Devices for high-frequency technology, liquid-crystalline media and compounds

Abstract

The present invention relates to a device for high-frequency technology, or for the microwave region and millimeter wave region of the electromagnetic spectrum, characterized in that it contains a liquid-crystal medium which consists of one or more compounds, which one or more compounds, which contain 6 to 15 five-, six- or seven-membered rings, preferably 1,4-linked phenylene rings, or in that it contains a liquid-crystal medium which itself comprises a component A, which itself consists of one or more of the said compounds, which one or more compounds, which contain 6 to 15 five-, six- or seven-membered rings, preferably 1,4-linked phenylene rings. The present invention additionally relates to compounds of the formula (I), in which the parameters have the meanings given in the text, and to the corresponding, novel liquid-crystal media, to the use and preparation thereof, and to the production and use of the devices. The devices according to the invention are particularly suitable phase shifters in the microwave and millimeter wave region, for microwave and millimeter wave array antennas and very particularly for so-called tunable reflectarrays.

Claims

1. A compound of the of the formula IA ##STR00289## in which n and m, independently of one another, denote an integer from 1 to 15, preferably 3 to 12, p denotes an integer from 1 to 4, q denotes an integer from 1 to 6, and (p+q) denotes an integer from 4 to 12.

2. A compound of the of the formula IB ##STR00290## in which n and m, independently of one another, denote an integer from 1 to 15, preferably 3 to 12, denotes an integer from 1 to 4, q denotes an integer from 1 to 6, and (p+q) denotes an integer from 4 to 12.

3. A compound of one of the formula IA-1 to IA-3 ##STR00291## in which k denotes 2.

4. A compound of the of the formula IB-1 ##STR00292##

5. A compound of the of the formula IB-2 ##STR00293##

6. A process for the preparation of a compound of the IA according to claim 1, wherein the product or one or more intermediates from an aryl borate compound are linked to an aryl-halogen compound or to an aryl triflate compound by palladium-catalysed homocoupling and/or cross-coupling.

7. A process for the preparation of a compound of the formula IB according to claim 2, wherein the product or one or more intermediates from an aryl borate compound are linked to an aryl-halogen compound or to an aryl triflate compound by palladium-catalysed homocoupling and/or cross-coupling.

8. A process for the preparation of a compound of one of the formula IA-1 to IA-3 according to claim 3, wherein the product or one or more intermediates from an aryl borate compound are linked to an aryl-halogen compound or to an aryl triflate compound by palladium-catalysed homocoupling and/or cross-coupling.

9. A process for the preparation of a compound of the formula IB-1 according to claim 4, wherein the product or one or more intermediates from an aryl borate compound are linked to an aryl-halogen compound or to an aryl triflate compound by palladium-catalysed homocoupling and/or cross-coupling.

10. A process for the preparation of a compound of the formula IB-2 according to claim 5, wherein the product or one or more intermediates from an aryl borate compound are linked to an aryl-halogen compound or to an aryl triflate compound by palladium-catalysed homocoupling and/or cross-coupling.

11. A device for high-frequency technology or for the microwave region and millimeter wave region of the electromagnetic spectrum, comprising: an antenna, and a liquid-crystal medium comprising one or more compounds of the formula IA of claim 1.

12. A device for high-frequency technology or for the microwave region and millimeter wave region of the electromagnetic spectrum, comprising: an antenna, and a liquid-crystal medium comprising one or more compounds of the formula IB of claim 2.

13. A device for high-frequency technology or for the microwave region and millimeter wave region of the electromagnetic spectrum, comprising: an antenna, and a liquid-crystal medium comprising one or more compounds of the formula IA-1 to IA-3 of claim 3.

14. A device for high-frequency technology or for the microwave region and millimeter wave region of the electromagnetic spectrum, comprising: an antenna, and a liquid-crystal medium comprising one or more compounds of the formula IB-1 of claim 4.

