TW201245421A

TW201245421A - Compounds for a liquid-crystalline medium, and the use thereof for high-frequency components

Info

Publication number: TW201245421A
Application number: TW101109742A
Authority: TW
Inventors: Christian Jasper; Atsutaka Manabe; Detlef Pauluth; Volker Reiffenrath
Original assignee: Merck Patent Gmbh
Priority date: 2011-03-22
Filing date: 2012-03-21
Publication date: 2012-11-16
Also published as: WO2012126570A1; TWI545180B; DE102012004393A1

Abstract

The present invention relates to compounds having at least one bi- or tri-cyclic ring system which is connected by means of acetylene or difluoro-ethylene bridges, to the use thereof for high-frequency components, to liquid-crystalline media comprising the compounds, and to high-frequency components, in particular antennae, especially for the gigahertz range, containing these media. The liquid-crystalline media serve, for example, for the phase shifting of microwaves for tuneable phased-array antennae.

Description

201245421 六、發明說明：【發明所屬之技術領域】本發明係關於一種具有至少一個藉由伸乙醯基或二氟伸乙基橋連接之二環或三環體系之化合物，其用於高頻構件之用途，包括該類化合物之液晶介質，及包含該類介質之高頻構件，特定言之天線，尤其係用於千兆赫範圍之天線。液晶介質用於例如相位陣列天線之微波相移。【先前技術】液晶介質已經在電光顯示器（液晶顯示器-LCD)中應用以顯不資訊達一段時曰。在說明書EP 0968988 Al、DE 19907941 Al、DE 10120024 A1及JP 08012599 A中提出1，4·二乙炔基苯衍生物作為液晶組分。其中未揭示在兩環之間具有（二氟）伸乙基橋之化合物。然而，近來，在DE 10 2004 029 429 A 及 JP 2005-120208(A)中亦已經提出液晶介質用於微波技術之構件中〇液晶介質在高頻技術中之一種具有工業價值之應用係基於其具有可藉由可變電壓控制之介電性之性質，尤其係用於千兆赫範圍。因此，可設計不含移動部件之可調式天線 (A. Gaebler、A. Moessinger、F. Goelden 等人，「Liquid Crystal-Reconfigurable Antenna Concepts for Space Applications at Microwave and Millimeter Waves，」 International Journal of Antennas and Propagation, Vol. 2009,論文 ID 876989，7 162172.doc 201245421 頁，2009. doi:l〇.1 155/2009/876989)。出版物 A. Penirschke、S. Mtiller、P. Scheele、C. Weil、 M. Wittek、C. Hock及 R. Jakoby : 「Cavity Perturbation201245421 VI. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a compound having at least one bicyclic or tricyclic ring system linked by an exoethyl or difluoroextended ethyl bridge for use in high frequency components The use thereof includes liquid crystal media of such compounds, and high frequency components including such media, in particular antennas, especially for antennas in the gigahertz range. Liquid crystal media are used for, for example, microwave phase shifting of phased array antennas. [Prior Art] Liquid crystal media have been used in electro-optical displays (LCDs) to display information for a period of time. The 1,4·diethynylbenzene derivative is proposed as a liquid crystal component in the specification EP 0 968 988 Al, DE 19907941 Al, DE 10120024 A1 and JP 08012599 A. There is no disclosure of a compound having a (difluoro)extended ethyl bridge between the two rings. However, recently, in DE 10 2004 029 429 A and JP 2005-120208 (A), liquid crystal media have also been proposed for use in components of microwave technology. One of the industrial applications of liquid crystal media in high frequency technology is based on It has the property of dielectric properties controllable by variable voltage, especially for the gigahertz range. Therefore, it is possible to design a tunable antenna without moving parts (A. Gaebler, A. Moessinger, F. Goelden et al., "Liquid Crystal-Reconfigurable Antenna Concepts for Space Applications at Microwave and Millimeter Waves," International Journal of Antennas and Propagation , Vol. 2009, paper ID 876989, 7 162172.doc 201245421, 2009. doi: l〇.1 155/2009/876989). Publications A. Penirschke, S. Mtiller, P. Scheele, C. Weil, M. Wittek, C. Hock and R. Jakoby: "Cavity Perturbation

Method f〇r Characterization of Liquid Crystals up to 35 GHz」，34th European Microwave Conference - Amsterdam, 545-548尤其敘述已知之液晶個別物質K15(Merck KGaA，Method f〇r Characterization of Liquid Crystals up to 35 GHz", 34th European Microwave Conference - Amsterdam, 545-548, in particular, the known liquid crystal individual substance K15 (Merck KGaA,

Germany)在9 GHz之頻率下之性質。熟習此項技術者知曉在中央伸苯基環上具有烷基取代基之1-(苯基乙炔基）二苯乙炔類（下文亦稱為雙二苯乙炔化合物）。例如，出版物 S._T. Wu、C.-S. Hsu、K.-F. ShyuGermany) Properties at a frequency of 9 GHz. Those skilled in the art are aware of 1-(phenylethynyl)diphenylacetylenes (hereinafter also referred to as bisdiphenylacetylene compounds) having an alkyl substituent on a central phenyl ring. For example, publication S._T. Wu, C.-S. Hsu, K.-F. Shyu

Appl. Phys. Lett.(1 999)，74(3)，344-346揭示下式之具有側曱基之各種液晶雙二苯乙炔化合物， ch3Appl. Phys. Lett. (1 999), 74(3), 344-346 discloses various liquid crystal bis-diphenylacetylene compounds having pendant fluorenyl groups of the formula: ch3

CnH2n+rH^-CEC-^)-CEC^^~CmH2(n+1 除了具有側曱基之該類型之液晶雙二苯乙炔化合物外， C. S· Hsu、K. F. Shyu、Y.Y. Chuang、S.-T. Wu Liq. Cryst. (2000), 27(2), 283-287亦揭示具有側乙基之相應化合物及提出其用途，尤其用於「液晶光學相位陣列」中。 DE 10 2004 〇29 429 A(參考以上）敘述常規液晶介質於微波技術，尤其於相移器中之用途。其中’已經就其在對應頻率範圍内之性質研究該液晶介質。一種下式之化合物’ 162172.doc 201245421CnH2n+rH^-CEC-^)-CEC^^~CmH2(n+1 In addition to this type of liquid crystal bis-phenylacetylene compound having a side fluorenyl group, C. S·Hsu, KF Shyu, YY Chuang, S. -T. Wu Liq. Cryst. (2000), 27(2), 283-287 also discloses corresponding compounds having pendant ethyl groups and their use, especially in "liquid crystal optical phase arrays". DE 10 2004 〇29 429 A (cf. above) describes the use of conventional liquid crystal media in microwave technology, especially in phase shifters, where 'the liquid crystal medium has been studied for its properties in the corresponding frequency range. A compound of the formula '162172.doc 201245421

及其衍生物被敘述為有機薄膜電晶體之成分（EP 2 073 290 A1)’作為用於控制「光酸產生系統」之光敏染料（w〇 2008/021208 A2)及作為數據記錄介質之成分（Jp 2〇〇4_ 082439 A)。液晶性質及其在液晶介質中之用途迄今未有敘述。此外，EP 2 073 290 A1命名下列化合物： (H, ch3, cf3, F)And its derivatives are described as components of organic thin film transistors (EP 2 073 290 A1)' as photosensitive dyes for controlling "photoacid generating systems" (w〇2008/021208 A2) and as components of data recording media ( Jp 2〇〇4_ 082439 A). The properties of liquid crystals and their use in liquid crystal media have not been described so far. In addition, EP 2 073 290 A1 names the following compounds: (H, ch3, cf3, F)

(H，cH3. CF3, F) (H，c ch3. cf3, F) 在每一情形下，可提及四種經對稱取代之分子。然而’迄今已知的組合物或個別化合物一般受其缺點所影響。除其他缺陷外，其中大多數導致不利的高損失及/ 或不充分的相移或不足的材料品質。爲了用於高頻技術’要求具有特定、迄今為止相當不平常 '非標準性質或性質組合之液晶介質。因此’需要具有改良性質之用於液晶介質之新賴k分。特定言之，必須減少微波區中之損失及必須改良材料品質 (η) °對於可調式天線而言’還要求對在電池電極之間之電壓變化具有快速反應時間的液晶介質。此外’需要改良構件之低溫行為。於此需要改良操作性 162172.doc 201245421 及儲存性。因此’對於具有用於相應實際應用之適當性質的液晶介質存在諸多要求。出人意料地’已經發現根據本發明之化合物具有寬向列相及南澄清點（由向列相轉變為各向同性相）。同時，光學各向異性（Δη)位於有利微波之相移的區域。利用該影響，現已出人意料地發現，利用根據本發明之化合物可實現具有適當向列相範圍及高^之液晶介質，而不具有先前技術之材料之缺點或，至少達至顯著減少的程度。【發明内容】本發明係關於式I之化合物，(H, cH3. CF3, F) (H, c ch3. cf3, F) In each case, four symmetrically substituted molecules may be mentioned. However, the compositions or individual compounds known to date are generally affected by their disadvantages. Most of these, among other defects, result in unfavorable high losses and/or inadequate phase shifts or insufficient material quality. In order to be used in high frequency technology, a liquid crystal medium having a specific, to date, rather unusual 'non-standard property or combination of properties is required. Therefore, there is a need for a new grading for liquid crystal media having improved properties. In particular, it is necessary to reduce the loss in the microwave region and to improve the material quality (η) ° For a tunable antenna, a liquid crystal medium having a fast reaction time for a voltage change between battery electrodes is also required. In addition, there is a need to improve the low temperature behavior of the components. This requires improved operability 162172.doc 201245421 and storage. Therefore, there are many requirements for liquid crystal media having suitable properties for the respective practical applications. Surprisingly, it has been found that the compounds according to the invention have a broad nematic phase and a southern clearing point (transition from a nematic phase to an isotropic phase). At the same time, the optical anisotropy (Δη) is located in a region where the phase shift of the microwave is favorable. Utilizing this effect, it has now surprisingly been found that the use of the compounds according to the present invention achieves a liquid crystal medium having a suitable nematic phase range and high throughput without the disadvantages of prior art materials or at least to a significant extent. SUMMARY OF THE INVENTION The present invention is directed to a compound of formula I,

