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HETEROAROMATIC ISOTHIOCYANATES

20240124780 · 2024-04-18

Assignee

Inventors

Cpc classification

International classification

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 ##STR00589## in which R.sup.N denotes H, alkyl or alkoxy each having 1 to 12 C atoms, or alkenyl, alkenyloxy or alkoxyalkyl each having 2 to 12 C atoms, in which one or more CH.sub.2-groups may be replaced by or ##STR00590## 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, CCCC or a single bond, X denotes CH, N, CF or CCl, Y.sup.1 and Y.sup.2, identically or differently, denote H, Cl, F, methyl or ethyl, ##STR00591## 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 be replaced by N and in which one or more H atoms may 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 be replaced by O and/or S and in which one or more H atoms may be replaced by F, 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 also 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, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, and t is 0, 1 or 2.

2. The compound according to claim 1, wherein the compound is selected from the compounds of the formulae N-1 to N-3 ##STR00592## ##STR00593## in which R.sup.N Z.sup.N1 Z.sup.N2, and have the meanings given in claim 1, Y.sup.1 and Y.sup.2, identically or differently, denote H, F, Cl or CH.sub.3, and t is 0 or 1.

3. The compound according to claim 1, wherein ##STR00594## independently of one another, denote ##STR00595## where ##STR00596## alternatively denotes ##STR00597## and L.sup.1 and L.sup.2 identically or differently, denote H, F, Cl or alkyl having 1 to 12 C atoms or alkenyl having 2 to 12 C atoms or branched or cyclic alkyl or alkenyl each having 3 to 12 C atoms.

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

5. The compound according to claim 1, wherein the compound is selected from the group consisting of the formulae N-1-1 to N-1-12 and N-2-1 ##STR00598## ##STR00599## ##STR00600## in which L.sup.1 and L.sup.2, identically or differently, denote H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and R.sup.N, Y.sup.1 and Y.sup.2 have the meanings given in claim 1.

6. The compound according to claim 1, wherein one or both of Y.sup.1 and Y.sup.2 denote H.

7. The compound according to claim 1, wherein R.sup.N denotes alkyl having 1 to 12 C atoms.

8. The compound according to claim 1, wherein the group R.sup.N denotes R.sup.P as defined in claim 1.

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

10. The liquid crystal medium according to claim 9, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae I, II and III, ##STR00601## 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 be replaced by ##STR00602## ##STR00603## on each occurrence, 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, and wherein ##STR00605## alternatively denotes ##STR00606## 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 be replaced by ##STR00607## Z.sup.21 denotes trans-CH?CH, trans-CF?CF or CC, and ##STR00608## independently of one another, denote ##STR00609## 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 be replaced by ##STR00610## one of Z.sup.31 and Z.sup.32, denotes trans-CH?CH, trans-CF?CF or CC and the other one, independently thereof, denotes CC, trans-CH?CH, trans-CF?CF or a single bond, and ##STR00611## independently of one another, denote ##STR00612## in which R.sup.L, on each occurrence identically or differently, denotes H or alkyl having 1 to 6 C atoms, and wherein ##STR00613## alternatively denotes or ##STR00614##

11. The liquid-crystal medium according to claim 10, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae I-1 to I-5 ##STR00615## 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, ##STR00616## and have the meanings given for formula I in claim 10.

12. The liquid-crystal medium according to claim 10, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae II-1 to II-3 ##STR00617## in which R.sup.2, ##STR00618## and have the meanings given in claim 10 for formula II.

13. The liquid-crystal medium according to claim 10, wherein the medium comprises one or more compounds selected from the group of compounds of the formulae III-1 to III-6 ##STR00619## in which R.sup.3, ##STR00620## and have the meanings given in claim 10 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 CC.

