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HETEROAROMATIC ISOTHIOCYANATES

20240124779 · 2024-04-18

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Abstract

The present invention relates to heteroaromatic isothiocyanates of formula N

##STR00001##

as defined in claim 1, to liquid-crystalline media comprising one or more compounds of formula N and to high-frequency components comprising these media, especially microwave components for high-frequency devices, such as devices for shifting the phase of microwaves, tunable filters, tunable metamaterial structures, and electronic beam steering antennas, e.g. phased array antennas.

Claims

1. A compound of formula N ##STR00582## in which R.sup.N denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or more CH.sub.2-groups may be replaced by ##STR00583## or denotes a group R.sup.P, R.sup.P denotes halogen, CN, NCS, R.sup.F, R.sup.FO, or R.sup.FS, wherein R.sup.F denotes fluorinated alkyl having 1 to 9 C atoms or fluorinated alkenyl having 2 to 9 C atoms, Z.sup.N1 and Z.sup.N2, identically or differently, denote CH?CH, CF?CF, CH?CF, CF?CH, C?C, C?CC?C, or a single bond, W denotes N, CF or CCl, X.sup.1 and X.sup.2, identically or differently, denote H, Cl, F, methyl, or ethyl, ##STR00584## on each occurrence, identically or differently, denote a radical selected from the following groups: a) the group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, in which one or two CH groups may each be replaced by N and in which one or more H atoms may each be replaced by L, b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, 4,4-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl, and spiro[3.3]heptane-2,6-diyl, in which one or more non-adjacent CH.sub.2 groups may each be replaced by O or S and in which one or more H atoms may each be replaced by F, and c) the group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may be mono- or polysubstituted by L, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF.sub.5 or straight-chain or branched, in each case optionally fluorinated, alkyl having 1 to 12 C atoms, alkoxy having 1 to 12 C atoms, alkylcarbonyl having 2 to 12 C atoms, alkoxycarbonyl having 2 to 12 C atoms, alkylcarbonyloxy having 2 to 12 C atoms, or alkoxycarbonyloxy having 2 to 12 C atoms, and n is 0, 1 or 2.

2. The compound according to claim 1, wherein the compound is selected from formulae N-1, N-2 and N-3: ##STR00585## in which R.sup.N denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or more CH.sub.2-groups may each be replaced by ##STR00586## Z.sup.N1 Z.sup.N2, X.sup.1, X.sup.2 and n, have the respective meanings given in claim 1 for formula N.

3. The compound according to claim 1, wherein the compound is selected from the group consisting of the formulae N-1, N-2 and N-3: ##STR00587## in which R.sup.N denotes halogen, CN, NCS, R.sup.F, R.sup.FO or R.sup.FS, wherein R.sup.F denotes fluorinated alkyl having 1 to 9 C atoms or fluorinated alkenyl having 2 to 9 C atoms and ##STR00588## Z.sup.N1 Z.sup.N2, X.sup.1, X.sup.2 and n, have the respective meanings given in claim 1 for formula N.

4. The compound according to claim 1, in which X.sup.1 and X.sup.2 denote H.

5. The compound according to claim 1, in which X.sup.1 denotes H and X.sup.2 denotes F or Cl.

6. The compound according to claim 1, in which X.sup.1 denotes F or Cl and X.sup.2 denotes H.

7. The compound according to claim 1, wherein X.sup.1 and X.sup.2 denote F.

8. The compound according to claim 1, wherein ##STR00589## on each occurrence, identically or differently denote ##STR00590## in which R.sup.L, on each occurrence, identically or differently, denotes H or alkyl having 1 to 6 C atoms, L denotes F or alkyl having 1 to 6 C atoms, and r is 0, 1, 2, 3, 4, 5 or 6, wherein ##STR00591## alternatively denotes ##STR00592## in which R.sup.H denotes H or CH.sub.3.

9. The compound according to claim 1, wherein Z.sup.N1 and Z.sup.N2, identically or differently, denote C?C or a single bond.

10. A liquid-crystal medium comprising one or more compounds according to claim 1.

11. The liquid-crystal medium according to claim 10, wherein the medium comprises a compound of formula NI ##STR00593## in which R.sup.N denotes H, alkyl or alkoxy having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl having 2 to 12 C atoms, in which one or more CH.sub.2-groups may be replaced by ##STR00594## or denotes a group R.sup.P, R.sup.P denotes halogen, CN, NCS, R.sup.F, R.sup.FO, or R.sup.FS, wherein R.sup.F denotes fluorinated alkyl having 1 to 9 C atoms or fluorinated alkenyl having 2 to 9 C atoms, Z.sup.N1 and Z.sup.N2, identically or differently, denote CH?CH, CF?CF, CH?CF, CF?CH, C?C, C?CC?C, or a single bond, W denotes N, CF or CCl, X.sup.1 and X.sup.2, identically or differently, denote H, Cl, F, methyl, or ethyl, ##STR00595## on each occurrence, identically or differently, denote a radical selected from the following groups: a) the group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, in which one or two CH groups may each be replaced by N and in which one or more H atoms may each be replaced by L, b) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, 4,4-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl, and spiro[3.3]heptane-2,6-diyl, in which one or more non-adjacent CH.sub.2 groups may each be replaced by O or S and in which one more H atoms may each be replaced by F, and c) the group consisting of thiophene-2,5-diyl, thieno[3.2-b]thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may be mono- or polysubstituted by L, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF.sub.5 or straight-chain or branched, in each case optionally fluorinated, alkyl having 1 to 12 C atoms, alkoxy having 1 to 12 C atoms, alkylcarbonyl having 2 to 12 C atoms, alkoxycarbonyl having 2 to 12 C atoms, alkylcarbonyloxy having 2 to 12 C atoms, or alkoxycarbonyloxy having 2 to 12 C atoms, and n is 0, 1 or 2.

