preferably [Chemical formula]

[0116] L 61 represents R 61 and when Z 61 and / or Z 62 represents trans-CH=CH- or trans-CF=CF-, alternatively X 61 also represents, L 62 represents R 62 and when Z 61 and / or Z 62 represents trans-CH=CH- or trans-CF=CF-, alternatively X 62 also represents, R 61 and R 62are, independently of each other, a non-fluorinated alkyl or non-fluorinated alkoxy having H, 1 to 17 C atoms, preferably 3 to 10 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15 C atoms, preferably 3 to 10 C atoms, preferably alkyl or non-fluorinated alkenyl, X 61 and X 62 are, independently of each other, F or Cl, -CN, -SF5, a fluorinated alkyl or alkoxy having 1 to 7 C atoms or a fluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 7 C atoms, Z 61 and Z 62 one of them represents trans-CH=CH-, trans-CF=CF- or -C≡C-, and independently of it the other represents trans-CH=CH-, trans-CF=CF- or a single bond, preferably one of them represents -C≡C- or trans-CH=CH-, and the other represents a single bond,

Chemical formula

Chemical formula

[0117] x represents 0 or 1, L 71 is R 71 or X 71 represents, L 72 is R 72 or X 72 represents, R 71 and R 72are, independently of one another, a non-fluorinated alkyl or non-fluorinated alkoxy having H, 1 to 17, preferably 3 to 10 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably an alkyl or non-fluorinated alkenyl, X 71 and X 72 are, independently of one another, H, F, Cl, -CN, -NCS, -SF5, a fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, or a fluorinated alkenyl, non-fluorinated or fluorinated alkenyloxy or non-fluorinated or fluorinated alkoxyalkyl having 2 to 7 C atoms, preferably a fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and Z 71 ~Z 73 are, independently of one another, trans-CH=CH-, trans-CF=CF-, -C≡C- or a single bond, one of them preferably represents a single bond, particularly preferably all represent a single bond, [Chemical formula] Preferably [Chemical formula] represents,

[0118] R 81 and R 82 are, independently of one another, H, a non-fluorinated alkyl or alkoxy having 1 to 15, preferably 3 to 10 C atoms, or a non-fluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably a non-fluorinated alkyl or alkenyl, Z 81 and Z 82One of them represents trans-CH=CH-, trans-CF=CF- or -C≡C-, and the other independently represents trans-CH=CH-, trans-CF=CF- or a single bond, one of them preferably represents -C≡C- or trans-CH=CH-, and the other represents a single bond, and [Chemical formula] [Chemical formula] represents,

[0119] L 91 represents R 91 or X 91 represents, L 92 represents R 92 or X 92 represents, R 91 and R 92 are independently of each other H, non-fluorinated alkyl or alkoxy having 1 to 15 C atoms, preferably 3 to 10 C atoms, or non-fluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 15 C atoms, preferably 3 to 10 C atoms, preferably non-fluorinated alkyl or alkenyl, X 91 and X 92 are independently of each other H, F, Cl, -CN, -NCS, -SF5, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, or fluorinated alkenyl having 2 to 7 C atoms, non-fluorinated or fluorinated alkenyloxy or non-fluorinated or fluorinated alkoxyalkyl, preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and Z 91 ~Z 93 are independently of each other trans-CH=CH-, trans-CF=CF-, -C≡C- or a single bond, one of them preferably represents a single bond, particularly preferably all represent a single bond, [Chemistry] [Chemistry] represents.

[0120] In a preferred embodiment of the present invention, the liquid crystal medium comprises one or more compounds selected from the group of compounds of formula V, preferably of formulae V-1 to V-3, preferably of formulae VI-1 and / or V-2 and / or V-3, preferably of formulae V-1 and V-2.

[0121] [Chemistry]

[0122] wherein the parameters each have the meaning shown above in formula V, preferably R 51 represents non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms, R 52 represents non-fluorinated alkyl having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms or non-fluorinated alkoxy having 1 to 7 C atoms, X 51 and X 52 each independently represent F, Cl, -OCF3, -CF3, -CN, -NCS or -SF5, preferably F, Cl, -OCF3 or -CN. The compounds of formula V-1 are preferably selected from the group of compounds of formulae V-1a to V-1d, preferably of formulae V-1c and V-1d.

[0123] [Chemistry]

[0124] wherein the parameters each have the meaning shown above in formula V-1, provided that Y 51and Y 52 represents H or F independently of each other in each case, and preferably R 51 represents alkyl or alkenyl, and X 51 represents F, Cl or -OCF3. The compound of formula V-2 is preferably selected from the group of compounds of formulae V-2a to V-2e and / or the group of compounds of formulae V-2f and V-2g.

[0125]

Chemical formula

[0126] In each case, the compound of formula V-2a is excluded from the compounds of formulae V-2b and V-2c, the compound of formula V-2b is excluded from the compound of formula V-2c, the compound of formula V-2f is excluded from the compound of formula V-2g, and provided that the parameters have the meanings shown above for formula V-1, provided that Y 51 and Y 52 represents H or F independently of each other in each case, and preferably Y 51 and Y 52 represents H or F independently of each other in each case, preferably also representing H.

[0127] The compound of formula V-3 is preferably the compound of formula V-3a.

[0128]

Chemical formula

[0129] wherein the parameters have the meanings shown above for formula V-1, provided that preferably X 51 represents F, Cl, preferably F, X 52 represents F, Cl or -OCF3, preferably -OCF3.

[0130] The compound of formula V-1a is preferably selected from the group of compounds of formula V-1a-1 and V-1a-2.

[0131]

Chemical formula

[0132] In the formula, R 51 has the meaning shown above, preferably represents C n H 2n+1 provided that n represents an integer within the range of 1 to 7, preferably within the range of 1 to 5 and particularly preferably 3 or 4.

[0133] The compound of formula V-1b is preferably the compound of formula V-1b-.

[0134]

Chemical formula

[0135] In the formula, R 51 has the meaning shown above, preferably represents C n H 2n+1 provided that n represents an integer within the range of 1 to 15, preferably within the range of 1 to 7 and particularly preferably 1 to 5.

[0136] The compound of formula V-1c is preferably selected from the group of compounds of formula V-1c-1 to V-1c-4, and particularly preferably selected from the group of compounds of formula V-1c-1 and V-1c-2.

[0137]

Chemical formula

[0138] In the formula, R 51 has the meaning shown above, preferably represents Cn H 2n+1 represents, provided that n represents an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5.

[0139] The compound of formula V-1d is preferably selected from the group of compounds of formula V-1d-1 and V-1d-2, and particularly preferably is the compound of formula V-1d-2.

[0140]

Chemical formula

[0141] In the formula, R 51 has the meaning shown above, and preferably represents C n H 2n+1 represents, provided that n represents an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5.

[0142] The compound of formula V-2a is preferably selected from the group of compounds of formula V-2a-1 and V-2a-2, and particularly preferably is the compound of formula V-2a-1.

[0143]

Chemical formula

[0144] In the formula, R 51 has the meaning shown above, and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 52 has the meaning shown above, and preferably represents C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m independently of one another represent integers in the range from 1 to 15, preferably in the range from 1 to 7 and particularly preferably in the range from 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0145] In particular, in the case of formula V-2a-1, the preferred combinations of (R 51 and R 52 ) are (C n H 2n+1 and C m H 2m+1 ), (C n H 2n+1 and O-C m H 2m+1 ), (CH2=CH-(CH2) Z and C m H 2m+1 ), (CH2=CH-(CH2) Z and O-C m H 2m+1 ) and (C n H 2n+1 and (CH2) Z -CH=CH2).

[0146] The preferred compounds of formula V-2b are the compounds of formula V-2b-1.

[0147]

Chemical formula

[0148] In the formula, R 51 has the meaning given above, preferably represents C n H 2n+1 or CH2=CH-(CH2) Z and R 52 has the meaning given above, preferably represents C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m independently of one another represent integers in the range from 1 to 15, preferably in the range from 1 to 7 and particularly preferably in the range from 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0149] Here, the preferred combination of (R 51 and R 52 ) is in particular (C n H 2n+1 and C m H 2m+1 ).

[0150] The preferred compound of formula V-2c is the compound of formula V-2c-1.

[0151]

Chemical formula

[0152] In the formula, R 51 has the meaning given above, preferably C n H 2n+1 or CH2=CH-(CH2) Z and R 52 has the meaning given above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m independently of one another represent integers in the range from 1 to 15, preferably in the range from 1 to 7 and particularly preferably in the range from 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0153] Here, the preferred combination of (R 51 and R 52 ) is in particular (C n H 2n+1 and C m H 2m+1 ).

[0154] The preferred compound of formula V-2d is the compound of formula V-2d-1.

[0155]

Chemical formula

[0156] In the formula, R 51 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 52 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0157] Here, the preferred combination of (R 51 and R 52 ) is particularly (C n H 2n+1 and C m H 2m+1 ).

[0158] The preferred compound of formula V-2e is the compound of formula V-2e-1.

[0159]

Chemical formula

[0160] In the formula, R 51 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Zrepresents, and R 52 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0161] Here, the preferred combination of (R 51 and R 52 ) is in particular (C n H 2n+1 and O-C m H 2m+1 ).