Rl-iAl-z1)m—A2—Ζ2—(A3)p-Z3—A4-(Z5-A5)n-R2 ι 其中A1 5彼此獨立地面向任何一邊地表示 a)下式之基團Rl-iAl-z1)m-A2—Ζ2—(A3)p-Z3—A4-(Z5-A5)n-R2 ι wherein A1 5 is oriented independently of each other, a) a group of the formula

I62172.doc 201245421I62172.doc 201245421

個不相連-CH2-可經X取代，及 R3 係如R1所定義， b) 1,4-伸苯基，其中一或多個、較佳言之一或兩個CH 基團可經N取代， c)下式之基團Unconnected -CH2- may be substituted by X, and R3 is as defined by R1, b) 1,4-phenylene, one or more, preferably one or two CH groups may be substituted by N , c) the group of the following formula

162172.doc 201245421162172.doc 201245421

兩個不相連CH2可經_〇_及/或_s_取代代，另外其中，一或及其中Η可經F取或 0選自基團Μ.二環Μ•小申辛基、環丁垸]，3_二基螺[3.3]庚烧-2,6.二基、„塞吩_2,5_二基、嗔吩_2,4_二基呋喃-2,5-二基、呋喃_2,4_二基之基團，其中在基團a)、b)、c)、d)及e)中，-或多個Η原子亦可經 ΒΓ、。、F、CN ' _NCS、-SCN、SF5、Cl_C 丨❶烷基、 1 C1G烧氧基、Cs-C6環烧基或單或多氟化之Ci_Cw烷基或烷氧基取代，及其中至少一個來自A2、A3及A4之基團表示根據a)之基團， R1及R2各彼此獨立地表示具有1至15個碳原子之鹵化或未經取代之烧基，另外其中，此類基團中之一或多個cH2 基團分別可彼此獨立地以使〇或S原子彼此不直接相連之方式經-CsC-、-CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、 -(CO)〇-、-〇(c〇)-、-(c〇)-、-〇-或-S-所取代， F、α、Br、CN、CF3、〇CF3、SCN、NCS 或 SF5， 162172.doc 201245421 丫1 z2、z3彼此獨立地表示{^。或 Y1、Y2彼此獨立地表示h、f、ci 之Η或F，特別佳係f， c=〇— V2 ,、c ! - C ! 0烧基’較佳古、-CH2CF2-、-CH2CH2-’其中不對稱橋可向兩邊 ^ 。从〜网儿吧衣示單鍵、_( 、-(C0)0-、-cf2〇_、_CF2Cf” 、-(CH2)4-、-CH=CF-或 _Cf=Cf 定向， ρ表示1或2，及 m、η彼此獨立地表示〇或 1或2， R^CA^Z1),^2-示下式之基團或-At 亦可獨立地視需要表 (ΑΑ5)η·Two unconnected CH2 may be replaced by _〇_ and/or _s_, in which one or a sputum may be taken by F or 0 is selected from the group Μ. Bicyclic Μ•小申辛基, 环丁垸], 3_二基螺 [3.3] Geng-2,6. Diyl, „ phenophene-2,5-diyl, porphin-2,4-diylfuran-2,5-diyl, a group of a furan-2,4-diyl group, wherein in the groups a), b), c), d) and e), - or a plurality of deuterium atoms may also pass through ΒΓ, ., F, CN ' _NCS , -SCN, SF5, Cl_C decyl, 1 C1G alkoxy, Cs-C6 cycloalkyl or mono- or polyfluorinated Ci_Cw alkyl or alkoxy, and at least one of them from A2, A3 and A4 The group denotes a group according to a), R1 and R2 each independently represent a halogenated or unsubstituted alkyl group having 1 to 15 carbon atoms, and wherein one or more of such groups are cH2 The groups may be independently of each other such that -CsC-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -() are not directly connected to each other. CO) 〇-, -〇(c〇)-, -(c〇)-, -〇- or -S-, F, α, Br, CN, CF3, 〇CF3, SCN, NCS or SF5, 162172 .doc 201245421 丫1 z2 Z3 independently of each other represents {^. or Y1, Y2 independently of each other represents h, f, ci or F, particularly good f, c = 〇 - V2, c! - C! 0 burning base 'better ancient , -CH2CF2-, -CH2CH2-' where the asymmetric bridge can be on both sides. From the ~ net, the clothing shows a single key, _ ( , -(C0)0-, -cf2〇_, _CF2Cf", -(CH2) 4-, -CH=CF- or _Cf=Cf orientation, ρ represents 1 or 2, and m, η independently represent 〇 or 1 or 2, R^CA^Z1), ^2 shows the basis of the following formula Group or -At can also independently view the table (ΑΑ5) η·

