Liquid-crystalline media, components for high-frequency technology, and mesogenic compounds

Abstract

The present invention relates to a liquid-crystal medium which comprises a component A which consists of one or more compounds of the formula I ##STR00001##
in which the parameters have the respective meanings given in the claims or in the text, and to the corresponding, novel mesogenic compounds and to the preparation thereof. The present invention likewise relates to the use of these liquid-crystal media, in particular in components for high-frequency technology, and to components of this type which contain media according to the invention, and to the production and use of these components. The components according to the invention are suitable, in particular, as phase shifters in the microwave and millimeter wave region, for microwave and millimeter wave array antennae and very particularly for so-called tuneable reflectarrays.

Claims

1. A compound selected from the group of the compounds of the formulae I-3 and I-4, ##STR00347## in which R.sup.11 and R.sup.12, independently of one another, denote unfluorinated alkyl having 1 to 15 C atoms, unfluorinated alkenyl having 2 to 15 C atoms, or cycloalkyl, alkylcycloalkyl, cycloalkenyl, alkylcycloalkenyl, alkylcycloalkylalkyl or alkylcycloalkenylalkyl, each having up to 15 C atoms, and R.sup.13 and R.sup.14, independently of one another, denote unfluorinated alkyl or unfluorinated alkoxy, each having 1 to 15 C atoms, unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated 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 of R.sup.13 and R.sup.14 also denotes H.

2. A liquid crystal mixture comprising a compound selected from the group of the compounds of the formulae I-3 and I-4 of claim 1.

3. A liquid-crystal mixture according to claim 2, which comprises one or more compounds of the formula I-3.

4. A liquid-crystal mixture according to claim 2, which comprises one or more compounds of the formula I-4.

5. A liquid-crystal mixture according to claim 2, which further comprises one or more compounds of the formula I-1 or I-2: ##STR00348## in which L.sup.1 denotes alkyl having 1 to 6 C atoms, cycloalkyl having 3 to 6 C atoms or cycloalkenyl having 4 to 6 C atoms, X.sup.1 denotes H, alkyl having 1 to 3 C atoms or halogen, and R.sup.11 and R.sup.12, independently of one another, denote unfluorinated alkyl having 1 to 15 C atoms, unfluorinated alkenyl having 2 to 15 C atoms, or cycloalkyl, alkylcycloalkyl, cycloalkenyl, alkylcycloalkenyl, alkylcycloalkylalkyl or alkylcycloalkenylalkyl, each having up to 15 C atoms.

6. A liquid-crystal mixture according to claim 2, which additionally comprises one or more components selected from the group of the following components B to E: a strongly dielectrically positive component, component B, which has a dielectric anisotropy of 10 or more, a strongly dielectrically negative component, component C, which has a dielectric anisotropy having a value of 5 or more, a component D which has a dielectric anisotropy in the range from more than 5.0 to less than 10.0 and consists of compounds having seven or more five- or six-membered rings, and a component E which has a dielectric anisotropy in the range from more than 5.0 to less than 10.0 and consists of compounds having up to six five- or six-membered rings.

7. A liquid-crystal mixture according to claim 6, which comprises a component B.

8. A liquid-crystal mixture according to claim 6, which comprises a component C.

9. A liquid-crystal mixture according to claim 6, which comprises a component D.

10. A liquid-crystal mixture according to claim 6, which comprises a component E.

11. A liquid-crystal mixture according to claim 2, which further comprises one or more compounds of the formula VI: ##STR00349## in which L.sup.61 denotes R.sup.61 and, in the case where Z.sup.61 and/or Z.sup.62 denote trans-CHCH or trans-CFCF, alternatively also denotes X.sup.61, L.sup.62 denotes R.sup.62 and, in the case where Z.sup.61 and/or Z.sup.62 denote trans-CHCH or trans-CFCF, alternatively also denotes X.sup.62, R.sup.61 and R.sup.62, independently of one another, denote 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, X.sup.61 and X.sup.62, independently of one another, denote F or Cl, CN, NCS, SF.sub.5, fluorinated alkyl or alkoxy having 1 to 7 C atoms or fluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 7 C atoms, or NCS, one of Z.sup.61 and Z.sup.62 denotes trans-CHCH, trans-CFCF or CC and the other, independently thereof, denotes trans-CHCH, trans-CFCF or a single bond, and ##STR00350## to ##STR00351## independently of one another, denote ##STR00352##

12. A component for high-frequency technology, comprising a liquid-crystal mixture according to claim 2.

13. A microwave antenna array, comprising one or more components according to claim 12.

14. A compound of claim 1, which is a compound of formula I-3.

15. A compound of claim 1, which is a compound of formula I-4.

Description

EXAMPLES

(1) The following examples illustrate the present invention without limiting it in any way. However, it becomes 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.