[0162] The preferred compound of formula V-2f is the compound of formula V-2f-1.

[0163]

Chemical formula

[0164] In the formula, R 51 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 52 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0165] Here, the preferred combination of (R 51 and R 52 ) is in particular (C n H 2n+1 and C m H 2m+1 ), as well as (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0166] The preferred compound of formula V-2g is the compound of formula V-2g-1.

[0167] [Chemical formula]

[0168] In the formula,[[]] R 51 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 52 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0169] Here, the preferred combination of (R 51 and R 52 ) is in particular (C n H 2n+1 and C m H 2m+1 ), as well as (Cn H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and O-C m H 2m+1 ).

[0170] The compound of formula VI is preferably selected from the group of compounds of formulae VI-1 to VI-5.

[0171] [Chemical formula]

[0172] In the formula,[[]] Z 61 and Z 62 represents -C≡C-, trans-CH=CH- or trans-CF=CF-, preferably -C≡C- or trans-CH=CH- and the other occurring groups and parameters have the meanings given above in formula VI, preferably R 61 and R 62 each independently represent H, non-fluorinated alkyl or alkoxy having 1 to 7 C atoms or non-fluorinated alkenyl having 2 to 7 C atoms X 62 represents F, Cl, -OCF3 or -CN.

[0173] The compound of formula VI-1 is preferably selected from the group of compounds of formulae VI-1a and VI-1b, more preferably from the compound of formula VI-1a.

[0174] [Chemical formula]

[0175] In the formula,[[]] R 61 has the meaning shown above, preferably C n H 2n+1or CH2=CH-(CH2) Z represents, and R 62 has the meaning given above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m independently of one another represent integers in the range from 1 to 15, preferably in the range from 1 to 7 and particularly preferably in the range from 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0176] In the present specification, the preferred combination of (R 61 and R 62 ) is in particular (C n H 2n+1 and C m H 2m+1 ) as well as (C n H 2n+1 and O-C m H 2m+1 ). In the case of formula U-1a, it is particularly preferably (C n H 2n+1 and C m H 2m+1 ), and in the case of formula U-1b it is particularly preferably (C n H 2n+1 and O-C m H 2m+1 ).

[0177] The compound of formula VI-3 is preferably selected from the compounds of formulae VI-3a to VI-3e.

[0178]

Chemical formula

[0179] In the formula, the parameters have the meaning given above for formula VI-3, preferably R 61 has the meaning given above, preferably C n H 2n+1 represents, provided that n represents an integer within the range of 1 to 7, preferably within the range of 1 to 5, and X 62 represents -F, -Cl, -OCF3 or -CN.

[0180] The compound of formula VI-4 is preferably selected from the compounds of formula VI-4a to VI-4e.

[0181]

Chemical formula

[0182] In the formula, the parameters have the meanings given above in formula VI-4, preferably R 61 has the meaning shown above, preferably C n H 2n+1 represents, provided that n represents an integer within the range of 1 to 7, preferably within the range of 1 to 5, and X 62 represents -F, -Cl, -OCF3 or -CN.

[0183] The compound of formula VI-5 is preferably selected from the compounds of formula VI-5a to VI-5d, preferably VI-5b.

[0184]

Chemical formula

[0185] In the formula, the parameters have the meanings given above in formula VI-5, preferably R 61 has the meaning shown above, preferably C n H 2n+1 represents, provided that n represents an integer within the range of 1 to 7, preferably within the range of 1 to 5, and X 62 represents -F, -Cl, -OCF3 or -CN, particularly preferably -OCF3.

[0186] The compound of formula VII is preferably selected from the group of compounds of formulas VII-1 to VII-6.

[0187]

Chemical formula

[0188] However, the compound of formula VII-5 is excluded from the compound of formula VII-6, and wherein the parameters each have the meaning shown above in formula VII, Y 71 、Y 72 、Y 73 each independently represents H or F, and preferably R 71 each represents non-fluorinated alkyl or alkoxy having 1 to 7 C atoms, or non-fluorinated alkenyl having 2 to 7 C atoms, R 72 each represents non-fluorinated alkyl or alkoxy having 1 to 7 C atoms, or non-fluorinated alkenyl having 2 to 7 C atoms, and X 72 represents F, Cl, NCS or -OCF3, preferably F or NCS, and particularly preferably R 71 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 72 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0189] The compound of formula VII-1 is preferably selected from the group of compounds of formulae VII-1a to VII-1d.

[0190] [Chemical formula]

[0191] In the formula, X 72 has the meaning given above for formula VII-2, and R 71 has the meaning shown above, preferably C n H 2n+1 represents, provided that n represents 1 to 7, preferably 2 to 6, particularly preferably 2, 3 or 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2, and X 72 preferably represents F.

[0192] The compound of formula VII-2 is preferably selected from the group of compounds of formulae VII-2a and VII-2b, particularly preferably the compound of formula VII-2a.

[0193] [Chemical formula]

[0194] In the formula, R 71 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 72 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0195] Here, the preferred combinations of (R 71 and R 72 ) are in particular (C n H 2n+1 and C m H 2m+1 ), as well as (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0196] The compound of formula VII-3 is preferably the compound of formula VII-3a.

[0197]

Chemical formula

[0198] In the formula, R 71 has the meaning shown above, preferably represents C n H 2n+1 or CH2=CH-(CH2) Z , and R 72 has the meaning shown above, preferably represents C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0199] Here, (R71 and R 72 ) The preferred combination is especially (C n H 2n+1 and C m H 2m+1 ), as well as (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0200] The compound of formula VII-4 is preferably the compound of formula VII-4a.

[0201]

Chemical formula

[0202] In the formula,[[]] R 71 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 72 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0203] Here, the preferred combination of (R 71 and R 72 ) is especially (C n H 2n+1 and C m H 2m+1 ), as well as (C n H 2n+1 and O-Cm H 2m+1 )), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0204] The compound of formula VII-5 is preferably selected from the group of compounds of formula VII-5a and VII-5b, more preferably the compound of formula VII-5a.

[0205]

Chemical formula

[0206] In the formula,[[]] R 71 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z and R 72 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0207] Here, the preferred combinations of (R 71 and R 72 ) are in particular (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0208] The compound of formula VII-6 is preferably selected from the group of compounds of formula VII-6a and VII-6b.

[0209]

Chemical formula

[0210] In the formula, R 71 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 72 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0211] Here, the preferred combinations of (R 71 and R 72 ) are in particular (C n H 2n+1 and C m H 2m+1 ) as well as (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0212] The compound of formula VII-7 is preferably selected from the group of compounds of formula VII-7a to VII-7d.

[0213]

Chemical formula

[0214] In the formula, R 71 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, X 72 represents F, -OCF3 or -NCS, n represents an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0215] The compound of formula VIII is preferably selected from the group of compounds of formula VIII-1 to VIII-3, more preferably these compounds of formula VIII mainly consist of them, even more preferably essentially consist of them, and very particularly preferably completely consist of them.

[0216]

Chemical formula

[0217] In the formula, Y 81 and Y 82 one of them represents H, the other represents H or F, and R 81 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 82 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0218] Here, the preferred combination of (R 81 and R 82 ) is in particular (C n H 2n+1 and C m H 2m+1 ) as well as (C n H 2n+1 and O - C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0219] The compound of formula VIII - 1 is preferably selected from the group of compounds of formula VIII - 1a to VIII - 1c.

[0220]

Chemical formula

[0221] In the formula, R 81 has the meaning shown above, preferably represents C n H 2n+1 or CH2 = CH-(CH2) Z , and R 82 has the meaning shown above, preferably represents C m H 2m+1 or O - C m H 2m+1 or (CH2) Z -CH = CH2, provided that n and m independently of each other represent integers in the range from 1 to 15, preferably in the range from 1 to 7 and particularly preferably in the range from 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0222] Here, the preferred combination of (R 81 and R 82 ) is in particular (Cn H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and O-C m H 2m+1 ) and particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0223] The compound of formula VIII-2 is preferably a compound of formula VIII-2a.

[0224]

Chemical formula

[0225] In the formula,[[]] R 81 has the meaning shown above and is preferably C n H 2n+1 or CH2=CH-(CH2) Z and R 82 has the meaning shown above and is preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0226] Here, the preferred combination of (R 81 and R 82 ) is particularly (C n H 2n+1 and C m H 2m+1 ), (C n H 2n+1 and O-C m H 2m+1 ) and (CH2=CH-(CH2)Z and C m H 2m+1 ) and particularly preferably (C n H 2n+1 and C m H 2m+1 ).

[0227] The compound of formula VIII-3 is preferably a compound of formula VIII-3a.

[0228]

Chemical formula

[0229] In the formula,[[]] R 81 has the meaning shown above and is preferably C n H 2n+1 or CH2=CH-(CH2) Z and R 82 has the meaning shown above and is preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0230] Here, the preferred combinations of (R 81 and R 82 ) are particularly (C n H 2n+1 and C m H 2m+1 ) as well as (C n H 2n+1 and O-C m H 2m+1 ).

[0231] The compound of formula IX is preferably selected from the group of compounds of formulae IX-1 to IX-3.