12. The liquid-crystal medium according to claim 10, wherein the medium further comprises one or more compounds selected from the group of compounds of the formulae I, II and III, ##STR00596## in which R.sup.1 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms, or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, in which one or more CH.sub.2-groups may each be replaced by ##STR00597## n is 0, 1 or 2, ##STR00598## on each occurrence, independently of one another, denote ##STR00599## in which R.sup.L, on each occurrence identically or differently, denotes H or alkyl having 1 to 6 C atoms, and wherein ##STR00600## alternatively denotes ##STR00601## R.sup.2 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms, or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, in which one or more CH.sub.2-groups may each be replaced by ##STR00602## Z.sup.21 denotes trans-CH?CH, trans-CF?CF or C?C, and ##STR00603## independently of one another, denote ##STR00604## in which R.sup.L, on each occurrence identically or differently, denotes H or alkyl having 1 to 6 C atoms; R.sup.3 denotes H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms, or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, in which one or more CH.sub.2-groups may each be replaced by ##STR00605## one of Z.sup.31 and Z.sup.32, denotes trans-CH?CH, trans-CF?CF or C?C and the other one, independently thereof, denotes C?C, trans-CH?CH, trans-CF?CF, or a single bond, and ##STR00606## independently of one another, denote ##STR00607## in which R.sup.L, on each occurrence identically or differently, denotes H or alkyl having 1 to 6 C atoms, and wherein ##STR00608## alternatively denotes ##STR00609##

13. The liquid-crystal medium according to claim 12, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae I-1 to I-5 ##STR00610## in which L.sup.1, L.sup.2 and L.sup.3 on each occurrence, identically or differently, denote H or F, and R.sup.1, ##STR00611## have the meanings given for formula I in claim 12.

14. The liquid-crystal medium according to claim 12, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae II-1 to II-3 ##STR00612## in which R.sup.2, ##STR00613## have the meanings given in claim 12 for formula II.

15. The liquid-crystal medium according to claim 12, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae III-1 to III-6 ##STR00614## in which R.sup.3, ##STR00615## have the meanings given in claim 12 for formula III, and Z.sup.31 and Z.sup.32 independently of one another, denote trans-CH?CH or trans-CF?CF, and in formula III-6 one of Z.sup.31 and Z.sup.32 alternatively denotes C?C.

16. The liquid-crystal medium according to claim 10, wherein the medium further comprises one or more compounds of the formula T ##STR00616## in which R.sup.T denotes halogen, CN, NCS, R.sup.F, R.sup.FO or R.sup.FS, wherein R.sup.F denotes fluorinated alkyl having 1 to 12 C atoms or fluorinated alkenyl having 2 to 12 C atoms, ##STR00617## on each occurrence, independently of one another, denote ##STR00618## L.sup.4 and L.sup.S identically or differently, denote F, Cl, straight chain alkyl having 1 to 12 C atoms, branched alkyl having 3 to 12 C atoms, cyclic alkyl having 3 to 12 C atoms, straight chain alkenyl having 2 to 12 C atoms, branched alkenyl having 3 to 12 C atoms or cyclic alkenyl each having 3 to 12 C atoms; Z.sup.T3, Z.sup.T4 identically or differently, denote CH?CH, CF?CF, CH?CF, CF?CH, C?C, or a single bond, and t is 0 or 1.

17. A component for high-frequency technology comprising a liquid crystal medium according to claim 10.

18. The component according to claim 17, wherein the component is a liquid-crystal based antenna element, a phase shifter, a tunable filter, a tunable metamaterial structure, a matching network or a varactor.

19. A microwave antenna array comprising one or more components according to claim 17.

Description

EXAMPLES

[0711] The following examples illustrate the present invention without limiting it in any way. It is clear to the person skilled in the art from the physical properties what properties can be achieved and in what ranges they can be modified. In particular, the combination of the various properties which can preferably be achieved is thus well defined for the person skilled in the art.