162172.doc 201245421 R1-162172.doc 201245421 R1-

R2 均表示F或均表示CF3之彼其中不包括R1及R2均表示CH3，等。在環Al V之間之式_CYi=CY2_之雙鍵及在基n z5 中之視需要之雙鍵較佳地具有反式組態⑵组態）。根據本發明之化合物具有高澄清點、低㈣及高光學各向異性（Δη)。非所需的化合物之旋轉得以限制意味著其特別適合用於千兆赫範圍内。在微波光譜中之較低損失因子係有利的。單獨或呈與其他液晶原基組分之混合物之化合物在較廣溫度範圍内具有向列相。此類性質使其特別適合用於高頻技術之構件，特定言之用於液晶相穿多器。根據本發明之液晶介質具有相應性質。較佳之式I之化合物的特徵為對一或多個下列參數之選擇：指數m較佳係〇或1，特別佳係〇 ^指數η較佳係〇或丨，特別佳係0。m+n較佳係〇或1及特別佳係〇。m+n+p較佳係1或 2 ’即該式I中之環體系之總數較佳係3或4。按照定義a) ’基團A2、A3及A4較佳地合計包括一或兩個二環或三環基團。按照定義a)，基團A3特別佳地表示環基。按照定義b)或c)，環基A2及A4及可存在之A1及A5特別佳地獨立地表示視需要經取代之環基，特定言之視需要經取代之1，4·伸苯基。 162172.doc -10- 201245421 橋連基團z及z5較佳彼此獨立地表示單鍵、_CsC_、 _CF=CF·或-CH=CH- ’特別佳係單鍵。 z2及z3較佳係_c=ckf=cf_，特別佳係《_。此類基團尤其有利於尚Δη值及優良的相性質。 Υ /Υ 較佳係 H/F、F/H、F/F、Cl/F、CH3/F、F/CH3 或 F/C1及特別佳係F/F。基團R1或R2之一者或兩者，較佳係尺|，較佳地表示具有 1至15個、特定言之2至15個碳原子之直鏈烷基，另外其中，此類基團中之一或多個CH2基團可分別彼此獨立地以使Ο原子彼此不直接相連之方式經_(^(3-、-(^11=(^1'1-、_((110)0~ 、-O(CO)-、_(CO)-、_〇-所取代。基團尺1及R2特別佳均為具有2至7個碳原子之烷基。於此，Ri及R2表示例如丙基及己基或丁基及丁基，另外表示丙基及戊基、丙基及己基、或丁基及戊基。在本發明之另一較佳實施例中’基團R2為極性基團（基團 X)。於此，基團 R2=X表示 F、Cl、Br、CN、CF3、〇CF3、SCN、NCS、SF5或另一具有1至9個碳原子之鹵化烷基，另外其中，該基團中之一或多個CH2基團分別可彼此獨立地以使〇或S原子彼此不直接相連之方式經-c s C -、 -CH=CH-、-CF=CF-、-CF=CH-、-CH=CF-、-((：〇)〇_、_〇(C〇)· 、-(CO)-、-〇-或-S-所取代。於此’ R2特別佳地表示ρ、 CF3或OCF3。對應之式I之化合物具有明顯正值的介電各向異性（Δε)。Δε值較佳係3或更大。該兩項實施例之基團R2因而一起較佳地表示具有2至15 162172.doc 201245421 個碳原子之烷基，另外其中，此類基團中之一或多個ch2 基團分別可彼此獨立地以使〇原子彼此不直接相連之方式經-CsC-、-CH=CH-、-(CO)O-、-O(CO)-、-(CO)-、-0-所取代，或表示 F、Cl、Br、CN、CF3、0CF3、SCN、 NCS、SF5或具有1至9個碳原子之鹵化院基，另外其中該基團中之一或多個CH2基團分別可彼此獨立地以使〇或s 原子彼此不直接相連之方式經《_、_CH=CH、、-CF=CH-、-CH^CF-、或所取代。 -(CO)O-、_〇(c〇)_、 -(CO)·、-0- 按照定義b) ’環基較佳地具有子結構R2 means that F or both means CF3, and R1 and R2 both represent CH3, and so on. The double bond of the formula _CYi=CY2_ between the rings Al V and the optional double bonds in the base n z5 preferably have a trans configuration (2) configuration). The compounds according to the invention have a high clearing point, a low (four) and a high optical anisotropy (Δη). The limitation of the rotation of the undesired compound means that it is particularly suitable for use in the gigahertz range. The lower loss factor in the microwave spectrum is advantageous. Compounds, either alone or in admixture with other liquid crystal priming components, have a nematic phase over a wide temperature range. This property makes it particularly suitable for components used in high frequency technology, in particular for liquid crystal phase-through devices. The liquid crystal medium according to the present invention has corresponding properties. Preferably, the compound of formula I is characterized by one or more of the following parameters: The index m is preferably 〇 or 1, particularly preferably 〇 ^ index η is preferably 〇 or 丨, particularly preferably 0. m+n is preferably a system or a particularly good system. m+n+p is preferably 1 or 2', that is, the total number of ring systems in the formula I is preferably 3 or 4. Preferably, the groups a2, A3 and A4, by definition, include one or two bicyclic or tricyclic groups in total. According to the definition a), the group A3 particularly preferably represents a ring group. According to the definition b) or c), the cyclic groups A2 and A4 and the optionally present A1 and A5 particularly preferably independently represent the optionally substituted cyclic group, and in particular, the substituted 1,4·phenylene group. 162172.doc -10- 201245421 The bridging groups z and z5 preferably represent, independently of each other, a single bond, _CsC_, _CF=CF· or -CH=CH- ', particularly preferably a single bond. Z2 and z3 are preferably _c=ckf=cf_, especially good for "_. Such groups are particularly advantageous for still Δη values and excellent phase properties. Υ /Υ is preferably H/F, F/H, F/F, Cl/F, CH3/F, F/CH3 or F/C1 and especially good F/F. One or both of the groups R1 or R2, preferably a flank|, preferably a linear alkyl group having 1 to 15, in particular 2 to 15 carbon atoms, in addition, such a group One or more of the CH 2 groups may be independently of each other such that Ο atoms are not directly connected to each other by _(^(3-, -(^11=(^1'1-, _((110)0) And -O(CO)-, _(CO)-, _〇- are substituted. The group 1 and R2 are particularly preferably an alkyl group having 2 to 7 carbon atoms. Here, Ri and R2 represent, for example. Propyl and hexyl or butyl and butyl, additionally denotes propyl and pentyl, propyl and hexyl, or butyl and pentyl. In another preferred embodiment of the invention 'the group R2 is a polar group (Group X). Here, the group R2=X represents F, Cl, Br, CN, CF3, 〇CF3, SCN, NCS, SF5 or another halogenated alkyl group having 1 to 9 carbon atoms, in addition One or more CH 2 groups in the group may be independently of each other such that - C C -, -CH=CH-, -CF=CF-, -CF are not directly connected to each other. =CH-, -CH=CF-, -((:〇)〇_,_〇(C〇)·, -(CO)-, -〇- or -S- are substituted. Here 'R2 Particularly preferably, ρ, CF3 or OCF3 is present. The corresponding compound of formula I has a significantly positive dielectric anisotropy (Δε). The value of Δε is preferably 3 or more. The groups R2 of the two examples are thus Preferably, together with an alkyl group having 2 to 15 162172.doc 201245421 carbon atoms, wherein one or more of the such groups may be independently of each other such that the germanium atoms are not directly connected to each other. The mode is substituted by -CsC-, -CH=CH-, -(CO)O-, -O(CO)-, -(CO)-, -0-, or represents F, Cl, Br, CN, CF3, 0CF3, SCN, NCS, SF5 or a halogenated substituent having 1 to 9 carbon atoms, wherein in addition one or more of the CH2 groups in the group may be independently of each other such that the 〇 or s atoms are not directly connected to each other The mode is replaced by "_, _CH=CH, , -CF=CH-, -CH^CF-, or . -(CO)O-, _〇(c〇)_, -(CO)·,-0- According to the definition b) 'the ring group preferably has a substructure

而係由下列說明性結構表示And is represented by the following illustrative structure

本發明之較佳實施例因 I62172.doc -12· 201245421The preferred embodiment of the present invention is I62172.doc -12· 201245421

其中基團係如在式I中所定義’特定言之R1及R2獨立地表示具有2至7個碳原子之烷基，例如一個基團表示丙基及另一個基團表示己基或兩個基團同時表示丙基、丁基、戊基或己基。【實施方式】式I之化合物宜按照下列說明性合成反應圖（反應圖1及2) 所表明之方式而製備。式I之對稱性化合物可藉由單 Sonogashira反應（反應圖1)而製備：Wherein the group is as defined in formula I, in particular, R1 and R2 independently represent an alkyl group having 2 to 7 carbon atoms, for example one group represents a propyl group and the other group represents a hexyl group or two groups. The group also means a propyl group, a butyl group, a pentyl group or a hexyl group. [Embodiment] The compound of the formula I is preferably prepared in the manner indicated by the following illustrative synthesis scheme (reaction schemes 1 and 2). The symmetrical compound of formula I can be prepared by a single Sonogashira reaction (reaction Figure 1):

反應圖1:用於製備式I之化合物之合成反應圖。式⑴之非對稱性化合物可藉由與在反應圖2中所描繪之反應順序相似的方式而製備： 162172.doc -13· 201245421Reaction Scheme 1: Scheme for the synthesis of the compounds of Formula I. The asymmetric compound of formula (1) can be prepared in a similar manner to the reaction sequence depicted in Figure 2: 162172.doc -13· 201245421

反應圖2 :用於製備非對稱性式I之化合物之合成反應圖。反應圖1及2中之R1/2具有如針對式I所定義之ri/2之含義。反應圖1及2顯示某些化合物之合成。苯基「Rl苯基」及「R2-苯基」於此可分別根據式〗概括為任何所需之基團-A2-(Z丨-Ai)m-R丨及-A4-(Z5-A5)n-R2。其中之參數Rl/2、 A1·5、Z1/5、m及η係如上文及下文所定義。根據本發明之液晶介質包括一或多種式〗之化合物及視需要之至少一種其他、較佳言之液晶原基化合物。液晶介質因而較佳地包括兩種或多種較佳為液晶之化合物。較佳的介質包括較佳之式I之化合物。液晶介質之其他組分較佳地選自式II之化合物：Reaction Scheme 2: Synthesis reaction scheme for the preparation of asymmetrical compounds of formula I. R1/2 in Reaction Schemes 1 and 2 has the meaning of ri/2 as defined for Formula I. Reaction Schemes 1 and 2 show the synthesis of certain compounds. The phenyl "Rl phenyl" and "R2-phenyl" can be summarized herein according to the formula to any desired group -A2-(Z丨-Ai)mR丨 and -A4-(Z5-A5)n. -R2. The parameters Rl/2, A1·5, Z1/5, m and η are as defined above and below. The liquid-crystalline medium according to the present invention comprises one or more compounds of the formula and, if desired, at least one other, preferably liquid crystal, primordial compound. The liquid crystal medium thus preferably comprises two or more compounds which are preferably liquid crystals. Preferred media include the preferred compounds of formula I. The other components of the liquid crystal medium are preferably selected from the compounds of formula II:

I62I72.doc -14- 201245421 其中 Ln L12 R11 及 R12 X11 及 X12 p ' q z11 至 z13 表示R11或X11，表示R12或X12，彼此獨立地表不具有1至17個 '較佳具有3至 10個碳原子之非氟化烷基或非氟化烷氧基，或具有2至15個、較佳言之3至1 〇個碳原子之非氟化烯基、非氟化炔基、非氟化烯氧基或非氟化烷氧基烷基，彼此獨立地表示F、C卜Br、-CN、-NCS、-SCN 、-SFs、具有1至7個碳原子之氟化烷基或氟化烧氧基或具有2至7個碳原子之氟化烯基、氟化稀氧基或氟化烷氧基烷基，較佳係氟化院氧基、氟化烯氧基、F或C1，獨立地表示〇或1，彼此獨立地表示反式-CH=CH-、反式-CF=CF-、-C = C-或單鍵，及I62I72.doc -14- 201245421 where Ln L12 R11 and R12 X11 and X12 p ' q z11 to z13 represent R11 or X11, representing R12 or X12, independently of each other, having from 1 to 17 'preferably having 3 to 10 carbons a non-fluorinated alkyl or non-fluorinated alkoxy group of an atom, or a non-fluorinated alkenyl group having 2 to 15, preferably 3 to 1 carbon atoms, a non-fluorinated alkynyl group, a non-fluorinated alkene An oxy or non-fluorinated alkoxyalkyl group, independently of each other, denotes F, C, Br, -CN, -NCS, -SCN, -SFs, a fluorinated alkyl group having 1 to 7 carbon atoms or a fluorinated group An oxy group or a fluorinated alkenyl group having 2 to 7 carbon atoms, a fluorinated dioxy group or a fluorinated alkoxyalkyl group, preferably a fluorinated alkoxy group, a fluorinated alkenyloxy group, F or C1, independently The ground represents 〇 or 1, independently of each other, representing trans-CH=CH-, trans-CF=CF-, -C=C- or a single bond, and