15. A device for high-frequency technology or for the microwave region and millimeter wave region of the electromagnetic spectrum, comprising: an antenna, and a liquid-crystal medium comprising one or more compounds of the formula IB-2 of claim 5.

16. The compound of claim 1 wherein p is 2.

17. The compound of claim 1 wherein q is 1 or 4.

18. The compound of claim 1 wherein (p+q) is 4, 6 or 8.

19. The compound of claim 2 wherein p is 2.

20. The compound of claim 2 wherein q is 1 or 4.

21. The compound of claim 2 wherein (p+q) is 4, 6 or 8.

Description

EXAMPLES

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

(2) 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.

Substance Examples

Substance Example 1

(3) Preparation of the Compound

(4) ##STR00271##
Step 1.1

(5) ##STR00272##

(6) 24.0 g of sodium metaborate are dissolved in 60.0 ml of demineralised water. 1.50 g of bis(triphenylphosphine)palladium(II) chloride (15.2% of Pd) for synthesis, 0.100 ml of hydrazinium hydroxide (approximately 100% pure) and 25.0 g of 2-bromo-5-chlorobenzaldehyde are then added successively, and the mixture is stirred at ambient temperature for 10 min. 19.7 g of the borate dissolved in 120.0 ml of tetrahydrofuran are then added dropwise, and the mixture is heated to the boil. The mixture is heated under reflux for 16 h. The product is subjected to conventional purification. A yellow oil is obtained.

(7) Step 1.2

(8) ##STR00273##

(9) 18.0 ml of a 20% solution of methylmagnesium chloride in tetrahydrofuran are initially introduced. 11.2 g of the product from the final step are dissolved in 100 ml of THF and added dropwise with cooling at a temperature of about 5 C. The reaction mixture is subsequently stirred at a temperature of 5 C. for 1 h. The product is subjected to conventional purification. As clear, pale-yellow, viscous oil is obtained.

(10) Step 1.3

(11) ##STR00274##

(12) 9.20 g of the product from the final step are dissolved in 150.0 ml of tetrahydrofuran at ambient temperature under a nitrogen atmosphere. 49.0 ml of a solution of boron trfluoride/diehyl ether complex (for synthesis) are then added dropwise. During this addition, the temperature of the reaction mixture rises to about 28 C. 17.40 g of sodium cyanoborohydride are then added in portions. During this addition, the temperature rises to about 35 C. The mixture is subsequently heated under reflux for 70 h. 60 g of crude product are obtained as a yellow, viscous oil. The product is subjected to conventional purification.

(13) Step 1.4

(14) ##STR00275##

(15) 7.20 g of the product from the final step are dissolved in 100.0 ml of 1,4-dioxane with 13.3 g of bis(pinacolato)diboron, 490.0 mg of tris(dibenzylideneacetone)dipalladium(0), 510 mg of 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl and 7.70 g of potassium acetate. The mixture is heated under reflux at 100 C. for 16 h. The product is subjected to conventional purification.

(16) Step 1.5

(17) ##STR00276##

(18) 3.00 g of the product from the final step are dissolved in 50.0 ml of 1,4-dioxane with 1.28 g of 4,4-dibromophenyl for synthesis, 300.0 mg of tris(dibenzylideneacetone)dipalladium(0), 35.0 mg of 2-dicyclohexylphosphino-2,6dimethoxybiphenyl and 4.80 g of potassium phosphate monohydrate (prepared from potassium phosphate trihydrate at 140 C. after 16 h). The reaction mixture is heated under reflux at 100 C. for 16 h. The crude product (green-blue crystals) is isolated. The product is subjected to conventional purification.

(19) The product has the phase sequence C 197 C. N 330.4 C. I and, extrapolated from a 5% solution in ZLI-4792, a of 2.8 and a n of 0.351.

Substance Example 2

(20) The following compound is prepared analogously to Substance Example 1

(21) ##STR00277##

(22) For simplicity, only the final synthetic step is described in detail here.

