Liquid crystal medium

Abstract

The present invention relates to compounds of formula (A) wherein the groups and parameters occurring have the meanings defined in claim 1, to liquid-crystalline media comprising compounds of formula (A) and to high-frequency components comprising these media, in particular for high-frequency devices, such as devices for shifting the phase of microwaves, tunable filters, tunable metamaterial structures and electron beam controlled antennas, such as phased array antennas.

Description

[0001] The present invention relates to compounds, to liquid-crystalline media comprising said compounds, to high-frequency components comprising said media, in particular to microwave components for high-frequency devices, such as devices for microwave phase shifting, tunable filters, tunable metamaterial structures and electron beam control antennas (such as phased array antennas), to devices comprising said components. The present invention further relates to optical components comprising said liquid-crystalline media, which are operable in the infrared region (IR) of the electromagnetic spectrum. The present invention further relates to the use of said LC media in the infrared region, and to devices comprising said optical components.

[0002] For displaying information, liquid-crystalline media have been used for many years in electro-optical displays (liquid crystal displays: LCD). However, recently, it has also been proposed to use liquid-crystalline media for components of microwave technology, for example in DE 10 2004 029 429 A and JP 2005-120208 (A).

[0003] A. Gaebler, F. Goelden, S. Muller, A. Penirschke and R. Jakoby, "Direct Simulation of Material Permittivities using an Eigen-Susceptibility Formulation of the Vector Variational Approach", 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pages 463-467 describe the respective properties of the known liquid-crystalline mixture E7 (Merck KGaA, Germany).

[0004] DE 10 2004 029 429 A describes the use of liquid-crystalline media in microwave technology, in particular in phase shifters. Therein, liquid-crystalline media have been discussed as well as their properties in the respective frequency range, and liquid-crystalline media based on mixtures of mainly aromatic nitriles and isothiocyanates have been shown.

[0005] However, compositions which can be used in microwave applications still have several drawbacks. There is a need to improve the general physical properties, the shelf life and the stability when operated in devices of these media. In view of the multiple different parameters which have to be considered and improved for the development of liquid-crystalline media for microwave applications, it would be desirable to have a wider range of possible mixture components for the development of such liquid-crystalline media.

[0006] It was an object of the present application to provide compounds for use in liquid-crystalline media which have improved properties in connection with applications in the microwave range of the electromagnetic spectrum.

[0007] To solve this problem, the compounds of the formula A defined below and liquid-crystalline media comprising them are provided.

[0008] The present application relates to compounds of the formula A

[0009]

[0010] in which

[0011] R A represents H, a straight-chain alkyl group having 1 to 12 C atoms, or a straight-chain alkenyl or straight-chain alkynyl group each having 2 to 12 C atoms, or a branched alkyl group having 3 to 12 C atoms or a branched alkenyl group having 3 to 12 C atoms or a branched alkynyl group having 4 to 12 C atoms, it being possible for one or more CH2-groups to be replaced, independently of one another, by or alternatively, and in which one or more non-adjacent CH2-groups can be replaced, independently of one another, by -O- and in which one or more H atoms in all these radicals can be replaced by F,

[0012] Z A1 represents -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, CH2CH2, -CHFCHF-, -CF2CH2, CH2CF2 or CF2CF2, preferably -CH=CH- or CH2CH2, very preferably -CH=CH-,

[0013] Z A2 represents -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or -C≡C-C≡C-, preferably -C≡C-,

[0014] U 1 , U 2 , V 1 and V 2 identically or differently, represent -N= or -CR 0 =,

[0015] R 0 represents H, Cl, F, CF3, CHF2 or an alkyl or alkoxy group each having 1 to 6 C atoms,

[0016] X Arepresents -NCS, -CºC-CN or -CºC-NCS, preferably -NCS,

[0017] represents 1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexylene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2groups can be replaced by -0- and / or -S- and wherein one or more H atoms can be replaced by F,

[0018] represents 1,4-phenylene, 1,4-naphthylene, wherein one or two CH groups can be replaced by N and wherein one or more H atoms can be replaced by R L ; benzo[1,2-b:4,5-b']dithiophene-2,6-diyl, thiophene-2,5-diyl or thieno[3,2- b]thiophene-2,5-diyl, wherein one or more H atoms can be replaced by R L

[0019] R L identically or differently in each occurrence, F, Cl, CN, SCN, SF5 or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms in each case, which is optionally fluorinated,

[0020] n is 0, 1 or 2.

[0021] According to a further aspect of the present application, a liquid-crystalline medium comprising one or more compounds of formula A is provided.

[0022] The preferred embodiments of the present application are subject matter of the independent claims or can be derived from the description.

[0023] Surprisingly, it has been found that by using compounds of formula A in a liquid-crystalline medium, a liquid-crystalline medium having excellent stability, while at the same time having a high dielectric anisotropy, a suitable fast switching time, a suitable nematic phase range, a high tunability and a low dielectric loss (in the microwave range of the electromagnetic spectrum) can be achieved.

[0024] In particular, the medium according to the present application comprising the compounds according to the present application is characterized by an improved figure of merit η due to a higher tunability τ and a lower dielectric loss.

[0025] The medium according to the present application is further characterized by a high clearing temperature, a wide nematic phase range and an excellent low temperature stability (LTS). Thus, a device containing this medium can be operated under extreme temperature conditions. ​

[0026] The medium is further characterized by a high dielectric anisotropy value and a low rotational viscosity. Thus, the threshold voltage, i.e. the minimum voltage at which the device can switch, is very low. In order to achieve a device with improved switching characteristics and high energy efficiency, a low operating voltage and a low threshold voltage are required. The low rotational viscosity enables the device according to the present application to switch rapidly.

[0027] These properties make the medium particularly suitable for components and devices used in high frequency technology and microwave range applications, in particular for devices for microwave phase shifting, tunable filters, tunable metamaterial structures and electron beam control antennas, such as phased array antennas, in general.

[0028] According to a further aspect of the present application, there is thus provided components and devices comprising said components, both of which can be operated in the microwave region of the electromagnetic spectrum. Preferred components are phase shifters, varactor diodes, wireless and radio wave antenna arrays, matching circuits and adaptive filters.

[0029] The medium according to the present application is equally suitable for use in the infrared region of the electromagnetic spectrum.

[0030] The present application thus further relates to the use of the medium defined above in the infrared region of the electromagnetic spectrum, preferably in the A-band and / or B-band and / or C-band, for phase modulation of said infrared light.

[0031] According to a further aspect of the present application, there is provided an optical component comprising a liquid crystal medium according to the present application sandwiched between a pair of substrates.

[0032] The present application further relates to a device comprising an optical component according to the present application. Preferred devices are infrared imagers, wavelength selective switches, LCoS-SLMs, LIDAR systems, wavelength division multiplexing (WDM) systems, reconfigurable optical add-drop multiplexers (ROADMs) and non-mechanical beam steering, such as the steerable electrically induced optical refraction (SEEOR) prism disclosed in the article P. McManamon, 2006, "Agile Nonmechanical Beam Steering," Opt. Photon. News 17(3): 24-29.

[0033] According to a further aspect of the present application, there is provided a method of spatially modulating infrared light, the method comprising:

[0034] i) providing an optical component comprising a first substrate and a second substrate facing each other, each having a surface, the first substrate comprising at least one first electrode and the second substrate comprising at least one second electrode, the component further comprising a liquid crystal layer sandwiched between the first substrate and the second substrate, wherein the liquid crystal comprises one or more compounds selected from the group consisting of the compounds of formula A indicated above;

[0035] ii) receiving incident infrared light at the surface of the optical assembly;

[0036] iii) applying a predetermined voltage to each individual electrode formed on the first substrate and the second substrate to modulate the refractive index of the liquid crystal layer.

[0037] According to another aspect of the present application, a method for manufacturing an optical phase modulator is provided, comprising at least the steps of

[0038] a) providing a first substrate with a first electrode, optionally with a two- dimensional array of individually electrically drivable cells;

[0039] b) depositing a liquid crystal medium as defined in claim 1 on the first substrate;

[0040] and

[0041] c) mounting a second substrate with a second electrode onto the liquid crystal material.

[0042] The optical assembly according to the present application is characterized by an excellent operational stability when exposed to the environment, due to the high clearing temperature, the wide nematic phase range and the excellent low temperature stability (LTS) of the liquid crystal medium used therein. Thus, the assembly and the devices comprising the assembly can be operated under extreme temperature conditions.

[0043] The medium used for the assembly according to the present application is characterized by a high dielectric anisotropy value and a low rotational viscosity. Thus, the threshold voltage, i.e. the minimum voltage at which the device can switch, is very low. A low operating voltage and a low threshold voltage are required in order to have devices with improved switching characteristics and high energy efficiency. The low rotational viscosity enables the assembly and the devices according to the present application to switch rapidly.

[0044] Herein, "high frequency technology" means an application of electromagnetic radiation with a frequency in the range of 1 MHz to 1 THz, preferably 1 GHz to 500 GHz, more preferably 2 GHz to 300 GHz, in particular preferably about 5 GHz to 150 GHz.

[0045] As used herein, the infrared region of the electromagnetic spectrum refers to the spectral region of electromagnetic radiation with wavelengths in the range of 0.75 μm to 1000 μm.

[0046] As used herein, Infrared A (IR-A) refers to the spectral region of electromagnetic radiation with wavelengths in the range of 0.75 µm to 1.4 µm.

[0047] As used herein, Infrared B (IR-B) refers to the spectral region of electromagnetic radiation with wavelengths in the range of 1.4 µm to 3 µm.

[0048] As used herein, infrared C (IR-C) refers to the spectral region of electromagnetic radiation with wavelengths in the range from 3 pm to 1000 pm.

[0049] Preferably, the optical assembly according to the application operates at wavelengths in the range from 750 nm to 2500 nm, in particular from 1530 nm to 1565 nm.

[0050] Very preferred light sources for use according to the application are IR lasers emitting light at a wavelength of 1,55 pm or IR lasers emitting light at a wavelength of 905 nm.

[0051] As used herein, halogen is F, CI, Br or I, preferably F or CI, in particular F.

[0052] Herein, alkyl is linear or branched or cyclic and has 1 to 12 C atoms, is preferably linear and has, unless indicated otherwise, 1, 2, 3, 4, 5, 6 or 7 C atoms, thus preferably is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl.

[0053] Herein, branched alkyl is preferably isopropyl, sec-butyl, isobutyl, iso-pentyl, 2-methylbutyl, 2-methylhexyl or 2-ethylhexyl.

[0054] As used herein, cyclic alkyl refers to linear or branched alkyl or alkenyl groups having up to 12 C atoms, preferably alkyl groups having 1 to 7 C atoms, wherein a group CH2is replaced by a carbocyclic ring having 3 to 5 C atoms, very preferably selected from the group consisting of cyclopropylalkyl, cyclobutylalkyl, cyclopentylalkyl and cyclopentenylalkyl.

[0055] Herein, alkoxy is linear or branched and contains 1 to 15 C atoms. It is preferably linear and has, unless indicated otherwise, 1, 2, 3, 4, 5, 6 or 7 C atoms, thus preferably is methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy or n-heptoxy.

[0056] In the present context, alkenyl preferably is an alkenyl group having 2 to 12 C atoms, which is straight-chain or branched, and which contains at least one C-C double bond. It is preferably straight-chain and has 2 to 7 C 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. If the two C atoms of the C-C double bond are substituted, the alkenyl group can be in the form of the E and / or Z isomer (trans / cis). In general, the corresponding E isomer is preferred. Among the alkenyl groups, particular preference is given to prop-2-enyl, but-2- and -3-enyl and pent-3- and -4-enyl.

[0057] In the present context, alkynyl means an alkynyl group having 2 to 12 C atoms, which is straight-chain or branched, and which contains at least one C-C triple bond. Preference is given to terminal alkynes, in which the triple bond is bonded to the aromatic ring, very preferably n-prop-1-yn-1-yl, n-but-1-yn-1-yl, n-pent-1-yn-1-yl and n-hex-1-yn-1-yl.

[0058] If R F represents a halogenated alkyl-, alkoxy-, alkenyl or alkenyloxy group, which can be branched or unbranched. Preference is given to it being unbranched, monofluorinated, polyfluorinated or perfluorinated, preferably perfluorinated, and having 1, 2, 3, 4, 5, 6 or 7 C atoms, if it is an alkenyl group, 2, 3, 4, 5, 6 or 7 C atoms.

[0059] R P Preference is given to representing CN, NCS, CI, F, -(CH2) n -CH=CF2, -(CH2) n -CH=CHF, -(CH2) n -CH=CI2, -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 CHCI2, -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, wherein n is an integer from 0 to 7.

[0060] The compounds of general formula A are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), under reaction conditions which are known and suitable for the reactions. Here too, it is possible to use the various variations of the methods known per se, which are not mentioned here in greater detail.

[0061] If desired, the starting materials can also be formed in situ without isolation from the reaction mixture, and are then immediately reacted further to the compounds of general formula A.

[0062] Preferred synthesis routes for the compounds of the application are illustrated in the schemes below and further illustrated by way of working examples. By selecting appropriate starting materials, the synthesis shown can be adapted to a particular desired compound of general formula A.

[0063] In a preferred embodiment of the application, a process for the manufacture of a compound of formula A is provided, wherein a terminal alkyne is reacted in a Sonogashira reaction to give a compound of formula A, wherein the group Z A2represents a triple bond, as shown in Scheme 1 below, wherein the occurring groups and parameters have the meanings given for formula A, and X represents a leaving group, such as CI, Br, I or triflate. A suitable starting material for compound (1) is, for example, an aryl halide (3) known in the prior art, such as cyclohexylethylphenyl bromide or cyclohexylethenylphenyl bromide (cf. CN103242133 A: Jian Li, Minggang Hu, Juanli Li, Zhongwei An, Xiaozhe Yang, Zhi Yang and Zhaoyi Che (2014) Highly fluorinated liquid crystals with wide nematic phase interval and good solubility, Liquid Crystals, 41 : 12, 1783-1790, DOI: 10.1080 / 02678292.2014.950617), which is converted to compound 1 by reaction with, for example, trimethylsilyl acetylene and subsequent deprotection. The difluorovinyl bridge element Z A1 is set forth in JP08059525 A. The fluorinated ethene bridge can be prepared in analogy to the process set forth in EP1149885 A1. Anilines 2 and 4 are commercially available or can be prepared by known processes.

[0064] Scheme 1

[0065]

[0066] Compound 1 is also an intermediate for the synthesis of compounds of formula A by hydroboration (Scheme 2), followed by Suzuki coupling with compound 2, wherein Z A2 represents a double bond (5).

[0067] Scheme 2

[0068]

[0069] Therefore, a preferred precursor for the synthesis of compounds of formula A is an amino derivative of formula N1.

[0070]

[0071] (N1)

[0072] reacting a compound of formula N1 with a thiocarbonic acid derivative wherein X and Y are leaving groups, or CS2 to give a compound of formula A.

[0073] A preferred reagent for the process of the present application for converting a compound of formula Nl to a compound of formula A is carbon disulfide, thiophosgene, thiocarbonyldiimidazole, di-2-pyridylthiocarbonate, bis(dimethylthiocarbamoyl)disulfide, dimethylthiocarbamoyl chloride and phenyl chlorothioformate, very preferably thiophosgene.

[0074] Another preferred route for the synthesis of isothiocyanates of formula A comprises the reaction of N-hydroxycarboimidoyl chloride N2 with e.g. thiourea or thiocarbonic acid ester.

[0075]

[0076] (N2)

[0077] Compounds of formula A (wherein the terminal group X D represents -C≡C-CN) can be synthesized analogous to the process set forth in DE 19831093 Al.

[0078] Compounds of formula A (wherein the terminal group X D represents -C≡C-NCS) can be prepared according to the process set forth in M. S. Shvartsberg et al., Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1976), (10), 2292-5: ethyne 1 can be converted to chloride 2 by deprotonation and chlorination using N-chlorosuccinimide, chloride 2 can be reacted with sodium amide to give the amine of formula N-3, from which compounds of formula A can be obtained using e.g. the known reagents listed above.

[0079] Scheme 3

[0080]

[0081] The reactions set forth are to be considered only as illustrative. A person skilled in the art can carry out corresponding variations of the syntheses set forth and also follow other suitable synthetic routes to obtain compounds of formula A.

[0082] In a preferred embodiment of the present application, the group Z A1 represents -CH=CH-, -CF=CF-, -CH=CF- or -CF=CH-.

[0083] In another preferred embodiment of the present application, the group Z A1 represents CH2CH2, CF2CH2, CH2CF2 or CF2CF2.

[0084] In a preferred embodiment of the present application, the compound of formula A is selected from the group consisting of compounds of formulae A-l, A-2, A-3 and A-4: In a preferred embodiment of the present application, the compound of formula A is selected from the group consisting of compounds of formulae A-l, A-2, A-3 and A-4:

[0085]

[0086] wherein the occurring radicals have the meanings given above for formula A.

[0087] in formula A and its subformulae, preferably denotes or ,

[0088] wherein R L identically or differently at each occurrence, denotes H or alkyl having 1 to 6 C atoms or cycloalkyl having 3 to 5 C atoms, and

[0089] have the meanings given for and alternatively denote or ,

[0090] wherein

[0091] W denotes N, C-H, C-F or C-Cl, and

[0092] Y 1 and Y 2 identically or differently, denote H, CI, F, methyl or ethyl.