SYNTHESIS EXAMPLES

Abbreviations

[0712] RT room temperature (20? C.?1? C.) [0713] MTB ether tert-butyl methyl ether [0714] DABCO 1,4-Diazabicyclo[2.2.2]octane [0715] dist. distilled [0716] THE tetrahydrofuran [0717] XPhos 2-Dicyclohexylphosphino-2,4,6-triisopropylbiphenyl [0718] XPhos Pd G2 Chloro(2-dicyclohexylphosphino-2,4,6-triisopropyl-1,1-biphenyl)[2-(2-amino-1,1-biphenyl)palladium (II)

Synthesis Example 1: 2-[4-(4-Butylcyclohexyl)phenyl]-5-isothiocyanato-pyrazine

Step 1.1: 5-[4-(4-Butylcyclohexyl)phenyl]pyrazin-2-amine

[0719] ##STR00456##

[0720] A mixture of [4-(4-butylcyclohexyl)phenyl]boronic acid (CAS 516510-90-0, 6.0 g, 23 mmol), 5-bromopyrazin-2-amine (CAS 59489-71-3, 4.0 g, 23 mmol) and potassium carbonate (6.4 g, 46 mmol) in dist. water (20 ml) and 1,4-dioxane (80 ml) is treated with [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II)-dichloromethane complex (1.0 g, 1 mmol) under argon atmosphere, and the reaction mixture is stirred at 90? C. overnight. Then it is cooled down to room temperature and filtered through Celite. The filtrate is diluted with MTB ether and dist. water is added. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with brine, dried (sodium sulfate), filtered and concentrated in vacuo. The residue is purified by silica gel chromatography (MTB ether) to give yellow crystals of 5-[4-(4-butylcyclohexyl)phenyl]pyrazin-2-amine.

Step 1.2: 2-[4-(4-Butylcyclohexyl)phenyl]-5-isothiocyanato-pyrazine

[0721] ##STR00457##

[0722] Thiophosgene (2.1 ml, 27 mmol) is slowly added to a solution of 5-[4-(4-butylcyclohexyl)phenyl]pyrazin-2-amine (6.8 g, 22 mmol) and DABCO (6.2 g, 55 mmol) in dichloromethane (230 ml) at 0? C. under argon atmosphere. The reaction mixture is stirred at room temperature overnight. Then it is quenched with dist. water and brine. The aqueous phase is separated and extracted with dichloromethane. The combined organic phases are washed with brine, dried (sodium sulfate), filtered and concentrated in vacuo. The residue is purified by silica gel chromatography (1-chlorobutane) and crystallization (heptane) to give yellow crystals of 2-[4-(4-butylcyclohexyl)phenyl]-5-isothiocyanato-pyrazine.

[0723] Phase sequence [0724] K 99 SmA 134 N 233 I. [0725] ??=8.9 [0726] ?n=0.3189

Synthesis Example 2: 2-[2-(4-Butylphenyl)ethynyl]-5-isothiocyanato-pyrazine

Step 2.1: 5-[2-(4-Butylphenyl)ethynyl]pyrazin-2-amine

[0727] ##STR00458##

[0728] A solution of 1-butyl-4-ethynyl-benzene (CAS 79887-09-5, 5.1 g, 32 mmol), 5-bromopyrazin-2-amine (CAS 59489-71-3, 5.0 g, 28.7 mmol) and diisopropylamine (70 ml) in THE (70 ml) is treated with copper(I)iodide (5.5 mg), chloro(2-dicyclohexylphosphino-2,4,6-triisopropyl-1,1-biphenyl)(2-amino-1,1-biphenyl-2-yl)palladium(II) (46 mg) and 2-dicyclohexylphosphino-2,4,6-tri-isopropyl-1,1-biphenyl (28 mg) under argon atmosphere at room temperature. The reaction mixture is stirred at 70? C. overnight. Then it is cooled down to room temperature and concentrated in vacuo. The residue is purified by silica gel chromatography (heptane and dichloromethane) to give 5-[2-(4-butylphenyl)ethynyl]pyrazin-2-amine as a brown solid.

Step 2.2: 2-[2-(4-Butylphenyl)ethynyl]-5-isothiocyanato-pyrazine

[0729] ##STR00459##

[0730] A solution of 5-[2-(4-butylphenyl)ethynyl]pyrazin-2-amine (7.8 g, 31 mmol) and DABCO (10.4 g, 93 mmol) in dichloromethane (100 ml) is cooled to 0? C. and treated with thiophosgene (3.7 ml, 47 mmol). The suspension is stirred at room temperature overnight. Then it is hydrolyzed with dist. water and brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (heptane and dichloromethane) and crystallization (heptane). 2-[2-(4-Butylphenyl)ethynyl]-5-isothiocyanato-pyrazine is isolated as a beige solid.