(23) ##STR00278##

(24) 3.80 g of the borate are dissolved in 50.0 ml of 1,4-dioxane with 1.560 g of 4,4-dibromobiphenyl (for synthesis), 90.0 mg of tris(dibenzylideneacetone)dipalladium(0), 170 mg of 2-dicyclohexylphosphino-2,6dimethoxybiphenyl and 5.80 g of potassium phosphate monohydrate (prepared from potassium phosphate trihydrate at 140 C. after 16 h). The reaction mixture is heated under reflux at 100 C. for 16 h. The crude product is isolated. The product is subjected to conventional purification. Pale-beige crystals are obtained.

(25) The product has the phase sequence C 174 C. N 252.7 C. I and, extrapolated from a 5% solution in ZLI-4792, a of 1.6 and a n of 0.319.

Substance Example 3

(26) Preparation of the Compound

(27) ##STR00279##
Step 3.1

(28) ##STR00280##

(29) 33.50 g of 1,4-di-n-dodecylbenzene, are dissolved in 100 ml of dichloromethane. 200 mg of iodine (double-sublimed) are added as catalyst. 8.5 ml of bromine (extra pure) are subsequently rapidly added dropwise. The brown reaction mixture is stirred at ambient temperature for 16 h with exclusion of light. A further 100 ml of dichloromethane are then added, and the mixture is stirred for a further 50 h. The crude product (pale-yellow crystals) is isolated and subjected to conventional purification. White crystals are obtained.

(30) Step 3.2

(31) ##STR00281##

(32) 20.0 g of the product from the final step, 100.0 ml of toluene (extra pure), 12.0 g of anhydrous sodium carbonate (extra pure) and 50.0 ml of demineralised water are initially introduced and warmed to a temperature in the range from about 75 C. to 80 C. with vigorous stirring. 0.40 g of tetrakis(triphenylphosphine)Pd(0) is subsequently added, and a solution of 9.40 g of the boronic acid in 50.0 ml of ethanol (absolute, extra pure) is added dropwise. The alcoholic solution of the boronic acid is advantageously slightly warmed in advance in order completely to dissolve the boronic acid. The reaction mixture is heated under reflux for 16 h. The crude product (a brown oil) is isolated and subjected to conventional purification. A clear oil is obtained.

(33) Step 3.3

(34) ##STR00282##

(35) 13.60 g of the product from the final step are dissolved in 100.0 ml of 1,4-dioxane (extra pure). 0.40 g of PdCl.sub.2-dppf, (bisdiphenylphosphinoferrocenepalladium dichloride) 5.50 g of bis(pinacolato)diboron and 5.40 g of potassium acetate (extra pure) are subsequently added, and the reaction mixture is heated under reflux for 4 h. The crude product is isolated (black oil) and subjected to conventional purification. The product is obtained as an oil.

(36) Step 3.4

(37) ##STR00283##

(38) 3.00 g of 4-bromo-4-iodobiphenyl are dissolved in 80.0 ml of toluene (extra pure). 3.00 g of anhydrous sodium carbonate (extra pure), 50.0 ml of demineralised water, 6.20 g of the product from the final step are then added successively. The crude product (yellow-brown crystals) is isolated and subjected to conventional purification. Yellow-brown crystals are obtained.

(39) Step 3.5

(40) ##STR00284##

(41) 4.70 g of the product from the final step and 0.680 g of bis(pincalto)-diboron are dissolved in 25.0 ml of 1,4-dioxane (extra pure) with gentle warming. Then, firstly 200.0 mg of PdCl.sub.2(PCy.sub.3).sub.2 (bistricyclohexylphosphinopalladuim dichloride) and subsequently 3.50 g of caesium fluoride and one drop of water are added. The reaction mixture is stirred at a temperature of 100 C. for 16 h under a nitrogen atmosphere. The crude product (yellow crystals) is isolated. The product is subjected to conventional purification. Yellow crystals are obtained.