[0093] in the compounds of formula A, the radical X A very preferably denotes NCS.

[0094] very preferably denotes or wherein Y identically or differently denotes F, CI, CH3or C2H5, preferably F.

[0095] Preferably, the compounds of formula A-1 are selected from the group consisting of the compounds of formulae A-1-1 to A-1-21

[0096] Preferably, the compounds of formula A-2 are selected from the group consisting of the compounds of formulae A-2-1 to A-2-21

[0097] Preferably the compound of formula A-3 is selected from the group consisting of formulae A-3-1 to A-3-21

[0098] Preferably the compound of formula A-4 is selected from the group consisting of formulae A-4-1 to A-4-21

[0099] In a preferred embodiment the medium according to the present application comprises one or more compounds selected from the group of compounds of formulae I, II and III:

[0100] wherein

[0101] R 1 represents H; a non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10 C atoms; or a non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, wherein one or more CH2-groups can be replaced by or instead of,

[0102] preferably a non-fluorinated alkyl, non-fluorinated alkenyl or non-fluorinated alkynyl,

[0103] n is 0, 1 or 2,

[0104]

[0105]

[0106] preferably

[0107]

[0108] more preferably

[0109]

[0110] R 2The substance represents H, and is a non-fluorinated alkyl or non-fluorinated alkoxy group having 1 to 17, preferably 2 to 10, carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenyloxy, or non-fluorinated alkoxyalkyl group having 2 to 15, preferably 3 to 10, carbon atoms, wherein one or more CH2- groups may be , , , or The preferred alternatives are non-fluorinated alkyl groups, non-fluorinated alkenyl groups, or non-fluorinated alkynyl groups.

[0111] Z 21 This represents the trans form -CH=CH-, trans form -CF=CF-, or -C≡C-, preferably -C≡C- or trans form -CH=CH-, and

[0112]

[0113] Preferred

[0114]

[0115] R 3 The substance represents H, and is a non-fluorinated alkyl or non-fluorinated alkoxy group having 1 to 17, preferably 2 to 10, carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenyloxy, or non-fluorinated alkoxyalkyl group having 2 to 15, preferably 3 to 10, carbon atoms, wherein one or more CH2- groups may be , , , or The preferred alternatives are non-fluorinated alkyl groups, non-fluorinated alkenyl groups, or non-fluorinated alkynyl groups.

[0116] Z 31 and Z 32 One of them, Z is preferred 32 This indicates trans-CH=CH-, trans-CF=CF-, or -C≡C-, and another independently indicates -C≡C-, trans-CH=CH-, trans-CF=CF-, or a single bond, preferably, one of which, Z. 32 This indicates -C≡C- or trans-CH=CH-, and the other indicates a single bond.

[0117] Preferably

[0118] More

[0119] In the compounds of the formulae I, II and III, R L preferably denotes H.

[0120] In another preferred embodiment, in the compounds of the formulae I, II and III, one or two radicals R L , preferably one radical R L denotes H.

[0121] In a preferred embodiment of the application, the compounds of the formula I are selected from the group of the compounds of the formulae I-1 to I-5:

[0122] wherein

[0123] L 1 , L 2 and L 3 denote, on each occurrence identically or differently, H or F,

[0124] and the other radicals have the respective meanings indicated above for the formula I, and

[0125] preferably,

[0126] R 1 denotes non-fluorinated alkyl having 1 to 7 C atoms, or non-fluorinated alkenyl having 2 to 7 C atoms, or non-fluorinated alkynyl having 2 to 7 C atoms.

[0127] Preferably, the medium comprises one or more compounds selected from the group of the compounds of the formula I-a, and optionally one or more compounds selected from the group of the compounds of the formula Cy-1

[0128] wherein the radicals occurring have the meanings given above for formula I-1. The total amount of the compounds of the formulae I-1 and / or Cy-I in the medium according to the application is less than 10%, more preferably less than 5%, in particular less than 2%. It is particularly preferred that the medium is free of compounds of the formula Cy-1.

[0129] The medium preferably comprises one or more compounds of the formula I-1, which are preferably selected from the group of the compounds of the formulae I-1 a to I-1 d, preferably the compounds of the formula I-1 b:

[0130] wherein R 1has one of the meanings indicated above for formula I, and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms, or non-fluorinated alkenyl having 2 to 7 C atoms, or non-fluorinated alkynyl having 2 to 7 C atoms.

[0131] The medium preferably comprises one or more compounds of formula I-2, which are preferably selected from the group consisting of compounds of formulae I-2a to I-2e, preferably compounds of formula I-2c:

[0132] wherein R 1 has one of the meanings indicated above for formula I, and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms, or non-fluorinated alkenyl having 2 to 7 C atoms, or non-fluorinated alkynyl having 2 to 7 C atoms.

[0133] The medium preferably comprises one or more compounds of formula I-3, which are preferably selected from the group consisting of compounds of formulae I-3a to I-3d, particularly preferably compounds of formula I-3b:

[0134] wherein R 1 has one of the meanings indicated above for formula I, and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms, or non-fluorinated alkenyl having 2 to 7 C atoms, or non-fluorinated alkynyl having 2 to 7 C atoms.

[0135] The medium preferably comprises one or more compounds of formula I-4, which are preferably selected from the group consisting of compounds of formulae I-4a to I-4e, particularly preferably compounds of formula I-4b:

[0136] wherein R 1 has one of the meanings indicated above for formula I, and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms, or non-fluorinated alkenyl having 2 to 7 C atoms, or non-fluorinated alkynyl having 2 to 7 C atoms.

[0137] The medium preferably comprises one or more compounds of formula I-5, which are preferably selected from the group consisting of compounds of formulae I-5a to I-5d, particularly preferably compounds of formula I-5b:

[0138] wherein R 1 has one of the meanings indicated above for formula I, and preferably denotes non-fluorinated alkyl having 1 to 7 C atoms, or non-fluorinated alkenyl having 2 to 7 C atoms, or non-fluorinated alkynyl having 2 to 7 C atoms.

[0139] The medium preferably comprises one or more compounds of the formula II, which are preferably selected from the group of compounds of the formulae II-1 to II-3, preferably from the group of compounds of the formulae II-1 and II-2:

[0140] wherein the radicals occurring have the meanings given above under formula II, and preferably

[0141] R 2 represents a non-fluorinated alkyl group having 1 to 7 C atoms, or a non-fluorinated alkenyl group having 2 to 7 C atoms, or a non-fluorinated alkynyl group having 2 to 7 C atoms,

[0142] and

[0143] and preferably

[0144] R 2 represents C n H 2n+1 or CH2=CH-(CH2) Z , and

[0145] n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6, and particularly preferably in the range from 3 to 5, and

[0146] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0147] The compounds of the formula II-1 are preferably selected from the group of compounds of the formulae II-1 a to II-1 e:

[0148] wherein

[0149] R 2 has the meanings indicated above, and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z or C n H 2n+1 -C≡C-,

[0150] n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6, and particularly preferably in the range from 3 to 5, and

[0151] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0152] The compounds of the formula II-2 are preferably selected from the group of compounds of the formulae II-2a and II-2b:

[0153] wherein

[0154] R 2 have the meanings indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z , or C n H 2n+1 -C≡C-,

[0155] n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and

[0156] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0157] The compounds of the formula II-3 are preferably selected from the group of the compounds of the formulae II-3a to II-3d:

[0158] wherein

[0159] R 2 have the meanings indicated above and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z , or C n H 2n+1 -C≡C-,

[0160] n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably 3 to 5, and

[0161] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0162] The compounds of the formula III are preferably selected from the group of the compounds of the formulae III-1 to III-6, more preferably from the group of the compounds of the formulae III-1, III-2, III-3 and III-4, particularly preferably the compounds of the formula III-1 :

[0163] wherein

[0164] Z 31 and Z 32 independently of one another denote trans-CH=CH- or trans-CF=CF-, preferably trans-CH=CH-, and in the formula III-6 alternatively one of Z 31 and Z 32 may denote -C≡C- and the other radical has the meaning given above under formula III,

[0165] and preferably

[0166] R 3 denotes non-fluorinated alkyl with 1 to 7 C atoms, or non-fluorinated alkenyl with 2 to 7 C atoms, or non-fluorinated alkynyl with 2 to 7 C atoms,

[0167] and

[0168] and preferably

[0169] R 3 denotes C n H 2n+1 or CH2=CH-(CH2) Z or C n H 2n+1 -C≡C-,

[0170] n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably in the range from 3 to 5, and

[0171] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0172] The compounds of the formula III-1 are preferably selected from the group of the compounds of the formulae III-1 a to III-1 j, more preferably from the group of the compounds of the formulae III-1 a, III-1 b, III-1 g and III-1 h, particularly preferably the compounds of the formulae III-1 b and / or III-1 h:

[0173] wherein

[0174] R 3 has the above indicated meaning and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z or C n H 2n+1 -C≡C-,

[0175] n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably in the range from 3 to 5, and

[0176] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0177] The compounds of the formula III-2 are preferably the compounds of the formulae III-2a to III-2l, very preferably the compounds of the formulae III-2b and / or III-2j:

[0178] wherein

[0179] R 3 have the above indicated meanings and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z or C n H 2n+1 -C≡C-,

[0180] n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0181] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0182] The compounds of the formula III-5 are preferably selected from the group of compounds of the formula III-5a:

[0183] R 3 have the above indicated meanings for the formula III-5 and preferably denote C n H 2n+1 wherein

[0184] n denotes an integer in the range from 1 to 7, preferably in the range from 2 to 6 and particularly preferably from 3 to 5, and

[0185] In a preferred embodiment, the medium according to the application comprises one or more compounds selected from the group of compounds of the formulae IIA-1-1 to IIA-1-12, very preferably IIA-1-1 or IIA-1-2:

[0186] wherein

[0187] R 2 denote alkyl or alkenyl having up to 7 C atoms or alkynyl, preferably ethyl, n-propyl, n-butyl or n-pentyl, n-hexyl,

[0188] R L denote, on each occurrence identically or differently, alkyl or alkenyl having 1 to 5 C atoms, or cycloalkyl or cycloalkenyl each having 3 to 6 C atoms, preferably methyl, ethyl, n-propyl, n-butyl, i-propyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopent-1-enyl, very preferably ethyl,

[0189] and which excludes the compounds of the formula II-1.

[0190] Further, in certain embodiments, the liquid-crystalline medium according to the present application comprises, preferably, one or more compounds of formula IV, which embodiments can be identical with or different from the aforementioned preferred embodiments,

[0191] wherein

[0192]

[0193] s is 0 or 1, preferably 1, and

[0194] Preferably

[0195] Particularly preferably

[0196] L 4 denotes H or alkyl having 1 to 6 C atoms, cycloalkyl having 3 to 6 C atoms, or cycloalkenyl having 4 to 6 C atoms, preferably CH3, C2H5, n-C3H7, i-C3H7, cyclopropyl, cyclobutyl, cyclohexyl, cyclopent-1 - enyl or cyclohex-1 -enyl, and particularly preferably CH3, C2H5, cyclopropyl or cyclobutyl,

[0197] X 4 denotes H, alkyl having 1 to 3 C atoms or halogen, preferably H, F or CI, more preferably H or F and very particularly preferably F,

[0198] R 41 to R 44 , independently of one another, denote non-fluorinated alkyl or non-fluorinated alkoxy each having 1 to 15 C atoms, non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl each having 2 to 15 C atoms, or cycloalkyl, alkylcycloalkyl, cycloalkenyl, alkylcycloalkenyl, alkylcycloalkylalkyl or alkylcycloalkenylalkyl each having up to 15 C atoms, and alternatively one or both of R 43 and R 44 denote H,

[0199] Preferably

[0200] R 41 and R 42 , independently of one another, denote non-fluorinated alkyl or non-fluorinated alkoxy each having 1 to 7 C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl each having 2 to 6 C atoms,

[0201] Particularly preferably

[0202] R 41denotes non-fluorinated alkyl with 1 to 7 C atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl each with 2 to 6 C atoms, and

[0203] Particularly preferably

[0204] R 42 denotes non-fluorinated alkyl with 1 to 7 C atoms or non-fluorinated alkoxy,

[0205] Preferably

[0206] R 43 and R 44 denote H, non-fluorinated alkyl with 1 to 5 C atoms, non-fluorinated cycloalkyl or cycloalkenyl with 3 to 7 C atoms, non-fluorinated alkylcyclohexyl or non-fluorinated cyclohexylalkyl each with 4 to 12 C atoms, or non-fluorinated alkylcyclohexylalkyl with 5 to 15 C atoms, particularly preferably cyclopropyl, cyclobutyl or cyclohexyl, and very particularly preferably R 43 and R 44 at least one of which denotes n-alkyl, particularly preferably methyl, ethyl or n-propyl, and the other H or n-alkyl, particularly preferably H, methyl, ethyl or n-propyl.

[0207] Very particularly preferably, the compound of the formula IV is selected from the group of compounds of the formula IV-1

[0208] in which R 41 and R 42 denote, identically or differently, alkyl with 2, 3, 4, 5 or 6 C atoms.

[0209] In a preferred embodiment of the present application, the liquid-crystalline medium additionally comprises one or more compounds selected from the group of compounds of the formulae V, VI, VII, VIII and IX:

[0210] in which

[0211] L 51 denotes R 51 or X 51 ,

[0212] L 52 denotes R 52 or X 52 ,

[0213] R 51 and R 52 independently of one another, H, non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10 C atoms, or non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably alkyl or non-fluorinated alkenyl,

[0214] X 51 and X 52 independently of one another, H, F, Cl, -CN, SF5, 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 or Cl, and

[0215] L 61 denotes R 61 in the case where Z 61 and / or Z 62 denotes trans-CH=CH- or trans-CF=CF-, alternatively also X 61 ,

[0216] L 62 denotes R 62 in the case where Z 61 and / or Z 62 denotes trans-CH=CH- or trans-CF=CF-, alternatively also X 62 ,

[0217] R 61 and R 62 independently of one another, H, non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10 C atoms, or non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably alkyl or non-fluorinated alkenyl,

[0218] X 61 and X 62 independently of one another, F or Cl, -CN, SF5, fluorinated alkyl or alkoxy having 1 to 7 C atoms, or fluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 7 C atoms,

[0219] Z 61 and Z 62one of the two represents trans-CH=CH-, trans-CF=CF- or -C≡C- and the other independently thereof 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 is a single bond, and

[0220] and

[0221] x represents 0 or 1 ;

[0222] L 71 represents R 71 or X 71 ,

[0223] L 72 represents R 72 or X 72 ,

[0224] R 71 and R 72 independently of one another represent H, non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10 C atoms, or non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably alkyl or non-fluorinated alkenyl,

[0225] X 71 and X 72 independently of one another represent H, F, Cl, -CN, -NCS, -SF5, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, or fluorinated alkenyl, non-fluorinated or fluorinated alkenyloxy or non-fluorinated or fluorinated alkoxyalkyl having 2 to 7 C atoms, preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and

[0226] Z 71 to Z 73 independently of one another represent trans-CH=CH-, trans-CF=CF-, -C≡C- or a single bond, preferably one or more of them represent a single bond, particularly preferably all represent a single bond, and

[0227] R 81 and R 82 independently of one another represent H, non-fluorinated alkyl or alkoxy having 1 to 15, preferably 2 to 10 C atoms, or non-fluorinated alkenyl, alkynyl, alkenyloxy or alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably non-fluorinated alkyl or alkenyl,

[0228] Z 81 and Z 82one of the two represents trans-CH=CH-, trans-CF=CF- or -CºC- and the other independently thereof represents trans-CH=CH-, trans-CF=CF- or a single bond, preferably one of them represents -CºC- or trans-CH=CH- and the other represents a single bond, and

[0229] L 91 represents R 91 or X 91 ,

[0230] L 92 represents R 92 or X 92 ,

[0231] R 91 and R 92 independently of one another represent H, non-fluorinated alkyl or alkoxy having 1 to 15, preferably 2 to 10 C atoms, or non-fluorinated alkenyl, alkynyl, alkenyloxy or alkoxyalkyl having 2 to 15, preferably 3 to 10 C atoms, preferably non-fluorinated alkyl or alkenyl,

[0232] X 91 and X 92 independently of one another represent H, F, Cl, -CN, -NCS, -SF5, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, or fluorinated alkenyl, non-fluorinated or fluorinated alkenyloxy or non-fluorinated or fluorinated alkoxyalkyl having 2 to 7 C atoms, preferably fluorinated alkoxy, fluorinated alkenyloxy, F or Cl, and

[0233] Z 91 to Z 93 independently of one another represent trans-CH=CH-, trans-CF=CF-, -CºC- or a single bond, preferably one or more of them represent a single bond, and particularly preferably all represent a single bond,

[0234] In a preferred embodiment of the present application, the liquid-crystalline medium comprises one or more compounds of formula V, preferably selected from compounds of formulae V-1 to V-3, preferably compounds of formulae V-1 and / or V-2 and / or V-3, preferably compounds of formulae V-1 and V-2:

[0235] wherein the groups occurring have the respective meanings indicated above for formula V, and preferably

[0236] R 51denotes 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,

[0237] R 52 denotes 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,

[0238] X 51 and X 52 independently of one another F, CI, -OCF3, -CF3, -CN or -SF5, preferably F, CI, -OCF3or -CN.