彼此獨立地表示Express independently of each other

162172.doc •15· 201245421162172.doc •15· 201245421

或非支鏈烷基、烯基或炔基，其中，一或多個「-CH2·」基團亦可彼此獨立地經〇所取代’或表示CVC6環烷基、C3-C6環烯基、氟化烷基或烯基、氟化烷氧基或烯氧基、F、 C卜 Br、CN ' NCS、SCN或 SF5。在本發明之一較佳實施例中，液晶介質包括一或多種式 I之化合物及一或多種式II之化合物。根據本申請案之液晶介質較佳地包括合計5至95%、較佳a之10至90%及特別佳15至8〇%之式I之化合物。根據本發明之液晶介質較佳地包括選自式〗及式π之化合物之群之化合物，更佳言之主要由其組成，尤其更佳言之基本上由其組成及極佳言之完全由其組成。在該申請案中，與組合物有關t「包括」表示有關主體 (即介質或組分）包括以較佳言之丨〇%或更大及極佳言之 20%或更大之總濃度之所指組分或化合物。 /、此相關主要由其組成」表示有關主體包括5 5 %或更大、較佳言之60%或更大及極佳言之7〇%或更大之所指 162172.doc 201245421 組分或化合物》與此相關，「基本上由其組成」表示有關主體包括80% 或更大、較佳言之90%或更大及極佳言之95%或更大之所指組分或化合物。與此相關，「完全由其組成」表示有關主體包括98%或更大、較佳言之99%或更大及極佳言之100.0%之所指組分或化合物。根據本申請案之液晶介質較佳包括合計1〇至1〇〇%、較佳言之20至95%及特別佳25至90%之式I及II之化合物。根據本發明’式II之化合物較佳地以佔總混合物之丨〇% 至90。/。、更佳言之15%至85%、尤其更佳25%至8〇%及極佳言之30%至75%之總濃度使用。此外’液晶介質可包括其他添加劑，諸如安定劑、對掌性摻雜劑及奈米顆粒。該等個別添加之化合物係以〇〇〇5 至6 /〇、較佳§之〇· 1至3%之濃度使用。此類其他成分佔總混合物之總濃度係於0%至10%、較佳言之〇 1%至6%之範圍内。然而，;夜晶混合物之剩餘成分(即液晶或液晶原基化合物）之濃度數據係不考慮此類添加劑之濃度而表示。液晶介質較佳地包括0至10重量％、特定言之〇〇1至5重重％及特別佳0.1至3會暑％夕立々 Τ』王j置里/。之文疋劑。該介質較佳地包括一或多種選自2,6-二-第=丁其钻必 ^ _ 弟一丁基本酚、2,2,6,6-四甲基哌啶或2-苯并***-2-基苯酚之安定劑。 ^ 此4助劑為熟習此項技術者所知曉及可作為例如光安定劑而購得。本發明之一實施例因而亦為-種製備液晶介質之方法， 162172.doc -17- 201245421 其特徵在於：將一或多種式i之化合物與一或多種其他化合物及視需要與一或多種添加劑混合。該等其他化合物較佳地選自上述式π之化合物及視需要選自一或多種其他化合物。在本申請案中，表述介電正性敘述其中Δε>3.0之化合物或組分’介電中性敘述其中_1·55Δε<3·〇之彼等及介電負性敘述其中Δε<-1.5之彼等。各化合物之介電各向異性係由各個別化合物溶於向列型主混合物之1 〇%溶液之結果而破定。若各化合物在主混合物中之溶解度小於1〇%，則將濃度減至5%。測試混合物之電容係在具有垂直配向之電池及具有平行配向之電池中測定。兩種類型電池之電池厚度為約20 μπι。施加之電壓為具有j让112頻率及一般而言〇 5 V至1.0 V之有效值之矩形波，但其總是選為低於各測試混合物之電容臨限值。 △ ε疋義為（ε|| - ε丄），，而ε平均為（ε||+2 ε丄）/ 3 〇用於介電正性化合物之主混合物為混合物ZLI_4792及用於"電中性及介電負性化合物者為混合物ZLI_3〇86，該兩者均購自Merck KGaA，Germany。化合物之介電常數之絕對值係由主混合物在添加受關注化合物時各數值之變化而確定。該類數值可外推至100。/。之受關注化合物之濃度。在2(TC之測量溫度下具有向列相之組分係按照如此測量’所有其他係以如化合物之方式進行處理。在本申請案中之術語臨限電壓表示光學臨限值及引用為 10%相對對比度（V1C)，及術語飽和電壓表示光學飽和及引 162172.doc -18- 201245421 用為90%相對對比度a%)，在該兩種情形中另外明確說明的除外。若明確提及，則僅使用電容臨限電壓（v〇)(亦稱為Or an unbranched alkyl, alkenyl or alkynyl group, wherein one or more "-CH2." groups may also be substituted by hydrazine independently of each other' or represent CVC6 cycloalkyl, C3-C6 cycloalkenyl, Fluorinated alkyl or alkenyl, fluorinated alkoxy or alkenyloxy, F, CbBr, CN ' NCS, SCN or SF5. In a preferred embodiment of the invention, the liquid crystal medium comprises one or more compounds of formula I and one or more compounds of formula II. The liquid crystal medium according to the present application preferably comprises a compound of the formula I in a total amount of from 5 to 95%, preferably from 10 to 90% and particularly preferably from 15 to 8% by weight. The liquid-crystalline medium according to the present invention preferably comprises a compound selected from the group consisting of a compound of the formula π and a compound of the formula π, and more preferably consists essentially of it, and more preferably, consists essentially of it and is extremely well-known Its composition. In this application, the term "comprising" with respect to the composition means that the subject (ie, the medium or component) comprises, in a preferred embodiment, % or greater and, optimally, a total concentration of 20% or greater. The component or compound referred to. / / This correlation consists mainly of "represented" 162172.doc 201245421 component of the subject concerned, including 55% or more, preferably 60% or more, and 7% or more of the best words or Compounds are related to this, and "consisting essentially of" means that the subject comprises 80% or more, preferably 90% or more, and preferably 95% or more of the indicated components or compounds. In connection with this, "completely composed of" means that the subject comprises 98% or more, preferably 99% or more, and 100.0% of the indicated components or compounds. The liquid crystal medium according to the present application preferably comprises a total of from 1 to 1%, preferably from 20 to 95% and particularly preferably from 25 to 90% of the compounds of the formulae I and II. The compound of formula II according to the invention preferably comprises from 丨〇% to 90% of the total mixture. /. More preferably, 15% to 85%, especially preferably 25% to 8%, and excellent 30% to 75% of the total concentration. Further, the liquid crystal medium may include other additives such as a stabilizer, a palmitic dopant, and nanoparticle. These individually added compounds are used at a concentration of from 〇〇5 to 6 /〇, preferably §·1 to 3%. The total concentration of such other ingredients in the total mixture is in the range of 0% to 10%, preferably 〇 1% to 6%. However, the concentration data of the remaining components of the night crystal mixture (i.e., liquid crystal or liquid crystal primordial compound) is expressed irrespective of the concentration of such additives. The liquid crystal medium preferably comprises from 0 to 10% by weight, in particular, from 1 to 5% by weight, and particularly preferably from 0.1 to 3, which may be caused by the heat of the sun. The sputum agent. Preferably, the medium comprises one or more selected from the group consisting of 2,6-di-di-D-Dings, butyl butyl phenol, 2,2,6,6-tetramethylpiperidine or 2-benzotriene A stabilizer for oxazol-2-ylphenol. ^ This 4 adjuvant is known to those skilled in the art and is commercially available, for example, as a light stabilizer. An embodiment of the invention is thus also a method of preparing a liquid crystal medium, 162172.doc -17- 201245421 characterized by one or more compounds of formula i and one or more other compounds and optionally one or more additives mixing. These other compounds are preferably selected from the compounds of the above formula π and optionally selected from one or more other compounds. In the present application, the expression dielectric positively describes a compound or component of Δε > 3.0 'dielectric neutral description wherein -1·55 Δε <3·〇 and their dielectric negative description Δε<-1.5 They are the same. The dielectric anisotropy of each compound was determined as a result of dissolving each individual compound in a 1% solution of the nematic main mixture. If the solubility of each compound in the main mixture is less than 1%, the concentration is reduced to 5%. The capacitance of the test mixture was determined in a battery with a vertical alignment and a battery with parallel alignment. The battery thickness of both types of batteries is about 20 μm. The applied voltage is a rectangular wave having an effective value of j to 112 and, in general, 〇 5 V to 1.0 V, but it is always selected to be lower than the capacitance threshold of each test mixture. △ ε 疋 is (ε|| - ε丄), and ε is average (ε||+2 ε丄) / 3 〇 for the main mixture of dielectric positive compounds is the mixture ZLI_4792 and for " Neutral and dielectric negative compounds are mixtures ZLI_3〇86, both available from Merck KGaA, Germany. The absolute value of the dielectric constant of a compound is determined by the change in each value of the main mixture upon addition of the compound of interest. This type of value can be extrapolated to 100. /. The concentration of the compound of interest. The component having a nematic phase at the measured temperature of TC is treated as such by the measurement. All other systems are treated as a compound. The term threshold voltage in the present application means the optical threshold and reference is 10 % relative contrast (V1C), and the term saturation voltage means optical saturation and 162172.doc -18- 201245421 is used as 90% relative contrast a%), unless otherwise explicitly stated in the two cases. If explicitly mentioned, only the capacitor threshold voltage (v〇) is used (also known as