[0232] [Chemical formula]

[0233] In the formula, the parameters each have the meaning shown in Formula IX above, preferably [Chemical formula] and in the formula, R 91 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 92 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0234] Here, the preferred combinations of (R 91 and R 92 ) are in particular (C n H 2n+1 and C m H 2m+1 ) as well as (C n H 2n+1 and O-C m H 2m+1 ).

[0235] The compound of Formula IX-1 is preferably selected from the group of compounds of Formulas IX-1a to IX-1e.

[0236] [Chemical formula]

[0237] The parameters in the formula each have the meaning given above, preferably R 91 has the meaning shown above, preferably C n H 2n+1 represents, and n represents an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and X 92 preferably represents F or Cl.

[0238] The compound of formula IX-2 is preferably selected from the group of compounds of formula IX-2a and IX-2b.

[0239]

Chemical formula

[0240] In the formula, R 91 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z represents, and R 92 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2 represents, provided that n and m each independently represent an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0241] Here, the preferred combination of (R 91 and R 92 ) is particularly (C n H 2n+1 and C m H 2m+1 ).

[0242] The compound of formula IX-3 is preferably selected from the group of compounds of formula IX-3a and IX-3b.

[0243]

Chemical formula

[0244] wherein R 91 has the meaning shown above, preferably C n H 2n+1 or CH2=CH-(CH2) Z and R 92 has the meaning shown above, preferably C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, provided that n and m each independently represent an integer in the range of 1 to 15, preferably in the range of 1 to 7 and particularly preferably in the range of 1 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0245] Here, the preferred combinations of (R 91 and R 92 ) are in particular (C n H 2n+1 and C m H 2m+1 ) as well as (C n H 2n+1 and O-C m H 2m+1 ), particularly preferably (C n H 2n+1 and O-C m H 2m+1 ).

[0246] In a preferred embodiment of the present invention, the medium comprises one or more compounds of formula X.

[0247]

Chemical formula

[0248] In the formula, R 101 represents H, alkyl or alkoxy having 1 to 15, preferably 3 to 10 C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably alkyl or alkenyl, X 101 represents H, F, Cl, -CN, SF5, NCS, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, or fluorinated alkenyl, fluorinated alkenyloxy or fluorinated alkoxyalkyl having 2 to 7 C atoms, preferably fluorinated alkoxy, fluorinated alkenyloxy, F, Cl or NCS, particularly preferably NCS, Y 101 represents methyl, ethyl or Cl, Y 102 represents H, methyl, ethyl, F or Cl, preferably H or F, Z 101 Z 102 are the same or different and represent a single bond, -CH=CH-, -CF=CF- or -C≡C-,

Chemical formula

Chemical formula

Chemical formula

[0249] Preferably, the compound of formula X is selected from sub-formulas X-1 and X-2.

[0250]

Chemical formula

[0251] In the formula, the groups and parameters that appear have the meanings given above for formula X.

[0252] Particularly preferably, the medium according to the invention comprises one or more compounds selected from the group of compounds of formulae X-1-1 to X-1-9.

[0253] [Chemical formula]

[0254] In a preferred embodiment, the medium according to the invention comprises one or more compounds of formula XI.

[0255] [Chemical formula]

[0256] In the formula, R S represents H, alkyl or alkoxy having 1 to 12 C atoms or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, and in the group, one or more CH2 groups may be [Chemical formula] replaced by, and in the group, one or more H atoms may be replaced by F, [Chemical formula] represents In the formula, R L represents, in each occurrence, the same or different, H, Cl or linear, branched or cyclic alkyl having 1 to 6 C atoms, L S1 , L S2 represents, the same or different, H, Cl or F, R S1 R S2is, identical or different, H, alkyl or alkenyl having up to 6 C atoms or cyclopropyl, cyclobutyl, cyclopentenyl or cyclopentyl, representing, R Th1 、R Th2 is, identical or different, H, alkyl or alkenyl or alkoxy having up to 6 C atoms or cyclopropyl, cyclobutyl, cyclopentenyl or cyclopentyl, representing, Z S1 、Z S2 、Z S3 is, identical or different, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C≡C- or a single bond, representing, a, b are, identical or different, 0 or 1.

[0257] Preferably, the compound of formula XI is selected from the group of compounds of formula XI-1 to formula XI-24.

[0258]

Chemical formula

[0259]

Chemical formula

[0260]

Chemical formula

[0261]

Chemical formula

[0262] In the formula, the groups appearing have the meanings given above for formula XI, preferably R S represents alkyl or alkenyl having 2 to 6 C atoms, and in the group, one or more CH2 groups are

Chemical formula

[0263] In a preferred embodiment, the medium contains one or more compounds of formula XII.

[0264]

Chemical formula

[0265] wherein R 12 represents H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, and in which one or more CH₂ groups in said group may be

Chemical formula

Chemical formula

[0266] The compound of formula XII is preferably selected from the group of compounds of sub-formulas XII-1 to XII-11.

[0267] [Chemistry]

[0268] [Chemistry]

[0269] In the formula, L 1 、L 2 and L 3 are the same or different and represent H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and R T 、X 11 、X 12 、X 13 and X 14 have the meanings given above, and very preferably R T represents an alkyl having 1 to 7 C atoms, and X 11 、X 12 、X 13 and X 14 represent F.

[0270] In a preferred embodiment, the medium according to the invention comprises one or more compounds of formula T.

[0271] [Chemistry]

[0272] In the formula, R T represents halogen, CN, NCS, R F 、R F -O- or R F -S-, where R F represents fluorinated alkyl or fluorinated alkenyl having up to 12 C atoms, [Chemistry] represents, L 4 and L 5 are, the same or different, and represent F, Cl or a linear or branched or cyclic alkyl or alkenyl having up to 12 C atoms, Z T3 , Z T4 are, the same or different, represent -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or a single bond, and t is 0 or 1.

[0273] In a preferred embodiment, the liquid crystal medium according to the invention comprises one or more compounds selected from the group of compounds of the following formulas T-1a to T-3b.

[0274]

Chemical formula

[0275] wherein,

Chemical formula

[0276] In a particularly preferred embodiment of the invention, the medium comprises one or more compounds selected from the compounds of formula T-1a and formula T-2a.

[0277] Preferred compounds of formula T-1a are selected from the group of compounds of the following sub-formulas.

[0278]

Chemical formula

[0279] wherein n is 1, 2, 3 or 4, preferably 1.

[0280] Preferred compounds of formula T-2a are selected from the group of compounds of the following sub-formulas.

[0281]

Chemical formula

[0282] Wherein n is 1, 2, 3 or 4, preferably 1.

[0283] Very preferably, the medium according to the invention comprises one or more compounds of formula T-1a-5.

[0284] In certain embodiments, the medium according to the invention is a group R 1 , R 2 , R 3 , R 41 , R 42 , R 51 , R 52 , R 61 , R 62 , R 71 , R 72 , R 81 , R 82 , R 91 , R 92 , R 101 , R 102 and R S each being a cyclic alkyl group, and comprises one or more compounds of formulas I, II, III, IV, V, VI, VII, VIII, IX, X.

[0285] Highly preferred compounds containing a cyclic alkyl group are selected from the compounds of formulas Cy-1 to Cy-14.

[0286]

Chemical formula

[0287]

Chemical formula

[0288] The medium according to the present invention contains one or more chiral dopants. Preferably, these chiral dopants are in the range of 1 μm -1 ~150 μm -1 and preferably in the range of 10 μm -1 ~100 μm -1 have an absolute value of helical twisting power (HTP). When the medium contains two or more chiral dopants, they can have opposite signs of their HTP values. This condition is preferred for some specific embodiments because it allows compensating to some extent the chirality of each compound and thus can be used to compensate the various temperature-dependent properties of the medium obtained in the device. However, generally, it is preferred that most, preferably all, of the chiral compounds present in the medium according to the present invention have the same arithmetic sign of their HTP values.

[0289] Preferably, the chiral dopants present in the medium according to the present application are mesogenic compounds, and most preferably, they exhibit a mesophase alone.

[0290] In a preferred embodiment of the present invention, the medium contains two or more chiral compounds all having the same arithmetic sign of HTP.

[0291] The temperature dependence of the HTP of the individual compounds may be high or low. The temperature dependence of the pitch of the medium can be compensated by mixing compounds having different temperature dependences of HTP in corresponding ratios.

[0292] For the optically active components, a number of chiral dopants, some of which are commercially available, are available to those skilled in the art, such as cholesteryl nonanoate, R- and S-811, R- and S-1011, R- and S-2011, R- and S-3011, R- and S-4011, or CB15 (all from Merck, Darmstadt).

[0293] Particularly suitable dopants are compounds containing one or more chiral groups and one or more mesogenic groups, or one or more aromatic or alicyclic groups that form a mesogenic group together with a chiral group.

[0294] Suitable chiral groups are, for example, chiral branched hydrocarbon groups, chiral ethanediol, binaphthol or dioxolane, and furthermore sugar derivatives, sugar alcohols, sugar acids, lactic acid, chiral substituted glycols, steroid derivatives, terpene derivatives, amino acids or monovalent or polyvalent chiral groups selected from the group consisting of sequences of several, preferably 1 to 5 amino acids.