(42) The product has the phase sequence C 103 C. N 199.9 C. I and, extrapolated from a 5% solution in ZLI-4792, a of 0.3 and a n of 0.255.

Substance Example 4

(43) The following compound is prepared analogously to Substance Example 3

(44) ##STR00285##

(45) For simplicity, only the final synthetic step is described in detail here.

(46) ##STR00286##

(47) 1.70 g of the product from the final step and 0.280 g of bis(pincalto)-diboron are dissolved in 10.0 ml of 1,4-dioxane with gentle warming. Then, firstly 80.0 mg of PdCl.sub.2(PCy.sub.3).sub.2 (bistricyclohexylphosphinopalladuim dichloride) and subsequently 1.40 g of caesium fluoride are added. The reaction mixture is heated under reflux for 16 h under a nitrogen atmosphere. The product is subjected to conventional purification. Yellow crystals are obtained.

(48) The product has the phase sequence: C 154 C. N 283.9 C. I and, extrapolated from a 5% solution in ZLI-4792, a of 3.0 and a n of 0.308.

Substance Example 5

(49) The following compound is prepared analogously to Substance Example 3

(50) ##STR00287##

(51) For simplicity, only the final synthetic step is described in detail here.

(52) ##STR00288##

(53) 5.0 g of the product from the final step and 0.863 g of bis(pincalto)diboron are dissolved in 35.0 ml of 1,4-dioxane with gentle warming. Then, firstly 250 mg of PdCl.sub.2(PCy.sub.3).sub.2 (bistricyclohexylphosphinopalladuim dichloride) and subsequently 1.40 g of caesium fluoride and 1 drop of water are added. The reaction mixture is stirred at a temperature of 100 C. for 16 h under a nitrogen atmosphere. The crude product (an amorphous, yellowish/yellowish-orange mass) is isolated. The product is subjected to conventional purification. Greyish crystals are obtained.

(54) The product has the phase sequence: C 147 C. N 238.4 C. I and, extrapolated from a 10% solution in ZLI-4792, a of 0.4 and a n of 0.267.

Use Examples

Comparative Example 1

(55) The known liquid-crystalline compound 4-pentyl-4-cyanobiphenyl (also known as 5CB or K15, Merck KGaA, Darmstadt, Germany) is investigated with respect to its physical properties, in particular in the microwave region, at 20 C.

(56) TABLE-US-00008 TABLE 1 Properties of compound K15 at 30 GHz T/ C. .sub.r, .sub.r, .sub. tan .sub., r, tan .sub., r, 20 2.87 2.55 0.110 0.0114 0.026 4.3

(57) This compound has a phase sequence of: C 23 C. N 35.1 C. and a of 11.0 at a temperature of 26 C. and a of 9.9 at a temperature of 29 C., and, extrapolated from a 10% solution in ZLI-4792, a of 20.1 and a n of 0.212.

(58) The compound has very low material quality and is not particularly highly suitable for applications in the microwave region since it has a very narrow phase range and a rather low .

Comparative Example 2

(59) 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), p. 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 of 108 C.

(60) TABLE-US-00009 TABLE 2 Properties of compound PTP(2)TP-6-3 at 30 GHz T/ C. .sub.r, .sub.r, .sub. tan .sub., r, tan .sub., r, 20 3.17 2.38 0.249 0.0018 0.0063 40 22 3.22 2.44 0.242 0.0018 0.0064 38

(61) The compound has a phase sequence of: T.sub.g54 C. N 119.2 C. and, extrapolated from a 10% solution in ZLI-4792, a of 1.8 and a n of 0.393.

(62) The compound is suitable for applications in the microwave region, but it has a low , in particular for phase shifters.