[0731] Phase sequence: K 67 N 72 I. [0732] ??=10.3 [0733] ?n=0.4282 [0734] ?1=61 mPas

Synthesis Example 3: 5-[4-(4-Butylcyclohexyl)phenyl]-4-fluoro-2-isothiocyanato-pyridine

Step 3.1: 5-[4-(4-Butylcyclohexyl)phenyl]-4-fluoro-pyridin-2-amine

[0735] ##STR00460##

[0736] A mixture of [4-(4-butylcyclohexyl)phenyl]boronic acid (CAS 516510-90-0, 5.5 g, 21 mmol), 5-bromo-4-fluoro-pyridin-2-amine (2) (CAS 944401-69-8, 4.0 g, 20 mmol) and potassium carbonate (5.7 g, 41 mmol) in dist. water (20 ml) and 1,4-dioxane (80 ml) is treated with [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II)-dichloromethane complex (0.9 g, 1 mmol) at room temperature under argon atmosphere. The reaction mixture is stirred at 90? C. overnight. Then it is cooled down to room temperature and filtered through Celite. The filtrate is diluted with MTB ether and dist. water. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with brine, dried (sodium sulfate), filtered and concentrated in vacuo. The residue is purified by silica gel chromatography (MTB ether) to give yellow crystals of 5-[4-(4-butylcyclohexyl)phenyl]-4-fluoro-pyridin-2-amine.

Step 3.2: 5-[4-(4-Butylcyclohexyl)phenyl]-4-fluoro-2-isothiocyanato-pyridine

[0737] ##STR00461##

[0738] Thiophosgene (1.8 ml, 23 mmol) is slowly added to a solution of 5-[4-(4-butylcyclohexyl)phenyl]-4-fluoro-pyridin-2-amine (6.1 g, 19 mmol) and DABCO (5.3 g, 47 mmol) in dichloromethane (120 ml) at 0? C. under argon atmosphere, and the reaction mixture is stirred at room temperature overnight. Then it is quenched with dist. water and brine. The aqueous phase is separated and extracted with dichloromethane.

[0739] The combined organic phases are washed with brine, dried (sodium sulfate), filtered and concentrated in vacuo. The residue is purified by silica gel chromatography (1-chlorobutane) and crystallization (heptane) to give yellow crystals of 5-[4-(4-butylcyclohexyl)phenyl]-4-fluoro-2-isothiocyanato-pyridine.

[0740] Phase sequence: K 60 N 169 I. [0741] ??=7.3 [0742] ?n=0.2549

Synthesis Example 4: 5-[4-(4-Butylcyclohexyl)phenyl]-4-chloro-2-isothiocyanato-pyridine

Step 4.1: 5-[4-(4-Butylcyclohexyl)phenyl]-4-chloro-pyridin-2-amine

[0743] ##STR00462##

[0744] A mixture of [4-(4-butylcyclohexyl)phenyl]boronic acid (CAS 516510-90-0, 4.2 g, 16.1 mmol), 5-bromo-4-chloro-pyridin-2-amine (CAS 942947-94-6, 3.5 g, 16 mmol) and potassium carbonate (4.5 g, 33 mmol) in 1,4-dioxane (60 ml) and dist. water (15 ml) is treated with [1,1-bis(diphenylphosphino)ferrocene]-dichloropalladium(II)-dichloromethane complex (680 mg, 0.8 mmol) at room temperature under argon atmosphere, and the reaction mixture is stirred at reflux temperature overnight. Then it is cooled down to room temperature, diluted with MTB ether and dist. water, and filtered over Celite. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with dist. water and brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (MTB ether) to give 5-[4-(4-butylcyclohexyl)phenyl]-4-chloro-pyridin-2-amine (3) as a grey solid.

Step 4.2: 5-[4-(4-Butylcyclohexyl)phenyl]-4-chloro-2-isothiocyanato-pyridine

[0745] ##STR00463##

[0746] A solution of 5-[4-(4-butylcyclohexyl)phenyl]-4-chloro-pyridin-2-amine (5.2 g, 15 mmol) and DABCO (4.3 g, 38 mmol) in dichloromethane (150 ml) is cooled to 0? C. and treated with thiophosgene (1.5 ml, 19 mmol). The suspension is stirred at room temperature overnight. Then it is hydrolyzed with dist. water, filtered over silica gel and concentrated in vacuo. The residue is purified by silica gel chromatography (1-chlorobutane) and crystallization (heptane). 5-[4-(4-butylcyclohexyl)phenyl]-4-chloro-2-isothiocyanato-pyridine is isolated as a yellow solid.

[0747] Phase sequence: K 70 N 89 I. [0748] ??=6.31 [0749] ?n=0.2082

Synthesis Example 5: 5-[4-(4-Butylcyclohexyl)phenyl]-3-chloro-2-isothiocyanato-pyrazine

Step 5.1: 5-[4-(4-Butylcyclohexyl)phenyl]-3-chloro-pyrazin-2-amine

[0750] ##STR00464##

[0751] A mixture of [4-(4-butylcyclohexyl)phenyl]boronic acid (CAS 516510-90-0, 4.4 g, 17 mmol), 5-bromo-3-chloro-pyrazin-2-amine (CAS 38185-55-6, 3.5 g, 17 mmol) and potassium carbonate (4.7 g, 34 mmol) in 1,4-dioxane (60 ml) and dist. water (15 ml) is treated with [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(Il)-dichloromethane complex (700 mg, 0.8 mmol) at room temperature under argon atmosphere, and the reaction mixture is stirred at reflux temperature overnight. Then it is cooled down to room temperature, diluted with MTB ether and dist. water, and filtered over Celite. The aqueous phase is separated and extracted with MTB ether. The combined organic phases are washed with dist. water and brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (dichloromethane) to give 5-[4-(4-butylcyclohexyl)phenyl]-3-chloro-pyrazin-2-amine as an orange solid.