[0295] Preferred chiral groups are sugar derivatives such as glucose, mannose, galactose, fructose, arabinose and dextrose; sugar alcohols such as sorbitol, mannitol, iditol, galactitol or their anhydro derivatives, in particular dianhydrohexitols such as dianhydrosorbitol (1,4:3,6-dianhydro-D-sorbitol, isosorbide), dianhydromannitol (isomannide) or dianhydroiditol (isoidide); sugar acids such as gluconic acid, gluconic acid and ketogluconic acid; chiral substituted glycol groups such as mono- or oligoethylene or propylene glycol in which one or more CH2 groups are substituted by alkyl or alkoxy; amino acids such as alanine, valine, phenylglycine or phenylalanine, or sequences of 1 to 5 of these amino acids; steroid derivatives such as cholesteryl or cholanic acid groups; terpene derivatives such as menthyl, neomenthyl, campheyl, pinel, terpinel, isolongiferyl, fenchyl, careyl, myrtenyl, nopyr, geranyl, linaloyl, neryl, citronellyl or dihydrocitronellyl.

[0296] The medium according to the invention preferably comprises a chiral dopant selected from the group of known chiral dopants. Suitable chiral groups and mesogenic chiral compounds are described, for example, in German Patent No. 3425503, German Patent No. 3534777, German Patent No. 3534778, German Patent No. 3534779 and German Patent No. 3534780, German Patent No. 4342280, European Patent No. 01038941 and German Patent No. 19541820. Examples are also the compounds listed in Table F below.

[0297] The chiral compounds preferably used according to the invention are selected from the group consisting of the formulas shown below.

[0298] Particularly preferred are chiral dopants selected from the group consisting of the compounds of the following formulas A-I to A-III and A-Ch.

[0299] [Chemical formula]

[0300] In the formula, R a11 , R a12 and R b12 each independently represent an alkyl having 1 to 15 carbon atoms, where furthermore, one or more non-adjacent CH2 groups, independently of each other, so that O and / or S atoms are not directly bonded to each other, are replaced by -C(R z )=C(R z )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, and where furthermore, one or more H atoms may be replaced by F, Cl, Br, I or CN, preferably represents an alkyl, more preferably an n-alkyl, provided that R a12 is different from R b12 , R a21 and R a22represents, independently of one another, alkyl having 1 to 15 carbon atoms, where furthermore, one or more non-adjacent CH2 groups, independently of one another, so that O and / or S atoms are not directly bonded to each other, are replaced by -C(R z )=C(R z )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, where furthermore, one or more H atoms may also be replaced by F, Cl, Br, I or CN, preferably both represent alkyl, more preferably n-alkyl, R a31 , R a32 and R b32 represent, independently of one another, linear or branched alkyl having 1 to 15 carbon atoms, where furthermore, one or more non-adjacent CH2 groups, independently of one another, so that O and / or S atoms are not directly bonded to each other, are replaced by -C(R z )=C(R z )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, where furthermore, one or more H atoms may also be replaced by F, Cl, Br, I or CN, preferably represent alkyl, more preferably n-alkyl, provided that R a32 is different from R b32 , R z represents H, CH3, F, Cl, or CN, preferably H or F, R 8 has one of the meanings of R a11 given above, preferably alkyl having 1 to 15 carbon atoms, more preferably n-alkyl, Z 8 represents -C(O)O-, -CH2O-, -CF2O- or a single bond, preferably -C(O)O-, A 11 is as defined below for A 12 , or

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0301] Dopants selected from the group consisting of compounds of the following formula are particularly preferred.

[0302]

Chemical formula

[0303] [Chemical formula]

[0304] In the formula, m is an integer from 1 to 9, the same or different in each occurrence, and n is an integer from 2 to 9, the same or different in each occurrence.

[0305] Particularly preferred compounds of formula A are compounds of formula A-III.

[0306] Even more preferred dopants are derivatives of isosorbide, isomannitol or isoiditol of formula A-IV below.

[0307] [Chemical formula]

[0308] In the formula, the group [Chemical formula] is [Chemical formula] and is preferably dianhydrosorbitol.

[0309] And chiral ethanediols such as diphenylethane diol (hydrobenzoin), especially mesogenic hydrobenzoin derivatives of formula A-V below, including the unshown (S,S) enantiomer.

[0310] [Chemical formula]

[0311] In the formula, [Chemical formula] Each is independently 1,4-phenylene or 1,4-cyclohexylene, which may be mono-substituted, di-substituted or tri-substituted with L, wherein L is H, F, Cl, CN, or an optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1 to 7 carbon atoms, c is 0 or 1, X is CH2 or -C(O)-, Z 0 is -COO-, -OCO-, -CH2CH2- or a single bond, R 0 is alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyloxy having 1 to 12 carbon atoms.

[0312] It is an example of the compound of formula IV.

[0313]

Chemical formula

[0314]

Chemical formula

[0315] The compounds of formula A-IV are described in WO 98 / 00428. The compounds of formula A-V are described in GB 2,328,207.

[0316] Particularly highly preferred dopants are chiral binaphthyl derivatives described in WO 02 / 94805, chiral binaphthol acetal derivatives described in WO 02 / 34739, chiral TADDOL derivatives described in WO 02 / 06265, and chiral dopants having at least one fluorinated bridging group and a terminal or central chiral group described in WO 02 / 06196 and WO 02 / 06195.

[0317] The chiral compound of formula A-VI is particularly preferred.

[0318]

Chemical formula

[0319] In the formula, X 1 and X 2 Y 1 and Y 2 are each independently of the other, F, Cl, Br, I, CN, SCN, SF5, a linear or branched alkyl having 1 to 25 carbon atoms (which may be mono- or polysubstituted with F, Cl, Br, I or CN, and wherein furthermore, one or more non-adjacent CH2 groups are each independently of the other, -O-, -S-, -NH-, NR 0 -, -CO-, -COO-, -OCO-, -OCOO-, -S-CO-, -CO-S-, -CH=CH- or -C≡C- may be replaced), a polymerizable group or a cycloalkyl or aryl having up to 20 carbon atoms (which may be optionally mono- or polysubstituted with halogen, preferably F, or a polymerizable group), x 1 and x 2 are each independently of the other, 0, 1 or 2, y 1 and y 2 are each independently of the other, 0, 1, 2, 3 or 4, B 1 and B 2 are each independently of the other, an aromatic or partially saturated or fully saturated aliphatic six-membered ring, where one or more CH groups may each be replaced with an N atom, and one or more non-adjacent CH2 groups may each be replaced with O and / or S, W 1 and W 2 are each independently of the other, -Z 1 -A 1 -(Z2 -A 2 ) m -R, or one of the two is R 1 or A 3 but both are not H at the same time, or [Chemical formula] is [Chemical formula] and is U 1 and U 2 are each independently of the other CH2, O, S, CO or CS, V 1 and V 2 are each independently of the other (CH2) n (where 1 to 4 non-adjacent CH2 groups may be replaced by O and / or S), and V 1 and V 2 one of which is [Chemical formula] when [Chemical formula] are both single bonds, n is 1, 2 or 3, Z 1 and Z 2 are each independently of the other -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -, -NR 0-CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S-, -CF2-O-, -O-CF2-, -CF2-S-, -S-CF2-, -CH2-CH2-, -CF2-CH2-, -CH2-CF2-, -CF2-CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -C≡C-, combinations of two of these groups (where two O and / or S and / or N atoms are not directly bonded to each other), (preferably -CH=CH-COO- or -COO-CH=CH-), or a single bond, R x represents alkyl having 1 to 6 C atoms, A 1 A 2 and A 3 each independently of one another may be 1,4-phenylene in which one or two non-adjacent CH groups may be replaced by N, 1,4-cyclohexylene in which one or two non-adjacent CH2 groups may be replaced by O and / or S, 1,3-dioxolane-4,5-diyl, 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl (each of these groups may be mono- or polysubstituted by L), and further A 1 can be a single bond, L is a halogen atom, preferably F, CN, NO2, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1 to 7 carbon atoms (where one or more H atoms may be replaced by F or Cl), m is each independently 0, 1, 2 or 3, R and R 1are each independently H, F, Cl, Br, I, CN, SCN, SF5, 1 or a linear or branched alkyl having 3 to 25 carbon atoms (which may be mono- or polysubstituted with F, Cl, Br, I or CN, and one or more non-adjacent CH2 groups are -O-, -S-, -NH-, -NR 0 -, -CO-, -COO-, -OCO-, -O-COO-, -S-CO-, -CO-S-, -CH=CH- or -C≡C- may be replaced), or a polymerizable group.

[0320] The chiral binaphthyl derivative of formula A-VI-1 is particularly preferred.

[0321] [Chemical formula]

[0322] In the formula, ring B, R 0 and Z 0 are as defined for formulas A-IV and A-V, and b is 0, 1, or 2.

[0323] In particular, those selected from the following formulas A-VI-1a to A-VI-1c.

[0324] [Chemical formula]

[0325] In the formula, ring B, R 0 and Z 0 are as defined for formula A-VI-1, R 0 is as defined for formula A-IV or is H or an alkyl having 1 to 4 carbon atoms, b is 0, 1 or 2, Z 0 is particularly -OC(O)- or a single bond.