14. The liquid-crystal medium according to claim 9, wherein the medium comprises one or more compounds of the formula T ##STR00621## 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 or fluorinated alkenyl having up to 12 C atoms, ##STR00622## on each occurrence, independently of one another, denote ##STR00623## L.sup.4 and L.sup.5 identically or differently, denote F, Cl or straight chain or branched or cyclic alkyl or alkenyl each having up to 12 C atoms; Z.sup.T3 Z.sup.T4 identically or differently, denote CH?CH, CF?CF, CH?CF, CF?CH, CC or a single bond, and t is 0 or 1.

15. A component for high-frequency technology, characterized in that it comprises the liquid crystal medium according to claim 9.

16. The component according to claim 15, 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.

17. A microwave antenna array, characterized in that it comprises one or more components according to claim 15.

Description

EXAMPLES

[0556] 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

[0557] RT room temperature (20? C.?1? C.) [0558] THF Tetrahydrofuran [0559] MTB ether Methyl-tert-butyl ether [0560] dist. distilled [0561] XPhos 2-Dicyclohexylphosphino-2,4,6-triisopropylbiphenyl [0562] XPhos Pd G2 Chloro(2-dicyclohexylphosphino-2,4,6-triisopropyl-1,1-biphenyl)[2-(2-amino-1,1-biphenyl)palladium (II)

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

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

[0563] ##STR00408##

[0564] A mixture of [4-(4-butylcyclohexyl)phenyl]boronic acid (CAS-no. 516510-90-0) (5.1 g, 19.7 mmol), 2-bromopyrimidin-5-amine (CAS-no.1072-97-5) (3.0 g, 16.4 mmol), potassium carbonate (6.8 g, 49.1 mmol) in ethanol (7.6 ml), dist. water (7.6 ml) and toluene (25.4 ml) is treated with bis(triphenylphosphine)palladium(II)dichloride (345 mg), heated to reflux and stirred under argon atmosphere at reflux temperature overnight. It is cooled down to RT and concentrated in vacuo. The residue is purified by silica gel chromatography (dichloromethane and ethyl acetate) to give 2-[4-(4-butylcyclohexyl)phenyl]pyrimidin-5-amine as a colorless solid.

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

[0565] ##STR00409##

[0566] A solution of 2-[4-(4-butylcyclohexyl)phenyl]pyrimidin-5-amine (6.1 g, 19.7 mmol) and DABCO (5.5 g, 49.3 mmol) in dichloromethane (75 ml) is cooled to 0? C., and thiophosgene (2.1 ml, 27.4 mmol) is added dropwise by syringe. The suspension is stirred at RT for 1 h. Then the reaction mixture is hydrolyzed with dist. water and brine. The mixture is stirred for 5 min, then the aqueous phase is separated and extracted with dichloromethane. The combined organic phases are washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (n-heptane and toluene) and crystallization (n-heptane) to give 2-[4-(4-butylcyclohexyl)phenyl]-5-isothiocyanato-pyrimidine as a colorless solid.

[0567] Phase sequence: K 128 I.

[0568] ??=3.72

[0569] ?n=0.3113

[0570] ?.sub.1=463 mPas

Example 2: 2-[4-(4-butylcyclohexyl)phenyl]-3-chloro-5-isothiocyanato-pyridine

Step 2.1: 6-[4-(4-butylcyclohexyl)phenyl]-5-chloro-pyridin-3-amine

[0571] ##STR00410##

[0572] A mixture of [4-(4-butylcyclohexyl)phenyl]boronic acid (CAS-no. 516510-90-0) (4.33 g, 16.5 mmol), 6-bromo-5-chloro-3 pyridinamine (CAS-no.130284-52-5) (3.5 g, 16.5 mmol), potassium carbonate (4.6 g, 33.3 mmol) in dioxane (60 ml), dist. water (15 ml) is treated with bis(triphenylphosphine)-palladium(II)dichloride (710 mg), heated up to reflux and stirred under argon atmosphere at reflux temperature overnight. It is then cooled down to RT and concentrated in vacuo. The residue is purified by silica gel chromatography (dichloromethane and ethyl acetate) to give 6-[4-(4-butylcyclohexyl)phenyl]-5-chloro-pyridin-3-amine as a colorless solid.