Step 5.2: 5-[4-(4-Butylcyclohexyl)phenyl]-3-chloro-2-isothiocyanato-pyrazine

[0752] ##STR00465##

[0753] A solution of 5-[4-(4-butylcyclohexyl)phenyl]-3-chloro-pyrazin-2-amine (5.4 g, 15 mmol) and DABCO (4.2 g, 37 mmol) in dichloromethane (100 ml) is cooled to 0? C. and treated with thiophosgene (1.5 ml, 19 mmol). The suspension is stirred at room temperature overnight. Then it is hydrolyzed with dist. water, filtered over silica gel and concentrated in vacuo. The residue is purified by silica gel chromatography (1-chlorobutane) and crystallization (n-heptane). 5-[4-(4-Butylcyclohexyl)phenyl]-3-chloro-2-isothiocyanato-pyrazine is isolated as a yellow solid.

[0754] Phase sequence: Tg ?35 K 46 N 61 I.

[0755] ??=6.9

[0756] ?n=0.2592

[0757] In analogy to Synthesis Examples 1 to 5 the following compounds are obtained:

TABLE-US-00007 No. Compound 5 [00466]embedded image 6 [00467]embedded image 7 [00468]embedded image 8 [00469]embedded image 9 [00470]embedded image 10 [00471]embedded image 11 [00472]embedded image 12 [00473]embedded image 13 [00474]embedded image 14 [00475]embedded image 15 [00476]embedded image 16 [00477]embedded image 17 [00478]embedded image 18 [00479]embedded image 19 [00480]embedded image 20 [00481]embedded image 21 [00482]embedded image 22 [00483]embedded image 23 [00484]embedded image 24 [00485]embedded image 25 [00486]embedded image 26 [00487]embedded image 27 [00488]embedded image 28 [00489]embedded image 29 [00490]embedded image 30 [00491]embedded image 31 [00492]embedded image 32 [00493]embedded image 33 [00494]embedded image 34 [00495]embedded image 35 [00496]embedded image 36 [00497]embedded image 37 [00498]embedded image 38 [00499]embedded image 39 [00500]embedded image 40 [00501]embedded image 41 [00502]embedded image 42 [00503]embedded image 43 [00504]embedded image 44 [00505]embedded image 45 [00506]embedded image 46 [00507]embedded image 47 [00508]embedded image 48 [00509]embedded image 49 [00510]embedded image 50 [00511]embedded image 51 [00512]embedded image 52 [00513]embedded image 53 [00514]embedded image 54 [00515]embedded image 55 [00516]embedded image 56 [00517]embedded image 57 [00518]embedded image 58 [00519]embedded image 59 [00520]embedded image 60 [00521]embedded image 61 [00522]embedded image 62 [00523]embedded image 63 [00524]embedded image 64 [00525]embedded image 65 [00526]embedded image 66 [00527]embedded image 67 [00528]embedded image 68 [00529]embedded image 69 [00530]embedded image 70 [00531]embedded image 71 [00532]embedded image 72 [00533]embedded image 73 [00534]embedded image 74 [00535]embedded image 75 [00536]embedded image 76 [00537]embedded image 77 [00538]embedded image 78 [00539]embedded image 79 [00540]embedded image 80 [00541]embedded image 81 [00542]embedded image 82 [00543]embedded image 83 [00544]embedded image 84 [00545]embedded image 85 [00546]embedded image 86 [00547]embedded image 87 [00548]embedded image 88 [00549]embedded image 89 [00550]embedded image 90 [00551]embedded image 91 [00552]embedded image 92 [00553]embedded image 93 [00554]embedded image 94 [00555]embedded image 95 [00556]embedded image 96 [00557]embedded image 97 [00558]embedded image 98 [00559]embedded image 99 [00560]embedded image 100 [00561]embedded image 101 [00562]embedded image 102 [00563]embedded image 103 [00564]embedded image 104 [00565]embedded image 105 [00566]embedded image 106 [00567]embedded image 107 [00568]embedded image 108 [00569]embedded image 109 [00570]embedded image 110 [00571]embedded image 111 [00572]embedded image 112 [00573]embedded image 113 [00574]embedded image 114 [00575]embedded image 115 [00576]embedded image 116 [00577]embedded image 117 [00578]embedded image 118 [00579]embedded image 119 [00580]embedded image 120 [00581]embedded image

MIXTURE EXAMPLES

[0758] Liquid-crystal mixtures H1, H2, and M1 to M11 having the compositions and properties as indicated in the following tables are prepared and characterized with respect to their general physical properties and their applicability in microwave components at 19 GHz and 20? C.