[0326] The concentration of one or more chiral dopants (one or more types) in the LC medium is preferably in the range of 0.001% to 20%, preferably 0.05% to 5%, more preferably 0.1% to 2%, and most preferably 0.5% to 1.5%. These preferred concentration ranges apply particularly to chiral dopants S-4011 or R-4011 (both manufactured by Merck) and chiral dopants having the same or similar HTP. For chiral dopants with a higher or lower absolute value of HTP compared to S-4011, these preferred concentrations must be decreased or increased proportionally according to the ratio of their HTP values to the HTP value of S-4011, respectively.

[0327] The pitch p of the LC medium or host mixture according to the present invention is preferably in the range of 5 to 50 μm, more preferably 8 to 30 μm, and particularly preferably 10 to 20 μm.

[0328] Preferably, the medium according to the present invention contains a stabilizer selected from the group of compounds of formulas ST-1 to ST-18.

[0329]

Chemical formula

[0330]

Chemical formula

[0331]

Chemical formula

[0332]

Chemical formula

[0333] Among the compounds of formula ST, the compounds of the following formula are particularly preferred.

[0334] [Chemical formula]

[0335] [Chemical formula]

[0336] [Chem.]

[0337] In the compounds of formulae ST-3a and ST-3b, n preferably represents 3. In the compound of formula ST-2a, n preferably represents 7.

[0338] A particularly highly preferred mixture according to the invention comprises one or more stabilizers from the group of the compounds of formulae ST-2a-1, ST-3a-1, ST-3b-1, ST-8-1, ST-9-1 and ST-12.

[0339] [Chem.]

[0340] [Chem.]

[0341] The compounds of formulae ST-1 to ST-18 are preferably present in the liquid crystal mixture according to the invention in an amount of from 0.005 to 0.5% by weight, based on the mixture.

[0342] If the mixture according to the invention contains two or more compounds from the group of the compounds of formulae ST-1 to ST-18, correspondingly in the case of two compounds, the concentration increases to from 0.01 to 1% by weight, based on the mixture.

[0343] However, the total proportion of the compounds of formulae ST-1 to ST-18, based on the mixture according to the invention, should not exceed 2% by weight.

[0344] The compounds according to the invention can be synthesized by known methods described in the literature (for example, standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart) or analogously thereto under reaction conditions suitable for the known reactions. Modifications which are known per se but not mentioned herein can also be used. In particular, they can be prepared as described in the following reaction schemes or analogously thereto. Further methods for preparing the compounds of the invention can be seen from the examples.

[0345] Other mesogenic compounds not explicitly mentioned above can optionally and advantageously be used in the media according to the invention. Such compounds are known to the person skilled in the art.

[0346] In a preferred embodiment of the invention, the total concentration of the compounds of formula U in the liquid-crystalline medium is 1% or more, preferably 4% or more, very preferably 7% or more, particularly preferably 9% or more.

[0347] In a preferred embodiment of the invention, the liquid-crystalline medium preferably contains, in total, 2% to 30%, preferably 5% to 25%, particularly preferably 10% to 20% of the compounds of formula U.

[0348] In a preferred embodiment of the invention, the liquid-crystalline medium preferably contains, in total, 10% to 45%, preferably 15% to 40%, particularly preferably 20% to 35% of the compounds of formula T, selected from formulae T-1a, T-2a and T-3a, very preferably from T-1a-5 and T-2a-4.

[0349] In a preferred embodiment of the invention, the liquid-crystalline medium contains, in total, 15% to 35%, preferably 18% to 32%, particularly preferably 20% to 30% of the compounds of formula T-1a.

[0350] In a preferred embodiment of the present invention, the medium contains one or more compounds of formula I, preferably formula I-2 or I-3, at a total concentration in the range of 2% to 50%, more preferably 5% to 30%, particularly preferably 10% to 25%.

[0351] In a preferred embodiment, the medium contains one or more compounds of formula I-2, preferably formula I-2c and / or I-2d, at a total concentration in the range of 1% to 30%, more preferably 5% to 25%, particularly preferably 10% to 20%.

[0352] In a preferred embodiment, the medium contains one or more compounds of formula I-3, preferably formula I-3b and / or I-3d, at a total concentration in the range of 1% to 35%, more preferably 10% to 30%, particularly preferably 15% to 25%.

[0353] In a preferred embodiment of the present invention, the medium contains one or more compounds of formula II, preferably formula II-1, at a total concentration in the range of 5% to 30%, more preferably 10% to 25%, particularly preferably 12% to 20%.

[0354] In a preferred embodiment of the present invention, the medium contains one or more compounds of formula IIA-1 at a total concentration in the range of 5% to 25%, more preferably 8% to 20%, particularly preferably 10% to 15%.

[0355] In a preferred embodiment of the present invention, the medium contains one or more compounds of formula II-1 at a total concentration of 30% or less, more preferably 25% or less, particularly preferably 20% or less.

[0356] In a preferred embodiment of the present invention, the medium contains one or more compounds of formula III, preferably III-1 and / or III-2, more preferably III-1i and / or III-1b, at a total concentration in the range of 15% to 70%, more preferably 25% to 60%, particularly preferably 35% to 50%.

[0357] Further preferred embodiments of the present invention are as follows, either alone or in combination with each other, provided that some compounds are abbreviated using the initials shown in Table C below.

[0358] · The medium contains one, two, three, four or more compounds selected from the compounds of formula III-1, preferably the compounds of formula III-1b, III-1f and III-1i, more preferably III-1b and III-1i.

[0359] · The medium preferably contains the compound of formula III-1b at a total concentration in the range of 2% to 30%, more preferably 5% to 25%, particularly 10% to 20%.

[0360] · The medium contains the compound of formula III-1b at a total concentration of 10% or more.

[0361] · The medium preferably contains the compound of formula III-1i at a total concentration in the range of 10% to 40%, more preferably 15% to 38%, particularly 20% to 35%.

[0362] · The medium contains the compound PPU-TO-S and / or PPTU-TO-S and / or PTPU-TO-S and / or PP(1)-TO-S.

[0363] · The medium preferably contains one or more compounds of formula U and one or more compounds of formula T at a total concentration in the range of 25% to 55%, particularly 30% to 50%.

[0364] · The medium contains one or more compounds of formula I-2d, preferably the compound PGU-2-S and / or PGU-3-S and / or PGU-4-S.

[0365] · The medium contains one or more compounds of formula I-2d and one or more compounds of formula II-1b, preferably the compound PGU-3-S and / or PGU-4-S and PTU-3-S and / or PTU-4-S and / or PTU-5-S.

[0366] · The medium contains one or more compounds of formula PPTU-n-S and / or PTPU-n-S in a total concentration in the range of 10 - 20%.

[0367] · The medium contains one or more compounds of formula PPTU-n-S and / or PTPU-n-S and / or PGTU-n-S in a total concentration in the range of 15 - 30%, where n is 2, 3, 4, 5 or 6.

[0368] · The medium contains compounds of formula CPTU-n-S and PPTU-n-S, where n is 2, 3, 4, 5 or 6.

[0369] · The medium contains a compound of formula XII-3, preferably formula CPU(F,F)-n-S, where n is 2, 3, 4 or 5.

[0370] · The medium contains one or more compounds of formula ST-3, preferably ST-3a and / or ST-3b, particularly preferably ST-3b-1, in a total concentration in the range of 0.01 - 1%, preferably 0.05 - 0.5%, particularly 0.10 - 0.15%.

[0371] The liquid crystal medium according to the present invention preferably has a clearing point of 90°C or higher, more preferably 100°C or higher, still more preferably 110°C or higher, yet more preferably 120°C or higher, still more preferably 130°C or higher, particularly preferably 140°C or higher, very particularly preferably 150°C or higher.

[0372] The liquid crystal medium according to the present invention preferably has a clearing point of 160°C or lower, more preferably 140°C or lower, particularly preferably 120°C or lower, very particularly preferably 100°C or lower.

[0373] The nematic phase of the medium according to the invention preferably extends from at least 0 °C or lower to 90 °C or higher. The medium according to the invention advantageously exhibits a wider nematic phase range, preferably from at least -10 °C or lower to 120 °C or higher, very preferably from at least 20 °C or lower to 140 °C or higher, particularly preferably from at least 30 °C or lower to 150 °C or higher, and very particularly preferably from at least 40 °C or lower to 170 °C or higher.

[0374] The Δε of the liquid crystal medium according to the invention at 1 kHz and 20 °C is preferably 1 or more, more preferably 2 or more, and very preferably 3 or more.

[0375] The birefringence (Δn) of the liquid crystal medium according to the invention at 589 nm (Na D ) and 20 °C is preferably 0.280 or more, more preferably 0.300 or more, still more preferably 0.320 or more, very preferably 0.330 or more, and especially 0.350 or more.

[0376] The Δn of the liquid crystal medium according to the invention at 589 nm (Na D ) and 20 °C is preferably in the range of 0.200 to 0.900, more preferably in the range of 0.250 to 0.800, still more preferably in the range of 0.300 to 0.700, and very particularly preferably in the range of 0.350 to 0.600.

[0377] In a preferred embodiment of the present invention, the Δn of the liquid crystal medium according to the invention is preferably 0.50 or more, more preferably 0.55 or more.

[0378] In each case, the compounds of Formulas I to III include a dielectrically positive compound having a dielectric anisotropy greater than 3, a dielectrically neutral compound having a dielectric anisotropy less than 3 and greater than -1.5, and a dielectrically negative compound having a dielectric anisotropy of -1.5 or less.