(2) The acetylenes employed, if not commercially available, are synthesised in accordance with standard laboratory procedures.

(3) Example compounds of the formula I for component A

Substance Example 1

(4) ##STR00296##

(5) Phase sequence: C 87 C. N 178.5 C. I; n=0.436; =2.8.

Substance Example 2

(6) ##STR00297##

(7) Phase sequence: C 78 C. N 172.3 C. I; n=0.437; =2.6.

Substance Example 3

(8) ##STR00298##

(9) Phase sequence: C 107 C. N 211.0 C. I; n=0.464; =3.1.

Substance Example 4

(10) ##STR00299##

(11) Phase sequence: C 87 C. N 130.7 C. I; n=0.451; =2.1.

Substance Example 5

(12) ##STR00300##

(13) Phase sequence: C 57 C. N 151.7 C. I; n=0.445; =2.0.

Substance Example 6

(14) ##STR00301##

(15) Phase sequence: C 29 C. N 119.2 C. I; n=0.402; =1.7.

Substance Example 7

(16) ##STR00302##

(17) Phase sequence: T.sub.g 54 C. C 14 C. N 119.2 C. I; n=0.393; =1.8.

Substance Example 8

(18) ##STR00303##

(19) Phase sequence: C 60 C. N 121.8 C. I; n=0.394; =1.7.

Substance Example 9

(20) ##STR00304##

(21) Phase sequence: C 81 C. N 160.7 C. I; n=0.432; =3.2.

Substance Example 10

(22) ##STR00305##

Synthesis Example 10: 1,4-Bis(2-(4-butylphenyl)ethynyl)-2-cyclopropylbenzene

10.1) 1,4-Dichloro-2-cyclopropylbenzene 2

(23) ##STR00306##

(24) 20 g (73 mmol) of 1,4-dichloro-2-iodobenzene, 9.4 g (110 mmol) of cyclopropylboronic acid, 32 g (147 mmol) of potassium phosphate, 421 mg (0.7 mmol) of bis(dibenzylideneacetone)palladium(0) (Pd(dba).sub.2) and 1096 mg (1.5 mmol) of 1,2,3,4,5-pentaphenyl-1-(di-t-butylphosphine)ferrocene (CTC-Q-PHOS) are dissolved in 600 ml of toluene and heated at 100 C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with toluene (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography, giving the title compound as a colourless solid.

10.2) 1,4-Bis(2-(4-butylphenyl)ethynyl)-2-cyclopropylbenzene (1)

(25) ##STR00307##

(26) 5 g (26 mmol) of 1,4-dichloro-2-cyclopropylbenzene, 9.4 g (58 mmol) of 1-n-butyl-4-ethynylbenzene, 19 g (58 mmol) of caesium carbonate, 69 mg (0.3 mmol) of bis(acetonitrile)palladium(II) chloride and 382 mg (0.8 mmol) of 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl are dissolved in 80 ml of dioxane under nitrogen, and the mixture is heated at 100 C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography and recrystallised from ethanol, giving the title compound 1 as a solid.

(27) .sup.1H-NMR (250 MHz, CDCl.sub.3): 7.4-7.08 (11H, m); 2.5 (4H, m); 1.6-1.3 (9H, m); 0.96 (6H, m); 0.6-0.4 (4H, m).

(28) Phase sequence: C 72 C. N 84.5 C. I; n=0.378; =1.5.

Substance Example 12

(29) ##STR00308##

(30) Phase sequence: T.sub.g 43 C. C 46 C. N 86.0 C. I; n=0.379; =1.1.

Substance Example 13

(31) ##STR00309##

Synthesis Example 13: 1,4-Bis(2-(4-butylphenyl)ethynyl)-2-cyclobutylbenzene 3

(32) ##STR00310##

13.1) 1-(2,5-Dibromophenyl)cyclobutanol 4

(33) ##STR00311##

(34) 21.09 g (67 mmol) of 1,2,4-tribromobenzene are initially introduced in 100 ml of THF under nitrogen, cooled to 45 C., and a solution (1.3 M) of 51.54 ml (67 mmol) of isopropylmagnesium chloride/lithium chloride complex in THF is added dropwise. After 1 hour, the batch is warmed to 10 C., and 5 ml (66.34 ml) of cyclobutanone are added dropwise at this temperature. The batch is allowed to thaw, and sat. NH.sub.4Cl solution is added, the mixture is extracted with methyl t-butyl ether, the organic phase is dried over sodium sulfate and filtered, the solvent is removed in vacuo, and the residue is filtered through silica gel with dichloromethane, giving 4, which is employed in the next step without further purification.