[0239] The compounds of the formula V-1 are preferably selected from the group of the compounds of the formulae V-1 a to V-1 d, preferably V-1 c and V-1 d:

[0240] wherein the parameters have the respective meanings indicated above for the formula V-1, and wherein

[0241] Y 51 and Y 52 in each case independently of one another H or F, and preferably

[0242] R 51 denotes alkyl or alkenyl, and

[0243] X 51 denotes F, CI or -OCF3.

[0244] The compounds of the formula V-2 are preferably selected from the group of the compounds of the formulae V-2a to V-2e and / or from the group of the compounds of the formulae V-2f and V-2g:

[0245] wherein in each case the compounds of the formula V-2a are excluded from the compounds of the formulae V-2b and V-2c, the compounds of the formula V-2b are excluded from the compounds of the formula V-2c, and the compounds of the formula V-2f are excluded from the compounds of the formula V-2g, and

[0246] wherein the parameters have the respective meanings indicated above for the formula V-1, and wherein

[0247] Y 51 and Y 52 in each case independently of one another H or F, and

[0248] preferably

[0249] Y 51 and Y 52denotes H and the other one denotes H or F, preferably likewise H.

[0250] The compound of the formula V-3 is preferably a compound of the formula V-3a:

[0251] wherein the parameters have the respective meanings indicated above for the formula V-1, and wherein preferably

[0252] X 51 denotes F, CI, preferably F,

[0253] X 52 denotes F, CI or -OCF3, preferably -OCF3.

[0254] The compound of the formula V-1 a is preferably selected from the group consisting of the compounds of the formulae V-1 a-1 and V-1 a-2:

[0255] wherein

[0256] R 51 have the meanings indicated above, and preferably denote C n H 2n+1 wherein n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably in the range from 3 to 5.

[0257] The compound of the formula V-1 b is preferably a compound of the formula V-1 b-1 :

[0258] wherein

[0259] R 51 have the meanings indicated above, and preferably denote C n H 2n+1 wherein n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably in the range from 3 to 5.

[0260] The compound of the formula V-1 c is preferably selected from the group consisting of the compounds of the formulae V-1 c-1 to V-1 c-4, particularly preferably from the group consisting of the compounds of the formulae V-1 c-1 and V-1 c-2:

[0261] wherein

[0262] R 51 have the meanings indicated above, and preferably denote C n H 2n+1 wherein

[0263] n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5.

[0264] The compounds of the formula V-1 d are preferably selected from the group of compounds of the formulae V-1 d-1 and V-1 d-2, particularly preferably the compounds of the formula V-1 d-2:

[0265] wherein

[0266] R 51 have the above indicated meanings and preferably denote C n H 2n+1 wherein

[0267] n denotes an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5.

[0268] The compounds of the formula V-2a are preferably selected from the group of compounds of the formulae V-2a-1 and V-2a-2, particularly preferably the compounds of the formula V-2a-1:

[0269] wherein

[0270] R 51 have the above indicated meanings and preferably denote C n H 2n+1 or CH2=CH-(CH2) Z , and

[0271] R 52 have the above indicated meanings and preferably denote C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0272] n and m, independently of one another, denote an integer in the range from 1 to 7, preferably in the range from 1 to 6 and particularly preferably 3 to 5, and

[0273] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0274] R 51 in combination with the preferred combinations of R 52 , particularly in the case of the formula V-2a-1, are (C n H 2n+1 and C m H 2m+1 ), (C n H 2n+1 and O-C m H2m+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).

[0275] Preferred compounds of formula V-2b are compounds of formula V-2b-1 :

[0276] wherein

[0277] R 51 has the above indicated meaning and preferably denotes C n H 2n+1 or CH2=CH-(CH2) Z , and

[0278] R 52 has the above indicated meaning and preferably denotes C m H 2m+1 or O-C m H 2m+1 or (CH2) Z -CH=CH2, and wherein

[0279] n and m, independently of each other, denote an integer in the range of 1 to 7, preferably in the range of 1 to 6 and particularly preferably 3 to 5, and

[0280] z denotes 0, 1, 2, 3 or 4, preferably 0 or 2.

[0281] wherein R 51 is a preferred combination with R 52 here particularly C n H 2n+1 and C m H 2m+1 .

[0282] Preferred compounds of formula V-2c are compounds of formula V-2c-1 :

[0283] wherein

[0284] R 51 has the above indicated meaning and preferably denotes C n H 2n+1 or CH2=CH-(CH2)Z ,and

[0285] R 52 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and where

[0286] n and m represent integers independently of each other, ranging from 1 to 7, preferably from 1 to 6, and particularly preferably from 3 to 5, and

[0287] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0288] (R 51 and R 52 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ).

[0289] Preferred compounds of formula V-2d are compounds of formula V-2d-1:

[0290] in

[0291] R 51 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0292] R 52 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0293] n and m represent integers independently of each other, ranging from 1 to 7, preferably from 1 to 6, and particularly preferably from 3 to 5, and

[0294] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0295] (R 51 and R 52 The preferred combination here is specifically (C) n H 2n+1 and C m H2m+1 ).

[0296] Preferred compounds of formula V-2e are compounds of formula V-2e-1:

[0297] in

[0298] R 51 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0299] R 52 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and where

[0300] n and m represent independent integers 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

[0301] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0302] (R 51 and R 52 The preferred combination here is specifically (C) n H 2n+1 and OC m H 2m+1 ).

[0303] The preferred compound of formula V-2f is the compound of formula V-2f-1:

[0304] in

[0305] R 51 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0306] R 52 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and where

[0307] n and m represent independent integers 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

[0308] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0309] (R 51 and R 52 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), especially preferred (C) n H 2n+1 and C m H 2m+1 ).

[0310] The preferred compound of formula V-2g is the compound of formula V-2g-1:

[0311] in

[0312] R 51 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0313] R 52 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0314] n and m represent independent integers 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

[0315] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0316] (R 51 and R 52 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OCm H 2m+1 ), especially preferred (C) n H 2n+1 and OC m H 2m+1 ).

[0317] The compounds of formula VI are preferably selected from compounds of formulas VI-1 to VI-5:

[0318] in

[0319] Z 61 and Z 62 This indicates -C≡C-, trans-CH=CH-, or trans-CF=CF-, preferably -C≡C- or trans-CH=CH-, and other appearing groups and parameters have the meanings given above in Formula VI.

[0320] And preferably

[0321] R 61 and R 62 Each of these can independently represent H, a non-fluorinated alkyl or alkoxy group having 1 to 7 carbon atoms, or a non-fluorinated alkenyl group having 2 to 7 carbon atoms.

[0322] X 62 This indicates F, Cl, -OCF3, or -CN.

[0323] The compounds of formula VI-1 are preferably selected from compounds of formulas VI-1a and VI-1b, and more preferably from compounds of formula VI-1a:

[0324] in

[0325] R 61 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0326] R 62 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0327] n and m represent independent integers 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

[0328] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0329] (R 61 and R 62 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 In the case of formula VI-1a, it is particularly preferred that (C) n H 2n+1 and C m H 2m+1 ), and is particularly preferred in the case of formula VI-1b (C) n H 2n+1 and OC m H 2m+1 ).

[0330] The compounds of formula VI-3 are preferably selected from compounds of formulas VI-3a to VI-3e:

[0331] The parameters have the meanings given in Equation VI-3 above, and are preferably...

[0332] R 61 It has the meaning of the above indications, and preferably represents C. n H 2n+1 ,in

[0333] n represents an integer in the range of 1 to 7, preferably in the range of 1 to 5, and

[0334] X 62 It represents -F, -Cl, -OCF3, or -CN.

[0335] The compounds of formula VI-4 are preferably selected from compounds of formulas VI-4a to VI-4e:

[0336] The parameters have the meanings given in Equation VI-4 above, and preferably...

[0337] R 61 It has the meaning of the above indications, and preferably represents C. n H 2n+1 ,in

[0338] n represents an integer in the range of 1 to 7, preferably in the range of 1 to 5, and

[0339] X62 It represents F, Cl, OCF3, or -CN.

[0340] The compounds of formula VI-5 are preferably selected from compounds of formula VI-5a to VI-5d, and preferably compounds of formula VI-5b:

[0341] The parameters have the meanings given in Equation VI-5 above, and preferably...

[0342] R 61 It has the meaning of the above indications, and preferably represents C. n H 2n+1 ,in

[0343] n represents an integer in the range of 1 to 7, preferably in the range of 1 to 5, and

[0344] X 62 It can be represented as -F, -Cl, -OCF3 or -CN, with -OCF3 being particularly preferred.

[0345] The compounds of formula VII are preferably selected from compounds of formulas VII-1 to VII-6:

[0346] The compounds of formula VII-5 are excluded from the compounds of formula VII-6, and

[0347] The parameters here have the corresponding meanings indicated by equation VII above.

[0348] Y 71 Y 72 Y 73 H or F can be represented independently of each other.

[0349] And preferably

[0350] R 71 This indicates a non-fluorinated alkyl or alkoxy group having 1 to 7 carbon atoms, or a non-fluorinated alkenyl group having 2 to 7 carbon atoms.

[0351] R 72 This indicates a non-fluorinated alkyl or alkoxy group having 1 to 7 carbon atoms, or a non-fluorinated alkenyl group having 2 to 7 carbon atoms.

[0352] X 72 Indicates F, Cl, NCS or -OCF3, preferably F or NCS, and

[0353] Particularly preferred

[0354] R 71 It has the meaning of the above indications, and preferably represents C.n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0355] R 72 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0356] n and m represent independent integers 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

[0357] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0358] The compounds of formula VII-1 are preferably selected from compounds of formulas VII-1a to VII-1d:

[0359] Where X 72 Having the meaning given above for equation VII-2, and

[0360] R 71 It has the meaning of the above indications, and preferably represents C. n H 2n+1 ,in

[0361] n represents 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

[0362] z represents 0, 1, 2, 3, or 4, preferably 0 or 2, and

[0363] X 72 The preferred option is F.

[0364] The compounds of formula VII-2 are preferably selected from those of formulas VII-2a and VII-2b, with compounds of formula VII-2a being particularly preferred.

[0365] in

[0366] R 71 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0367] R 72 It has the meaning of the above indications, and preferably represents C.m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0368] n and m represent independent integers 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

[0369] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0370] (R 71 and R 72 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), especially preferred (C) n H 2n+1 and C m H 2m+1 ).

[0371] The compounds of formula VII-3 are preferably compounds of formula VII-3a:

[0372] in

[0373] R 71 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0374] R 72 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0375] n and m represent independent integers 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

[0376] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0377] (R 71 and R 72The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), especially preferred (C) n H 2n+1 and C m H 2m+1 ).

[0378] The compounds of formula VII-4 are preferably compounds of formula VII-4a:

[0379] in

[0380] R 71 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0381] R 72 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0382] n and m represent independent integers 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

[0383] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0384] (R 71 and R 72 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), especially preferred (C) n H 2n+1 and C m H 2m+1 ).

[0385] The compounds of formula VII-5 are preferably selected from compounds of formula VII-5a and VII-5b, and more preferably compounds of formula VII-5a:

[0386] in

[0387] R 71 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0388] R 72 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0389] n and m represent independent integers 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

[0390] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0391] (R 71 and R 72 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), especially preferred (C) n H 2n+1 and C m H 2m+1 ).

[0392] The compounds of formula VII-6 are preferably selected from compounds of formulas VII-6a and VII-6b:

[0393] in

[0394] R 71 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0395] R 72It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0396] n and m, independently representing integers 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

[0397] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0398] (R 71 and R 72 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), especially preferred (C) n H 2n+1 and C m H 2m+1 ).

[0399] The compounds of formula VII-7 are preferably selected from compounds of formulas VII-7a to VII-7d:

[0400] in

[0401] R 71 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,

[0402] X 72 Indicates F, -OCF3, or -NCS.

[0403] n represents 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

[0404] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0405] The compounds of formula VIII are preferably selected from compounds of formulas VIII-1 to VIII-3, more preferably these compounds of formula VIII are mainly composed of them, even more preferably are substantially composed of them, and very particularly preferably are composed entirely of them:

[0406] in

[0407] Y 81 and Y 82 One of them represents H, and the other represents H or F, and

[0408] R 81 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0409] R 82 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0410] n and m, independently representing integers 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

[0411] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0412] (R 81 and R 82 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), especially preferred (C) n H 2n+1 and C m H 2m+1 ).

[0413] The compounds of formula VIII-1 are preferably selected from compounds of formulas VIII-1a to VIII-1c:

[0414] in

[0415] R 81 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0416] R 82It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0417] n and m, independently representing integers 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

[0418] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0419] (R 81 and R 82 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), especially preferred (C) n H 2n+1 and C m H 2m+1 ).

[0420] The compounds of formula VIII-2 are preferably compounds of formula VIII-2a:

[0421] in

[0422] R 81 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0423] R 82 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0424] n and m, independently representing integers 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

[0425] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0426] (R 81 and R82 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ), (C n H 2n+1 and OC m H 2m+1 (CH2=CH-(CH2)) and (CH2=CH-(CH2)) Z and C m H 2m+1 ), especially preferred (C) n H 2n+1 and C m H 2m+1 ).

[0427] The compounds of formula VIII-3 are preferably compounds of formula VIII-3a:

[0428] in

[0429] R 81 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0430] R 82 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0431] n and m, independently representing integers 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

[0432] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0433] (R 81 and R 82 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ).

[0434] The compounds of formula IX are preferably selected from compounds of formulas IX-1 to IX-3:

[0435] These parameters have the corresponding meanings indicated in Equation IX above, and preferably

[0436] And among them

[0437] R 91 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0438] R 92 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0439] n and m, independently representing integers 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

[0440] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0441] (R 91 and R 92 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ).

[0442] The compounds of formula IX-1 are preferably selected from compounds of formulas IX-1a to IX-1e:

[0443] The parameters have the meanings given above, and preferably...

[0444] R 91 It has the meaning of the above indications, and preferably represents C. n H 2n+1 ,and

[0445] n represents an integer in the range of 0 to 15, preferably in the range of 1 to 7, and particularly preferably in the range of 1 to 5, and

[0446] X 92 The preferred representation is F or Cl.

[0447] The compounds of formula IX-2 are preferably selected from compounds of formulas IX-2a and IX-2b:

[0448] in

[0449] R 91 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0450] R 92 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z -CH=CH2, and in which

[0451] n and m, independently representing integers 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

[0452] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0453] (R 91 and R 92 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ).

[0454] The compounds of formula IX-3 are preferably compounds of formulas IX-3a and IX-3b:

[0455] in

[0456] R 91 It has the meaning of the above indications, and preferably represents C. n H 2n+1 Or CH2=CH-(CH2) Z ,and

[0457] R 92 It has the meaning of the above indications, and preferably represents C. m H 2m+1 or OC m H 2m+1 Or (CH2) Z-CH=CH2, and in which

[0458] n and m, independently representing integers 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

[0459] z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0460] (R 91 and R 92 The preferred combination here is specifically (C) n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), especially preferred (C) n H 2n+1 and OC m H 2m+1 ).

[0461] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula X.

[0462] in

[0463] R 101 The symbol H represents an alkyl or alkoxy group having 1 to 15, preferably 2 to 10, carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy, or non-fluorinated alkoxyalkyl group having 2 to 15, preferably 3 to 10, carbon atoms, preferably alkyl or alkenyl.

[0464] X 101 The designation is H, F, Cl, -CN, SF5, NCS, a fluorinated alkyl group or fluorinated alkoxy group having 1 to 7 carbon atoms, or a fluorinated alkenyl group, fluorinated alkenyloxy group or fluorinated alkoxyalkyl group having 2 to 7 carbon atoms, preferably a fluorinated alkoxy group, a fluorinated alkenyloxy group, F, Cl or NCS, particularly preferably NCS.

[0465] Y 101 Indicates methyl, ethyl, or Cl.

[0466] Y 102 It represents H, methyl, ethyl, F or Cl, preferably H or F.

[0467] Z 101 Z 102 The same or different representations of single bonds, -CH=CH-, -CF=CF-, or -C≡C-,

[0468] n is 0 or 1.

[0469] Preferably, the compound of formula X is selected from sub-formulas X-1 and X-2.

[0470] The groups and parameters that appear have the meanings given above for formula X.

[0471] Particularly preferably, the medium according to the invention comprises one or more compounds selected from formulas X-1-1 to X-1-9.

[0472] Where R 101 This indicates an alkyl group having 1 to 7 carbon atoms.

[0473] In a preferred embodiment, the medium according to the invention comprises one or more compounds of formula XIa and / or XIb.

[0474] in

[0475] R S The symbol represents H, a straight-chain alkyl group having 1 to 12 carbon atoms, or a straight-chain alkenyl or straight-chain alkynyl group each having 2 to 12 carbon atoms, or a branched alkyl group having 2 to 12 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, or a branched alkynyl group having 4 to 12 carbon atoms, wherein one or more CH2- groups may be , , , , , or Substitution, wherein one or more non-adjacent CH2- groups may be substituted with O, and one or more H groups in all of these groups may be substituted with F;

[0476] -(S)- indicates -S- or a single bond, preferably a single bond.

[0477] L S1 L S2 They may represent H, Cl, or F in the same or different ways.

[0478] R S1 R S2 The same or different representations of H, alkyl or alkenyl groups having up to 6 carbon atoms, or cyclopropyl, cyclobutyl, cyclopentenyl or cyclopentyl.

[0479] R Th1 RTh2 The same or different representations of H, alkyl or alkenyl or alkoxy groups having up to 6 carbon atoms, or cyclopropyl, cyclobutyl, cyclopentenyl or cyclopentyl groups.