[0379] The compounds of Formulas I, II and III are preferably dielectrically positive.

[0380] In this application, compounds with a dielectrically positive expression are described as those with Δε > 3.0, those with a dielectrically neutral are described as those with -1.5 ≤ Δε ≤ 3.0, and those with a dielectrically negative are described as those with Δε < -1.5. Δε is determined at a frequency of 1 kHz and at 20°C. The dielectric anisotropy of each compound is determined from the results of a 10% solution of each individual compound in a nematic host mixture. If the solubility of each compound in the host mixture is less than 10%, the concentration is reduced to 5%. The capacitance of the test mixture is determined in both a cell with a homeotropic orientation and a cell with a homogeneous orientation. The cell thickness of both types of cells is approximately 20 μm. The applied voltage is a rectangular wave with a frequency of 1 kHz and an effective value typically between 0.5 V and 1.0 V, which is selected to always be lower than the capacitance threshold of each test mixture.

[0381] Δε is (ε ∥ - ε ⊥ ) as defined, while ε ave is (ε ∥ + 2ε ⊥ ) / 3.

[0382] The host mixture used to determine the physical constants of the pure compound by extrapolation is ZLI-4792 from Merck, Germany. The absolute value of the dielectric constant, the birefringence (Δn), and the rotational viscosity (γ1) of the compound are determined from the change in each value of the host mixture when the compound is added. The concentration in the host is 10%, or 5% if the solubility is insufficient. The values are extrapolated to 100% of the concentration of the added compound.

[0383] In the examples, the phase sequence of the pure compound is given using the following abbreviations: Tg: glass transition, K: crystal, N: nematic, SmA: smectic A, SmB: smectic B, I: isotropic.

[0384] Components having a nematic phase at a measurement temperature of 20°C are measured as they are, and the rest are treated in the same manner as the compound.

[0385] Unless otherwise stated, in this application, the expression "threshold voltage" refers to the optical threshold at 10% relative contrast (V 10 ), and the expression "saturation voltage" refers to the optical saturation at 90% relative contrast (V 90 ). Also, the capacitance threshold voltage (V0) is also called the Frederic threshold (V Fr ) and is used only when explicitly stated.

[0386] Unless otherwise stated, the ranges of parameters shown in this application all include the limit values.

[0387] The different upper and lower limit values shown for various ranges of characteristics in combination with each other give rise to additional preferred ranges.

[0388] Unless otherwise stated throughout this application, the following conditions and definitions apply. All concentrations are quoted in weight percent, with respect to the whole of each mixture, all temperatures are quoted in degrees Celsius, and all temperature differences are quoted in degrees of difference. All physical properties are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", November 1997 issue, Merck & Co., Inc., Germany, and are quoted for a temperature of 20 °C unless otherwise stated. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is determined at a frequency of 1 kHz. The threshold voltage as well as all other electro-optical properties are determined using a test cell manufactured by Merck & Co., Inc. The test cell for determining Δε has a cell thickness of approximately 20 μm. The electrodes are circular ITO electrodes with an area of 1.13 cm 2 and a guard ring. The alignment layer is SE-1211 manufactured by Nissan Chemical Industries, Ltd., Japan for homeotropic alignment (ε ∥ ), and polyimide AL-1054 manufactured by Nippon Synthetic Rubber Co., Ltd., Japan for homogeneous alignment (ε ⊥ ). The capacitance is 0.3 V rmsIt is determined using a Solatron 1260 frequency response analyzer that uses a sine wave having the voltage of. The light used for the electro-optical measurement is white light. In this specification, a device configuration that uses a DMS device commercially available from Autronic-Melchers of Germany is used. The characteristic voltage is determined under vertical observation. The threshold voltage (V 10 ), the medium gray voltage (V 50 ), and the saturation voltage (V 90 ) were determined at relative contrasts of 10%, 50%, and 90%, respectively.

[0389] As described on pages 545 to 548 of the 34th European Microwave Conference - Amsterdam, by A. Penirschke et al., "Cavity Perturbation Method for Characterisation of Liquid Crystals up to 35GHz", the liquid crystal medium is examined regarding its characteristics in the microwave frequency range. Also, in this regard, "Direct Simulation of Material Permittivites (abbreviated later)" by A. Gaebler et al., 12MTC2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pages 463 to 467 and German Patent Application Publication No. 10 2004 029 429 are also compared, and the measurement methods are described in detail in the same way in them.

[0390] Liquid crystals are introduced into a cylindrical polytetrafluoroethylene (PTFE) or quartz capillary. The capillary has an inner diameter of 180 μm and an outer diameter of 350 μm. The effective length is 2.0 cm. The filled capillary is introduced into the center of a cylindrical cavity having a resonance frequency of 19 GHz. This cavity has a length of 11.5 mm and a radius of 6 mm. Then an input signal (signal source) is applied and the results of the output signal are recorded using a commercially available vector network analyzer (N5227A PNA Microwave Network Analyzer, Keysight Technologies, USA). At other frequencies, the dimensions of the cavity are adapted accordingly.

[0391] Using the change in resonance frequency and the Q factor between measurements with a liquid crystal-filled capillary and measurements without a liquid crystal-filled capillary, the dielectric constant and loss angle at the corresponding target frequency are determined using equations 10 and 11 as described in the above-mentioned publication A. Penirschke et al., "Cavity Perturbation Method for Characterisation of Liquid Crystals up to 35GHz", 34th European Microwave Conference - Amsterdam, pages 545 - 548.

[0392] The values of the characteristic components perpendicular and parallel to the director of the liquid crystal are obtained by the orientation of the liquid crystal in a magnetic field. For this purpose, the magnetic field of a permanent magnet is used. The strength of the magnetic field is 0.35 tesla.

[0393] Preferred components are phase shifters, varactors, radios and radio wave antenna arrays, matching circuit adaptive filters and others.

[0394] In this application, the term "compound" is interpreted to mean both a single compound and multiple compounds unless otherwise specified.

[0395] The mixtures according to the invention are all nematic. The liquid-crystalline media according to the invention preferably have a nematic phase in the preferred range given above. Here, the expression having a nematic phase means on the one hand that no smectic phase and no crystallization are observed at low temperatures at the corresponding temperature, and on the other hand that no clearing occurs upon heating from the nematic phase. At high temperatures, the clearing point in the capillary is measured by conventional methods. The investigation at low temperatures is carried out at the corresponding temperature with a rheometer and confirmed by storage of the bulk sample. The storage stability (LTS) in the bulk of the media according to the invention at a given temperature T is determined by visual inspection. 2 g of the medium to be investigated are filled into a sealed glass container (bottle) of suitable size placed in a refrigerator at the given temperature. The bottles are checked at defined time intervals for the occurrence of a smectic phase and crystallization. Two bottles are stored for each material and each temperature. If crystallization or the appearance of a smectic phase is observed in at least one of the two corresponding bottles, the test is terminated and the last inspection time before the appearance of the higher-order phase is observed is recorded as the respective storage stability. Finally, the test is terminated after 1000 hours, i.e. an LTS value of 1000 hours means that the mixture is stable at the given temperature for at least 1000 hours.

[0396] The liquid crystals employed preferably have a positive dielectric anisotropy. This is preferably 2 or more, preferably 4 or more, particularly preferably 6 or more, very particularly preferably 10 or more.

[0397] Furthermore, the liquid-crystalline media according to the invention are characterized by having a high anisotropy value in the microwave range. The birefringence at about 19 GHz is, for example, preferably 0.14 or more, particularly preferably 0.15 or more, particularly preferably 0.20 or more, particularly preferably 0.25 or more, very particularly preferably 0.30 or more. In addition, the birefringence is preferably 0.80 or less.

[0398] Above and below V0 represents the capacitance threshold voltage [V] at 20 °C, n erepresents the abnormal refractive index at 20 °C and 589 nm, n0 represents the normal refractive index at 20 °C and 589 nm, Δn represents the optical anisotropy at 20 °C and 589 nm, ε ⊥ represents the dielectric constant perpendicular to the director at 20 °C and 1 kHz, ε ∥ represents the dielectric constant parallel to the director at 20 °C and 1 kHz, Δε represents the dielectric anisotropy at 20 °C and 1 kHz, cl.p, T(N,I) represents the clearing point [°C], γ1 represents the rotational viscosity [mPa·s] measured at 20 °C, K1 represents the elastic constant [pN] for the "splay" deformation at 20 °C, K2 represents the elastic constant [pN] for the "twist" deformation at 20 °C, K3 represents the elastic constant [pN] for the "bend" deformation at 20 °C, K avg. is, K avg. =(1.5K1 + K3) / 3 represents the average elastic constant [pN] at 20 °C defined as such, LTS (low-temperature stability) represents the low-temperature stability (nematic phase) determined in a test cell or in bulk as specified.

[0399] The dielectric anisotropy in the microwave region is defined as follows.

[0400]

Equation

[0401] The tunability (τ) is defined as follows.

[0402]

Equation

[0403] The material quality (η) is defined as follows.

[0404] [Number]

[0405] In the formula, the maximum dielectric loss is as follows.

[0406] [Number]

[0407] The tuning property τ of the medium according to the present invention measured at 20 °C and 19 GHz is 0.250 or more, preferably 0.300 or more, 0.310 or more, 0.320 or more, 0.330 or more, or 0.340 or more, very preferably 0.345 or more, particularly 0.350 or more.