13.2) 1,4-Dibromo-2-cyclobutylbenzene 5

(35) ##STR00312##

(36) 14.5 g (47.39 mmol) of 4 are dissolved in 50 ml of THF under nitrogen, and 35.72 ml (284.4 mmol) of boron trifluoride/diethyl ether complex are added dropwise at room temperature, and 12.54 g (189.6 mmol) of sodium cyanoborohydride are added dropwise in portions. The batch is heated under reflux overnight. The batch is allowed to cool to room temperature, sat. NaHCO.sub.3 solution is added, the mixture is extracted with methyl t-butyl ether, the organic phase is dried over sodium sulfate and filtered, the solvent is removed in vacuo, and the residue is filtered through silica gel with 1-chlorobutane, giving 5 as a yellow liquid.

13.3) 1,4-Bis(2-(4-butylphenyl)ethynyl)-2-cyclobutylbenzene 3

(37) ##STR00313##

(38) 7.8 g (47.0 mmol) of 1-butyl-4-ethynylbenzene are initially introduced in 100 ml of THF under nitrogen, cooled to 78 C., and 63.32 ml (63.20 mmol) of a 1 M solution of lithium bis(trimethylsilyl)amide in hexane are added dropwise. After 1 hour, 63.22 ml (63.20 mmol) of a 1 M solution of 9-methoxy-9-BBN in hexane are added, and the mixture is left to stir at 78 C. for 2 hours. In a second apparatus, 6.8 g (23.45 mmol) of 5, 0.916 g (1.0 mmol) of tris-(dibenzylideneacetone)dipalladium(0) and 1.64 g (4.0 mmol) of 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl in 100 ml of THF are initially introduced. The first solution is slowly added dropwise, and the batch is heated at 100 C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography and recrystallised from isopropanol, giving the title compound 3 as a solid.

(39) Phase sequence: T.sub.g 39 C. C 69 C. N 70.1 C. I; n=0.359; =0.9.

Substance Example 14

(40) ##STR00314##

(41) Phase sequence: T.sub.g 36 C. C 57 C. N(?) (7.0) C. I; n=0.334; =0.1.

Substance Example 15

(42) ##STR00315##

(43) Phase sequence: T.sub.g 34 C. C 47 C. N 53.1 C. I; n=0.337; =0.0.

Substance Example 16

(44) ##STR00316##

Synthesis Example 16: 2-Cyclohexyl-4-(4-hexylphenylethynyl)-1-(4-propylphenylethynyl)-benzene 6

16.1) 4-Chloro-2-cyclohexylbenzene trifluoromethanesulfonate 7

(45) ##STR00317##

(46) 19 g (90.2 mmol) of 4-chloro-2-cyclohexylbenzene are dissolved in 264 ml of dichloromethane, cooled to 5 C., and 4.64 ml (33.18 mmol) of triethylamine and 223 mg (1.8 mmol) of 4-(dimethylamino)pyridine are added dropwise. The batch is stirred at room temperature overnight and filtered through silica gel with dichloromethane, giving the product 7, which is employed in the next step without further purification.

16.2) (4-Chloro-2-cyclohexylphenylethynyl)trimethylsilane 8

(47) ##STR00318##

(48) 21 g (61.3 mmol) of 7, 25.8 ml (183.8 mmol) of trimethylsilylacetylene, 2.15 g (3 mmol) of bis(triphenylphosphine)palladium(II) chloride and 21.2 ml (153.2 mmol) of triethylamine are dissolved in 60 ml of N,N-dimethylformamide under nitrogen, and the mixture is heated at 100 C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography, giving the product 8, which is employed in the next step without further purification.

16.3) 4-Chloro-2-cyclohexyl-1-ethynylbenzene 9

(49) ##STR00319##

(50) 16.6 g (57.1 mmol) of 8 are dissolved in 154 ml of tetrahydrofuran, cooled to 0 C., and a 1 M solution of tetra-n-butylammonium fluoride (68.48 mmol) is added dropwise. The batch is stirred at room temperature overnight, water is added, the mixture is extracted with methyl t-butyl ether, the organic phase is dried over sodium sulfate and filtered, the solvent is removed in vacuo, and the residue is filtered through silica gel with heptane/toluene, giving the product 9, which is employed in the next step without further purification.