Step 2.2: 2-[4-(4-butylcyclohexyl)phenyl]-3-chloro-5-isothiocyanato-pyridine

[0573] ##STR00411##

[0574] A solution of 6-[4-(4-butylcyclohexyl)phenyl]-5-chloro-pyridin-3-amine (9) (5.3 g, 15.4 mmol) and DABCO (4.4 g, 39.2 mmol) in dichloromethane (100 ml) is cooled to 0? C., and thiophosgene (1.50 ml, 18.9 mmol) is added dropwise by syringe. The suspension is stirred at RT for 1 h. Then the reaction mixture is hydrolyzed with dist. water and brine. The mixture is stirred for 5 min, then aqueous phase is separated and extracted with dichloromethane. The combined organic phases are washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (n-heptane and toluene) and crystallization (n-heptane). 2-[4-(4-butylcyclohexyl)phenyl]-3-chloro-5-isothiocyanato-pyridine (10) is isolated as a colorless solid.

[0575] Phase sequence: K 69 N 112.9 I I.

[0576] ??=1.99

[0577] ?n=0.2351

Example 3: 2-[4-(4-butylcyclohexyl)phenyl]-5-isothiocyanato-pyridine

Step 3.1: 6-[4-(4-butylcyclohexyl)phenyl]pyridin-3-amine

[0578] ##STR00412##

[0579] A mixture of [4-(4-butylcyclohexyl)phenyl]boronic acid (CAS-no. 516510-90-0) (4.5 g, 17.3 mmol), 2-bromopyridin-5-amine (CAS-no.13534-97-9) (3.0 g, 16.8 mmol), potassium carbonate (4.7 g, 34 mmol) in dioxane (60 ml) and dist. water (15 ml) is treated with bis(triphenylphosphine)-palladium(II)dichloride (710 mg), heated to reflux and stirred under argon atmosphere at reflux temperature overnight. It is cooled down to RT and concentrated in vacuo. The residue is purified by silica gel chromatography (dichloromethane and ethyl acetate) to give 6-[4-(4-butylcyclohexyl)phenyl]pyridin-3-amine as a colorless solid.

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

[0580] ##STR00413##

[0581] A solution of 6-[4-(4-butylcyclohexyl)phenyl]pyridin-3-amine (4.5 g, 14.4 mmol) and DABCO (4.1 g, 36.5 mmol) in dichloromethane (50 ml) is cooled to 0? C., and thiophosgene (1.4 ml, 17.7 mmol) is added dropwise by syringe. The suspension is stirred at RT for 1 h and hydrolyzed 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) and concentrated in vacuo. The residue is purified by silica gel chromatography (n-heptane and toluene) and crystallization (n-heptane) to give 2-[4-(4-butylcyclohexyl)phenyl]-5-isothiocyanato-pyridine as a colorless solid.

[0582] Phase sequence: K 73 SmA 207 N 247.4 I

[0583] ??=5.42

[0584] ?n=0.3209

[0585] ?.sub.1=594 m Pas

Example 4: 6-[4-(4-butylcyclohexyl)phenyl]-2-chloro-3-isothiocyanato-pyridine

Step 4.1: 6-[4-(4-butylcyclohexyl)phenyl]-2-chloro-pyridin-3-amine

[0586] ##STR00414##

[0587] A mixture of [4-(4-butylcyclohexyl)phenyl]boronic acid (CAS-no. 516510-90-0) (4.3 g, 16.5 mmol), 6-bromo-2-chloro-3 pyridinamine (CAS-no.169833-70-9) (3.5 g, 16.5 mmol), potassium carbonate (4.6 g, 33 mmol) in dioxane (60 ml), dist. water (15 ml) is treated with bis(triphenylphosphine)-palladium(II)dichloride (700 mg), heated up to reflux and stirred under argon atmosphere at reflux temperature overnight. It is then cooled down to RT and concentrated in vacuo. The residue is purified by silica gel chromatography (dichloromethane and ethyl acetate) to give 6 6-[4-(4-butylcyclohexyl)phenyl]-2-chloro-pyridin-3-amine as a colorless solid.