(63) TABLE-US-00010 TABLE 3 Comparison of the properties of the various examples at 30 GHz and 20 C. Liquid tan Example cryst. .sub.r, .sub.r, .sub. r, max. Comp. 1 K15 20 2.87 2.55 0.110 0.026 4.3 Comp. 2 P2-6-3* 0.4 3.17 2.38 0.249 0.0063 40 Comp. 2 P2-6-3* 0.4 3.22.sup. 2.44.sup. 0.242.sup. 0.0064.sup. .sup.38.sup. 1 M-1 0.8 3.15 2.38 0.244 0.0057 45 2 M-2 t.b.d. 3.18 2.40 0.245 0.0055 46 3 M-3 0.8 3.14 2.37 0.245 0.0054 45 4 M-4 2.4 3.18 2.39 0.248 0.0074 34 5 M-5 0.9 3.13.sup. 2.40.sup. 0.233.sup. 0.0052.sup. .sup.45.sup. 6 M-6 3.0 3.23 2.42 0.250 0.0085 30 Notes: *P2-6-3: PTP(2)TP-6-3, .sup.at T = 22 C. and t.b.d.: to be determined.

Example 1

(64) A liquid-crystal mixture M-1 having the composition and properties as indicated in the following table is prepared and investigated with respect to its physical properties, in particular in the microwave region.

(65) TABLE-US-00011 Composition Compound No. Abbreviation 1 PTP(2)TP-6-3 95.0 2 6*P-1 5.0 100.0 Physical properties T(N, I) = 118.5 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n.sub.o (20 C., 589.3 nm) = t.b.d. .sub.|| (20 C., 1 kHz) = 3.4 (20 C., 1 kHz) = +0.8 k.sub.1 (20 C.) = 11.7 pN K.sub.3 (20 C.) = 52.2 pN Notes: t.b.d.: to be determined and

(66) TABLE-US-00012 TABLE 4 Properties of mixture M-1 at 30 GHz T/ C. .sub.r, .sub.r, .sub. tan .sub., r, tan .sub., r, 20 3.15 2.38 0.244 0.0013 0.0057 45

(67) This mixture is very highly suitable for applications in the microwave region, in particular for phase shifters.

Example 2

(68) A liquid-crystal mixture M-2 having the composition and properties as indicated in the following table is prepared and investigated with respect to its physical properties, in particular in the microwave region.

(69) TABLE-US-00013 Composition Compound No. Abbreviation 1 PTP(2)TP-6-3 93.0 2 10*P-1 7.0 100.0 Physical properties T(N, I) = 115.5 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n.sub.o (20 C., 589.3 nm) = t.b.d. .sub.|| (20 C., 1 kHz) = t.b.d. (20 C., 1 kHz) = t.b.d. Notes: t.b.d.: to be determined.

(70) TABLE-US-00014 TABLE 5 Properties of mixture M-2 at 30 GHz T/ C. .sub.r, .sub.r, .sub. tan .sub., r, tan .sub., r, 20 3.18 2.40 0.245 0.0015 0.0055 46

(71) This mixture is very highly suitable for applications in the microwave region, in particular for phase shifters.

Example 3

(72) A liquid-crystal mixture M-3 having the composition and properties as indicated in the following table is prepared and investigated with respect to its physical properties, in particular in the microwave region.

(73) TABLE-US-00015 Composition Compound No. Abbreviation 1 PTP(2)TP-6-3 90.0 2 10*P-3 10.0 100.0 Physical properties T(N, I) = 116.5 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n.sub.o (20 C., 589.3 nm) = t.b.d. .sub.|| (20 C., 1 kHz) = 3.4 (20 C., 1 kHz) = +0.8 k.sub.1 (20 C.) = 12.47 pN K.sub.3 (20 C.) = 51.2 pN Notes: t.b.d.: to be determined.

(74) TABLE-US-00016 TABLE 6 Properties of mixture M-3 at 30 GHz T/ C. .sub.r, .sub.r, .sub. tan .sub., r, tan .sub., r, 20 3.14 2.37 0.245 0.0015 0.0054 45

(75) This mixture is very highly suitable for applications in the microwave region, in particular for phase shifters.