16.4) 4-Chloro-2-cyclohexyl-1-p-tolylethynylbenzene 10

(51) ##STR00320##

(52) 6.6 g (30.17 mmol) of 9, 7.28 g (30.17 mmol) of 1-bromo-4-hexylbenzene, 21.63 g (66.39 mmol) of caesium carbonate, 78 mg (0.3 mmol) of bis(acetonitrile)palladium(II) chloride and 431 mg (0.9 mmol) of 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl are dissolved in 90 ml of dioxane under nitrogen and heated at 100 C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography.

16.5) 2-Cyclohexyl-4-(4-hexylphenylethynyl)-1-(4-propylphenylethynyl)benzene 6

(53) ##STR00321##

(54) 4.5 g (11.87 mmol) of 10, 1.7 g (11.87 mmol) of 1-n-propyl-4-ethynylbenzene, 8.5 g (26.12 mmol) of caesium carbonate, 30 mg (0.1 mmol) of bis(acetonitrile)-palladium(II) chloride and 170 mg (0.35 mmol) of 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl are dissolved in 35 ml of dioxane under nitrogen and heated at 100 C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography, giving the title compound 6 as a solid.

(55) Phase sequence: T.sub.g 23 C. I; n=0.294; =0.6.

Substance Example 17

(56) ##STR00322##

(57) The compound is prepared analogously to Example 11.

(58) Phase sequence: C 90 C. N 193.9 C. I; n=0.435; =3.0.

Substance Example 18

(59) ##STR00323##

(60) The compound is prepared analogously to Example 11.

(61) Phase sequence: C 53 C. N 143.5 C. I; n=0.401; =2.5.

Substance Example 19

(62) ##STR00324##

(63) The compound is prepared analogously to Example 11.

(64) Phase sequence: T.sub.g 49 C 32 C. N 126.0 C. I; n=0.373; =1.6.

Substance Example 20

(65) ##STR00325##

Substance Example 21

(66) ##STR00326##

(67) Phase sequence: T.sub.g 45 C. C 60 C. N 89.1 C. I; n=0.348; =1.3.

Substance Example 22

(68) ##STR00327##

(69) Phase sequence: T.sub.g 32 C. C 66 C. N (44.1) C. I; n=0.322; =0.6.

Substance Example 23

(70) ##STR00328##

(71) Phase sequence: T.sub.g 37 C. C 52 C. N 78.2 C. I; n=0.339; =0.9.

Synthesis Example 24

(72) ##STR00329##

Step 24.1

(73) ##STR00330##

(74) 25.4 g of 2-bromo-1,4-dichlorobenzene, 8.9 ml of iodoethane and 13.3 ml of DMPU are dissolved in 230 ml of THF, and a solution of 16.2 g of lithium tetra-methylpiperidite in THF is added dropwise at 70 C. After a further 2 h at 70 C., the reaction mixture is allowed to warm to ambient temperature, and the batch is hydrolysed using water and subjected to extractive work-up. The crude product is purified by fractional distillation.

(75) B.p.: 73 C./0.1 bar. Colourless liquid.

Step 24.2

(76) ##STR00331##

(77) 12.5 ml of a 5% solution of methyllithium in diethyl ether are added to 2.4 g of anhydrous zinc bromide in 50 ml of THF at 25-40 C. 0.3 g of PdCl.sub.2-dppf, bis-(diphenylphosphinoferrocene)palladium dichloride, is then added, the mixture is heated to the boil, and 4.6 g of the product from step 1.1, dissolved in a little THF, are added dropwise. The reaction mixture is subsequently heated under reflux for 15 h. The batch is hydrolysed using water and subjected to extractive work-up.

(78) The crude product is purified by chromatography (pentane/silica gel). Colourless liquid.

Step 24.3

(79) ##STR00332##

(80) 2.4 g of 4-butylphenylacetylene are initially introduced in 30 ml of THF and cooled to 78 C. 14.3 ml of a 1 M solution of lithium bis(trimethylsilyl)amide in hexane are added dropwise to this solution and allowed to react at 78 C. for a further 1 h. 14.3 ml of a 1 M solution of methoxy-9-BBN are then added dropwise, and the mixture is stirred at 78 C. for a further 2 h. In a second apparatus, 1.0 g of the product from the last step, dissolved in 40 ml of THF, is initially introduced with the catalyst comprising 0.2 g of tris(dibenzylideneacetone)dipalladium and 0.35 g of 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl, and the reaction solution from the first reaction is added at room temperature. The mixture is heated at the boil for 15 h. The batch is hydrolysed using water and subjected to extractive work-up. The crude product is purified by chromatography (pentane/silica gel). Recrystallisation from pentane gives the purified title product.