[0588] Step 4.2: 6-[4-(4-butylcyclohexyl)phenyl]-2-chloro-3-isothiocyanato-pyridine

##STR00415##

[0589] A solution of 6-[4-(4-butylcyclohexyl)phenyl]-2-chloro-pyridin-3-amine (4.3 g, 12.5 mmol) and DABCO (3.6 g, 32 mmol) in dichloromethane (100 ml) is cooled to 0? C., and thiophosgene (2.1 ml, 27.4 mmol) is added dropwise by syringe. The suspension is stirred at RT for 1 h. Then the reaction mixture is hydrolyzed with dist. water and brine. The mixture is stirred for 5 min, then aqueous phase is separated and extracted with dichloromethane. The combined organic phases are washed with brine, dried (sodium sulfate) and concentrated in vacuo. The residue is purified by silica gel chromatography (n-heptane and toluene) and crystallization (n-heptane) to give 6-[4-(4-butylcyclohexyl)phenyl]-2-chloro-3-isothiocyanato-pyridine as a colorless solid.

[0590] Phase sequence: K 105 SmA (81) N 171.3 I.

[0591] ??=5.52

[0592] ?n=0.2989

[0593] In analogy to Synthesis Examples 1 to 4 the following compounds are obtained:

TABLE-US-00007 No. Compound 5 [00416]embedded image 6 [00417]embedded image 7 [00418]embedded image 8 [00419]embedded image 9 [00420]embedded image 10 [00421]embedded image 11 [00422]embedded image 12 [00423]embedded image 13 [00424]embedded image 14 [00425]embedded image 15 [00426]embedded image 16 [00427]embedded image 17 [00428]embedded image 18 [00429]embedded image 19 [00430]embedded image 20 [00431]embedded image 21 [00432]embedded image 22 [00433]embedded image 23 [00434]embedded image 24 [00435]embedded image 25 [00436]embedded image 26 [00437]embedded image K 56 SmA 102 N 206 I ?? = 3.01 ?n = 0.2997 ?.sub.1 = 325 mPas 27 [00438]embedded image 28 [00439]embedded image 29 [00440]embedded image 30 [00441]embedded image 31 [00442]embedded image 32 [00443]embedded image 33 [00444]embedded image 34 [00445]embedded image 35 [00446]embedded image 36 [00447]embedded image 37 [00448]embedded image 38 [00449]embedded image 39 [00450]embedded image 40 [00451]embedded image 41 [00452]embedded image 42 [00453]embedded image 43 [00454]embedded image 44 [00455]embedded image 45 [00456]embedded image 46 [00457]embedded image 47 [00458]embedded image 48 [00459]embedded image 49 [00460]embedded image 50 [00461]embedded image 51 [00462]embedded image 52 [00463]embedded image 53 [00464]embedded image 54 [00465]embedded image 55 [00466]embedded image 56 [00467]embedded image 57 [00468]embedded image 58 [00469]embedded image 59 [00470]embedded image 60 [00471]embedded image 61 [00472]embedded image 62 [00473]embedded image 63 [00474]embedded image 64 [00475]embedded image 65 [00476]embedded image 66 [00477]embedded image 67 [00478]embedded image 68 [00479]embedded image 69 [00480]embedded image 70 [00481]embedded image 71 [00482]embedded