[0480] Z S1 Z S2 Z S3 The same or different representations of -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C≡C-, or single bonds,

[0481] a and b are either the same or different, and are either 0 or 1.

[0482] Preferably, the compound of formula XI is selected from compounds of formulas XI-1 to XI-24:

[0483] The groups appearing therein have the meanings given above for formula XI, and preferably...

[0484] R S It represents an alkyl or alkenyl group having 2 to 6 carbon atoms, wherein one or more CH2- groups can be... , , or Replacement

[0485] R S1 and R S2 H or alkyl groups having 1 to 6 carbon atoms, either the same or different, are preferred.

[0486] R S3 The symbol represents H, F, or an alkyl group having up to 6 carbon atoms, or a cyclopropyl group, preferably H, F, or an ethyl group, with H being very preferred.

[0487] L S1 and L S2 H or F may be represented in the same or different ways, with F being preferred.

[0488] Preferably, the medium comprises one or more compounds of formula XII.

[0489] in

[0490] R 12The symbol represents H, a straight-chain alkyl group having 1 to 12 carbon atoms, or a straight-chain alkenyl or straight-chain alkynyl group each having 2 to 12 carbon atoms, or a branched alkyl group having 2 to 12 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, or a branched alkynyl group having 4 to 12 carbon atoms, wherein one or more CH2- groups may be , , , , , or Substitution, or indicating group R P ,

[0491] R P Indicates halogen, CN, NCS, R F R F -O- or R F -S-, where R F It indicates a fluorinated alkyl or fluorinated alkenyl group having up to 9 carbon atoms.

[0492] Z 121 Z 122 The same or different representations can be -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, or single bonds, with -C≡C- or single bonds being preferred.

[0493] X 1 X 2 X 3 and X 4 Cl or F may be represented in the same or different ways, with F being preferred.

[0494] t is 0 or 1, and

[0495] a) 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or both CH groups can be substituted with N, and one or more H atoms can be substituted with L, excluding tetrafluoro-1,4-phenylene.

[0496] b) trans-1,4-cyclohexene, 1,4-cyclohexenyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexene, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and wherein one or more H atoms may be substituted with F.

[0497] c) Thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, and selenophene-2,5-diyl, each of which may be mono- or poly-substituted by L.

[0498] L, each time it appears, may represent F, Cl, CN, SCN, SF5, or a straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group having 1 to 12 C atoms, optionally fluorinated in each case.

[0499] Furthermore, compounds of formula XII are excluded from compounds of formulas I, II, and III.

[0500] Compounds of formula XII are preferably selected from compounds of sub-formulas XII-1 to XII-11:

[0501] in

[0502] L 1 L 2 and L 3 The same or different representations of H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclopentenyl, and

[0503] R 12 X 1 X 2 X 3 and X 4 It has the meaning given in Equation XII above.

[0504] Very preferably, the medium comprises a compound of formula XII-3, wherein the groups present have the meanings given above, and particularly preferably L 1 H and X represent 1 X 2 X 3 and X 4 Let F be an integer, and R be an integer. 12 This indicates an alkyl group having 1 to 7 carbon atoms.

[0505] The medium according to the invention preferably comprises one or more compounds of formula XIII.

[0506] in

[0507] R 13The symbol represents H, a straight-chain alkyl group having 1 to 12 carbon atoms, or a straight-chain alkenyl or straight-chain alkynyl group each having 2 to 12 carbon atoms, or a branched alkyl group having 2 to 12 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, or a branched alkynyl group having 4 to 12 carbon atoms, wherein one or more CH2- groups may be , , , , , or Substitution, or indicating group R P ,

[0508] R P Indicates halogen, CN, NCS, R F R F -O- or R F -S-, where

[0509] R F It indicates a fluorinated alkyl or fluorinated alkenyl group having up to 9 carbon atoms.

[0510] Z 131 Z 132 Z 133 The same or different representations can be -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, or single bonds, with -C≡C- or single bonds being preferred.

[0511] X 1 X 2 The same or different representations may be H, Cl, F, CH3 or C2H5, with H or F preferred.

[0512] Y 1 Y 2 Y 3 Y 4 , representing H, F, Cl or straight-chain or branched or cyclic alkyl, alkenyl, alkoxy or alkenyloxy groups having up to 12 C atoms, respectively, wherein Y 1 Y 2 Y 3 and Y 4 At least one of them is different from F.

[0513] s can be 0, 1, or 2, preferably 0 or 1.

[0514] t is 0, 1, or 2, preferably 0 or 1, and

[0515] s + t can be 0, 1, or 2, preferably 0 or 1.

[0516] a) 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or both CH groups can be substituted with N, and one or more H atoms can be substituted with L.

[0517] b) trans-1,4-cyclohexene, 1,4-cyclohexenyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexene, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and wherein one or more H groups may be substituted with F.

[0518] c) Thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, and selenophene-2,5-diyl, each of which can be mono- or poly-substituted by L.

[0519] L, each time it appears, may represent F, Cl, CN, SCN, SF5, or a straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group having 1 to 12 C atoms, optionally fluorinated in each case.

[0520] In a preferred embodiment of the invention, the compounds of formula XIII are selected from compounds of formulas XIII-1 to XIII-20, and are very preferably selected from compounds of formulas XIII-1 to XIII-13:

[0521] The groups appearing therein have the meanings indicated above for formula XIII and its sub-formulas, and preferably R 13 Y represents an alkyl group having 1 to 7 carbon atoms. 1 Y 2 Y 3 and Y 4 The same or different may represent H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclopentenyl, and more preferably Y 1 and Y 2 Independently represent H or F, especially H, and Y 3 and Y 4 The most preferred expression is H, and L 1 and L 2 The same or different, very preferably, represent H, F, methyl or ethyl, especially H.

[0522] Preferably, the medium according to the invention comprises one or more compounds of formula XIV.

[0523] XIV

[0524] in

[0525] R 14 The symbol represents H, a straight-chain alkyl group having 1 to 12 carbon atoms, or a straight-chain alkenyl or straight-chain alkynyl group each having 2 to 12 carbon atoms, or a branched alkyl group having 2 to 12 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, or a branched alkynyl group having 4 to 12 carbon atoms, wherein one or more CH2- groups may be , , , , , or Substitution, or indicating group R P ,

[0526] R P Indicates halogen, CN, NCS, R F -、R F -O- or R F -S-, where R F Represents fluorinated alkyl groups with 1 to 9 carbon atoms.

[0527] Z 141 Z 142 Z 143 and Z 144 The same or different representations of -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -N=N-, -C=NN=C-, -CH=N-, -N=CH-, -C≡C-, -C CC≡C- or a single bond, where

[0528] Z 141 Alternatively, -O-, -S-, -CO-O-, -O-CO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2-, -CH2CH2-, -(CH2)3-, -(CH2)4-, -C2F4-, -CH2CF2-, -CF2CH2-, -CH=CH-CH2O-, -CH=CH-CO-O-, -OCH2-CH=CH-, or -O-CO-CH=CH-.

[0529] X 14 This indicates -C≡C-CN, -NCS, or -C≡C-NCS, with -NCS being preferred.

[0530] a) 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or both CH groups can be substituted with N, and one or more H atoms can be substituted with L.

[0531] b) trans-1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydronaphthyl-2,6-diyl, tetrahydronaphthyl-5,8-diyl, decahydronaphthyl-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, wherein one or both CH groups may be substituted with N, one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and one or more H atoms may be substituted with L.

[0532] c) Thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, and selenophene-2,5-diyl, each of which can be mono- or poly-substituted by L.

[0533] express , , or One or more H atoms are optionally replaced by L.

[0534] L, in each occurrence, may refer to F, Cl, CN, SCN, SF5, or a straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group, each having 1 to 12 C atoms, optionally fluorinated in each case.

[0535] t1, t2, t3, and t4 may be the same or different from 0, 1, or 2, preferably 0 or 1.

[0536] Where t1 + t2 + t3 + t4 can be 1, 2 or 3, preferably 1 or 2.

[0537] In a preferred embodiment of the invention, the compounds of formula XIV are selected from compounds of formulas XIV-1 and XIV-2:

[0538] The groups appearing therein have the meanings given above for formula XIV, and

[0539] t2 is 0, 1, or 2.

[0540] t4 is 0 or 1.

[0541] Furthermore, t2+t4 can be 1, 2, or 3, with 1 or 2 being preferred.

[0542] In equation XIV and its sub-equations

[0543] , , and Preferred representation , , , , , , , , or ,

[0544] Where R L Each time it appears, it represents H or an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 5 carbon atoms, either the same or different.

[0545] X 14 Indicates -NCS,

[0546] Z 141 Z 142 Z 143 and Z 144 The same or different can represent -CH=CH-, -CF=CF-, -C≡C-, or single bonds.

[0547] in

[0548] alternative representation or ,

[0549] in

[0550] W represents N, CH, CF, or C-Cl, and

[0551] Y 1 and Y 2 They may represent H, Cl, F, methyl, or ethyl, either the same or different.

[0552] In equations XIV-1 and XIV-2, t2 and t4 are preferably 0 or 1, where t2 + t4 is 1 or 2.

[0553] The preferred compounds of formula XIV-1 are selected from the following sub-formulas:

[0554] Where R 14X 14 , and Having the meaning of the above definition, and preferably

[0555] R 14 This refers to a straight-chain alkyl or alkoxy group having 1 to 12 carbon atoms, or a straight-chain alkenyl or ynyl or alkenyloxy group having 2 to 12 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 12 carbon atoms, more preferably a straight-chain alkyl group having 1 to 7 carbon atoms, or an ynyl group having 2 to 7 carbon atoms.

[0556] X 14 Indicates NCS, and

[0557] express , , , , or Where Y may represent F, Cl or CH3, with F being preferred.

[0558] More preferably , or ,

[0559] L, in each occurrence, either represents F, Cl, CH3, or C2H5, and

[0560] n can be 1 or 2, preferably 1.

[0561] Compounds of the following formulas are highly preferred: XIV-1-1, XIV-1-2, XIV-1-3, XIV-1-4, XIV-1-9, XIV-1-10, XIV-1-11, XIV-1-12, XIV-2-1, XIV-2-2, XIV-2-3, XIV-2-4, XIV-2-9, XIV-2-10, XIV-2-11 and XIV-2-12.

[0562] Preferably, the medium according to the invention comprises one or more compounds of formula T.

[0563] in

[0564] R T Indicates halogen, CN, NCS, R F R F -O- or R F -S-, where R FIt indicates a fluorinated alkyl or fluorinated alkenyl group having up to 12 carbon atoms.

[0565] L 4 and L 5 The same or different F, Cl or straight-chain or branched or cyclic alkyl or alkenyl groups each having up to 12 C atoms;

[0566] Z T3 Z T4 The same or different representations of -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or single bonds, and

[0567] t is 0 or 1.

[0568] In a preferred embodiment, the liquid crystal medium according to the invention comprises one or more compounds selected from the following formulas T-1a to T-3b:

[0569] in

[0570] , and Having the meanings given above, and

[0571] n can be 1, 2, 3, 4, 5, 6 or 7, preferably 1, 2, 3 or 4, and especially preferably 1.

[0572] In a particularly preferred embodiment of the invention, the medium comprises one or more compounds selected from formulas T-1a and T-2a.

[0573] The preferred compounds of formula T-1a are selected from compounds of the following formulas:

[0574] Where n is 1, 2, 3 or 4, preferably 1.

[0575] Preferred compounds of formula T-2a are selected from compounds with the following formulas:

[0576] Where n can be 1, 2, 3 or 4, preferably 1.

[0577] The preferred compounds of formula T-3a are selected from the following compounds:

[0578] Where n can be 1, 2, 3 or 4, preferably 1.

[0579] Very preferably, the medium according to the invention comprises one or more compounds of formula T-1a-5.

[0580] In embodiments, the medium according to the invention comprises one or more compounds of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, wherein the 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 They are cyclic alkyl groups, respectively.

[0581] The most preferred compounds containing cyclic alkyl groups are those selected from compounds of formula Cy-1 to Cy-14.

[0582] In a preferred embodiment, the medium according to the invention comprises a compound of formula N.

[0583] in

[0584] R N The symbol represents H, a straight-chain alkyl group having 1 to 12 carbon atoms, or a straight-chain alkenyl or straight-chain alkynyl group each having 2 to 12 carbon atoms, or a branched alkyl group having 2 to 12 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, or a branched alkynyl group having 4 to 12 carbon atoms, wherein one or more CH2- groups may be , , , , , or Substitution, or indicating group R P ,

[0585] R P Indicates halogen, CN, NCS, R F R F -O- or R F -S-, where RF This indicates a fluorinated alkyl group having 1 to 9 carbon atoms, or a fluorinated alkenyl group having 2 to 9 carbon atoms.

[0586] Z N1 and Z N2 The same or different representations can be -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, or single bonds, with -C≡C- or single bonds being preferred.

[0587] W represents N, CF, or C-Cl.

[0588] X 1 and X 2 The same or different representations of H, Cl, F, methyl or ethyl

[0589] and

[0590] It indicates that the group is selected from the following:

[0591] a) 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or both CH groups can be substituted with N, and one or more H atoms can be substituted with L.

[0592] b) trans-1,4-cyclohexene, 1,4-cyclohexenyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexene, bicyclo[2.2.2]octane-1,4-diyl or spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and wherein one or more H groups may be substituted with F.

[0593] c) Thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, or selenophene-2,5-diyl, each of which can also be reacted with R L Single or multiple substitutions,

[0594] L, in each occurrence, may represent F, Cl, CN, SCN, SF5, or a straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group having 1 to 12 carbon atoms, optionally fluorinated in each case.

[0595] n is 0, 1, or 2.

[0596] Compounds of formula N are preferably selected from formulas N-1, N-2, and N-3:

[0597] Where R N , , Z N1 Z N2 X 1 X 2 And n has the corresponding meaning given for equation N above.

[0598] In formula N and its sub-formulas N-1, N-2 and N-3, preferably and Each occurrence represents the same or different meanings. , , , , , , , , or ,

[0599] in

[0600] R L In each occurrence, H is represented, either the same or different, or an alkyl group having 1 to 6 carbon atoms, preferably H, methyl, or ethyl, with H being particularly preferred.

[0601] L represents F or an alkyl group having 1 to 6 carbon atoms, and

[0602] r can be 0, 1, 2, 3, 4, 5, or 6, preferably 0 or 1.

[0603] in alternative representation , , , , , , , , , , , , , , or .

[0604] In a preferred embodiment, in formula N and its sub-formulas, group X 1 and X 2 Both represent H.

[0605] In a preferred embodiment, in formula N and its sub-formulas, group X 1 It represents H and group X 2 It represents F or Cl.

[0606] In a preferred embodiment, in formula N and its sub-formulas, group X 1 It represents F or Cl and the group X 2 H represents H.

[0607] In a preferred embodiment, in formula N and its sub-formulas, group X 1 and X 2 It can be represented by F or Cl, preferably both of which can be represented by F.

[0608] Compounds of formulas N-1, N-2, and N-3 are preferably selected from formulas N-1-1 to N-1-10, N-2-1 to N-2-10, and N-3-1 to N-3-10:

[0609] Where R N X 1 and X 2 It has the meanings given above, and L represents H, F, methyl, ethyl or cyclopropyl in each occurrence.

[0610] In a preferred embodiment, the medium according to the invention comprises a compound of the NI formula.

[0611] in

[0612] R N , , Z N1 Z N2 W, X 1 X 2 And n has the corresponding meaning given for formula N in claim 1.

[0613] Compounds of formula NI are preferably selected from compounds of formulas NI-1 and NI-2.

[0614] Where R N Z N1 Z N2 , and With the meanings given for equation N above, Y 1 and Y 2 H, F, or Cl can be represented in the same or different ways, and t can be 0 or 1.

[0615] In compounds of formula NI or NI-1 or NI-2, and Independently selected representations , , , , , or ,

[0616] in

[0617] alternative representation , , , , , or ,and

[0618] L 1 and L 2 The same or different F, Cl or straight-chain or branched or cyclic alkyl or alkenyl groups each having up to 12 C atoms.

[0619] In compounds of formula NI or NI-1 or NI-2, Z N1 and Z N2 Whether the representation is the same or different, it is preferred to indicate -C≡C- or a single bond.

[0620] In a preferred embodiment of the invention, the compounds of formula NI-1 and NI-2 are selected from compounds of formulas NI-1-1 to NI-1-12 and NI-2-1 to NI-2-12.

[0621] in

[0622] L 1 L 2 and L 3 The same or different representations of H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclopentenyl, and

[0623] R N Y 1 and Y 2 It has the meaning given for formulas N-1 and N-2, and wherein the most preferred group is... express

[0624]

[0625] or .

[0626] In a preferred embodiment, in compounds of formula NI and its sub-formulas, Y 1 and Y 2 One or both of them represent H, preferably both of them represent H.

[0627] In another preferred embodiment, in formula N and its sub-formula compounds, Y 1 and Y 2 All represent F.

[0628] Preferably, the medium of the present invention comprises one or more UI compounds.

[0629] in

[0630] R U The symbol represents H, a straight-chain alkyl group having 1 to 12 carbon atoms, or a straight-chain alkenyl or alkynyl group each having 2 to 12 carbon atoms, or a branched alkyl group having 2 to 12 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, or a branched alkynyl group having 4 to 12 carbon atoms, wherein one or more CH2- groups may be... or Replacement

[0631] Or it may represent the group R P ,

[0632] R P Indicates halogen, CN, NCS, fluorinated alkyl, R F -O- or R F -S-, where

[0633] R F This indicates a fluorinated alkyl or fluorinated alkenyl group having a maximum of 9 carbon atoms.