(81) Phase sequence: C 45 N 1801.

Substance Example 25

(82) ##STR00333##

(83) The compound is prepared analogously to Example 24.

(84) Phase sequence: C 118 N 222 I; n=0.435; =2.6.

Substance Example 26

(85) ##STR00334##

(86) The title compound is prepared analogously to Example 24.

(87) Phase sequence: C 41 N 161 I.

Substance Example 27

(88) ##STR00335##

Synthesis Example 27

27.1) Synthesis of 1-iodo-4-bromonaphthalene

(89) ##STR00336##

(90) 100 g (350 mmol) of 1,4-dibromonaphthalene are initially introduced in 1 l of THF, cooled to 70 C., and 235 ml of n-BuLi (1.6 M in hexane, 370 mmol) are added dropwise. After 1 h, 103 g (406 mmol) of I.sub.2 in 250 ml of THF are added dropwise, the mixture is stirred at 70 C. for a further 2 h, warmed to 0 C. and quenched by the addition of 50 ml (644 mmol) of aqueous NaHSO.sub.3 solution (w=39%). The phases are separated, and the aqueous phase is extracted once with MTB. The combined organic phases are washed with saturated sodium chloride soln., dried over sodium sulfate, filtered and evaporated in a rotary evaporator. The residue is purified by column chromatography (SiO.sub.2, heptane), and the further purification is carried out by recrystallisation from isopropanol, giving 1-iodo-4-bromonaphthalene as a yellow solid.

27.2) Synthesis of 1-bromo-4-(4-n-propylphenylethynyl)naphthalene

(91) ##STR00337##

(92) 15.3 g (43.6 mmol) of 1-iodo-4-bromonaphthalene and 7.25 g (5.3 mmol) of 4-n-propylphenylacetylene are initially introduced in 200 ml of NEt.sub.3, 170 mg (0.9 mmol) of copper(I) iodide and 600 mg (0.9 mmol) of bis(triphenylphosphine)palladium(II) chloride are added, and the mixture is refluxed for 30 minutes. The batch is cooled, water and heptane are added, and the phases are separated. The organic phase is washed with saturated sodium chloride soln., dried over sodium sulfate, filtered and evaporated in a rotary evaporator. The residue is purified by column chromatography (SiO.sub.2, heptane), and the further purification is carried out by recrystallisation from isopropanol.

27.3) Synthesis of 1-(4-n-butylphenylethynyl)-4-(4-n-propylphenylethynyl)-naphthalene

(93) ##STR00338##

(94) 2.35 g (6.3 mmol) of 1-bromo-4-(4-n-propylphenylethynyl)naphthalene and 1.33 g (8.4 mmol) of 4-n-butylphenylacetylene are initially introduced in 40 ml of NEt.sub.3, 60 mg (0.3 mmol) of copper(I) iodide and 200 mg (0.3 mmol) of bis-(triphenylphosphine)palladium(II) chloride are added, and the mixture is refluxed for 18 h.

(95) The batch is cooled, water and heptane are added, and the phases are separated. The organic phase is washed with saturated ammonium chloride solution and subsequently with saturated sodium chloride soln., dried over sodium sulfate, filtered and evaporated in a rotary evaporator. The residue of compound (I) is purified by column chromatography (SiO.sub.2, heptane), and the further purification is carried out by recrystallisation from isopropanol.

(96) MS (O): m/e (%)=426 (100, M.sup.+), 397 (11, [M-ethyl].sup.+), 383 (16, [Mpropyl].sup.+), 354 (18, [M-ethylpropyl].sup.+), 177 (14, [M-ethylpropyl].sup.2+).

(97) Phase sequence: C 78 N 1911; n=0.450; =2.9.

Substance Example 28

(98) ##STR00339##

(99) The compound is prepared analogously to Example 27.

(100) Phase sequence: C 108 C. N 194 C. I.

Substance Example 29

(101) ##STR00340##

(102) The compound is prepared analogously to Example 27.

(103) Phase sequence: C 63 C. N 171.7 C. I; n=0.435; =2.3.

Substance Example 30

(104) ##STR00341##

(105) The compound is prepared analogously to Example 27.

(106) Phase sequence: C 76 C. N 176.2 C. I; n=0.427; =2.4.

Substance Example 31

(107) ##STR00342##

(108) The compound is prepared analogously to Example 27.

(109) Phase sequence: C 100 C. N 162 C. I.

Substance Example 32

(110) ##STR00343##

(111) The compound is prepared analogously to Example 27.