image 72 [00483]embedded image 73 [00484]embedded image 74 [00485]embedded image 75 [00486]embedded image 76 [00487]embedded image 77 [00488]embedded image 78 [00489]embedded image 79 [00490]embedded image 80 [00491]embedded image 81 [00492]embedded image 82 [00493]embedded image 83 [00494]embedded image 84 [00495]embedded image 85 [00496]embedded image 86 [00497]embedded image 87 [00498]embedded image 88 [00499]embedded image 89 [00500]embedded image 90 [00501]embedded image 91 [00502]embedded image 92 [00503]embedded image 93 [00504]embedded image 94 [00505]embedded image 95 [00506]embedded image 96 [00507]embedded image 97 [00508]embedded image 98 [00509]embedded image 99 [00510]embedded image 100 [00511]embedded image 101 [00512]embedded image 102 [00513]embedded image 103 [00514]embedded image 104 [00515]embedded image 105 [00516]embedded image 106 [00517]embedded image 107 [00518]embedded image 108 [00519]embedded image 109 [00520]embedded image 110 [00521]embedded image 111 [00522]embedded image 112 [00523]embedded image 113 [00524]embedded image 114 [00525]embedded image 115 [00526]embedded image 116 [00527]embedded image 117 [00528]embedded image 118 [00529]embedded image 119 [00530]embedded image 120 [00531]embedded image 121 [00532]embedded image 122 [00533]embedded image 123 [00534]embedded image 124 [00535]embedded image 125 [00536]embedded image 126 [00537]embedded image 127 [00538]embedded image 128 [00539]embedded image 129 [00540]embedded image K 80 I ?n = 0.3649 ?? = 3.92 ?.sub.1 = 88 mPas 130 [00541]embedded image 131 [00542]embedded image 132 [00543]embedded image 133 [00544]embedded image 134 [00545]embedded image 135 [00546]embedded image 136 [00547]embedded image 137 [00548]embedded image 138 [00549]embedded image 139 [00550]embedded image 140 [00551]embedded image 141 [00552]embedded image 142 [00553]embedded image 143 [00554]embedded image 144 [00555]embedded image 145 [00556]embedded image 146 [00557]embedded image 147 [00558]embedded image 148 [00559]embedded image 149 [00560]embedded image 150 [00561]embedded image 151 [00562]embedded image 152 [00563]embedded image 153 [00564]embedded image 154 [00565]embedded image 155 [00566]embedded image 156 [00567]embedded image 157 [00568]embedded image 158 [00569]embedded image 159 [00570]embedded image 160 [00571]embedded image 161 [00572]embedded image 162 [00573]embedded image 163 [00574]embedded image 164 [00575]embedded image 165 [00576]embedded image 166 [00577]embedded image 167 [00578]embedded image 168 [00579]embedded image 169 [00580]embedded image 170 [00581]embedded image 171 [00582]embedded image 172 [00583]embedded image 173 [00584]embedded image 174 [00585]embedded image 175 [00586]embedded image 176 [00587]embedded image 177 [00588]embedded image