[0408] The material quality (η) of the preferred liquid crystal material is 6 or more, preferably 8 or more, preferably 10 or more, preferably 15 or more, preferably 17 or more, preferably 20 or more, particularly preferably 25 or more, very particularly preferably 30 or more.

[0409] The preferred liquid crystal material in the corresponding component has a phase shift amount of 15 ° / dB or more, preferably 20 ° / dB or more, preferably 30 ° / dB or more, preferably 40 ° / dB or more, preferably 50 ° / dB or more, particularly preferably 80 ° / dB or more, very particularly preferably 100 ° / dB or more.

[0410] However, depending on the embodiment, a liquid crystal having a negative dielectric anisotropy can also be used.

[0411] The liquid crystal used is either an individual substance or a mixture. They preferably have a nematic phase.

[0412] The liquid crystal medium according to the invention may contain further additives and chiral dopants in conventional concentrations. The total concentration of these further components is in the range of 0% to 10%, preferably 0.1% to 6%, based on the whole mixture. The concentration of each individual compound used is preferably in the range of 0.1% to 3%. The concentrations of these and similar additives are not taken into account when citing the values and concentration ranges of the liquid crystal compounds of the liquid crystal medium in this application.

[0413] Preferably, the medium according to the invention contains one or more chiral compounds as chiral dopants to adjust their cholesteric pitch. Their total concentration in the medium according to the invention is preferably in the range of 0.05% to 15%, more preferably 1% to 10%, and most preferably 2% to 6%.

[0414] Optionally, the medium according to the invention contains further liquid crystal compounds to adjust its physical properties. Such compounds are known to the experts. Their concentration in the medium according to the invention is preferably 0% to 30%, more preferably 0.1% to 20%, and most preferably 1% to 15%.

[0415] The response time is the time (t 90 -t0) for the change of the relative alignment for the electro-optical response from 0% to 90% respectively, i.e. the rise time (τ 10 ), including the delay time (t on -t0), and the decay time (τ 100 -t 10 ) for the change of the relative alignment for the electro-optical response from 100% back to 10% respectively, and the total response time (τ off ) is shown as τ total =τ on +τ off ).

[0416] The liquid crystal medium according to the invention consists of a plurality of compounds, preferably 3 to 30, more preferably 4 to 20, very preferably 4 to 16 compounds. These compounds are mixed by conventional methods. Generally, the desired amount of the compound to be used in a smaller amount is dissolved in the compound to be used in a larger amount. When the temperature is higher than the clearing point of the compound to be used at a higher concentration, it is particularly easy to observe the completion of the dissolution process. However, it is also possible to prepare the medium using other conventional methods, for example, so-called premixes which can be ready-to-use mixtures and which can be, for example, homogeneous mixtures or eutectic mixtures of the components, or using, for example, a so-called "multi-bottle" system.

[0417] All temperatures, such as, for example, the melting point T(C,N) or T(C,S), the transition T(S,N) from the smectic (S) phase to the nematic (N) phase and the clearing point T(N,I) of the liquid crystal, are quoted in degrees Celsius. All temperature differences are quoted as differences.

[0418] In the present invention and in particular in the following examples, the structure of the mesogenic compounds is indicated by abbreviations which are also called acronyms. The chemical formulae are abbreviated as follows using Tables A - D below in these acronyms. All groups C n H 2n+1 、C m H 2m+1 and C l H 2l+1 or C n H2 n-1 、C m H 2m-1 and C l H 2-1 represent straight-chain alkyl or alkenyl, preferably 1E-alkenyl, having n, m and l carbon atoms respectively. Table A lists the codes used for the ring elements of the core structure of the compounds, while Table B shows the linking groups. Table C gives the meaning of the codes for the left-hand or right-hand end groups. Table D shows the exemplary structures of the compounds together with their respective abbreviations.

[0419] <Table A: Ring elements>

[0420]

Table 1

[0421]

Table 2

[0422]

Table 3

[0423]

Table 4

[0424]

Table 5

[0425]

Table 6

[0426] <Table B: Linking Group>

[0427]

Table 7

[0428] <Table B: Terminal Group>

[0429]

Table 8

[0430]

Table 9

[0431] In the table, n and m each represent an integer, and the three dots "..." are for other abbreviations from this table.

[0432] The following table shows exemplary structures along with their respective abbreviations. These are presented to explain the meaning of the abbreviation rules. They further represent more preferably used compounds.

[0433] <Table C: Exemplary Structures> The following exemplary structures are compounds preferably additionally used in the medium.

[0434]

Table 10

[0435]

Table 11

[0436]

Table 12

[0437]

Table 13

[0438]

Table 14

[0439]

Table 15

[0440]

Table 16

[0441]

Table 17

[0442]

Table 18

[0443]

Table 19

[0444]

Table 20

[0445]

Table 21

[0446]

Table 22

[0447]

Table 23

[0448]

Table 24

[0449] In the table, m and n are the same or different and are 1, 2, 3, 4, 5, 6 or 7.

[0450] Preferably, the medium according to the present invention comprises one or more compounds selected from the compounds of Table C.

[0451] Table D below shows exemplary compounds that can be used as alternative stabilizers in the mesogenic medium according to the present invention. The total concentration of these and similar compounds in the medium is preferably 5% or less.

[0452]

[0453]

Table 25

[0454]

Table 26

[0455]

Table 27

[0456] In a preferred embodiment of the present invention, the mesogenic medium comprises one or more compounds selected from the group of compounds from Table D.

[0457] Table E below shows exemplary compounds that can be preferably used as chiral dopants in the mesogenic medium according to the present invention.

[0458]

[0459]

Table 28

[0460]

Table 29

[0461]

Table 30

[0462]

Table 31

[0463] In a preferred embodiment of the present invention, the mesogenic medium comprises one or more compounds selected from the group of compounds of Table E.

[0464] The mesogenic medium according to the present application preferably contains two or more, preferably four or more compounds selected from the group consisting of the compounds in the above table.

Examples

[0465] The following examples illustrate the present invention without any limitation. From the physical properties, it is obvious to those skilled in the art what properties can be achieved and in what ranges they can be changed. Therefore, the various combinations of properties that can be particularly preferably achieved are well defined for those skilled in the art.

[0466] <Synthesis Example>

[0467] Abbreviations RT Room temperature (typically around 20 °C ± 1 °C) THF Tetrahydrofuran MTB ether Methyl - tert - butyl ether DCM Dichloromethane dist. Distillation

[0468] <Example 1> 2 - Butyl - 5 - [2 - [4 - (3,5 - difluoro - 4 - isothiocyanatophenyl)phenyl]ethynyl] - 1,3 - difluorobenzene

[0469] <Step 1.1> 2 - (4 - Butyl - 3,5 - difluorophenyl)ethynyltrimethylsilane

[0470]

Chemical formula

[0471] A mixture of 5-bromo-2-butyl-1,3-difluorobenzene (CAS No. 160976-00-1, 15.1 g, 61 mmol), trimethylsilylacetylene (17.6 ml, 124 mmol), diisopropylamine (70 ml), copper(I) iodide (277 mg, 1.5 mmol) and bis(triphenylphosphine)palladium(II) chloride (1.7 g, 2.4 mmol) is heated at reflux temperature overnight. The reaction mixture is then cooled to room temperature and MTB ether and distilled water are added. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (n-heptane) to give 2-(4-butyl-3,5-difluorophenyl)ethynyltrimethylsilane as a yellow oil.

[0472] <Step 1.2> 2-Butyl-5-ethynyl-1,3-difluorobenzene

[0473]

Chemical formula

[0474] Tetra-n-butylammonium fluoride (1 M in THF, 60 ml) is added dropwise to a solution of 2-(4-butyl-3,5-difluorophenyl)ethynyltrimethylsilane (15.9 g, 60 mmol) in THF (350 ml) at room temperature and the reaction mixture is stirred overnight. Hydrolysis is then effected by the addition of HCl (1 N) and distilled water and MTB ether is added. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (heptane) to give 2-butyl-5-ethynyl-1,3-difluorobenzene as a pale yellow oil.

[0475] <Step 1.3> 4-[4-[2-(4-Butyl-3,5-difluorophenyl)ethynyl]phenyl]-2,6-difluoroaniline

[0476] [Chemical]

[0477] A solution of 2-butyl-5-ethynyl-1,3-difluorobenzene (4.6 g, 24 mmol), 4-(4-bromophenyl)-2,6-difluoroamine (CAS No. 2244281-20-5, 7.0 g, 23 mmol) and diisopropylamine (55 ml) in THF (60 ml) is heated at reflux temperature. Copper(I) iodide (4.4 mg), 2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl (22 mg) and chloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)(2′-amino-1,1′-biphenyl-2-yl)palladium(II) (37 mg) are added and the reaction mixture is stirred at reflux temperature overnight. It is then cooled to room temperature, filtered and concentrated in vacuo. The residue is purified by silica gel chromatography (heptane / MTB ether 5 / 1) and crystallization (heptane) to give 4-[2-(4-butyl-3,5-difluorophenyl)ethynyl]phenyl]-2,6-difluoroaniline as brown crystals.