[0634] Z U1 This indicates -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, or -C≡CC≡C-, preferably -CF=CF- or -C≡C-.

[0635] X U1 X U2 They may be represented by Cl or F, either the same or different, preferably F.

[0636] Groups selected from the following groups:

[0637] a) The group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or two CH groups may be substituted with N and one or more H atoms may be substituted with L.

[0638] b) The group consisting of trans-1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydronaphthyl-2,6-diyl, tetrahydronaphthyl-5,8-diyl, decahydronaphthyl-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, wherein one or two CH groups may be substituted with N, one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and one or more H atoms may be substituted with L.

[0639] c) The group consisting of thiophene-2,5-diyl, thiopheno[3,2-b]thiophene-2,5-diyl, and selenophene-2,5-diyl, each of which may also be mono- or poly-substituted by L.

[0640] L, in each occurrence, may refer to F, Cl, CN, SCN, SF5, or a straight or branched chain each having 1 to 12 C atoms, and in each case, optionally to a fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy.

[0641] u is 0 or 1.

[0642] v is 0 or 1.

[0643] The condition is and None of these indicate optional fluorinated 1,4-phenylene, and none of the compounds of formula UI and its sub-formulas are included in compounds of formulas I, II and III.

[0644] The UI compound is preferably selected from the group consisting of free-form compounds UI-1, UI-2, and UI-3.

[0645] Where R U , X U1 and X U2 It has the meaning given above for style UI, and is in style UI-3. and At least one of them represents trans-1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydronaphth-2,6-diyl, tetrahydronaphth-5,8-diyl, decahydronaphth-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexene, bicyclo[2.2.2]octane-1,4-diyl or spiro[3.3]heptane-2,6-diyl, wherein one or both CH groups may be substituted with N, one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and one or more H atoms may be substituted with L, wherein

[0646] L, in each occurrence, may refer to F, Cl, CN, SCN, SF5, or a straight or branched chain each having 1 to 12 C atoms, and in each case, optionally to a fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy.

[0647] And preferably

[0648] X U1 and X U2 Represents F, R U Preferably, it represents a straight-chain, branched, or cyclic alkyl or alkenyl group having 1 to 7 carbon atoms, or a fluorinated alkyl or fluorinated alkoxy group having 1 to 7 carbon atoms, and

[0649] Same or different, preferably represented , , , , , , , , , , , , , , or , , , , , , , , , , , , where R L Each time it appears, it may represent H or an alkyl group having 1 to 6 carbon atoms, either the same or different.

[0650] Or indicates or One or more H atoms may be replaced by alkyl groups or F having 1 to 6 C atoms.

[0651] Very preferably means or .

[0652] Preferably representing , , , , , , , , , , , , , , or More preferably or Most preferably ,

[0653] in

[0654] R L It represents H or an alkyl group having 1 to 6 carbon atoms.

[0655] The preferred compounds for formula UI are selected from the following sub-formulas:

[0656] Where R U Having the meaning given above and preferably referring to a straight-chain or branched alkyl group having 1 to 7 carbon atoms, specifically methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl.

[0657] The liquid crystal medium of the present invention preferably includes one or more UI compounds and another one or more UII compounds.

[0658] in

[0659] R U The symbol represents H, a straight-chain alkyl group having 1 to 12 carbon atoms, or a straight-chain alkenyl or alkynyl group each having 2 to 12 carbon atoms, or a branched alkyl group having 2 to 12 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, or a branched alkynyl group having 4 to 12 carbon atoms, wherein one or more CH2- groups may be... or Replacement

[0660] Or it may represent the group R P ,

[0661] R P Indicates halogen, CN, NCS, R F -、R F -O- or R F -S-, where

[0662] R F This indicates a fluorinated alkyl or fluorinated alkenyl group having a maximum of 9 carbon atoms.

[0663] Z U1 Z U2 The terms -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -C≡CC≡C-, or single bonds may be represented in the same or different ways. Preferably, -CF=CF-, -C≡C-, or single bonds are used, and most preferably -C≡C- or single bonds are used.

[0664] X U1 X U2 Cl or F may be represented in the same or different ways, preferably F.

[0665] a) The group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or two CH groups may be substituted with N and one or more H atoms may be substituted with L.

[0666] b) The group consisting of trans-1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydronaphthyl-2,6-diyl, tetrahydronaphthyl-5,8-diyl, decahydronaphthyl-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, wherein one or two CH groups may be substituted with N, one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and one or more H atoms may be substituted with L.

[0667] c) The group consisting of thiophene-2,5-diyl, thiopheno[3,2-b]thiophene-2,5-diyl, and selenophene-2,5-diyl, each of which may also be mono- or poly-substituted by L.

[0668] L, in each occurrence, may represent F, Cl, CN, SCN, SF5, or a straight or branched chain each having 1 to 12 C atoms, and in each case, optionally a fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy group.

[0669] u is 0, 1, or 2, preferably 1.

[0670] Compound of formula UI is not included in compound of formula UII, and compounds of formula UII and its sub-formulas are not included in compounds of formulas I, II and III.

[0671] Preferably, the compound of formula UII is selected from compounds of formulas UII-1, UII-2, and UII-3, preferably UII-1 and UII-2, and particularly compounds of UII-1.

[0672] The groups appearing therein have the meanings given above for formula UII and are preferably...

[0673] X U1 and X U2 Let F be an integer, and R be a constant. U Preferably, it refers to a straight-chain, branched, or cyclic alkyl or alkenyl group having 1 to 7 carbon atoms, or a fluorinated alkyl or fluorinated alkoxy group having 1 to 7 carbon atoms.

[0674] The most preferred compounds of formula UII are selected from the following sub-formulas:

[0675] Where R U Having the meaning given above and preferably referring to a straight-chain or branched alkyl group having 1 to 7 carbon atoms, specifically methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl.

[0676] The medium of this invention optionally includes one or more compounds of formulas GF-1-1 to GF-5-1:

[0677] Where R G It refers to a straight-chain or branched alkyl group having 1 to 7 carbon atoms, specifically methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or 2-methylbut-1-yl.

[0678] The liquid crystal medium of the present invention preferably includes one or more PT compounds.

[0679] in

[0680] R P The symbol represents H, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 12 carbon atoms, wherein one or more CH2- groups may be derived from H. or Substitution, and one or more non-adjacent CH2- groups may be substituted with O.

[0681] express or ,

[0682] Where L 1 L 2 and L 3 The same or different representations of H, F, Cl, or alkyl groups having 1 to 6 carbon atoms,

[0683] t1 is 0 and t2 is 1, or

[0684] t1 is 1 and t2 is 0.

[0685] The PT compound is preferably selected from the group consisting of free PT-1 to PT-4:

[0686] Where R P This indicates a straight-chain alkyl group having 1 to 7 carbon atoms or a branched alkyl group having 1 to 9 carbon atoms, wherein one or more CH2- groups may be derived from a chain containing 1 to 9 carbon atoms. or Replacement.

[0687] Compounds of formula PT-2 and PT-3 are highly preferred.

[0688] The medium according to the invention comprises one or more chiral dopants. Preferably, the absolute value of the helical twist force (HTP) of these chiral dopants is in the range of 1 μm. -1 Up to 150 μm -1 Within the range, preferably within 10 μm -1 Up to 100 μm -1Within the range. In the case that the medium contains two or more chiral dopants, these may have opposite signs for their HTP values. For some specific embodiments, this condition is preferred because it allows for some compensation of the chirality of the corresponding compounds, and thus can be used to compensate for various temperature-dependent properties of the resulting medium in the apparatus. However, generally, it is preferred that most, preferably all, chiral compounds present in the medium according to the invention have the same sign for their HTP values.

[0689] Preferably, the chiral dopants present in the medium according to this application are mesocrystalline compounds, and most preferably they themselves exhibit an intermediate phase.

[0690] In a preferred embodiment of the invention, the medium comprises two or more chiral compounds that all have the same algebraic symbol for HTP.

[0691] The temperature dependence of HTP on individual compounds can be high or low. The temperature dependence of the pitch of the medium can be compensated by mixing compounds with different HTP temperatures in appropriate ratios.

[0692] For optically active components, a variety of chiral dopants are available to those skilled in the art, some of which are commercially available, such as cholesterol 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 KGaA, Darmstadt).

[0693] Particularly suitable dopants are compounds containing one or more chiral groups and one or more mesomorphic groups, or one or more aromatic or alicyclic groups that form mesomorphic groups with chiral groups.

[0694] Suitable chiral groups are, for example, chiral branched hydrocarbon groups, chiral ethylene glycol, binaphthol, or dioxolane, and are also selected from mono- or polyvalent chiral groups such as sugar derivatives, sugar alcohols, sugar acids, lactic acids, chiral substituted diols, steroid derivatives, terpene derivatives, amino acids, or sequences of several (preferably 1 to 5) amino acids.

[0695] Preferred chiral groups are sugar derivatives, such as glucose, mannose, galactose, fructose, arabinose, and dextrose; sugar alcohols, such as sorbitol, mannitol, idoteol, galactitol, or their dehydrated derivatives, particularly disohydrated hexotols, such as disohydrated sorbitol (1,4:3,6-disohydrated-D-sorbitol, isosorbitol), disohydrated mannitol (isosorbitol), or disohydrated idoteol (isoidoteol); sugar acids, such as gluconic acid, gulonic acid, and ketogulonic acid; chiral substituted glycol groups, such as mono- or oligomeric polyethylene glycol or propylene glycol, wherein one or more CH2 groups are substituted with alkyl or alkoxy groups; amino acids, such as alanine, valine, phenylglycerol, etc. A sequence of amino acids or phenylalanine or 1 to 5 of these amino acids; steroid derivatives, such as cholesterol or bile acid groups; terpene derivatives, such as menthyl, neomenthyl, campheyl, pinenyl, terpineyl, isolongifolyl, frangyl, carreyl, myrthenyl, nopyl, geraniyl, linaloyl, neryl, citronellyl, or dihydrocitronellyl.

[0696] The medium according to the invention preferably contains a chiral dopant selected from the group consisting of known chiral dopants. Suitable chiral groups and mesocrystalline chiral compounds are described, for example, in DE 34 25 503, DE 35 34 777, DE 35 34 778, DE 35 34 779 and DE 35 34 780, DE 43 42 280, EP 01 038 941 and DE 195 41 820. Examples also include compounds listed in Table F below.

[0697] The chiral compounds preferred for use according to the present invention are selected from the following formulas.

[0698] Chiral dopants selected from compounds of the following formulas Al to A-III and A-Ch are particularly preferred:

[0699] in

[0700] R a11 R a12 and R b12 Each of the above can independently represent an alkyl group having 1-15 carbon atoms, wherein, in addition, one or more non-adjacent CH2 groups can each be independently represented by -C(R) z )=C(R z-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO-, or -O-CO-O- are substituted in such a way that the O and / or S atoms are not directly connected to each other, and wherein, in addition, one or more H atoms may be substituted by F, Cl, Br, I or CN, preferably alkyl, more preferably n-alkyl, provided that R a12 With R b12 different

[0701] R a21 and R a22 Each of the above can independently represent an alkyl group having 1-15 carbon atoms, wherein, in addition, one or more non-adjacent CH2 groups can each be independently represented by -C(R) z )=C(R z -, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO-, or -O-CO-O- are substituted in such a way that the O and / or S atoms are not directly connected to each other, and wherein, in addition, one or more H atoms can be replaced by F, Cl, Br, I or CN, preferably both being alkyl, more preferably n-alkyl.

[0702] R a31 R a32 and R b32 Each of the above can independently represent an alkyl group having a straight chain and branches of 1-15 carbon atoms, wherein, in addition, one or more non-adjacent CH2 groups can each be independently separated by -C(R) z )=C(R z -, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO-, or -O-CO-O- are substituted in such a way that the O and / or S atoms are not directly connected to each other, and wherein, in addition, one or more H atoms can be substituted by F, Cl, Br, I, or CN.

[0703] Alkyl groups are preferred, and n-alkyl groups are more preferred, provided that R a32 With R b32 different,

[0704] R z It can be represented by H, CH3, F, Cl, or CN, with H or F being preferred.

[0705] R 8 With the R given above a11 One meaning is that alkyl is preferred, and more preferably a n-alkyl group having 1-15 carbon atoms.

[0706] Z 8 It represents -C(O)O-, CH2O, CF2O or a single bond, preferably -C(O)O-.

[0707] n2, each time it appears, is either 0, 1, or 2, and...

[0708] n3 is 1, 2, or 3, and

[0709] r can be 0, 1, 2, 3 or 4.

[0710] Dopants selected from compounds of the following formula are particularly preferred:

[0711] in

[0712] m is an integer from 1 to 9, either identically or differently, in each occurrence, and

[0713] n is an integer from 2 to 9, either the same or different, each time it appears.

[0714] The particularly preferred compounds of formula A are compounds of formula A-III.

[0715] Further preferred dopants are derivatives of isosorbide, isomannitol, or isoidutol of formulas A-IV:

[0716] The preferred option is dehydrosorbitol.

[0717] And chiral ethylene glycols, such as diphenylethylene glycol (hydrogenated benzoin), especially mesocrystalline hydrogenated benzoin derivatives of the following formula AV:

[0718] Including (S,S) enantiomers, which are not shown.

[0719] in

[0720] L is H, F, Cl, CN, or an alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, or alkoxy carbonyl group having 1 to 7 carbon atoms, optionally halogenated.

[0721] c is 0 or 1

[0722] X is CH2 or -C(O)-,

[0723] Z 0 It is -COO-, -OCO-, -CH2CH2- or a single bond, and

[0724] R0 It is an alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl or alkyl carbonyloxy group having 1-12 carbon atoms.

[0725] Examples of compounds of formulas A-IV are:

[0726] Compounds of formulas A-IV are described in WO 98 / 00428. Compounds of formula AV are described in GB-A-2,328,207.

[0727] Very particularly preferred dopants are chiral binaphthyl derivatives as described in WO 02 / 94805, chiral binaphthol acetal derivatives as described in WO 02 / 34739, chiral TADDOL derivatives as described in WO 02 / 06265, and chiral dopants having at least one fluorinated bridging group and a terminal or central chiral group as described in WO 02 / 06196 and WO 02 / 06195.

[0728] Chiral compounds of formula A-VI are particularly preferred.

[0729] in

[0730] X 1 X 2 Y 1 and Y 2 Each of the following is an independent straight-chain or branched alkyl group consisting of F, Cl, Br, I, CN, SCN, SF5, having 1-25 carbon atoms, which is unsubstituted or mono- or polysubstituted by F, Cl, Br, I, or CN, and wherein one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, or -NR. x -, -CO-, -COO-, -OCO-, -OCOO-, -S-CO-, -CO-S-, -CH=CH-, or -C≡C- are substituted in such a way that the O and / or S atoms are not directly bonded to each other, polymerizable groups or cycloalkyl or aryl groups having up to 20 C atoms, which may optionally be halogenated, preferably F, or mono- or poly-substituted with polymerizable groups.

[0731] x 1 and x 2 Each is independently 0, 1, or 2.

[0732] y 1 and y 2 Each is independently 0, 1, 2, 3, or 4.

[0733] B 1 and B 2 Each is an aromatic or partially or fully saturated aliphatic six-membered ring, wherein one or more CH groups can be replaced by N atoms and one or more non-adjacent CH2 groups can be replaced by O or S atoms.

[0734] W 1 and W 2 Each is independent of the others as -Z 1 -A 1 -(Z 2 -A 2 ) m -R, and one of the two alternatively, R. 1 Or A 3 However, the two cannot both be H, or

[0735] U 1 and U 2 Each can be independently represented as CH2, O, S, CO, or CS.

[0736] V 1 and V 2 Each is independent of the other (CH2). n One to four non-adjacent CH2 groups may each be substituted with O or S, and V 1 and V 2 One of them, and in

[0737] n is 1, 2 or 3

[0738] Z 1 and Z 2 Each is independently of the others: -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR x -,-NR x The following groups are combinations of two of the following: -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-, where no two O and / or S and / or N atoms are directly bonded to each other, preferably -CH=CH-COO- or -COO-CH=CH- or a single bond.

[0739] Rx Indicates an alkyl group having 1 to 6 carbon atoms.

[0740] A 1 A 2 and A 3 Each is independently 1,4-phenylene, wherein one or two non-adjacent CH groups may be substituted with N; 1,4-cyclohexylene, wherein one or two non-adjacent CH2 groups may be substituted with O or S; 1,3-dioxolane-4,5-diyl, 1,4-cyclohexenyl, 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthyl-2,6-diyl, decahydronaphthyl-2,6-diyl, or 1,2,3,4-tetrahydronaphthyl-2,6-diyl, wherein each of these groups may be mono- or poly-substituted with L; and in addition, A 1 It can be a single key.

[0741] L is a halogen atom, preferably F, CN, NO2, or an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, or alkoxycarbonyloxy group having 1-7 carbon atoms, wherein one or more H atoms may be replaced by F or Cl.