Mixture Examples

[0594] Liquid-crystal mixtures H.sub.1 to H.sub.3 and M1 to M9 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 CPG-3-F 12.0% T(N, I) [? C.]: 92.5 CPG-5-F 10.0% ?n [589 nm, 20? C.]: 0.0969 CCEP-3-OT 5.0% n.sub.e [589 nm, 20? C.]: 1.5764 CCEP-5-OT 5.0% n.sub.o [589 nm, 20? C.]: 1.4795 CGPC-3-3 2.0% ?? [1 kHz, 20? C.]: 5.3 CGPC-5-3 2.0% ?.sub.? [1 kHz, 20? C.]: 8.4 CGPC-5-5 2.0% ?.sub.? [1 kHz, 20? C.]: 3.1 CP-6-F 8.0% ?.sub.1 [mPa s, 20? C.]: 128 CP-7-F 6.0% K.sub.1 [pN, 20? C.]: 13.2 CCP-2-OT 8.0% K.sub.3 [pN, 20? C.]: 19.6 CCP-3-OT 12.0% K.sub.3/K.sub.1 [pN, 20? C.]: 1.48 CCP-4-OT 7.0% V.sub.0 [V, 20? C.]: 1.66 CCP-5-OT 11.0% ? [20? C., 19 GHz]: 0.100 CP-5-F 10.0% ?.sub.r,? [20? C., 19 GHz]: 2.49 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.24 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0049 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0125 ? [20? C., 19 GHz]: 8.0 Host Mixture H2 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 LTS bulk [h, ?40? C.]: 0 ?.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.? r,? [20? C., 19 GHz]: 0.0106 ? [20? C., 19 GHz]: 0.311 ? [20? C., 19 GHz]: 29.3 Host Mixture H3 ST-3b-1 0.12% T(N, I) [? C.]: 153.5 PTU-3-S 5.99% ?n [589 nm, 20? C.]: 0.3716 PTU-5-S 9.99% n.sub.e [589 nm, 20? C.]: 1.9062 PPTU-4-S 5.99% n.sub.o [589 nm, 20? C.]: 1.5346 PPTU-5-S 9.99% ?? [1 kHz, 20? C.]: 16.4 CPU-2-S 25.97% ?.sub.? [1 kHz, 20? C.]: 20.3 CPU-4-S 19.98% ?.sub.? [1 kHz, 20? C.]: 3.9 PPU-TO-S 21.97% ?.sub.1 [mPa s, 20? C.]: 401 ? 100.0% K.sub.1 [pN, 20? C.]: 14.7 K.sub.3 [pN, 20? C.]: 23.8 K.sub.3/K.sub.1 [pN, 20? C.]: 1.62 V.sub.0 [V, 20? C.]: 1.01 LTS bulk [h, ?30? C.]: 1000 LTS bulk [h, ?40? C.]: 1000 ?.sub.r,? [20? C., 19 GHz]: 3.55 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0061 ?.sub.r,? [20? C., 19 GHz]: 2.43 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0101 ? [20? C., 19 GHz]: 0.315 ? [20? C., 19 GHz]: 31.1 Host Misture H4 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 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.? r,? [20? C., 19 GHz]: 0.0062 ? [20? C., 19 GHz]: 0.274 ? [20? C., 19 GHz]: 44.1 Mixture Example M1 CPMI-4-S 10.0% ?.sub.r,? [20? C., 19 GHz]: 2.58 H1 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0047 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.30 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0114 ? [20? C., 19 GHz]: 0.109 ? [20? C., 19 GHz]: 9.6

[0595] Addition of the compound CPMI-4-S according to the invention to the medium H.sub.1 results in an improvement of the figure of merit ? from 8.0 to 9.6 due to a higher tunability ti and a lower dielectric loss tan ?.sub.? r,?.

TABLE-US-00009 Mixture Example M2 CPNI-4-S 10.0% T(N, I) [? C.]: 159 H2 90.0% ?.sub.r,? [20? C., 19 GHz]: 3.54 ? 100.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0062 ?.sub.r,? [20? C., 19 GHz]: 2.46 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0118 ? [20? C., 19 GHz]: 0.306 ? [20? C., 19 GHz]: 26.0

[0596] Compared to the host mixture H.sub.2, the medium M2 has a significantly improved clearing temperature due to the presence of the compound CPNI-4-S according to the invention.

TABLE-US-00010 Mixture Example M3 CPNI(5Cl)-4-S 10.0% ?.sub.r,? [20? C., 19 GHz]: 3.51 H2 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0057 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.47 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0095 ? [20? C., 19 GHz]: 0.297 ? [20? C., 19 GHz]: 31.4

[0597] Addition of the compound CPNI(5Cl)-4-S according to the invention to the medium H.sub.2 results in an improvement of the figure of merit ? from 29.3 to 31.4 due to a lower dielectric loss tan ?.

TABLE-US-00011 Mixture Example M4 CPNI(2CI)-4-S 10.0% ?.sub.r,? [20? C., 19 GHz]: 3.56 H2 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0061 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.48 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0113 ? [20? C., 19 GHz]: 0.302 ? [20? C., 19 GHz]: 26.9

[0598] The compound CPNI(2Cl)-4-S is highly suitable for the use in a medium according to the invention due to its favourable application properties.

TABLE-US-00012 Mixture Example M5 CPMI-4-S 5.0% ?.sub.r,? [20? C., 19 GHz]: 3.51 H3 95.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0062 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.45 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0096 ? [20? C., 19 GHz]: 0.302 ? [20? C., 19 GHz]: 31.5

[0599] The medium M5 has a significantly lower dielectric loss than the host medium H.sub.3 alone, where the figure-of-merit is almost unchanged.