Freedericks臨限值（vFr))。除非另外明確說明，否則在該申請案中表明之參數範圍 . 均包括限值。，針對性質之各範圍所表明之不同上限及下限值彼此組合可產生其他較佳範圍。除非另外明確說明，否則整篇該申請案中，應用以下條件及定義。除非另外明確說明，否則所有濃度係以重量百刀比引用及係關於各自的總體混合物，所有溫度係以攝氏度引用及所有溫差係以差示度引用。對於液晶而言為典型的所有物理性質係按照「Merck Liquid Crystals，physicalFreedericks Threshold (vFr)). Unless otherwise expressly stated, the range of parameters indicated in this application includes the limits. The combination of the different upper and lower limits indicated for each range of properties may result in other preferred ranges. Unless otherwise expressly stated, the following conditions and definitions apply throughout the application. Unless otherwise specifically stated, all concentrations are quoted in weight percent and are related to the respective overall mixture, all temperatures are quoted in degrees Celsius and all temperature differences are quoted as differential. All physical properties typical of liquid crystals are in accordance with "Merck Liquid Crystals, physical"

Properties of Liquid Crystals」，status Nov. 1997, Merck KGaA，Germany測定及在2〇°C之溫度下引用。光學各向異性（Δη)係在589.3 nm之波長下測定。介電各向異性（Δε)係在1 kHz之頻率下測定。臨限電壓以及所有其他電光學性負係利用在Merck KGaA, Germany製造之測試電池測定。用於测疋Δε之測試電池具有約2〇 μηι之電池厚度。電極為具有M3 cm2之面積及保護環之圓形汀〇電極。定向層對於垂直定向（ε||)而言為購自Nissan Chemicals，Japan之SE-1211 ’及對於平行定向（£丄）而言為構自syntheticProperties of Liquid Crystals", status Nov. 1997, Merck KGaA, Germany, and referenced at a temperature of 2 °C. The optical anisotropy (Δη) was measured at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) was measured at a frequency of 1 kHz. The threshold voltage and all other electro-optical negatives were determined using test cells manufactured by Merck KGaA, Germany. The test cell used to measure 疋Δε has a battery thickness of about 2 μm. The electrode is a circular Ting electrode with an area of M3 cm2 and a guard ring. The orientation layer is SE-1211' from Nissan Chemicals, Japan for vertical orientation (ε||) and is synthetic for parallel orientation (丄)

Rubber，Japan之聚醯亞胺AL-1054。電容係在0.3 Vrms之電壓下’利用應用正弦波之Solatron 1260頻率響應分析儀測定。用於電光學測量中之光為白光。於此使用應用可購自 162172.doc •19- 201245421Rubber, Japan Polyimine AL-1054. The capacitance is measured at a voltage of 0.3 Vrms using a Solatron 1260 frequency response analyzer using a sine wave. The light used in electro-optical measurements is white light. Applications for use here are available from 162172.doc •19- 201245421