[0742] m is independently 0, 1, 2, or 3 in each case, and

[0743] R and R 1 Each of the following is independently H, F, Cl, Br, I, CN, SCN, SF5, a straight-chain or branched alkyl group having 1 or 3 to 25 carbon atoms, which may optionally be mono- or poly-substituted by F, Cl, Br, I or CN, and one or more non-adjacent CH2 groups may be respectively substituted with -O-, -S-, -NH-, or -NR. 0 -, -CO-, -COO-, -OCO-, -O-COO-, -S-CO-, -CO-S-, -CH=CH- or -C≡C- substitutions, wherein no two O and / or S atoms are directly bonded to each other, or polymerizable groups.

[0744] Chiral binaphthyl derivative of particularly preferred form A-VI-1

[0745] Among them, rings B and R 0 and Z 0 For example, for equations A-IV and AV, where b is 0, 1, or 2,

[0746] In particular, those selected from the following formulas A-VI-1a to A-VI-1c:

[0747] Among them, rings B and R 0 and Z0 As defined for formula A-VI-1, and

[0748] R 0 As defined in formulas A-IV, or H or an alkyl group having one carbon atom, and

[0749] b is 0, 1, or 2.

[0750] and Z 0 Specifically for -OC(O)- or single bonds.

[0751] In the LC medium, the concentration of one or more chiral dopants is preferably 0.001%-20%, more preferably 0.05%-5%, more preferably 0.1%-2%, and most preferably 0.5%-1.5%. These preferred concentration ranges are particularly suitable for chiral dopants S-4011 or R-4011 (both from Merck KGaA) and chiral dopants with the same or similar HTP. For chiral dopants with higher or lower absolute HTP values ​​compared to S-4011, these preferred concentrations must be reduced or increased proportionally according to their HTP values ​​relative to S-4011.

[0752] According to the present invention, the pitch p of the LC medium or bulk mixture is preferably 5-50 μm, more preferably 8-30 μm and particularly preferably 10-20 μm.

[0753] Preferably, the medium according to the invention comprises a stabilizer selected from compounds of formula ST-1 to ST-22.

[0754] in

[0755] R ST The group represents H, an alkyl or alkoxy group having 1 to 15 carbon atoms, wherein one or more of these groups may be independently coupled to each other such that the O atoms are not directly connected to each other by -C≡C-, -CF2O-, -OCF2-, -CH=CH-, -O-, -CO-O-, -O-CO-, , , , , , or Substitution, and in addition, one or more H atoms can be replaced by halogens.

[0756] Z ST Each of these can be independently represented as -CO-O-, -O-CO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH2-, -CH2CH2-, -(CH2)4-, -CH=CH-CH2O-, -C2F4-, -CH2CF2-, -CF2CH2-, -CF=CF-, -CH=CF-, -CF=CH-, -CH=CH-, -C≡C-, or a single bond.

[0757] L 1 and L 2 Each can be independently represented as F, Cl, CF3, or CHF2.

[0758] n is an integer from 0 to 12, preferably 5, 6, 7, 8 or 9, and very preferably 7.

[0759] n2, in each occurrence, is either the same or different, preferably an integer from 1 to 12, preferably 2, 3, 4, 5, or 6, very preferably 3, and...

[0760] R S In each occurrence, whether identically or differently, it preferably represents an alkyl group having 1 to 6 carbon atoms, preferably n-butyl.

[0761] p represents 1 or 2, and

[0762] q represents 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0763] Among compounds of formula ST, compounds of the following formula are particularly preferred.

[0764] In compounds of formula ST-3a and ST-3b, n preferably represents 3. In compounds of formula ST-2a, n preferably represents 7.

[0765] The mixture according to the invention is particularly preferred to contain one or more stabilizers selected from the formulas ST-2a-1, ST-3a-1, ST-3b-1, ST-8-1, ST-9-1, and ST-12:

[0766] The compounds of formulas ST-1 to ST-12 are preferably present in the liquid crystal mixture according to the invention in an amount of 0.005 to 0.5%, very preferably in an amount of 100 ppm, 250 ppm, 500 ppm or 1000 ppm, based on the mixture.

[0767] If the mixture according to the invention contains two or more compounds selected from formulas ST-1 to ST-18, in the case of two mixtures, the concentration is correspondingly increased to 0.01–1%, based on the mixture.

[0768] However, the total proportion of compounds of formulas ST-1 to ST-18 should not exceed 2%, based on the mixtures according to the invention.

[0769] Other mesocrystalline compounds not explicitly mentioned above may also be optionally and advantageously used in the media according to the invention. Such compounds are known to those skilled in the art.

[0770] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula A with a total concentration of 1% to 20%, more preferably 5% to 15%, and particularly preferably 8% to 12%.

[0771] In a preferred embodiment of the invention, the medium comprises one or more of a compound of formula A-1 and one or more of a compound of formula A-3, with a total concentration of 10% to 50%, more preferably 20% to 40%, and particularly preferably 25% to 35%.

[0772] In a preferred embodiment of the present invention, the medium comprises one or more compounds of formula A-1 and one or more compounds of formula A-2.

[0773] In a preferred embodiment of the present invention, the medium includes one or more compounds of formula A-1 and one or more compounds of formula A-3.

[0774] In a preferred embodiment of the present invention, the medium comprises one or more compounds of formula A-1 and one or more compounds of formula A-4.

[0775] In a preferred embodiment of the present invention, the medium includes one or more compounds of formula A-2 and one or more compounds of formula A-4.

[0776] In a preferred embodiment of the present invention, the medium includes one or more compounds of formula A-3 and one or more compounds of formula A-4.

[0777] In a preferred embodiment of the present invention, the medium includes one or more compounds of formula A-2 and one or more compounds of formula A-3.

[0778] In a preferred embodiment of the present invention, the liquid crystal medium comprises a compound of formula T with a total concentration preferably in the range of 5% to 35%, more preferably 6% to 30%, and particularly preferably 7% to 25%, preferably selected from formulas T-1a, T-2a, and T-3a, and very preferably selected from T-1a-5, T-2a-2, T-2a-4, and T-3a-2.

[0779] In a preferred embodiment, the medium comprises one or more compounds of formula I, preferably formula I-2 or I-3, in a total concentration range of 1% to 30%, more preferably 2% to 25%, very preferably 3% to 20%, and especially preferably 5% to 15%.

[0780] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula II, preferably formula II-1, at a total concentration of 2% to 35%, more preferably 3% to 30%, and particularly preferably 5% to 25%.

[0781] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula IIA-1 at a total concentration of 5% to 25%, more preferably 8% to 20%, and particularly preferably 12% to 17%.

[0782] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula II-1 with a total concentration of 30% or less, more preferably 25% or less, and particularly preferably 22% or less.

[0783] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula III, preferably III-1 and / or III-2, more preferably III-1f and / or III-1b and / or III-1h, with a total concentration of 15% to 60% or 65% or 70%, more preferably 20% to 58%, particularly preferably 30% to 55% or 35% to 53%.

[0784] In a preferred embodiment of the invention, the medium comprises one or more compounds of formula XII with a total concentration preferably from 5% to 30%, more preferably from 8% to 25%, and particularly preferably from 10% to 20%.

[0785] In a preferred embodiment, the medium comprises one or more compounds of formula A with a total concentration preferably 90% or higher, more preferably 95%, 96% or 97% or higher, very preferably 98% or higher, and particularly 99% or higher, and one or more compounds selected from the group consisting of formulas I, II and / or IIA, III, XII, and T.

[0786] In a preferred embodiment, the medium comprises one or more compounds of formula A with a total concentration ranging from 40% to 90%, one or more compounds selected from the group consisting of formulas I, II and / or IIA, III, XII, T, and one or more compounds of formula IV with a total concentration of 10% or higher.

[0787] In a preferred embodiment, the medium comprises one or more compounds of formula A with a total concentration ranging from 40% to 70%, and one or more compounds selected from the group consisting of formulas I, II and / or IIA, III, XII and T, as well as one or more compounds of formula IV with a total concentration of 30% or higher.

[0788] In a preferred embodiment, the medium comprises one or more compounds of formula A with a total concentration ranging from 40% to 60%, and one or more compounds selected from the group consisting of formulas I, II and / or IIA, III, XII and T, as well as one or more compounds of formula IV with a total concentration of 40% or higher.

[0789] Other preferred embodiments of the invention, individually or in combination with each other, are as follows, wherein some of the compounds are abbreviated as set forth in Tables A and B and given in Table C below, and n is 1, 2, 3, 4, 5, 6 or 7:

[0790] - The medium comprises one or more compounds of formula XII-3, preferably formula CPU(FF)-nS, with a concentration preferably in the range of 10% to 30%, and particularly 15% to 25%;

[0791] - The medium includes one, two, three, four or more compounds of formula III-1, preferably selected from formula III-1b, III-1f and III-1h; more preferably compounds III-1b and III-1h;

[0792] - The medium comprises a compound of formula III-1b in a total concentration preferably from 5% to 40%, more preferably from 10% to 35%, and particularly from 15% to 30%;

[0793] - The medium comprises a compound of formula III-1h with a total concentration preferably in the range of 7% to 35%, more preferably 10% to 30%, and specifically 12% to 25%;

[0794] - The media include compounds PPU-TO-S and / or PPTU-TO-S and / or PTPU-TO-S and / or PP(1)TO-nS;

[0795] - The medium includes one or more I-2d compounds, preferably compounds PGU-2-S and / or PGU-3-S and / or PGU-4-S and / or CPU-2-S and / or CPU-3-S and / or CPU-4-S;

[0796] - The medium comprises one or more compounds of formula II-1b, preferably compounds PTU-4-S and / or PTU-5-S;

[0797] - The medium includes one or more PPTU-nS and / or PTPU-nS compounds in a total concentration range of 15% to 25%;

[0798] - The medium comprises one or more PPTU-nS and / or PTPU-nS and / or PGTU-nS compounds in a total concentration range of 15 to 30%, wherein n is 1, 2, 3, 4, 5 or 6;

[0799] - The medium comprises one or more CPTU-nS compounds in a total concentration range of 10% to 30%, and specifically 14% to 25%;

[0800] - The medium comprises one or more compounds selected from the group consisting of compounds of formula UI and PT, preferably selected from compounds of formula UI-1, UI-2, PT-2 and PT-3, in a total concentration preferably ranging from 1% to 65%, more preferably from 2% to 60%, and particularly from 25% to 55%.

[0801] - The medium comprises one or more PT-2 compounds, preferably in the range of 1% to 10% in total concentration;

[0802] - The medium comprises one or more of the XIV compound in a total concentration preferably from 7% to 35%, more preferably from 10% to 30%, and particularly from 15% to 25%;

[0803] - The medium comprises one or more ST-3 compounds in a total concentration range of 0.01 to 1%, preferably 0.05 to 0.5%, and particularly preferably 0.10 to 0.15%, preferably ST-3a and / or ST-3b, and particularly preferably ST-3b-1.

[0804] The liquid crystal medium according to the invention preferably has a clearing point of 90°C or higher, more preferably 100°C or higher, more preferably 110°C or higher, more preferably 120°C or higher, more preferably 130°C or higher, particularly preferably 140°C or higher, and very particularly preferably 150°C or higher.

[0805] The nematic phase of the medium according to the invention preferably extends from at least 0°C or lower to 90°C or higher. Advantageously, the medium according to the invention exhibits an even wider range of nematic phases, preferably at least -10°C or lower to 120°C or higher, very preferably at least -20°C or lower to 140°C or higher, and particularly -30°C or lower to 150°C or higher, and very particularly preferably at least -40°C or lower to 170°C or higher.

[0806] The liquid crystal medium according to the present invention at 1 kHz and 20°C Preferably 5 or higher, more preferably 7 or higher, and very preferably 8 or higher.

[0807] According to the present invention, the liquid crystal medium at 589 nm (Na D The birefringence (Δn) at 20°C is preferably 0.280 or higher, more preferably 0.300 or higher, even more preferably 0.320 or higher, very preferably 0.330 or higher, and especially 0.350 or higher.

[0808] According to the present invention, the liquid crystal medium at 589 nm (Na D The Δn at 20°C is preferably in the range of 0.200 to 0.900, more preferably in the range of 0.250 to 0.800, even more preferably in the range of 0.300 to 0.700, and very particularly preferably in the range of 0.350 to 0.600.

[0809] In a preferred embodiment of this application, the Δn of the liquid crystal medium according to the present invention is preferably 0.50 or higher, more preferably 0.55 or higher.

[0810] The compounds of Formulas I to III each include, in each case, a dielectric positive compound with a dielectric anisotropy greater than 3, a dielectric neutral compound with a dielectric anisotropy less than 3 and greater than -1.5, and a dielectric negative compound with a dielectric anisotropy of -1.5 or lower.

[0811] Compounds of formulas A, I, II and III are preferably dielectric positive.

[0812] Preferably, the optical component according to the invention is designed and configured as an optical phase modulator.

[0813] In a preferred embodiment, the optical component according to the invention is designed and configured in a transparent device for phase modulation of IR radiation.

[0814] In another preferred embodiment, the optical components according to the invention are designed and configured for use in a reflective device for phase modulation of IR radiation.

[0815] A typical electro-optic modulator includes conductive infrared transmission windows, which are composed of, for example, Ge, spaced apart by spacers and have a cell gap in the range of 1 mm to 5 mm.

[0816] According to another aspect of the invention, a LIDAR scanning system as described in WO2018 / 156643A1 is provided, comprising a laser configured to emit light pulses at an operating wavelength in the infrared. The LIDAR scanning system includes a transmissive reconfigurable metasurface configured to reflect incident light pulses from the laser as an illumination beam directed at a selected portion of the field of view, preferably a two-dimensional field of view. The direction of the illumination beam is responsive to a first selected holographic beam manipulation mode implemented in the transmissive reconfigurable metasurface. The system further includes a receiving reconfigurable metasurface configured to reflect a return of the illumination beam from a selected portion of the field of view as a relay beam directed at an optical detector. The direction of the relay beam is responsive to a second selected holographic beam manipulation mode implemented in the receiving reconfigurable metasurface. The system includes an optical detector comprising an array of detector pixels. Each detector pixel includes (i) a photodetector configured to detect light in the return of an illumination beam; and (ii) a timing circuit configured to determine the time of flight of the detected light. The photodetector is also configured to output a detection signal indicating the detected light and the time of flight of the detected light for each pixel in the array. The transmissive reconfigurable metasurface includes a plurality of dynamically tunable high-Q dielectric resonators disposed on a surface of the reconfigurable metasurface, the surface having an inter-component spacing smaller than the operating wavelength of a laser, wherein the surface of the reconfigurable metasurface includes a conductive surface, and the plurality of resonators have corresponding plurality of tunable reflection phases that provide dynamically tunable reflected waves in response to an incident wave, wherein the conductive surface and the plurality of resonators define the metasurface. Each of the plurality of dielectric resonators includes (i) a pair of regions having a higher refractive index; and (ii) an electrically tunable material disposed in the gap between the regions, wherein the electrically tunable material is a liquid crystal material as described above and below.

[0817] According to another aspect of the invention, a reflective spatial light modulator, particularly an LCoS device, is provided, comprising a liquid crystal material according to the invention sandwiched between a transparent glass layer having transparent electrodes, a mirror mounted on a silicon CMOS substrate, and a PCB. The mirror is divided into a two-dimensional array of individually addressable pixels. Each pixel can be individually driven by a voltage signal to provide a local phase transition to at least one polarization component of an optical signal, thereby providing a two-dimensional array of phase manipulation regions. Pre-alignment of the liquid crystal is provided through an alignment layer.

[0818] This LCoS device is suitable for integration into optical devices. Preferred devices include wavelength selective switches (WSS), LiDAR scanners, infrared scene projectors, and other beam manipulation applications as shown in the following paper (2019) by Micallef, F.: Middle infrared beam-steering using liquid crystals for spatial light modulation (Doctoralthesis). https: / / doi.org / 10.17863 / CAM.39602(https: / / www.repository.cam.ac.uk / handle / 1810 / 292443).

[0819] In this application, the positive dielectric property is described as Δ Compounds or components with a dielectric neutrality greater than 3.0, where -1.5 ≤ Δ Those with a dielectric constant ≤ 3.0, and whose dielectric negativity describes Δ Those with values ​​less than or equal to 1.5. Δ The measurements were taken at a frequency of 1 kHz and at 20°C. The dielectric anisotropy of each compound was determined by the results of a 10% solution of each individual compound in the nematic host mixture. If the solubility of each compound in the host mixture was less than 10%, the concentration was reduced to 5%. The capacitance of the test mixtures was measured in both cells with vertical alignment and cells with planar alignment. The cell thickness of both types of cells was approximately 20 μm. The applied voltage was a rectangular wave with a frequency of 1 kHz and an effective value typically between 0.5 V and 1.0 V, but it was always selected to be below the capacitance threshold of each test mixture.

[0820]

[0821] The bulk mixture used to determine the physical constants of the pure compound by extrapolation was ZLI-4792 from Merck KGaA, Germany. The absolute value of the dielectric constant, birefringence (Δn), and rotational viscosity of the compound were determined. 1) This is measured by the change in various values ​​of the main mixture after the addition of the compound. The concentration in the main mixture is 10%, or 5% if the solubility is insufficient. This value is extrapolated to the 100% concentration of the added compound.

[0822] In the embodiments, the phase sequence of the pure compounds is given by the following abbreviations:

[0823] K: Crystalline, N: Nematic, SmA: Smectic A, SmB: Smectic B, I: Isotropic.

[0824] The nematic phase component was measured as is at a measurement temperature of 20°C, while all other components were treated similarly to the compound.