TABLE-US-00013 Mixture Example M6 CPMI-4-S 10.0% ?.sub.r,? [20? C., 19 GHz]: 3.52 H3 90.0% tan ?.sub.? r,? [20? C., 19 GHz]: 0.0059 ? 100.0% ?.sub.r,? [20? C., 19 GHz]: 2.42 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0092 ? [20? C., 19 GHz]: 0.312 ? [20? C., 19 GHz]: 33.9

[0600] Medium M6 shows that the effect shown in medium M5 is further improved when the concentration of the compound of formula CPMI-4-S according to the invention is increased from 5% to 10%.

TABLE-US-00014 Mixture Example M7 PPTU-4-S 6.0% T(N, I) [? C.]: 146 PPTU-5-S 15.0% ?? [1 kHz, 20? C.]: 14.2 CPTU-5-S 25.0% ?.sub.? [1 kHz, 20? C.]: 17.9 PTU-3-S 10.0% ?.sub.? [1 kHz, 20? C.]: 3.7 PTU-5-S 10.0% ?.sub.1 [mPa s, 20? C.]: 551 CPU(F.F)-3-S 18.0% K.sub.1 [pN, 20? C.]: 15.8 CPNI(5Cl)-4-S 16.0% K.sub.3 [pN, 20? C.]: 21.0 ? 100.0% K.sub.3/K.sub.1 [pN, 20? C.]: 1.33 V.sub.0 [V, 20? C.]: 1.12 ?.sub.r,? [20? C., 19 GHz]: 3.56 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0046 ?.sub.r,? [20? C., 19 GHz]: 2.47 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0069 ? [20? C., 19 GHz]: 0.305 ? [20? C., 19 GHz]: 44.2

[0601] Due to the presence of the compound CPNI(5Cl)-4-S according to the invention, mixture example M7 has a very high figure-of-merit h due to a high tunability and in particular a very low dielectric loss.

TABLE-US-00015 Mixture Example M8 PPTU-4-S 6.0% T(N, I) [? C.]: 155 PPTU-5-S 18.0% ?? [1 kHz, 20? C.]: 14.1 CPTU-5-S 26.0% ?.sub.? [1 kHz, 20? C.]: 17.7 PTU-3-S 8.0% ?.sub.? [1 kHz, 20? C.]: 3.6 PTU-5-S 8.0% ?.sub.1 [mPa s, 20? C.]: 596 CPU(F.F)-3-S 18.0% K.sub.1 [pN, 20? C.]: 16.7 CPNI(5Cl)-4-S 16.0% K.sub.3 [pN, 20? C.]: 21.7 ? 100.0% K.sub.3/K.sub.1 [pN, 20? C.]: 1.30 V.sub.0 [V, 20? C.]: 1.14 ?.sub.r,? [20? C., 19 GHz]: 3.54 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0042 ?.sub.r,? [20? C., 19 GHz]: 2.45 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0066 ? [20? C., 19 GHz]: 0.309 ? [20? C., 19 GHz]: 46.8

[0602] Due to the presence of the compound CPNI(5Cl)-4-S according to the invention, mixture example M8 has a very high figure-of-merit ? due to a high tunability and in particular a very low dielectric loss.

TABLE-US-00016 Mixture Example M9 H4 85.0 T(N, I) [? C.]: 112 CPNI(3CI)-4-S 14.0 ?? [1 kHz, 20? C.]: 1.0 CPMI-4-S 1.0 ?.sub.? [1 kHz, 20? C.]: 3.6 ? 100.0 ?.sub.? [1 kHz, 20? C.]: 2.6 ?.sub.r,? [20? C., 19 GHz]: 3.25 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0023 ?.sub.r,? [20? C., 19 GHz]: 2.40 tan ?.sub.? r,? [20? C., 19 GHz]: 0.0054 ? [20? C., 19 GHz]: 0.263 ? [20? C., 19 GHz]: 49.2

[0603] Addition of the compounds according to the invention to the host medium H.sub.4 results in an improved figure-of-merit due to a lower dielectric loss.