Autronic-Melchers之市售DMS儀器之裝置。特徵電壓係在垂直觀察下測定。臨限電壓（V1())、中間灰色電壓（V5〇)及飽和電壓（V9〇)係分別針對10%、50%及90%相對對比度而測定。如在 A. Penirschke 等人，「Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz」， 34th European Microwave Conference · Amsterdam，第 545 至548頁中所述，研究就其在微波頻率範圍中之性質而言之液晶介質。就此相比而言，亦有A. Gaebler等人，「Direct Simulation of Material Permittivities …」，12MTC 2009 - International Instrumentation及Measurement Technology Conference, Singapore, 2009(IEEE),第 463 至 467 頁，及 DE 10 2004 029 429 A，其中同樣詳述測量方法。可將液晶引入聚四氟乙烯（PTFE)或石英毛細管中。毛細管具有180 μηι之内部半徑及350 μηι之外部半徑。有效長度為2.0 cm。將經填充之毛細管引入具有19 GHz之共振頻率之圓柱空腔之中心。該空腔具有11.5 mm之長度及6 mm之半徑。然後施加輸入信號（源），及利用市售向量網路分析儀記錄輸出信號結果。對於其他頻率而言，可相應調整空腔之尺寸。共振頻率及在利用填充液晶之毛細管之測量值與不用填充液晶之毛細管之測量值之間之Q因數之變化可以用來藉由在上述出版物A. Penirschke等人，34th European Microwave Conference - Amsterdam,第 545至 548頁中所述 162172.doc •20- 201245421 之等式10及11，測定在相應目標頻率下之介電常數及角度損失。又用於垂直及平行於液晶之指向矢之構件性質之數值係藉由在磁場中液晶之配向而獲得。為此’使用具有永久磁鐵之磁場。磁場強度為0.35特斯拉。磁鐵之配向可對應調節及隨後相應旋轉90。。微波區中之介電各向異性定義為 △εΓΞ(εΓ，丨卜 er，丄）。可調制性或可調諧性（τ)定義為 τ Ξ(Δε r / ε r,丨丨）。材料品質（η)定義為 η =(τ / tan δε r>max.)，其中’最大介電損失因子tan δε ^max : tan δε r>Max = Max. { tan δε r> ± ; tan δε r, 11 } 其來自於tan δε之測量值之最大值。較佳液晶材料之材料品質（11)為6或更大，較佳言之7或更大，較佳言之10或更大’較佳言之15或更大特別佳言之25或更大及極佳言之3〇或更大。一在相應構件中，較佳液晶材料具有15。_或更大、較佳言之20VdB或更大、較佳言之3〇0/dB或更大、較佳言之 4〇 /dB或更大、較佳言之5GQ/dB或更大、特別佳⑼。·或更大及極佳言之100。规或更大之相移器品質。根據本發明之液晶介質較佳地在各情形下具有至少-抓至8〇t、較佳言之.坑至机及極佳言之·4〇t至刚。c之 162172.doc •21 · 201245421 向列相。該相特別佳增至120°C或更大、較佳地增至14〇°C 或更大及極佳低增至180°C或更大。該表述具有向列相此處表示：一方面，在相應溫度下，於低溫下未觀察到層列相及結晶及另一方面，在加熱時，向列相未出現相變。低溫下之研究係在相應溫度下之流式黏度計中進行及藉由儲存於具有5 μιη之電池厚度之測試電池中至少1 〇〇小時來檢查。在高溫下，澄清點係藉由常規方法在毛細管中測量。根據本發明之液晶介質較佳地具有90它或更大，更佳言之100°c或更大’尤其更佳120°C或更大，特別佳150。(：或更大及極佳170°C或更大之澄清點。根據本發明之液晶介質在i kHz及20。(：下之Δε較佳為1或更大’更佳言之2或更大及極佳言之3或更大。根據本發明之液晶介質在589 nm(NaD)及20。(：下之Δη較佳位於0.20或更大至0.90或更小之範圍内，更佳言之位於〇·25或更大至〇·9〇或更小之範圍内，尤其更佳位於〇3〇或更大至0.85或更小之範圍内及極佳位於〇 35或更大至〇 8〇或更小之範圍内。在本申請案之一較佳實施例中，根據本發明之液晶介質之Δη較佳為〇.50或更大，更佳言之〇 55或更大。而且，根據本發明之液晶介質的特徵為在微波區中之高各向異性。例如，雙折射率在約8 3 〇112下較佳為〇 μ或更大’特別佳0.15或更大’特別佳〇 2〇或更大，特別佳〇 25 或更大及極佳0.3G或更大。此外，雙折射率較佳係㈣或 162172.doc •22- 201245421 相所應用之液晶為個別物質或混合物。其較佳地具有向列 0 在本申請案中’除非另外明確說明，否則術語化合物表示一種化合物或多種化合物。包括根據本發明之液晶介質或至少一種化合物之較佳構件為相移器、變容二極體、天線陣列(例如用於調頻、手機通信、微波/雷達及其他數據傳輸者）、「匹配電路自適應遽波器」及其他。較佳為如上定義之用於高頻技術4 件。較佳亦為可藉由不同施加電壓調節之構件。極佳構件係可調式相移器。在較佳實施例中，在功能上連接複數個相移器，產生例如相控組天線（一般稱為「相位陣列」天線）。一組天線使用呈矩陣配置之傳輸或接受元件之才」目移以透過干涉實現集束。呈列或格形式之相移器之平行处構可構建所稱之「相位陣列」，其可充當用於高頻（例如千死赫範圍）之可調式或被動傳輸或接收天線。根據本發明之相位陣列天線具有極廣可用的接受光錐。 " 較佳應用為汽車、輪船、飛機、太空飛船及衛星技術領域，人力操作或無人操作工具上之雷達裝置及數據傳輸設備0 為製造用於高頻技術之適當構件（特定言之適當相移器）’根據本發明之液晶介質一般引入具有小於！毫米厚度、數毫米寬度及數爱米長度之矩形空腔中。空腔罝二兩條長邊Μ之相對電極。熟f此項技術者知曉該類: I62I72.doc -23- 201245421 構。透過施加可變電壓，液晶介質之介電性可在天線操作期間調節從而設置天線之不同頻率或方向。術β吾「函素」或「齒化」表示F、Ci、仏及丨，尤其？及 C1及特定言之F。術語「烷基」較佳地涵蓋具有丨至15個碳原子之直鏈及支鏈烷基，特定言之直鏈基團，曱基、乙基、丙基、丁基、戊基及己基。具有2至10個碳原子之基團一般係較佳。術語「烯基」較佳地涵蓋具有2至15個碳原子之直鏈及支鏈烯基，特定言之直鏈基團。特別佳烯基為稀基、C4-至CV3E-稀基、C5•至C7_4_稀基、C6JC7_5·稀基及C7-6-烯基，特定言之C2•至C7_1E_烯基、c4_iC7_3E_ 烯基及C5-至C7-4-烯基。其他烯基之實例為乙烯基、ie_丙稀基、1E-丁稀基、1E•戊稀基、1E•己稀基、ie•庚稀基、 3-丁烯基、3E·戊烯基、3E•己烯基、3E_庚烯基、扣戊烯基、4Z-己烯基、4E_己烯基、4Z庚烯基、$•己烯基、6-庚烯基等。具有至多5個碳原子之基團一般係較佳。術語「烷氧基」較佳地涵蓋具有式CnH2n+i_〇_之直鏈基團，其中η表示1至1〇。n較佳係丨至6。較佳烷氧基為例如甲氧基、乙氧基、正丙氧基、正丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、正壬氧基、正癸氧基。術語「氧雜院基」或「烷氧基烷基」較佳地涵蓋具有式A device for the commercial DMS instrument of Autronic-Melchers. The characteristic voltage is measured under vertical observation. The threshold voltage (V1()), the intermediate gray voltage (V5〇), and the saturation voltage (V9〇) were measured for 10%, 50%, and 90% relative contrast, respectively. As described in A. Penirschke et al., "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz", 34th European Microwave Conference · Amsterdam, pp. 545-548, the study is based on its properties in the microwave frequency range. Liquid crystal media. In this respect, there are also A. Gaebler et al., "Direct Simulation of Material Permittivities ...", 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pages 463 to 467, and DE 10 2004 029 429 A, in which the measurement method is also detailed. The liquid crystal can be introduced into a polytetrafluoroethylene (PTFE) or quartz capillary. The capillary has an inner radius of 180 μηι and an outer radius of 350 μηι. The effective length is 2.0 cm. The filled capillary is introduced into the center of a cylindrical cavity having a resonant frequency of 19 GHz. The cavity has a length of 11.5 mm and a radius of 6 mm. The input signal (source) is then applied and the output signal result is recorded using a commercially available vector network analyzer. For other frequencies, the size of the cavity can be adjusted accordingly. The resonance frequency and the change in the Q factor between the measured values of the capillary using the filled liquid crystal and the measured value of the capillary which does not fill the liquid crystal can be used by the above publication A. Penirschke et al., 34th European Microwave Conference - Amsterdam, Equations 10 and 11 of 162172.doc •20-201245421, pages 545 to 548, measure the dielectric constant and angular loss at the respective target frequencies. Also, the values of the properties of the members for the vertical and parallel directors of the liquid crystal are obtained by the alignment of the liquid crystals in the magnetic field. For this purpose, a magnetic field with a permanent magnet is used. The magnetic field strength is 0.35 Tesla. The alignment of the magnets can be adjusted accordingly and then rotated 90 accordingly. . The dielectric anisotropy in the microwave region is defined as ΔεΓΞ(εΓ, 丨 er, 丄). The modulatability or tunability (τ) is defined as τ Ξ(Δε r / ε r, 丨丨). The material quality (η) is defined as η = (τ / tan δ ε r > max.), where 'the maximum dielectric loss factor tan δ ε ^max : tan δ ε r > Max = Max. { tan δ ε r >±; tan δ ε r , 11 } which is the maximum value of the measured value of tan δε. Preferably, the material quality (11) of the liquid crystal material is 6 or more, preferably 7 or more, preferably 10 or more, preferably 15 or more, particularly preferably 25 or more. And very good 3 or more. Preferably, the liquid crystal material has 15 in the corresponding member. _ or greater, preferably 20VdB or greater, preferably 3〇0/dB or greater, preferably 4〇/dB or greater, preferably 5GQ/dB or greater, Especially good (9). · or greater and excellent 100. Or larger phase shifter quality. The liquid crystal medium according to the present invention preferably has at least - 8 〇 t, preferably a pit to a machine, and preferably a 4 〇 t to just in each case. c 162172.doc •21 · 201245421 Neighbor phase. This phase is particularly preferably increased to 120 ° C or more, preferably to 14 ° C or more and extremely low to 180 ° C or more. This expression has a nematic phase where: on the one hand, no smectic phase and crystallization are observed at low temperatures at the corresponding temperatures and, on the other hand, no phase change occurs in the nematic phase upon heating. The study at low temperature was carried out in a flow viscometer at the corresponding temperature and at least 1 hour by storage in a test cell having a battery thickness of 5 μηη. At elevated temperatures, the clarification point is measured in a capillary by conventional methods. The liquid crystal medium according to the present invention preferably has 90 or more, more preferably 100 ° C or more, particularly preferably 120 ° C or more, particularly preferably 150. (: or a larger and excellent clear point of 170 ° C or more. The liquid crystal medium according to the present invention is at i kHz and 20 ((: Δε is preferably 1 or more), more preferably 2 or more Large and excellent 3 or greater. The liquid crystal medium according to the present invention is preferably in the range of 589 nm (NaD) and 20% (where Δη is in the range of 0.20 or more to 0.90 or less, more preferably It is in the range of 〇·25 or more to 〇·9〇 or less, especially preferably in the range of 〇3〇 or more to 0.85 or less and excellently located in 〇35 or more to 〇8. In a preferred embodiment of the present application, the Δη of the liquid crystal medium according to the present invention is preferably 〇50 or more, more preferably 〇55 or more. The liquid crystal medium according to the present invention is characterized by high anisotropy in the microwave region. For example, the birefringence is preferably 〇μ or greater at a temperature of about 8 3 〇 112, particularly preferably 0.15 or more. 2〇 or larger, especially preferably 25 or more and excellent 0.3G or more. In addition, the birefringence is preferably (4) or 162172.doc •22-201245421 Individual substance or mixture. It preferably has a nematic 0. In the present application 'unless otherwise explicitly stated, the term compound means a compound or a plurality of compounds. Preferred components comprising a liquid-crystalline medium or at least one compound according to the invention are Phase shifters, varactors, antenna arrays (eg for frequency modulation, cell phone communications, microwave/radar and other data transmitters), "matching circuit adaptive choppers" and others. Preferably used as defined above 4 pieces of high frequency technology. It is preferably a member that can be adjusted by different applied voltages. An excellent component is an adjustable phase shifter. In a preferred embodiment, a plurality of phase shifters are functionally connected to produce, for example, Phased group antennas (generally referred to as "phase array" antennas). A group of antennas uses a matrix-configured transmission or receiving component to "mesh" to achieve bundling through interference. Parallelism of phase shifters in column or lattice form The structure can be constructed as a "phase array" that can serve as an adjustable or passive transmission or receiving antenna for high frequencies (eg, thousands of dead ranges). The phase array antenna has a widely available receiving cone. " Preferred applications are in the automotive, ship, aircraft, spacecraft and satellite technology fields, and radar devices and data transmission equipment on human-operated or unmanned tools are manufactured for manufacturing purposes. Suitable components for high frequency technology (specifically suitable phase shifters) 'The liquid crystal medium according to the invention is generally introduced into a rectangular cavity having a thickness of less than ! mm, a width of several millimeters and a length of several meters. The opposite electrode of the long side of the strip is familiar to the class: I62I72.doc -23- 201245421. By applying a variable voltage, the dielectric properties of the liquid crystal medium can be adjusted during antenna operation to set the antenna differently. Frequency or direction. What is the meaning of F, Ci, 仏 and 丨, especially? And C1 and the specific statement F. The term "alkyl" preferably encompasses straight-chain and branched alkyl groups having from 丨 to 15 carbon atoms, in particular straight-chain groups, fluorenyl, ethyl, propyl, butyl, pentyl and hexyl. Groups having 2 to 10 carbon atoms are generally preferred. The term "alkenyl" preferably encompasses straight-chain and branched alkenyl groups having from 2 to 15 carbon atoms, in particular straight-chain groups. Particularly preferred alkenyl groups are dilute groups, C4- to CV3E-saturated groups, C5• to C7_4_thinyl groups, C6JC7_5·thinyl groups and C7-6-alkenyl groups, specifically C2• to C7_1E-alkenyl groups, c4_iC7_3E_alkenyl groups And C5- to C7-4-alkenyl. Examples of other alkenyl groups are vinyl, i-propyl, 1E-butyl, 1E•pentyl, 1E•hexyl, ie•heptyl, 3-butenyl, 3E·pentenyl 3E•hexenyl, 3E-heptenyl, depentenyl, 4Z-hexenyl, 4E-hexenyl, 4Zheptenyl, hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred. The term "alkoxy" preferably encompasses a straight-chain group having the formula CnH2n+i_〇_, where η represents 1 to 1 Å. n is preferably 丨 to 6. Preferred alkoxy groups are, for example, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, positive Alkoxy. The term "oxaxy" or "alkoxyalkyl" preferably encompasses the formula