[0825] In both cases, unless otherwise expressly stated, the term "threshold voltage" used in this application refers to the optical threshold and is specific to a 10% relative contrast ratio (V). 10 The statement "saturation voltage" refers to optical saturation and is specific to 90% relative contrast (V). 90 The capacitive threshold voltage (V0), also known as the Freedericks threshold (V0), is used only when explicitly mentioned. Fr ).

[0826] Unless otherwise expressly stated, the parameter ranges specified in this application include limit values.

[0827] Different upper and lower limits indicated by different property ranges can be combined to obtain other preferred ranges.

[0828] Throughout this application, the following conditions and definitions apply unless otherwise stated. All concentrations are given as weight percentages and refer to their respective total mixtures; all temperature values ​​are given in Celsius and all temperature differences are given in differential degrees. All physical properties are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status November 1997, Merck KGaA (Germany) and given for a temperature of 20°C, unless otherwise explicitly stated. Optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. Dielectric anisotropy (Δn) is determined. The frequency was determined at 1 kHz. The threshold voltage and all other electro-optic properties were determined using a test box manufactured by Merck KGaA, Germany. This was used to determine Δ... The test chamber has a thickness of approximately 20 μm. The electrodes are 1.13 cm thick. 2 A circular ITO electrode with a defined area and guard ring. For vertical orientation ( || The orientation layer is SE-1211 from Nissan Chemicals, Japan, and for surface orientation ( The orientation layer is polyimide AL-1054 from Japan Synthetic Rubber. A Solatron 1260 frequency response analyzer was used, employing a sine wave and 0.3 V. rmsThe capacitance is measured by the voltage. White light is used in the electro-optic measurement. A DMS instrument, commercially available from Autronic-Melchers, Germany, is used. The characteristic voltage is measured under vertical observation. The threshold voltage (V) is measured at 10%, 50%, and 90% relative contrast. 10 ), medium gray voltage (V) 50 ) and saturation voltage (V 90 ).

[0829] As in A. Penirschke et al. “Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz”, 34 th The study of liquid crystal media in terms of their performance in the microwave frequency range is described in the European Microwave Conference – Amsterdam, pp. 545-548. In this regard, comparisons are also made with A. Gaebler et al., “Direct Simulation of Material Permittivities…”, 12MTC 2009 – International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467 and DE 10 2004 029 429 A, which also describe the measurement methods in detail.

[0830] Liquid crystal was introduced into a polytetrafluoroethylene (PTFE) or quartz capillary. The capillary had an inner diameter of 0.5 mm and an outer diameter of 0.78 mm. The effective length was 2.0 cm. The filled capillary was introduced into the center of a cylindrical cavity with a resonant frequency of 19 GHz. The cavity had a length of 11.5 mm and a radius of 6 mm. An input signal (source) was then applied, and the frequency-dependent response of the cavity was recorded using a commercial vector network analyzer (N5227APNA microwave network analyzer, Keysight Technologies Inc. USA). For other frequencies, the cavity dimensions were adapted accordingly.

[0831] The changes in resonant frequency and Q-factor between measurements using a capillary filled with liquid crystal and those using a capillary without liquid crystal were used to determine the dielectric constant and loss angle at the corresponding target frequency, as described in the aforementioned publication A. Penirschke et al., 34. thEuropean Microwave Conference – Amsterdam, pp. 545-548, determinations of equations 10 and 11 as described therein.

[0832] The values ​​of the components of the property perpendicular to and parallel to the liquid crystal director are obtained by the alignment of the liquid crystal in a magnetic field. For this purpose, a magnetic field of a permanent magnet is used. The magnetic field strength is 0.35 Tesla.

[0833] Preferred components include phase shifters, varactor diodes, wireless and radio wave antenna arrays, matching circuits, adaptive filters, and others.

[0834] In this application, the term "compound" means one compound and multiple compounds, unless otherwise expressly stated.

[0835] All mixtures according to the invention are nematic. The liquid crystal medium according to the invention preferably has a nematic phase within the preferred range given above. The statement "having a nematic phase" here means, on the one hand, that no smectic phase and no crystallization are observed at the corresponding temperature at low temperatures, and on the other hand, that no clearing occurs upon heating from the nematic phase. At high temperatures, the clearing point is measured in a capillary using conventional methods. Low-temperature studies are conducted using a flow viscometer at the corresponding temperature and examined by storing bulk samples: at a given temperature T, the storage stability (LTS) in the bulk of the medium according to the invention is determined by visual inspection. 2 g of the medium of interest is filled into a suitably sized closed glass container (bottle) placed in a refrigerator at a predetermined temperature. The bottle is checked at defined time intervals for smectic phase formation or crystallization. Two bottles are stored for each material and at each temperature. If crystallization or a smectic phase is observed in at least one of the two corresponding bottles, the test is terminated, and the time of the last check before the observation of a higher ordered phase is recorded as the corresponding storage stability. Finally, the experiment was terminated after 1000 hours, meaning that an LTS value of 1000 hours indicates that the mixture is stable at a given temperature for at least 1000 hours.

[0836] The liquid crystal used preferably has positive dielectric anisotropy. This is preferably 2 or greater, more preferably 4 or greater, particularly preferably 6 or greater, and very particularly preferably 10 or greater.

[0837] Furthermore, the liquid crystal medium according to the invention is characterized by high anisotropy values ​​in the microwave range. The birefringence at approximately 19 GHz is preferably 0.14 or higher, particularly preferably 0.15 or higher, particularly preferably 0.20 or higher, particularly preferably 0.25 or higher, and very particularly preferably 0.30 or higher. Additionally, the birefringence is preferably 0.80 or lower.

[0838] Dielectric anisotropy in the microwave range is defined as

[0839]

[0840] Tunability ( ) is defined as

[0841]

[0842] Material quality ) is defined as

[0843]

[0844] Maximum dielectric loss is

[0845]

[0846] Tunability of the medium according to the invention, measured at 20°C and 19 GHz It is 0.250 or greater, preferably 0.300 or greater, 0.310 or greater, 0.320 or greater, 0.330 or greater, or 0.340 or greater, very preferably 0.345 or greater and especially 0.350 or greater.

[0847] Preferred liquid crystal material material quality The value is 6 or greater, preferably 8 or greater, preferably 10 or greater, preferably 15 or greater, preferably 17 or greater, preferably 20 or greater, particularly preferably 25 or greater, and very particularly preferably 30 or greater.

[0848] In the corresponding components, the phase shifter quality of the preferred liquid crystal material is 15° / dB or greater, preferably 20° / dB or greater, preferably 30° / dB or greater, preferably 40° / dB or greater, preferably 50° / dB or greater, particularly preferably 80° / dB or greater, and very particularly preferably 100° / dB or greater.

[0849] However, in some implementations, liquid crystals with negative dielectric anisotropy can also be advantageously used.

[0850] The liquid crystals used are either a single substance or a mixture. They preferably have a nematic phase.

[0851] The liquid crystal medium according to the invention may contain other additives and chiral dopants at typical concentrations. The total concentration of these other components, based on the entire mixture, is 0% to 10%, preferably 0.1% to 6%. The concentration of each individual compound used is preferably 0.1% to 3%. When referring to values ​​and concentration ranges of liquid crystal components and liquid crystal compounds in this application, the concentrations of these, as well as similar additives, are not taken into consideration.

[0852] Preferably, the medium according to the invention contains one or more chiral compounds as chiral dopants to adjust their cholesterol-type pitch. The total concentration of these compounds 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%.

[0853] Optionally, the medium according to the invention may contain other liquid crystal compounds to adjust physical properties. Such compounds are known to those skilled in the art. 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%.

[0854] Specifically, the relative contrast for relative tuning or photoelectric response varies from 0% to 90% (t 90 The response time is measured in terms of rise time (t0) and t0 is measured in terms of rise time (t0). on The value is given, including the delay time (t). 10 – t0); for relative tuning or photoelectric response, the relative contrast changes from 100% back to 10% (t 100 – t 10 The response time is measured in terms of decay time. off ) is given, and is used as the total response time ( 总计 = on + off ).

[0855] The liquid crystal medium according to the invention comprises a variety of compounds, preferably 3-30, more preferably 4-20, and very preferably 4-16. These compounds are mixed in a conventional manner. Typically, a desired amount of compound used in a smaller quantity is dissolved in a larger quantity of compound used. The completion of the dissolution process is particularly easy to observe if the temperature is above the clearing point of the compound used at a higher concentration. However, the medium can also be prepared in other conventional ways, such as using so-called premixes, which can be, for example, homogeneous mixtures or eutectic mixtures of compounds, or using so-called "multi-bottle" systems, whose components are themselves ready-to-use mixtures.

[0856] All temperatures, such as melting point T(C, N) or T(C, S), the transition from smectic (S) phase to nematic (N) phase T(S, N), and the clearing point of liquid crystal T(N, I), are expressed in degrees Celsius. All temperature differences are expressed in degrees.

[0857] In this invention, and particularly in the following embodiments, the structure of the mesocrystalline compound is indicated by abbreviations (also known as acronyms). In these acronyms, the chemical formulas are abbreviated using Tables A to C below. All groups C n H 2n+1 C m H 2m+1 and C l H 2l+1 And C n H 2n-1 C m H 2m-1 and C l H 2l-1 These represent straight-chain alkyl or alkylene groups, each having n, m, or l C atoms, where n and m are independently 1, 2, 3, 4, 5, 6, or 7, and l is 1, 2, or 3. Table A lists the codes for the ring elements used in the core structure of the compound, while Table B shows the linking groups and terminal groups. Table C shows the illustrative structure of the compound and its corresponding abbreviations.

[0858] Table A: Ring Elements

[0859] Table B: Linking Groups

[0860] Table B: End bases

[0861] Where n and m each represent integers, and the three dots "..." are placeholders for other abbreviations from this table.

[0862] The side branches are numbered starting from the position next to the loop (1) of the longest chain. The smaller number indicates the length of the branch, and the superscript number in parentheses indicates the position of the branch. For example:

[0863] The table below shows illustrative structures and their corresponding abbreviations. These are shown to explain the meaning of the abbreviation rules. They also represent preferred compounds.

[0864] Table C: Explanatory Structure

[0865] The following illustrative structures are examples and compounds, which are preferably used additionally in the medium:

[0866]

[0867] CEPTU-nS

[0868]

[0869] CEPTU-nS

[0870]

[0871] CVPTU-nS

[0872]

[0873] Np(2H)TU-nS

[0874]

[0875] Np(2H)TU-n-AN

[0876]

[0877] Np(2H)TU-n-AS

[0878]

[0879] Np(2H)TU-nA-S

[0880]

[0881] PNp(2H)TU-nS

[0882]

[0883] Np(2H)ITU-nS

[0884]

[0885]

[0886]

[0887]

[0888]

[0889]

[0890]

[0891]

[0892] Where m and n are the same or different and are 1, 2, 3, 4, 5, 6 or 7.

[0893] Preferably, the medium of the present invention comprises one or more compounds selected from the compounds in Table C.

[0894] The table below (Table D) shows explanatory compounds that can be used as alternative stabilizers in the mesocrystalline media of this invention. The total concentration of these compounds and similar compounds in the media is preferably 5% or less.

[0895] Table D

[0896] In a preferred embodiment of the invention, the mesocrystalline medium comprises one or more compounds selected from the group consisting of compounds in Table D.

[0897] The following table (Table E) shows explanatory compounds that are preferably used as chiral dopants in the mesocrystalline media of the present invention.

[0898] Table E

[0899] In a preferred embodiment of the invention, the mesocrystalline medium comprises one or more compounds selected from the group consisting of compounds from Table E.

[0900] The mesocrystalline medium according to this application preferably comprises two or more compounds selected from the group consisting of compounds from the table above, preferably four or more compounds.

[0901] Unless otherwise indicated, part or percentage data are expressed as parts by weight or weight percentage.

[0902] In the preceding and following text:

[0903] V o Represents the threshold voltage at 20°C, capacitive [V].

[0904] n e This indicates the unusual refractive index at 20°C and 589 nm.

[0905] n o This represents the ordinary refractive index at 20℃ and 589 nm.

[0906] Δn represents the optical anisotropy at 20℃ and 589 nm.

[0907] This represents the dielectric permittivity perpendicular to the director at 20°C and 1 kHz.

[0908] || This represents the dielectric permittivity parallel to the director at 20°C and 1 kHz.

[0909] Δ Indicates the dielectric anisotropy at 20℃ and 1 kHz.

[0910] Cl.p, T(N,I) represents the clearing point [°C].

[0911] γ1 represents the rotational viscosity [mPa] measured at 20°C. s],

[0912] K1 represents the elastic constant at 20℃, and the "bending" deformation [pN].

[0913] K2 represents the elastic constant at 20℃, and the "torsional" deformation [pN].

[0914] K3 represents the elastic constant at 20℃, and the bending deformation [pN].

[0915] K avg. The mean elastic constant is represented by K. avg. = (1.5·K1 + K3), and

[0916] LTS indicates the low-temperature stability (nematic phase) measured in test kits or in bulk form, as detailed.

[0917] Unless otherwise expressly stated, all values ​​indicated in this application regarding temperatures (such as melting point T(C,N), transformation from smectic (S) to nematic (N) phase T(S,N), and clearing point T(N,I) or cl.p.) are indicated in degrees Celsius (°C). Mp represents the melting point. Furthermore, Tg = glassy state, C = crystalline state, N = nematic phase, S = smectic phase, and I = isotropic phase. The numbers between these symbols represent the transformation temperature.

[0918] Unless otherwise explicitly indicated, the term "threshold voltage" used in this invention refers to the capacitance threshold (V0), also known as the Freedericksz threshold. In embodiments, as is commonly used, the optical threshold (V0) may also be indicated for 10% relative contrast. 10 ).

[0919] The display used to measure the capacitance threshold voltage consists of two planar parallel glass plates spaced 20 µm apart, each with an electrode layer on its inner side and an unrubbed polyimide alignment layer on top, which enables vertical edge alignment of liquid crystal molecules.

[0920] The term "HTP" refers to the helical twisting force (in µm) of an optically active or chiral material in an LC medium. Unless otherwise indicated, HTP is measured at 20°C for commercially available nematic LC bulk mixtures MLD-6260 (MerckKGaA).

[0921] The cleaning point was measured using a Mettler Thermosystem FP900. Optical anisotropy (Δn) was measured using an AbbeRefractometer H005 (Na10 sodium spectroscopy lamp at 589 nm and 20°C). Dielectric anisotropy (Δn) was measured. LCR-Meter E4980A / Agilent (G005) with JALS 2096-R1 was used at 20°C. The on-state voltage (V0) is measured using an LCR-Meter E4980A / Agilent (G005) at 20°C (with JALS 2096-R1). The rotational viscosity (γ1) was measured at 20°C using a TOYO LCM-2 (0002) (γ1 negative cell with JALS-2096-R1). The elastic constant (K1, development) was measured at 20°C using an LCR-Meter E4980A / Agilent (G005) (with JALS 2096-R1). Parallel box) to measure. K3: Elastic constant (K3, flexural) at 20°C using LCR-MeterE4980A / Agilent (G005) (with JALS 2096-R1). Parallel boxes are used for measurement.

[0922] Unless otherwise expressly stated, all concentrations in this application are indicated by weight percentage and refer to the respective mixtures (solvent-free) comprising all solid or liquid crystal components as a whole. Unless otherwise expressly stated, all physical properties were determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status November 1997, Merck KGaA, Germany, and are applicable at a temperature of 20°C. Example

[0923] The invention is described in detail below through non-limiting working embodiments.

[0924] Synthesis Examples

[0925] Use the following abbreviations:

[0926] RT room temperature

[0927] MTB tert-butyl methyl ether

[0928] DABCO 1,4-diazabicyclo[2.2.2]octane

[0929] dist. (distillation)

[0930] RP inversion

[0931] THF Tetrahydrofuran

[0932] XPhos 2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl

[0933] XPhos Pd G2 Chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II)

[0934] Synthesis Example 1: 5-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-1,3-difluoro-2-isothiocyanate-based benzene

[0935] Step 1.1: 4-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-2,6-difluoroaniline

[0936]

[0937] A solution of 1-bromo-4-(2-(trans-4-butylcyclohexyl)ethyl)benzene (CAS 1450629-93-2) (43.0 g, 0.13 mol) in triethylamine (500 ml) was treated under an argon atmosphere with bis(triphenylphosphine)palladium(II) chloride (3.7 g, 5.3 mmol) and cuprous iodide (I) (1.0 g, 5.3 mmol), and the reaction mixture was heated to 60 °C. Then, a solution of 4-ethynyl-2,6-difluoroaniline (CAS 753501-37-0) (28.5 g, 0.19 mol) in triethylamine (200 ml) was slowly added, and the reaction mixture was stirred at 60 °C for 48 h. The mixture was cooled to room temperature, filtered, washed with triethylamine, and concentrated under vacuum. The residue was purified by rapid chromatography (silica gel, eluent heptane) followed by crystallization (heptane) to give rose-colored crystals of 4-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-2,6-difluoroaniline.

[0938] Step 1.2: 5-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-1,3-difluoro-2-isothiocyanate-based benzene

[0939]

[0940] A solution of 4-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-2,6-difluoroaniline (26.7 g, 0.07 mol) in dichloromethane (300 ml) was treated with 1,1-thiocarbonyldiimidazole (24.6 g, 0.14 mol) and DMF (5 drops) at room temperature and under an argon atmosphere, and the reaction mixture was stirred at 30 °C for 3 h. The mixture was then filtered through silica gel, washed with dichloromethane, and concentrated under vacuum. The residue was purified by rapid chromatography (silica gel, eluent heptane) and subsequent crystallization (heptane) to give colorless crystals of 5-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-1,3-difluoro-2-isothiocyanate benzene.