TABLE-US-00008 Host Mixture H1 ST-3b-1 0.12 T(N,I) [? C.]: 151 PTU-3-S 15.98 ?n [589 nm, 20? C.]: 0.3779 PGU-3-S 13.98 n.sub.e [589 nm, 20? C.]: 1.9169 PPTU-5-S 19.98 n.sub.o [589 nm, 20? C.]: 1.5390 CPU-2-S 34.96 ?? [1 kHz, 20? C.]: 22.7 CPU-4-S 14.98 ?.sub.? [1 kHz, 20? C.]: 27.0 ? 100.0 ?.sub.? [1 kHz, 20? C.]: 4.4 ?.sub.1 [mPa s, 20? C.]: 384 K.sub.1 [pN, 20? C.]: 16.8 K.sub.3 [pN, 20? C.]: 21.6 K.sub.3/K.sub.1 [pN, 20? C.]: 1.29 V.sub.0 [V, 20? C.]: 0.91 LTS bulk [h, ?20? C.]: 1000 LTS bulk [h, ?30? C.]: 216 ?.sub.r,? [20? C., 19 GHz]: 3.59 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0059 ?.sub.r,? [20? C., 19 GHz]: 2.47 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0106 ? [20? C., 19 GHz]: 0.311 ? [20? C., 19 GHz]: 29.3 Host Medium H2 PTP(2)TP-6-3 100.0 T(N,I) [? C.]: 114.5 ? 100.0 ?? [1 kHz, 20? C.]: 0.8 ?.sub.? [1 kHz, 20? C.]: 3.4 ?.sub.? [1 kHz, 20? C.]: 2.6 ?.sub.1 [mPa s, 20? C.]: 2100 K.sub.1 [pN, 20? C.]: 12.8 K.sub.3 [pN, 20? C.]: 48.1 K.sub.3/K.sub.1 [pN, 20? C.]: 3.76 V.sub.0 [V, 20? C.]: 4.11 ?.sub.r,? [20? C., 19 GHz]: 3.21 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0027 ?.sub.r,? [20? C., 19 GHz]: 2.33 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0062 ? [20? C., 19 GHz]: 0.274 ? [20? C., 19 GHz]: 44.1 Host Mixture H3 ST-3b-1 0.12% T(N,I) [? C.]: 158 PPTU-4-S 5.9928% ?n [589 nm, 20? C.]: 0.4015 PPTU-5-S 14.982% n.sub.e [589 nm, 20? C.]: 1.9286 PPU-TO-S 15.9808% n.sub.o [589 nm, 20? C.]: 1.5271 CPTU-5-S 24.97% ?? [1 kHz, 20? C.]: 15.0 PTU-3-S 9.988% ?.sub.? [1 kHz, 20? C.]: 18.6 PTU-5-S 9.988% ?.sub.? [1 kHz, 20? C.]: 3.6 CPU(F.F)-4-S 17.9784% ?.sub.1 [mPa s, 20? C.]: 492 ? 100.0% K.sub.1 [pN, 20? C.]: 17.6 K.sub.3 [pN, 20? C.]: 24.4 K.sub.3/K.sub.1 [pN, 20? C.]: 1.39 V.sub.0 [V, 20? C.]: 1.14 ?.sub.r,? [20? C., 19 GHz]: 3.59 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0052 ?.sub.r,? [20? C., 19 GHz]: 2.42 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0084 ? [20? C., 19 GHz]: 0.328 ? [20? C., 19 GHz]: 39.0 Mixture Example M1 CPPz-4-S 10.0% ?.sub.r,? [20? C., 19 GHz]: 3.53 H1 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0058 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.43 tan ?.sub.? .sub.r,?[20? C., 19 GHz]: 0.0099 ? [20? C., 19 GHz]: 0.312 ? [20? C., 19 GHz]: 31.6

[0759] Addition of the compound CPPz-4-S according to the invention to the medium H1 results in an improvement of the figure of merit h from 29.3 to 31.6 due to a significantly lower dielectric loss tan ?.sub.?r,?.