CnH2n+l-〇_(CH2)m之直鏈基團，其中n&m各彼此獨立地表不1至ίο。較佳而言，及m^^6。 162172.doc • 24 · 201245421 術語「氟化烷基」較佳地涵蓋單或多氟化基團。包括全氟化基團。特別佳係 cf3、CH2CF3、CH2CHF2、CHF2、 ch2f、chfcf3及 CF2CHFCF3。術語「氟化烷氧基J涵蓋單或多氟化基團。包括全氟化基團。特別佳係OCF3基團。表述「其中一或多個「-CH2-」基團可經_〇_取代之烷基 (稀基/炔基）」較佳地表示其中非端基CH2基團經取代之該類型基團》OH基團係以一般含義併入。術語「經取代環烷基」涵蓋經烷基（特定言之具有1至8 個碳原子之烷基）單或多取代之環烷基。術語「經取代之苯基」涵蓋經如…定義之基團單或多取代之苯基，特定言之經F、C1、烷基或烷氧基取代之苯基。在本申請案中，高頻技術意指具有位於1河沿至1〇 THz、較佳言之i GHzi3 THz、更佳言之2 GHz至1 、特別佳5至300 GHz範圍内之頻率之應用。該應用較佳地位於適合訊息傳輸之微波光譜或相鄰區域中，其中相位陣列模組可用於傳輸或接收天線。根據本發明之液晶介質係由一或多種化合物，較佳言之 2至30、更佳言之3至2〇及極佳言之3至16種化合物所組成。此類化合物係以常規方式混合。一般而言，將所需量之以較少量使用之化合物溶於以較多量使用之化合物中。若溫度高於以更高濃度使用之化合物之澄清點，則尤其容易觀察到溶解過程的完成。然而，亦可以其他常規方式製 162172.doc -25- 201245421A linear group of CnH2n+l-〇_(CH2)m, wherein n&m are each independently from 1 to ίο. Preferably, and m^^6. 162172.doc • 24 · 201245421 The term "fluorinated alkyl" preferably encompasses mono- or polyfluorinated groups. Includes perfluorinated groups. Particularly preferred are cf3, CH2CF3, CH2CHF2, CHF2, ch2f, chfcf3 and CF2CHFCF3. The term "fluorinated alkoxy J" encompasses mono- or polyfluorinated groups, including perfluorinated groups. Particularly preferred are OCF3 groups. The expression "one or more of the "-CH2-" groups may pass through _〇_ Substituted alkyl (thinyl/alkynyl)" preferably denotes a group of the type OH group in which the non-terminal CH2 group is substituted, in a general sense. The term "substituted cycloalkyl" encompasses a cycloalkyl group which is mono- or polysubstituted with an alkyl group (specifically, an alkyl group having from 1 to 8 carbon atoms). The term "substituted phenyl" embraces a phenyl group which is singly or substituted with a radical as defined herein, in particular a phenyl group substituted by F, C1, alkyl or alkoxy. In the present application, high frequency technology means an application having a frequency ranging from 1 riverside to 1 〇 THz, preferably i GHzi 3 THz, more preferably 2 GHz to 1, especially preferably 5 to 300 GHz. The application is preferably in a microwave spectrum or adjacent region suitable for message transmission, wherein the phase array module can be used to transmit or receive antennas. The liquid crystal medium according to the present invention is composed of one or more compounds, preferably 2 to 30, more preferably 3 to 2, and excellently 3 to 16 compounds. Such compounds are mixed in a conventional manner. In general, the required amount of the compound to be used in a smaller amount is dissolved in the compound used in a larger amount. The completion of the dissolution process is especially easy to observe if the temperature is above the clear point of the compound used at a higher concentration. However, it can also be made in other conventional ways. 162172.doc -25- 201245421

備介質，i I 列如利用所謂之預製混合物，其可為例如化合物之同系或共，这，曼a u 混a物，或利用所謂之「多瓶」體系，其成为自身為備用屍合物。液阳之所有溫度，諸如熔點T(C，N)或T(C，S)、由層列（S) 相轉隻成向列⑻相T(S，N)及澄清點T(N，I)，係以攝氏度引用。所有溫差係以差示度引用。在本申4案中及下列實例中’藉由首字母縮略詞指示液晶化合物之結構，其中化學式之轉換係按照下表A&B進行。所有基團CnH2n+1及CmH2m+1為分別具有n&m個碳原子之直鏈烷基；n、m及k為整數及較佳地表示〇、丨、2、3、 4、5、6、7' 8、9、10、11或12。表b中之代碼為不言自明的。在表A中’僅指示針對母結構之首字母縮略詞。在各例中’針對母結構之首字母縮略詞在針對取代基Rl·、 R2、L1‘及L”之代碼之後，由破折號分隔： L1· L2· 針對 R1·、R2、L1·、R1· R2· L2、L3+之代碼 nm nOm nO.m η nN.F nN.F.F nF nCl nOF nF.F nF.F.F nOCF3For the medium, the i I column utilizes a so-called pre-formed mixture, which may be, for example, a homologue or a mixture of the compounds, which may be a mixture of the so-called "multi-bottle" system, which is itself a spare corpse. All temperatures of liquid yang, such as melting point T (C, N) or T (C, S), phase transition from layer (S) to nematic (8) phase T (S, N) and clarification point T (N, I ), quoted in degrees Celsius. All temperature differences are quoted by differential. In the present invention and in the following examples, the structure of the liquid crystal compound is indicated by an acronym, wherein the conversion of the chemical formula is carried out according to the following Table A & B. All groups CnH2n+1 and CmH2m+1 are linear alkyl groups having n&m carbon atoms, respectively; n, m and k are integers and preferably represent 〇, 丨, 2, 3, 4, 5, 6 , 7' 8, 9, 10, 11 or 12. The code in Table b is self-explanatory. In Table A, only the acronym for the parent structure is indicated. In each case, the 'acronym for the parent structure is after the code for the substituents Rl·, R2, L1', and L", separated by a dash: L1· L2· for R1·, R2, L1·, R1 · R2· L2, L3+ code nm nOm nO.m η nN.F nN.FF nF nCl nOF nF.F nF.FF nOCF3

CnH2n+i CnH2n+|〇CnH2n+l CnH2n+i CnH2n+l CnH2n+IC〇H2n+l CnHin+l 〇CnH2n+l CnH2n+j CnH2n+l CnH2n+l OCmH2m+j CmH2m+l CN CN CN F Cl F F F 〇CF3CnH2n+i CnH2n+|〇CnH2n+l CnH2n+i CnH2n+l CnH2n+IC〇H2n+l CnHin+l 〇CnH2n+l CnH2n+j CnH2n+l CnH2n+l OCmH2m+j CmH2m+l CN CN CN F Cl FFF 〇CF3

Η H H H Η H H H F H F F H H H H Η H F H F F Η H I62172.doc • 26 - 201245421Η H H H Η H H H F H F F H H H H Η H F H F F Η H I62172.doc • 26 - 201245421

表ATable A

CCH CCPCCH CCP

針對R1、R2#、L”、 L2、L3#之代碼 R1* R2* L1* L2* nOCF3.F CnH2n+i OCF3 F H n-Vm CnH2n+i -CH=CH-CmH2m+1 H H nV-Vm CnH2n+1-CH=CH- -CH=CH-CmH2m+1 H H 適當混合物組分列於表A及B中。Code for R1, R2#, L", L2, L3# R1* R2* L1* L2* nOCF3.F CnH2n+i OCF3 FH n-Vm CnH2n+i -CH=CH-CmH2m+1 HH nV-Vm CnH2n +1-CH=CH--CH=CH-CmH2m+1 HH The appropriate mixture components are listed in Tables A and B.

CPTPCPTP

CEPTPCEPTP

162172.doc -27- 201245421 R1162172.doc -27- 201245421 R1

EPCHEPCH

R PCHR PCH

FF

CBC-nmFCBC-nmF

CnH2lCnH2l

PGP-n-m 162172.doc -28- 201245421PGP-n-m 162172.doc -28- 201245421

F F ^n^2n+1F F ^n^2n+1

CPGP-n-mCPGP-n-m

F FF F

PPGU-n-FPPGU-n-F

^GP-n-F PGIGI-n-F 以下實例說明本發明而不以任何方式限制其。然而’熟習此項技術者將明瞭從物理性質可以實現何種性質及其可在何範圍内調節。特定言之，可較佳地實現之各種性質之組合因而對熟習此項技術者而言為明確的。在本申請案中，除非另外明確翊, u 雉况明，否則術語之複數形式可同時表示單數形式及複數形式， — 、且反之亦然。貫施例之其他組合及根據敘述之本發明之辦货月之變形亦來自於隨附申嗜專利範圍。胃曱基第三丁基醚^GP-n-F PGIGI-n-F The following examples illustrate the invention without limiting it in any way. However, those skilled in the art will understand what properties can be achieved from physical properties and to what extent they can be adjusted. In particular, combinations of various properties that are preferably achieved are thus apparent to those skilled in the art. In the present application, the plural forms of the terms may mean both the singular and plural forms, and vice versa, unless otherwise stated. Other combinations of the embodiments and variations of the invention according to the invention described above also come from the scope of the patent application. Gastridecyl tertiary butyl ether

所用之縮寫 MTB 162172.doc •29· 201245421Abbreviation used MTB 162172.doc •29· 201245421

Si02 矽膠 RT 室溫（約20°C) 實例所用乙炔及硼酸為可購得或可按與熟習此項技術者知曉之已知合成法相似的方式製備。基團「C#9」表示非支鍵正丁基。同理亦適用於C3H7、c6h13等。合成實例1 1，4-雙-(4-正丁基苯基乙炔基）吹嘻之合成Si02 Silicone RT Room Temperature (about 20 ° C) Examples Acetylene and boric acid are commercially available or can be prepared in a manner similar to known syntheses known to those skilled in the art. The group "C#9" represents a non-branched n-butyl group. The same applies to C3H7, c6h13, etc. Synthesis Example 1 Synthesis of 1,4-bis-(4-n-butylphenylethynyl)