[0478] <Process 1.4> 2-Butyl-5-[2-[4-(3,5-difluoro-4-isothiocyanatophenyl)phenyl]ethynyl]-1,3-difluorobenzene

[0479] [Chemical]

[0480] A solution of 4-[4-[2-(4-butyl-3,5-difluorophenyl)ethynyl]phenyl]-2,6-difluoroaniline (7.4 g, 19 mmol) and 1,4-diazabicyclo[2.2.2]octane (5.2 g, 47 mmol) in DCM (70 ml) is cooled to 0 °C and treated with thiophosgene (1.6 ml, 20 mmol) dropwise. The reaction mixture is stirred at room temperature for 60 minutes. It is then hydrolyzed with brine, the aqueous phase is separated, and extracted with DCM. The combined organic phases are washed with brine, dried (sodium sulfate), and concentrated in vacuo. The residue is purified by silica gel chromatography (heptane) and crystallization (heptane) to give 2-butyl-5-[2-[4-(3,5-difluoro-4-isothiocyanatophenyl)phenyl]ethynyl]-1,3-difluorobenzene as pale orange crystals.

[0481] Phase sequence: K84N174I.K84N174.0I Δε = 7.40 Δn = 0.4180 γ1 = 735 mPas

[0482] Similar to Synthesis Example 1, the following compounds are obtained.

[0483]

Table 32

[0484]

Table 33

[0485]

Table 34

[0486]

Table 35

[0487]

Table 36

[0488] <Mixture Example> Liquid crystal mixtures N1 to N19 and comparative mixture C1 having the compositions and properties shown in the following table were prepared, and their general physical properties and properties were evaluated with respect to their applicability to microwave components at 19 GHz and 20 °C.

[0489] <Comparative Mixture C1>

[0490]

Table 37

[0491] <Example N1>

[0492]

Table 38

[0493] Example N1 corresponds to comparative mixture C1 and additionally contains the compound of formula U according to the present invention. An improvement in the material quality η from 34.5 to 39.7 is observed.

[0494] <Example N2>

[0495]

Table 39

[0496] <Example N3>

[0497]

Table 40

[0498] <Example N4>

[0499]

Table 41

[0500] <Example N5>

[0501]

Table 42

[0502] <Example N6>

[0503]

Table 43

[0504] <Example N7>

[0505]

Table 44

[0506] <Example N8>

[0507]

Table 45

[0508] <Example N9>

[0509]

Table 46

[0510] <Example N10>

[0511]

Table 47

[0512] <Example N11>

[0513]

Table 48

[0514] <Example N12>

[0515]

Table 49

[0516] <Example N13>

[0517]

Table 50

[0518] <Example N14>

[0519]

Table 51

[0520] <Example N15>

[0521]

Table 52

[0522] <Example N16>

[0523]

Table 53

[0524] <Example N17>

[0525]

Table 54

[0526] <Example N18>

[0527]

Table 55

[0528] <Example N19>

[0529]

Table 56

[0530] <Example N20>

[0531]

Table 57

[0532] <Example N21>

[0533]

Table 58

[0534] <Example N22>

[0535]

Table 59

[0536] <Example N23>

[0537]

Table 60

[0538] <Example N24>

[0539]

Table 61

[0540] <Example N25>

[0541]

Table 62

[0542] <Example N26>

[0543]

Table 63

[0544] <Example N27>

[0545]

Table 64

[0546] <Example N28>

[0547]

Table 65

[0548] <Example N29>

[0549]

Table 66

Claims

1. A compound selected from the compounds of formulas U-1 to U-20. 【Chemical 1】 [Chemical 2] [Chemical Formula 3] 【Chemical Formula 4】 (In the formula, L1, L2 are the same or different and represent H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and RU represents H, alkyl or alkoxy having 1 to 12 C atoms, halogen, CN, NCS, RF, RF-O- or RF-S-, provided that RF represents fluorinated alkyl or alkoxy or fluorinated alkenyl having up to 9 C atoms, X1 and X2 are the same or different and represent H, Cl, F, CH3 or C2H5, Y1 and Y2 independently represent H or F, and Y3 and Y4 represent H.)

2. Group X １ and X ２ The compound according to claim 1 , wherein represents H or F.

3. R Ｕ The compound according to claim 1 or 2, wherein R represents an alkyl having 1 to 12 carbon atoms.

4. Group R Ｕ represents halogen, CN, NCS, RF, RF-O- or RF-S-, provided that The compound according to claim 1 or 2, wherein RF represents fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms.

5. A compound selected from the compounds of formulas U-2, U-7, U-10, U-11 or U-12. 【Chemical Formula 5】 (In the formula, X １ and X ２ represents F, Y １ Y to Y4 represent H, R Ｕ represents n-propyl, n-butyl, n-pentyl, n-hexyl, CF ３ O-, CF ３ -, or NCS-, and L １ represents H, F, methyl or ethyl.)

6. A liquid crystal medium comprising one or more compounds according to any one of claims 1 to 5.

7. A liquid crystal medium comprising one or more compounds selected from the compounds of formulas U-2, U-7, U-10, U-11 or U-12. [[Chemical Formula 6]] (In the formula, X １ and X ２ represent F, Y １ Y to Y4 represent H, R Ｕ represents n-propyl, n-butyl, n-pentyl, n-hexyl, CF ３ O—, CF ３ — or NCS—, and L １ represents H, F, methyl or ethyl.)

8. The liquid crystal medium according to claim 6 or 7, comprising one or more compounds selected from the group of compounds of formulas I, II and III. 【Chemical Formula 7】 (In the formula, R １ represents H, non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17 C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15 C atoms, and in the group, one or more CH ２ groups are [Chemical Formula 8] may be replaced by, n is 0, 1 or 2, 【Chemical Formula 9】 represents, In the formula, R Ｌ represents, in each occurrence, the same or different H or an alkyl having 1 to 6 C atoms, and provided that, 【Chemical Formula 10】 represents, R ２ represents H, a non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15 C atoms, and in the group one or more CH ２ groups are 【Chemical 11】 may be replaced by, Z ２１ represents trans-CH=CH-, trans-CF=CF- or -C≡C-, and 【Chemical Formula 12】 represents, In the formula, R Ｌ represents, in each occurrence, the same or different H or an alkyl having 1 to 6 C atoms, R ３ represents H, a non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15 C atoms, and in the group, one or more CH ２ groups are 【Chemical 13】 may be replaced by, Z ３１ and Z ３２ One of them represents trans-CH=CH-, trans-CF=CF- or -C≡C-, and the other, independently thereof, represents -C≡C-, trans-CH=CH-, trans-CF=CF- or a single bond, and 【Chemical Formula 14】 represents, In the formula, R Ｌ represents, in each occurrence, the same or different H or an alkyl having 1 to 6 C atoms, and provided that, 【Chemical Formula 15】 represents, and 【Chemical 16】 represents.)

9. The liquid crystal medium according to claim 8, comprising one or more compounds selected from the group of compounds of formulas I-1 to I-5. 【Chemical 17】 (In the formula, L １ 、 L ２ and L ３ each occurrence independently represents H or F, and R １ 、 【Chemical Formula 18】 has the meaning given to formula I in claim 8.)

10. The liquid crystal medium according to claim 8 or 9, comprising one or more compounds selected from the group of compounds of formulas II-1 to II-3. 【Chemical Formula 19】 (In the formula, R ２ 、 【Chemical 20】 has the meaning given to formula II in claim 8.)

11. The liquid crystal medium according to any one of claims 8 to 10, comprising one or more compounds selected from the group of compounds of formulas III-1 to III-6. 【Chemical 21】 (In the formula, R ３ 、 【Chemical 22】 has the meaning given to formula III in claim 8, and Z ３１ and Z ３２ each independently represents trans-CH=CH- or trans-CF=CF-, or in formula III-6, Z ３１ and Z ３２ may represent -C≡C-.

12. A liquid crystal medium according to any one of claims 6 to 11, comprising one or more compounds of formula T. 【Chemical 23】 (In the formula, R Ｔ represents halogen, CN, NCS, R Ｆ , R Ｆ -O- or R Ｆ -S-, where R Ｆ represents fluorinated alkyl or fluorinated alkenyl having up to 12 C atoms, 【Chemical 24】 represents, L ４ and L ５ represent the same or different straight-chain, branched or cyclic alkyl or alkenyl having from 1 to 12 C atoms, F or Cl, Z Ｔ３ 、Z Ｔ４ are the same or different and represent -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or a single bond, and t is 0 or 1.)

13. A component for high-frequency technology, characterized by comprising a liquid crystal medium according to any one of claims 6 to 12.

14. A component for high-frequency technology, characterized by comprising a liquid crystal medium containing one or more compounds selected from the compounds of formula U-2, U-7, U-10, U-11 or U-12. 【Chemical 25】 (In the formula, X １ and X ２ represent F, Y １ Y to Y4 represent H, R Ｕ represents n-propyl, n-butyl, n-pentyl, n-hexyl, CF ３ O—, CF ３ — or NCS—, and L １ represents H, F, methyl or ethyl.)

15. The component according to claim 13 or 14, which is a liquid crystal-based antenna element, a phase shifter, a tunable filter, a tunable material structure, a matching network or a varactor.

16. A microwave antenna array, characterized by comprising one or more components according to any one of claims 13 to 15.

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