TABLE-US-00009 Mixture Example M2 P(2)TPz-4-S 10.0 % ?.sub.r,? [20? C., 19 GHz]: 3.51 H1 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0058 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.45 tan ?.sub.? .sub.r,?[20? C., 19 GHz]: 0.0099 ? [20? C., 19 GHz]: 0.303 ? [20? C., 19 GHz]: 30.7 Mixture Example M3 CPN(4CI-4-S 10.0 % ?.sub.r,? [20? C., 19 GHz]: 3.51 H1 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0060 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.50 tan ?.sub.? .sub.r,?[20? C., 19 GHz]: 0.0098 ? [20? C., 19 GHz]: 0.286 ? [20? C., 19 GHz]: 29.2 Mixture Example M4 CPPz(CI)-4-S 10.0 % ?.sub.r,? [20? C., 19 GHz]: 3.53 H1 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0057 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.48 tan ?.sub.? .sub.r,?[20? C., 19 GHz]: 0.0099 ? [20? C., 19 GHz]: 0.300 ? [20? C., 19 GHz]: 30.4 Mixture Example M5 PTPz4-S 10.0 % ?.sub.r,? [20? C., 19 GHz]: 3.65 H1 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0063 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.51 tan ?.sub.? .sub.r,?[20? C., 19 GHz]: 0.0113 ? [20? C., 19 GHz]: 0.312 ? [20? C., 19 GHz]: 27.7 Mixture Example M6 PPTU-4-S 6.0% T(N,I) [? C.]: 149 PPTU-5-S 15.0 % PPU-TO-S 3.0 % CPTU-5-S 5.0 % CPU(F.F)-4-S 18.0 % PTPz-4-S 3.0 % CPNI(2CI) 13.0 % CPPz-4-S 2.0 % CPPz(CI)-4-S 13.0 % CPN(4F)-4-S 13.0 % CPN(4CI)-4-S 7.0 % CPMI-4-S 2.0 % ? 100.0 % Mixture Example M7 CPTU-5-S 20.0% T(N,I) [? C.]: 160 M6 80.0% ?? [1 kHz, 20? C.]: 9.7 ? 100.0% ?.sub.? [1 kHz, 20? C.]: 13.5 ?.sub.? [1 kHz, 20? C.]: 3.7 K.sub.1 [pN, 20? C.]: 15.8 K.sub.3 [pN, 20? C.]: 18.0 K.sub.3/K.sub.1 [pN, 20? C.]: 1.14 V.sub.0 [V, 20? C.]: 1.33 ?.sub.r,? [20? C., 19 GHz]: 3.40 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0039 ?.sub.r,? [20? C., 19 GHz]: 2.45 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0050 ? [20? C., 19 GHz]: 0.280 ? [20? C., 19 GHz]: 56.0 Mixture Example M8 PPU-TO-S 20.0% T(N,I) [? C.]: 151.5 M6 80.0% ?? [1 kHz, 20? C.]: 7.6 ? 100.0% ?.sub.? [1 kHz, 20? C.]: 11.3 ?.sub.? [1 kHz, 20? C.]: 3.7 K.sub.1 [pN, 20? C.]: 14.0 K.sub.3 [pN, 20? C.]: 15.2 K.sub.3/K.sub.1 [pN, 20? C.]: 1.08 V.sub.0 [V, 20? C.]: 1.42 ?.sub.r,? [20? C., 19 GHz]: 3.41 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0045 ?.sub.r,? [20? C., 19 GHz]: 2.43 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0057 ? [20? C., 19 GHz]: 0.287 ? [20? C., 19 GHz]: 50.3 Mixture Example M9 PTN(4F)-4-S 10.0 % ?.sub.r,? [20? C., 19 GHz]: 3.60 H1 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0064 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.49 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0112 ? [20? C., 19 GHz]: 0.307 ? [20? C., 19 GHz]: 27.4 Mixture Example M10 PTPN(4F)-4-S 10.0% ?.sub.r,? [20? C., 19 GHz]: 3.61 H1 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0058 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.46 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0103 ? [20? C., 19 GHz]: 0.320 ? [20? C., 19 GHz]: 31.1 Mixture Example M11 PTP(2)TP-6-3 80.0 T(N,I) [? C.]: 108 CPPz-4-S 0.5 ?? [1 kHz, 20? C.]: 2.1 P(2)TPz-4-S 8.0 ?.sub.? [1 kHz, 20? C.]: 5.0 CPN(4CI)-4-S 3.0 ?.sub.? [1 kHz, 20? C.]: 2.9 CPPz(CI)-4-S 5.0 ?.sub.r,? [20? C., 19 GHz]: 3.26 PTPz4-S 3.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0028 PTN(4F)-4-S 0.5 ?.sub.r,? [20? C., 19 GHz]: 2.45 ? 100.0 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0059 ? [20? C., 19 GHz]: 0.247 ? [20? C., 19 GHz]: 41.9 Mixture Example M12 ST-3b-1 0.12 T(N,I) [? C.]: 148 PTU-3-S 10.98 PTP(1)-3-S 4.98 PGU-3-S 13.98 PPTU-5-S 19.98 CPU-2-S 34.98 CPU-4-S 14.98 ? 100.0 Mixture Example M13 ST-3b-1 0.12 T(N,I) [? C.]: 150 PTU-3-S 10.98 PGU-3-S 13.98 PPTN(4F)-4(1.sup.[2])-S 4.98 PPTU-5-S 19.98 CPU-2-S 34.98 CPU-4-S 14.98 ? 