[0941] Phase sequence: K 54 N 173 I.

[0942] Δ = 16.7

[0943] Δn = 0.3457

[0944] The compound 5-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-1,3-difluoro-2-isothiocyanate-benzene in Synthesis Example 1 has an extremely low melting point of only 54°C and an extremely wide nematic phase, which gives the LC medium excellent low-temperature stability and high brightness temperature.

[0945] Synthesis Example 2: 2-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-1,3-difluoro-5-isothiocyanate-based benzene

[0946] Step 2.1: 4-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-3,5-difluoroaniline

[0947]

[0948] A mixture of 3,5-difluoro-4-((trimethylsilyl)ethynyl)aniline (CAS 2171459-91-7) (CAS 2171459-91-7) (36.0 g, 0.16 mmol), DMF (500 ml), triethylamine (300 ml), methanol (40 ml), and potassium carbonate (23.5 g, 0.17 mmol) was treated at room temperature and under an argon atmosphere with 1-bromo-4-(2-(trans-4-butylcyclohexyl)ethyl)benzene (CAS 1450629-93-2) (43.0 g, 0.13 mol) and XPhosPdG2 (0.5 g, 0.60 mmol), DMF (500 ml), triethylamine (300 ml), methanol (40 ml), and potassium carbonate (23.5 g, 0.17 mmol). The reaction mixture was stirred overnight at 70 °C. It was cooled to room temperature, filtered, washed with triethylamine, and concentrated under vacuum. The residue was purified by rapid chromatography (silica gel, eluent heptane / dichloromethane) followed by crystallization (heptane) to obtain beige crystals of 4-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-3,5-difluoroaniline.

[0949] Step 2.2: 2-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-1,3-difluoro-5-isothiocyanate-benzene

[0950]

[0951] A solution of 4-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-3,5-difluoroaniline (38.4 g, 0.10 mol) in dichloromethane (550 ml) was treated with 1,1-thiocarbonyldiimidazole (44.8 g, 0.25 mol) and DMF (2 ml) at room temperature and under an argon atmosphere, and the reaction mixture was stirred at room temperature for 4 h. The mixture was then filtered through silica gel, washed with dichloromethane, and concentrated under vacuum. The residue was purified by rapid chromatography (silica gel, eluent heptane) and subsequent crystallization (heptane) to give colorless crystals of 2-((4-(2-(trans-4-butylcyclohexyl)ethyl)phenyl)ethynyl)-1,3-difluoro-5-isothiocyanate benzene.

[0952] Phase sequence: K 127 N 192 I.

[0953] Δ = 4.72

[0954] Δn = 0.3537

[0955] Synthesis Example 3: 5-((4-((E)-2-(trans-4-butylcyclohexyl)vinyl)phenyl)ethynyl)-1,3-difluoro-2-isothiocyanate-based benzene

[0956] Step 3.1: 1-Bromo-4-((E)-2-(trans-4-butylcyclohexyl)vinyl)benzene

[0957]

[0958] The suspension of (trans-4-butylcyclohexyl)methyltriphenylphosphonium bromide (CAS 2042455-50-3) in THF (2300 ml) was treated with potassium tert-butoxide (62.8 g, 0.56 mol) at -15 °C under an argon atmosphere and stirred for 1 h. A solution of 4-bromobenzaldehyde (100 g, 0.54 mol) in THF (200 ml) was added dropwise, and the reaction mixture was stirred overnight at 0 °C. It was then quenched with a saturated aqueous solution of ammonium chloride (500 ml) and diluted with MTB ether (1000 ml). The aqueous phase was separated and extracted with MTB ether, and the combined organic phases were washed with brine, dried (sodium sulfate), and concentrated under vacuum. The residue was suspended in heptane and filtered to remove excess triphenylphosphine oxide. The crude product was purified by silica gel chromatography (using heptane as solvent) to obtain grayish-white crystals of 1-bromo-4-((E,Z)-2-(trans-4-butylcyclohexyl)vinyl)benzene.

[0959] A solution of 1-bromo-4-((E,Z)-2-(trans-4-butylcyclohexyl)vinyl)benzene (31.6 g, 0.10 mol) and sodium benzenesulfinate (CAS 873-33-2) (16.2 g, 0.10 mol) in toluene (250 ml) was treated with 2N hydrochloric acid (25 ml, 0.05 mol) under an argon atmosphere and heated at reflux temperature for 2 h. The solution was then cooled to room temperature and quenched with distilled water (50 ml). The aqueous phase was separated and extracted with toluene, and the combined organic phases were washed with an aqueous solution of sodium bicarbonate, dried (sodium sulfate), and concentrated under vacuum. The residue was purified by silica gel chromatography (solvent heptane) to give white crystalline 1-bromo-4-((E)-2-(trans-4-butylcyclohexyl)vinyl)benzene.

[0960] Step 3.2: 4-((4-((E)-2-(trans-4-butylcyclohexyl)vinyl)phenyl)ethynyl)-2,6-difluoroaniline

[0961]

[0962] A solution of 1-bromo-4-((E)-2-(trans-4-butylcyclohexyl)vinyl)benzene (30.9 g, 0.10 mol) in triethylamine (400 ml) was treated under an argon atmosphere with bis(triphenylphosphine)palladium(II) chloride (2.8 g, 4.0 mmol) and cuprous iodide (I) (0.8 g, 4.0 mmol), and the reaction mixture was heated to 60 °C. Then, a solution of 4-ethynyl-2,6-difluoroaniline (CAS 753501-37-0) (22.1 g, 0.14 mol) in triethylamine (200 ml) was slowly added, and the reaction mixture was stirred overnight at 60 °C. It was cooled to room temperature, filtered, washed with triethylamine, and concentrated under vacuum. The residue was purified by rapid chromatography (silica gel, eluent heptane) followed by crystallization (heptane) to give off-white crystals of 4-((4-((E)-2-(trans-4-butylcyclohexyl)vinyl)phenyl)ethynyl)-2,6-difluoroaniline.

[0963] Step 3.3: 5-((4-((E)-2-(trans-4-butylcyclohexyl)vinyl)phenyl)ethynyl)-1,3-difluoro-2-isothiocyanate-benzene

[0964]

[0965] A solution of 4-((4-(((E)-2-(trans-4-butylcyclohexyl)vinyl)phenyl)ethynyl)-2,6-difluoroaniline (30.5 g, 0.08 mol) in dichloromethane (300 ml) was treated with 1,1-thiocarbonyldiimidazole (27.6 g, 0.16 mol) and DMF (2 ml) at room temperature and under an argon atmosphere, and the reaction mixture was stirred at 30 °C for 3 h. The mixture was then filtered through silica gel, washed with dichloromethane, and concentrated under vacuum. The residue was purified by rapid chromatography (silica gel, eluent heptane) and subsequent crystallization (heptane) to give colorless crystals of 5-((4-(((E)-2-(trans-4-butylcyclohexyl)vinyl)phenyl)ethynyl)-1,3-difluoro-2-isothiocyanate benzene.

[0966] Phase sequence: K 80 N 261 I.

[0967] Δ = 17.6

[0968] Δn = 0.4395

[0969] Synthesis Example 4: 5-(2-{4-[(1E)-2-(4-butylcyclohexyl-1-en-1-yl)vinyl]phenyl}ethynyl)-1,3-difluoro-2-isothiocyanate benzene

[0970]

[0971] Similar to Synthesis Example 3, 5-(2-{4-[(1E)-2-(4-butylcyclohexyl-1-en-1-yl)vinyl]benzene prepared as described in JP-H07-25794 A2)-bromo-4-[(1E)-2-(4-butylcyclohexyl-1-en-1-yl)vinyl]phenyl}ethynyl)-1,3-difluoro-2-isothiocyanate-benzene.

[0972] Δ = 19.6

[0973] Δn = 0.504

[0974] Synthesis Example 5: 5-(2-{4-[(1E)-2-(4-butylcyclohexyl-1-en-1-yl)-1,2-difluorovinyl]phenyl}ethynyl)-1,3-difluoro-2-isothiocyanate benzene

[0975]

[0976] Similar to Synthesis Example 4, 5-(2-{4-[(1E)-2-(4-butylcyclohexyl-1-en-1-yl)-1,2-difluorovinyl]benzene prepared as described in JP 06-025030 A, 5-(2-{4-[(1E)-2-(4-butylcyclohexyl-1-en-1-yl)-1,2-difluorovinyl]phenyl}ethynyl)-1,3-difluoro-2-isothiocyanate benzene.

[0977] Δ = 12.3

[0978] Δn = 0.418

[0979] Similar to synthesis example 3, the following compounds were obtained:

[0980] Mixture Examples

[0981] The main mixture H1 has the following composition and properties:

[0982] The main mixture H2 has the following composition and properties:

[0983] The following mixtures were prepared from the main mixture H1 and the corresponding compounds of the present invention:

[0984] Mixture Example M1

[0985] Mixture Example M2

[0986] Mixture Example M3

[0987] Mixture Example M4

[0988] Adding one or more compounds of the present invention to the main mixture H1 results in improved clearing temperature and quality factor.

[0989] Mixture Example M5

[0990] Mixture Example M6

[0991] Mixture Example M7

[0992] Mixture Example M8

[0993] Mixture Example M9

Claims

1. A compound of formula A in R A The symbol represents H, a straight-chain alkyl group having 1 to 12 carbon atoms, or a straight-chain alkenyl or straight-chain alkynyl group each having 2 to 12 carbon atoms, or a branched alkyl group having 3 to 12 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, or a branched alkynyl group having 4 to 12 carbon atoms, wherein one or more CH2- groups may be... or Substitution, wherein one or more non-adjacent CH2- groups may be substituted with O, and wherein one or more H atoms in all such groups may be substituted with F. Z A1 This represents -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -CH2CH2-, -CHFCHF-, -CF2CH2-, -CH2CF2-, or -CF2CF2-. Z A2 This indicates -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, or -C≡CC≡C-. U 1 U 2 V 1 and V 2 The same or different representations of -N= or -CR 0 =, R 0 It represents H, Cl, F, CF3, CHF2, or alkyl or alkoxy groups each having 1 to 6 carbon atoms. X A This indicates -NCS, -C≡C-CN, or -C≡C-NCS. The designation represents 1,4-cyclohexene, 1,4-cyclohexenyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexene, bicyclo[2.2.2]octane-1,4-diyl or spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and one or more H atoms may be substituted with F. This represents 1,4-phenylene or 1,4-naphthylene, where one or both CH groups may be substituted with N and one or more H atoms may be substituted with R. L Substitution; or benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl, thiophene-2,5-diyl, or thiophene[3,2-b]thiophene-2,5-diyl, wherein one or more H atoms may be via R L Replacement R L Each time it appears, it may be the same or different F, Cl, CN, SCN, SF5 or a straight or branched chain having 1 to 12 C atoms, and in each case, it may be optionally fluorinated alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy or alkoxy carbonyloxy.

2. The compound according to claim 1, wherein Z A1 This indicates -CH=CH-, -CF=CF-, -CH=CF-, or -CF=CH-.

3. The compound according to claim 1, wherein Z A1 It represents -CH2CH2-, -CHFCHF-, -CF2CH2-, -CH2CF2-, or -CF2CF2-.

4. The compound according to claim 1, wherein the compound is selected from compounds of formula A-1, A-2, A-3 and A-4. The groups appearing therein have the meanings defined in claim 1.

5. The compound according to one or more of claims 1 to 4, wherein X A Indicates -NCS.

6. A compound according to one or more of claims 1 to 5, wherein Z A2 This means -C≡C-.

7. The compound according to one or more of claims 1 to 6, wherein express or or , Where R L Each time it appears, it may represent H or an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 5 carbon atoms, in the same or different ways. With targeting The given meaning or alternative representation or , in W represents N, CH, CF, or C-Cl, and Y 1 and Y 2 They may represent H, Cl, F, methyl, or ethyl, either the same or different.

8. A liquid crystal medium comprising a compound according to one or more of claims 1 to 7.

9. The medium of claim 8, wherein the medium further comprises one or more compounds selected from the group consisting of compounds of formulas I, II, and III: in R 1 The expression represents H, a non-fluorinated alkyl or non-fluorinated alkoxy group having 1 to 17 carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenoxy, or non-fluorinated alkoxyalkyl group each having 2 to 15 carbon atoms, wherein one or more CH2- groups may be derived from H. or Replacement n is 0, 1, or 2. to Each occurrence is represented independently. or , Where R L Each time it appears, it may represent H or an alkyl group having 1 to 6 carbon atoms, preferably H, methyl or ethyl, especially preferably H; Or indicates or , One or more H atoms may be substituted with an alkyl group or F having 1 to 6 C atoms, and wherein alternatively , or ; R 2 The symbol represents H; a non-fluorinated alkyl or non-fluorinated alkoxy group having 1 to 17 carbon atoms; or a non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenyloxy, or non-fluorinated alkoxyalkyl group having 2 to 15 carbon atoms, wherein one or more CH2- groups may be derived from H. or Replacement Z 21 This indicates the trans form -CH=CH-, the trans form -CF=CF-, or -C≡C-, preferably -C≡C- or the trans form -CH=CH-, and and Representing each other independently , or , where R L Each time it appears, it may represent H or an alkyl group having 1 to 6 carbon atoms, preferably H, methyl or ethyl, especially preferably H; Or indicates or One or more H atoms may be replaced by alkyl groups or F atoms having 1 to 6 C atoms. R 3 The symbol represents H; a non-fluorinated alkyl or non-fluorinated alkoxy group having 1 to 17 carbon atoms; or a non-fluorinated alkenyl, non-fluorinated alkynyl, non-fluorinated alkenyloxy, or non-fluorinated alkoxyalkyl group having 2 to 15 carbon atoms, wherein one or more CH2- groups may be derived from H. or Replacement Z 31 and Z 32 One of them represents the trans-CH=CH-, trans-CF=CF-, or -C≡C-, and the other independently represents -C≡C-, trans-CH=CH-, trans-CF=CF-, or a single bond. to Representing each other independently , or , where R L Each occurrence may represent H or an alkyl group having 1 to 6 carbon atoms, either identically or differently; or represent or One or more H atoms may be replaced by alkyl groups or F atoms having 1 to 6 C atoms. And among them alternatively or , Furthermore, compound A of formula is not included in compound III of formula.

10. The medium according to claim 8 or 9, wherein the medium comprises one or more UI compounds. in R U The symbol represents H, a straight-chain alkyl group having 1 to 12 carbon atoms, or a straight-chain alkenyl or alkynyl group each having 2 to 12 carbon atoms, or a branched alkyl group having 2 to 12 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, or a branched alkynyl group having 4 to 12 carbon atoms, wherein one or more CH2- groups may be... or Replacement Or it may represent the group R P , R P Indicates halogen, CN, NCS, fluorinated alkyl, R F -O- or R F -S-, where R F This indicates a fluorinated alkyl or fluorinated alkenyl group having a maximum of 9 carbon atoms. Z U1 This indicates -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, or -C≡CC≡C-, preferably -CF=CF- or -C≡C-. X U1 X U2 Cl or F may be represented in the same or different ways, preferably F. a) The group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or two CH groups may be substituted with N and one or more H atoms may be substituted with L. b) The group consisting of trans-1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydronaphthyl-2,6-diyl, tetrahydronaphthyl-5,8-diyl, decahydronaphthyl-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-biscyclohexene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, wherein one or two CH groups may be substituted with N, one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and one or more H atoms may be substituted with L. c) The group consisting of thiophene-2,5-diyl, thiopheno[3,2-b]thiophene-2,5-diyl, and selenophene-2,5-diyl, each of which may also be mono- or poly-substituted by L. L, in each occurrence, may refer to F, Cl, CN, SCN, SF5, or a straight or branched chain each having 1 to 12 C atoms, and in each case, optionally to a fluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy. u is 0 or 1, and v is 0 or 1. Compound UI is not included in compounds I, II and III.

11. The medium according to one or more of claims 8 to 10, wherein the medium comprises one or more PT compounds. in R P The symbol represents H, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 12 carbon atoms, wherein one or more CH2- groups may be derived from H. or Substitution, and one or more non-adjacent CH2- groups may be substituted with O. express or , Where L 1 L 2 and L 3 The same or different representations of H, F, Cl, or alkyl groups having 1 to 6 carbon atoms, t1 is 0 and t2 is 1, or t1 is 1 and t2 is 0.

12. An electronic component comprising a first substrate and a second substrate facing each other, a liquid crystal layer sandwiched between the substrates, and electrodes provided on each substrate or two electrodes provided on only one of the substrates for providing a potential across the liquid crystal layer to drive liquid crystal in a predetermined configuration. Its features The liquid crystal layer comprises a liquid crystal medium according to one or more of claims 8 to 11.

13. The electronic component of claim 12, wherein the component is configured for high-frequency technology.

14. The electronic component of claim 13, wherein the component is a liquid crystal-based antenna assembly, phase shifter, tunable filter, tunable metamaterial structure, matching network, or varactor diode.

15. A microwave antenna array, characterized in that... It includes one or more components according to claim 13 or 14.

16. The component of claim 12, wherein the component is a transmissive or reflective spatial light modulator.

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