Example 4

(76) A liquid-crystal mixture M-4 having the composition and properties as indicated in the following table is prepared and investigated with respect to its physical properties, in particular in the microwave region.

(77) TABLE-US-00017 Composition Compound No. Abbreviation 1 PTP(2)TP-3-1 10.0 2 PTP(2)TP-6-3 63.0 3 PTP(2)TP-3-O5 10.0 4 PGUQU-3-F 5.0 5 PU[QGU].sub.2-5-F 5.0 6 10*P-3 7.0 100.0 Physical properties T(N, I) = 123.5 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n.sub.o (20 C., 589.3 nm) = t.b.d. .sub.|| (20 C., 1 kHz) = 5.2 (20 C., 1 kHz) = 2.4 k.sub.1 (20 C.) = t.b.d. pN K.sub.3 (20 C.) = t.b.d. pN Notes: t.b.d.: to be determined, PU[QGU].sub.2-5-F: PUQGUQGU-5-F, Phase sequence: C 86 C. N 236.4 C.I.

(78) TABLE-US-00018 TABLE 7 Properties of mixture M-4 at 30 GHz T/ C. .sub.r, .sub.r, .sub. tan .sub., r, tan .sub., r, 20 3.18 2.39 0.248 0.0021 0.0074 34

(79) This mixture is very highly suitable for applications in the microwave region, in particular for phase shifters. It has, in particular, a relatively high .

Example 5

(80) A liquid-crystal mixture M-5 having the composition and properties as indicated in the following table is prepared and investigated with respect to its physical properties, in particular in the microwave region.

(81) TABLE-US-00019 Composition Compound No. Abbreviation 1 PTP(2)TP-6-3 70.0 2 PTP(c3)TP-4-4 10.0 3 PT(1,4N)BP-3-4 10.0 4 10*P-3 10.0 100.0 Physical properties T(N, I) = 119.0 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n.sub.o (20 C., 589.3 nm) = t.b.d. .sub.|| (20 C., 1 kHz) = 3.6 (20 C., 1 kHz) = +0.9 k.sub.1 (20 C.) = 10.9 pN K.sub.3 (20 C.) = 46.4 pN Notes: t.b.d.: to be determined.

(82) TABLE-US-00020 TABLE 8 Properties of mixture M-5 at 30 GHz T/ C. .sub.r, .sub.r, .sub. tan .sub., r, tan .sub., r, 22 3.13 2.40 0.233 0.0015 0.0052 45

(83) This mixture is very highly suitable for applications in the microwave region, in particular for phase shifters.

Example 6

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

(85) TABLE-US-00021 Composition Compound No. Abbreviation 1 PTP(2)TP-3-1 15.0 2 PTP(2)TP-3-3 15.0 3 PTP(2)TP-3-O5 15.0 4 PTP(2)TP-6-3 42.0 5 D(fN)UQU-3-F 8.0 6 10*P-3 5.0 100.0 Physical properties T(N, I) = 129.5 C. n.sub.e (20 C., 589.3 nm) = t.b.d. n.sub.o (20 C., 589.3 nm) = t.b.d. .sub.|| (20 C., 1 kHz) = 6.5 (20 C., 1 kHz) = 3.0 k.sub.1 (20 C.) = t.b.d. K.sub.3 (20 C.) = t.b.d. Notes: t.b.d.: to be determined and D(fN)UQU-3-F, phase sequence: C 80 C. N 120 C.I.

(86) TABLE-US-00022 TABLE 9 Properties of mixture M-6 at 30 GHz T/ C. .sub.r, .sub.r, .sub. tan .sub., r, tan .sub., r, 20 3.23 2.42 0.250 0.0023 0.0085 30

(87) This mixture is very highly suitable for applications in the microwave region, in particular for phase shifters. It has, in particular, a relatively high .