(112) Phase sequence: C 61 C. N 139 C. I.

Substance Example 33

(113) ##STR00344##

(114) This compound is prepared analogously to the preceding compounds in accordance with the right-hand reaction path of Scheme 13.

(115) Phase sequence: C 85 C. N 202.4 C. I; n=0.446; =2.0.

Substance Example 34

(116) ##STR00345##

(117) The compound is prepared analogously to Example 33.

(118) Phase sequence: C 112 C. N 253.5 C. I; n=0.484; =4.1.

Substance Example 35

(119) ##STR00346##

(120) This compound is prepared analogously to the preceding compounds in accordance with the left-hand reaction path of Scheme 13.

(121) Phase sequence: C 93 C. N 212.4 C. I; n=0.527; =0.8.

USE EXAMPLES

Comparative Example 1

(122) A liquid-crystalline substance having the abbreviation PTP(2)TP-6-3 is prepared by the method of Hsu, C. S., Shyu, K. F., Chuang, Y. Y. and Wu, S.-T., Liq. Cryst., 27 (2), (2000), pp. 283-287, and investigated with respect to its physical properties, in particular in the microwave region. The compound has a nematic phase and a clearing point (T(N,I)) of 114.5 C. Further physical properties at 20 C. are: n.sub.e(589.3 nm)=1.8563; n (589.3 nm)=0.3250; .sub. (1 kHz), 4.3; (1 kHz)=1.8 and .sub.1=2.100 mPa.Math.s. The compound is suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(123) TABLE-US-00007 TABLE 1 Properties of the compound PTP(2)TP-6-3 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 3.35 2.42 0.278 0.0029 0.0061 45.2

(124) TABLE-US-00008 TABLE 2 Comparison of the properties of the various examples at 19 GHz and 20 C. Example LC .sub.r,|| .sub.r, tan .sub. max. Comparison P2-6-3* 3.35 2.42 0.278 0.0061 45.2 1 M-1 3.41 2.47 0.275 0.0059 46.4 2 M-2 3.44 2.47 0.280 0.0070 40.1 3 M-3 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. 4 M-4 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. 5 M-5 3.50 2.48 0.290 0.0044 66 6 M-6 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. 7 M-7 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. 8 M-8 3.38 2.42 0.285 0.0057 50.4 9 M-9 3.34 2.41 0.277 0.0060 46.4 10 M-10 3.34 2.40 0.281 0.0060 46.7 11 M-11 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. 12 M-12 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. Notes: *P2-6-3: PTP(2)TP-6-3, LC: liquid crystal and t.b.d.: to be determined.

Example 1

(125) A liquid-crystal mixture M-1 having the composition and properties as indicated in the following table is prepared.

(126) TABLE-US-00009 Composition Compound No. Abbreviation 1 PTGI(c3)TP-4-4 40.0 2 PTGI(c4)TP-4-4 20.0 3 PTN(1,4)TP-4-4 15.0 4 PTN(1,4)TP-3-6 25.0 100.0 Physical properties T(N,I) = 136.5 C. n.sub.e (20 C., 589.3 nm) = 1.553 n (20 C., 589.3 nm) = 0.408 .sub. (20 C., 1 kHz) = 3.7 (20 C., 1 kHz) = 0.9 k.sub.11 (20 C.) = 11.3 pN k.sub.33/k.sub.11 (20 C.) = 3.88 V.sub.0 (20 C.) = 3.71 V .sub.1 (20 C.) = 2.903 mPa .Math. s

(127) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(128) TABLE-US-00010 TABLE 3 Properties of mixture M-1 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 3.41 2.47 0.275 0.0026 0.0059 46.4

Example 2

(129) A liquid-crystal mixture M-2 having the composition and properties as indicated in the following table is prepared.

(130) TABLE-US-00011 Composition Compound No. Abbreviation 1 PTGI(c3)TP-4-4 40.0 2 PPTUI-3-4 20.0 3 PTN(1,4)TP-4-4 15.0 4 PTN(1,4)TP-3-6 25.0 100.0 Physical properties T(N,I) = 150 C. n.sub.e (20 C., 589.3 nm) = 1.548 n (20 C., 589.3 nm) = 0.41 .sub. (20 C., 1 kHz) = 3.7 (20 C., 1 kHz) = 1.0 k.sub.11 (20 C.) = 13.6 pN k.sub.33/k.sub.11 (20 C.) = 3.17 V.sub.0 (20 C.) = 3.93 V .sub.1 (20 C.) = 2.114 mPa .Math. s

(131) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(132) TABLE-US-00012 TABLE 4 Properties of mixture M-2 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 3.44 2.47 0.280 0.0023 0.0070 40.1

Example 3

(133) A liquid-crystal mixture M-3 having the composition and properties as indicated in the following table is prepared.