100.0 Mixture Example M14 PPTU-(c3)1-S 6.0 % T(N,I) [? C.]: 146 PPTU-5-S 15.0 % PPU-TO-S 3.0 % CPTU-5-S 5.0 % CPU(F.F)-4-S 18.0 % PTPz-4-S 3.0 % CPNI(2CI) 13.0 % CPPz-4-S 2.0 % CPPz(CI)-4-S 13.0 % CPN(4F)-4-S 13.0 % CPN(4CI)-4-S 7.0 % CPMI-4-S 2.0 % ? 100.0 % Mixture Example M15 PPTU-4-S 6.0 % PPTU-5-S 15.0 % PPU-TO-S 3.0 % CPTU-5-S 5.0 % CPU(F.F)-4-S 18.0 % PTPz-4-S 3.0 % CPNI(2CI) 13.0 % CPPz-4-S 2.0 % CPPz(CI)-4-S 13.0 % CPN(4F)-(c3)1-S 13.0 % CPN(4CI)-4-S 7.0 % CPMI-4-S 2.0 % ? 100.0 % Mixture Example M16 PPTU-4-S 6.0 % PPTU-5-S 15.0 % PPU-TO-S 3.0 % CPTU-5-S 5.0 % CPU(F.F)-4-S 18.0 % PTPz-4-S 3.0 % CPNI(2CI) 13.0 % CPPz-4-S 2.0 % CPPz(CI)-4-S 13.0 % CPN(4F)-(c5)-S 13.0 % CPN(4CI)-4-S 7.0 % CPMI-4-S 2.0 % ? 100.0 % Mixture Example M17 PTP(2)TP-6-3 80.0 T(N,I) [? C.]: 108 CPPz-4-S 0.5 ?? [1 kHz, 20? C.]: 2.1 CPN(4F)-4-S 8.0 ?.sub.? [1 kHz, 20? C.]: 5.0 CPN(4CI)-4-S 3.0 ?.sub.? [1 kHz, 20? C.]: 2.9 CPPz(CI)-4-S 5.0 ?.sub.r,? [20? C., 19 GHz]: 3.26 PTPz-4-S 3.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0028 PTN(4F)-4-S 0.5 ?.sub.r,? [20? C., 19 GHz]: 2.45 ? 100.0 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0059 ? [20? C., 19 GHz]: 0.247 ? [20? C., 19 GHz]: 41.9 Mixture Example M18 PTN(4F)-4-S 10.0 ?.sub.r,? [20? C., 19 GHz]: 3.60 H1 90.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0064 ? 100.0 ?.sub.r,? [20? C., 19 GHz]: 2.49 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0112 ? [20? C., 19 GHz]: 0.307 ? [20? C., 19 GHz]: 27.4 Mixture Example M19 CPPz(CI)I-4-S 10.0 ?.sub.r,? [20? C., 19 GHz]: 3.54 H1 90.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0057 ? 100.0 ?.sub.r,? [20? C., 19 GHz]: 2.46 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0098 ? [20? C., 19 GHz]: 0.305 ? [20? C., 19 GHz]: 31.1 Mixture Example M20 P(2)TPz-4-S 10.0 ?.sub.r,? [20? C., 19 GHz]: 3.52 H1 90.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0062 ? 100.0 ?.sub.r,? [20? C., 19 GHz]: 2.45 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0101 ? [20? C., 19 GHz]: 0.305 ? [20? C., 19 GHz]: 30.2 Mixture Example M21 PTPN(4F)-4-S 10.0 ?.sub.r,? [20? C., 19 GHz]: 3.61 H1 90.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0058 ? 100.0 ?.sub.r,? [20? C., 19 GHz]: 2.46 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0103 ? [20? C., 19 GHz]: 0.320 ? [20? C., 19 GHz]: 31.1 Mixture Example M22 PTPPz-4-S 10.0 ?.sub.r,? [20? C., 19 GHz]: 3.66 H1 90.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0058 ? 100.0 ?.sub.r,? [20? C., 19 GHz]: 2.49 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0103 ? [20? C., 19 GHz]: 0.320 ? [20? C., 19 GHz]: 31.2 Mixture Example M23 PPTN(4F)-4(1.sup.[2])-S 10.0 ?.sub.r,? [20? C., 19 GHz]: 3.56 H1 90.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0057 ? 100.0 ?.sub.r,? [20? C., 19 GHz]: 2.42 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0097 ? [20? C., 19 GHz]: 0.319 ? [20? C., 19 GHz]: 33.1 Mixture Example M24 Pz(F)I-4-S 10.0 ?.sub.r,? [20? C., 19 GHz]: 3.59 H1 90.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0063 ? 100.0 ?.sub.r,? [20? C., 19 GHz]: 2.46 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0112 ? [20? C., 19 GHz]: 0.316 ? [20? C., 19 GHz]: 28.3 Mixture Example M25 PPTPz-4-S 10.0 ?.sub.r,? [20? C., 19 GHz]: 3.62 H1 90.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0057 ? 100.0 ?.sub.r,? [20? C., 19 GHz]: 2.45 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0100 ? [20? C., 19 GHz]: 0.323 ? [20? C., 19 GHz]: 32.3 Mixture Example M26 PTPPz(F)I-4-S 10.0 ?.sub.r,? [20? C., 19 GHz]: 3.63 H1 90.0 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0059 ? 100.0 ?.sub.r,? [20? C., 19 GHz]: 2.46 tan ?.sub.? .sub.r,? [20? C., 19 GHz]: 0.0108 ? [20? C., 19 GHz]: 0.321 ? [20? C., 19 GHz]: 29.9