(134) TABLE-US-00013 Composition Compound No. Abbreviation 1 PTP(c3)TP-4-4 10.0 2 PTP(c3)TP-6-3 20.0 3 PTP(c4)TP-4-4 15.0 4 PTGI(c4)TP-4-4 15.0 5 PTGI(e5)TP-4-4 20.0 6 PTPI(2)PP(2)-4-4 10.0 7 PTPI(2)P(2)TP-4-4 10.0 100.0 Physical properties T(N,I) = 104 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = t.b.d. (20 C., 1 kHz) = 1.0 k.sub.11 (20 C.) = t.b.d. pN k.sub.33/k.sub.11 (20 C.) = t.b.d. V.sub.0 (20 C.) = t.b.d. V .sub.1 (20 C.) = t.b.d. mPa .Math. s Note: t.b.d.: to be determined.

(135) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(136) TABLE-US-00014 TABLE 5 Properties of mixture M-3 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. Note: t.b.d.: to be determined.

Example 4

(137) A liquid-crystal mixture M-4 having the composition and properties as indicated in the following table is prepared.

(138) TABLE-US-00015 Composition Compound No. Abbreviation 1 PTPI(2)TP(2)TP-4-4 10.0 2 GGP-3-CL 10.0 3 GGP-5-CL 20.0 4 PPTUI-3-2 20.0 5 PPTUI-3-4 20.0 6 PPTUI-4-4 20.0 100.0 Physical properties T(N,I) = 153 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = 7.7 (20 C., 1 kHz) = 4.4 k.sub.11 (20 C.) = 16.6 pN k.sub.33 (20 C.) = 34.5 pN V.sub.0 (20 C.) = 2.06 V .sub.1 (20 C.) = 874 mPa .Math. s Note: t.b.d.: to be determined.

(139) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(140) TABLE-US-00016 TABLE 6 Properties of mixture M-4 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. Note: t.b.d.: to be determined.

Example 5

(141) A liquid-crystal mixture M-5 having the composition and properties as indicated in the following table is prepared.

(142) TABLE-US-00017 Composition Compound No. Abbreviation 1 PTN(1,4)TP-3-3 5.0 2 PTN(1,4)TP-5-5 5.0 3 PTN(1,4)TP-4-4 30.0 4 PTN(1,4)TP-6-6 30.0 5 PTN(1,4)TP-3-6 30.0 100.0 Physical properties T(N,I) = 166.5 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = 3.5 (20 C., 1 kHz) = 0.9 k.sub.11 (20 C.) = 17.2 pN k.sub.33 (20 C.) = 31.4 pN V.sub.0 (20 C.) = 4.6 V .sub.1 (20 C.) = t.b.d. mPa .Math. s Note: t.b.d.: to be determined.

(143) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(144) TABLE-US-00018 TABLE 7 Properties of mixture M-5 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 3.50 2.48 0.290 0.0017 0.0044 66

Example 6

(145) A liquid-crystal mixture M-6 having the composition and properties as indicated in the following table is prepared.

(146) TABLE-US-00019 Composition Compound No. Abbreviation 1 PTPI(2)P(2)TP-4-4 10.0 2 PTP(2)TP-6-3 90.0 100.0 Physical properties T(N,I) = 125.5 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = 3.4 (20 C., 1 kHz) = 0.9 k.sub.11 (20 C.) = 12.7 pN k.sub.33/k.sub.11 (20 C.) = 4.1 V.sub.0 (20 C.) = 4.08 V .sub.1 (20 C.) = t.b.d. mPa .Math. s Note: t.b.d.: to be determined.

(147) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(148) TABLE-US-00020 TABLE 8 Properties of mixture M-6 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. Note: t.b.d.: to be determined.

Example 7

(149) A liquid-crystal mixture M-7 having the composition and properties as indicated in the following table is prepared.

(150) TABLE-US-00021 Composition Compound No. Abbreviation 1 PTPP(2)TP-4-4 10.0 2 PTP(2)TP-6-3 90.0 100.0 Physical properties T(N,I) = 125.5 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = 3.4 (20 C., 1 kHz) = 0.9 k.sub.11 (20 C.) = 13.0 pN k.sub.33/k.sub.11 (20 C.) = 4.7 V.sub.0 (20 C.) = 4.10 V .sub.1 (20 C.) = t.b.d. mPa .Math. s Note: t.b.d.: to be determined.

(151) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(152) TABLE-US-00022 TABLE 9 Properties of mixture M-7 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. Note: t.b.d.: to be determined.

Example 8

(153) A liquid-crystal mixture M-8 having the composition and properties as indicated in the following table is prepared.

(154) TABLE-US-00023 Composition Compound No. Abbreviation 1 PTPI(2)TP(2)TP-4-4 10.0 2 PTP(2)TP-6-3 90.0 100.0 Physical properties T(N,I) = 127 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = 3.4 (20 C., 1 kHz) = 0.9 k.sub.11 (20 C.) = 13.3 pN k.sub.33/k.sub.11 (20 C.) = 3.8 V.sub.0 (20 C.) = 4.14 V .sub.1 (20 C.) = t.b.d. mPa .Math. s Note: t.b.d.: to be determined.

(155) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(156) TABLE-US-00024 TABLE 10 Properties of mixture M-8 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 3.38 2.42 0.285 0.0024 0.0057 50.4

Example 9

(157) A liquid-crystal mixture M-9 having the composition and properties as indicated in the following table is prepared.

(158) TABLE-US-00025 Composition Compound No. Abbreviation 1 PTP(c3)TP-4-4 10.0 2 PTP(2)TP-6-3 90.0 100.0 Physical properties T(N,I) = 116 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = t.b.d. (20 C., 1 kHz) = t.b.d. k.sub.11 (20 C.) = t.b.d. pN k.sub.33/k.sub.11 (20 C.) = t.b.d. V.sub.0 (20 C.) = t.b.d. V .sub.1 (20 C.) = t.b.d. mPa .Math. s Note: t.b.d.: to be determined.

(159) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(160) TABLE-US-00026 TABLE 11 Properties of mixture M-9 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 3.34 2.41 0.277 0.0025 0.0060 46.4

Example 10

(161) A liquid-crystal mixture M-10 having the composition and properties as indicated in the following table is prepared.

(162) TABLE-US-00027 Composition Compound No. Abbreviation 1 PTGI(c3)TP-4-4 10.0 2 PTP(2)TP-6-3 90.0 100.0 Physical properties T(N,I) = 120 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = t.b.d. (20 C., 1 kHz) = t.b.d. k.sub.11 (20 C.) = t.b.d. pN k.sub.33/k.sub.11 (20 C.) = t.b.d. V.sub.0 (20 C.) = t.b.d. V .sub.1 (20 C.) = t.b.d. mPa .Math. s Note: t.b.d.: to be determined.

(163) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(164) TABLE-US-00028 TABLE 12 Properties of mixture M-10 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 3.34 2.40 0.281 0.0025 0.0060 46.7

Example 11

(165) A liquid-crystal mixture M-11 having the composition and properties as indicated in the following table is prepared.

(166) TABLE-US-00029 Composition Compound No. Abbreviation 1 PTP(c4)TP-4-4 10.0 2 PTP(2)TP-6-3 90.0 100.0 Physical properties T(N,I) = 114 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = t.b.d. (20 C., 1 kHz) = t.b.d. k.sub.11 (20 C.) = t.b.d. pN k.sub.33/k.sub.11 (20 C.) = t.b.d. V.sub.0 (20 C.) = t.b.d. V .sub.1 (20 C.) = t.b.d. mPa .Math. s Note: t.b.d.: to be determined

(167) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(168) TABLE-US-00030 TABLE 13 Properties of mixture M-11 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. Note: t.b.d.: to be determined.

Example 12

(169) A liquid-crystal mixture M-12 having the composition and properties as indicated in the following table is prepared.

(170) TABLE-US-00031 Composition Compound No. Abbreviation 1 PTGI(c4)TP-4-4 10.0 2 PTP(2)TP-6-3 90.0 100.0 Physical properties T(N,I) = 117 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n (20 C., 589.3 nm) = t.b.d. .sub. (20 C., 1 kHz) = t.b.d. (20 C., 1 kHz) = t.b.d. k.sub.11 (20 C.) = t.b.d. pN k.sub.33/k.sub.11 (20 C.) = t.b.d. V.sub.0 (20 C.) = t.b.d. V .sub.1 (20 C.) = t.b.d. mPa .Math. s Note: t.b.d.: to be determined.

(171) This mixture is very highly suitable for applications in the microwave region and/or millimeter wave region, in particular for phase shifters.

(172) TABLE-US-00032 TABLE 14 Properties of mixture M-12 at 19 GHz T/ C. .sub.r,|| .sub.r, tan .sub.,r,|| tan .sub.,r, 20 t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. t.b.d. Note: t.b.d.: to be determined.