將 10 g(50 mmo丨）1，4-二氣呔嗪及 g(U4 mmol) 4-正丁基苯基乙炔先引入250 mL三乙胺中，添加200 mg(l mmol) 碘化銅（I)及700 mg(l mmol)雙（三笨基膦）氣化鈀（II)，及使混合物回流1.5 h。冷卻該批料，添加水及曱苯，及相分離。有機相係利用飽和氣化銨溶液洗滌一次及利用飽和氣化鈉溶液洗滌一次’在硫酸鈉上乾燥，過濾及在旋轉蒸發器中蒸發。殘質係藉由管柱層析法（Si〇2，甲苯+甲苯/乙酸乙酯=10:1)純化。進一步純化係藉由從曱苯或曱笨/庚烷混合物再結晶而進行。 MS (El): m/e (%) = 442 (1〇〇，m+)，414 (13)，399 (13)， 328 (1 1)，313 (9)。 162172.doc •30- 20124542110 g (50 mmo丨) 1,4-dioxazine and g (U4 mmol) 4-n-butylphenylacetylene were first introduced into 250 mL of triethylamine, and 200 mg (1 mmol) of copper iodide was added. I) and 700 mg (1 mmol) of bis(triphenylphosphine) gasified palladium (II), and the mixture was refluxed for 1.5 h. The batch was cooled, water and terpene were added, and the phases were separated. The organic phase was washed once with a saturated solution of ammonium sulphate and once with a saturated sodium sulphate solution, dried over sodium sulfate, filtered and evaporated in a rotary evaporator. The residue was purified by column chromatography (Si 2 , toluene + toluene / ethyl acetate = 10:1). Further purification is carried out by recrystallization from a mixture of toluene or hydrazine/heptane. MS (El): m/e (%) = 442 (1〇〇, m+), 414 (13), 399 (13), 328 (1 1), 313 (9). 162172.doc •30- 201245421

Δ ε=-3.2 Δη=0.41 γ,=3475 mPa-s C 148 Ν 179 I 下列貫例2至5係以相似方式合成： 2) 4,7·雙-(心正丁基笨基乙炔基）-2，1，3-苯并嗔二唾（2)Δ ε=-3.2 Δη=0.41 γ,=3475 mPa-s C 148 Ν 179 I The following examples 2 to 5 are synthesized in a similar manner: 2) 4,7·bis-(ino-butyl phenyl) -2,1,3-1,3-benzoindole (2)

MS (El): m/e (〇/。）= 448 (1〇〇, Μ+)，4〇5 (35, [Μ•丙基门， 362 (22, [Μ-2丙基]+)，181 (1〇, [Μ_2丙基]2+)。MS (El): m/e (〇/.) = 448 (1〇〇, Μ+), 4〇5 (35, [Μ•propyl, 362 (22, [Μ-2 propyl]+) , 181 (1〇, [Μ_2propyl]2+).

Δε=+1,3 Δη=0.48 γ,= 1703 mPa-s C 87 Ν 165 I 3) 4,7-雙-(4·正丁基苯基乙炔基）·二氫化茚Δε=+1,3 Δη=0.48 γ,= 1703 mPa-s C 87 Ν 165 I 3) 4,7-bis-(4·n-butylphenylethynyl)·indan

MS (El): m/e (%) = 430 (100, M+)，387 (25, [M-丙基]+)， 344 (8, [M-2 丙基]+ )，172 (12, [M-2 丙基]2+)。 Δε=+1.7 Δη=0.42 γ,= 1532 mPa-s 162172.doc -31 - 201245421MS (El): m/e (%) = 430 (100, M+), 387 (25, [M-propyl]+), 344 (8, [M-2 propyl]+ ), 172 (12, [M-2 propyl]2+). Δε=+1.7 Δη=0.42 γ,= 1532 mPa-s 162172.doc -31 - 201245421

C 109 N 178 I 4) 5,8-雙-(4-正丁基苯基乙炔基）-1，2,3,4-四氫萘C 109 N 178 I 4) 5,8-bis-(4-n-butylphenylethynyl)-1,2,3,4-tetrahydronaphthalene

MS (El): m/e (%) = 444 (100，M+)，401 (15，[Μ-丙基]+ )。MS (El): m/e (%) = 444 (100, M+), 401 (15, [Μ-propyl]+ ).

Δε=+2.4 Δη=0.39 γ,= 3238 mPa-s C 77 Ν 160 I 5) 5,8-雙-(4-正丁基苯基乙炔基）喹啉Δε=+2.4 Δη=0.39 γ,= 3238 mPa-s C 77 Ν 160 I 5) 5,8-bis-(4-n-butylphenylethynyl)quinoline

MS (El): m/e (%) = 441 (100, M+)，398 (40, [M-丙基]+ )， 3 55 (20, [M-2 丙基]+)，177.5(13, [M-2 丙基]2+)。MS (El): m/e (%) = 441 (100, M+), 398 (40, [M-propyl]+ ), 3 55 (20, [M-2 propyl]+), 177.5 (13 , [M-2 propyl]2+).

Δε=+6.5 Δη=0·44 γ,= 3347 mPa-s C 85 Ν 152 I 6a) 3’，6’-二三氟甲烷黃醯基苯并硼烷Δε=+6.5 Δη=0·44 γ,= 3347 mPa-s C 85 Ν 152 I 6a) 3',6'-tritrifluoromethanexanthylbenzoborane

162172.doc -32- 201245421 將4 g(22 mmol) 3’，6’-二羥基苯并硼烧先引入8〇 mL二氣曱烧中，添加 15 mL(108 mmol)三乙胺及 1〇2 mg(0,8 mmol) 4-二曱基胺基吼啶，及將混合物在冰浴中冷卻。然後滴加 17.5 g(61 mmol)三氟曱磺酸酐及攪拌該批料整夜，其間升溫至RT。接著小心加水，及相分離。有機相係利用水及飽和碳酸氫鈉溶液洗滌，在硫酸鈉上乾燥，過濾及在旋轉蒸發器中蒸發。殘質係藉由管柱層析法（Si〇2，二氣曱烷）純化’產生呈黃色油之產物。 6b) 3’，6’-雙-(4-正丁基苯基乙炔基）苯并硼烷162172.doc -32- 201245421 4 g (22 mmol) of 3',6'-dihydroxybenzoboron was first introduced into 8 mL of dioxane, and 15 mL (108 mmol) of triethylamine and 1 添加 were added. 2 mg (0,8 mmol) 4-didecylamino acridine, and the mixture was cooled in an ice bath. Then, 17.5 g (61 mmol) of trifluorosulfonate anhydride was added dropwise and the batch was stirred overnight, during which time the temperature was raised to RT. Then carefully add water and phase separation. The organic phase was washed with water and a saturated sodium bicarbonate solution, dried over sodium sulfate, filtered and evaporated in a rotary evaporator. The residue is purified by column chromatography (Si 2 , dioxane) to give the product as a yellow oil. 6b) 3',6'-bis-(4-n-butylphenylethynyl)benzoborane

將7.1 g(42 mmol) 4-正丁基苯基乙炔先引入5〇 mL四氫0夫。南中，將混合物冷卻至_75。(： ’及添加42 mL(1.0 Μ己烷溶液’ 42 mmol)六曱基二矽疊氮化鋰。1 h後，添加42 mL(l.〇 Μ 己院溶液，42 mmol) B-甲氧基-9-蝴二環[3.3.1] 壬烧’及另授拌混合物1 h。隨後將該批料升溫至_2〇°c，添加含於50 mL四氫吱喃中之5〇〇 mg(〇.55 mmol)三（二亞节基丙酮）二鈀、16〇1^(〇.39 111111〇1)2-二環己基膦基-2，,6，-二曱氧基二苯基及在前一反應中獲得之8 5 g(19 mm〇l)三氣甲確酸鹽’及使混合物回流16 h。藉由添加MTB及水進行處理，及相分離’及水相係利用MTB萃取一次。合併之有機相係利用飽和氯化鈉溶液洗滌，在硫酸鈉上乾燥，過據及在旋轉蒸發器中蒸發。殘質係藉由管柱層析法（Si〇2， 162172.doc *33- 201245421 庚烷/曱苯=9:1)純化，產生呈橘黃色固體之產物。進一步純化係藉由自異丙醇及乙醇/甲苯混合物再結晶而進行。 MS (El): m/e (%) = 456 (刚，M+)，428 (46, [m 伸乙7.1 g (42 mmol) of 4-n-butylphenylacetylene was first introduced into 5 〇 mL of tetrahydro ke. In the middle, cool the mixture to _75. (: 'And add 42 mL (1.0 Μ hexane solution '42 mmol) of hexamethylenedifluoride lithium azide. After 1 h, add 42 mL (l. 己院院, 42 mmol) B-methoxy Base-9-female ring [3.3.1] simmering and mixing the mixture for 1 h. The batch was then warmed to _2 〇 ° C and added to 5 四 in 50 mL of tetrahydrofuran. Mg (〇.55 mmol) tris(diphenylidene acetonide) dipalladium, 16〇1^(〇.39 111111〇1)2-dicyclohexylphosphino-2,6,-didecyloxydiphenyl The base and the 8 5 g (19 mm 〇l) tri-methane acid salt obtained in the previous reaction and refluxing the mixture for 16 h. Treatment by adding MTB and water, phase separation, and water phase utilization The MTB is extracted once. The combined organic phase is washed with a saturated sodium chloride solution, dried over sodium sulfate, and evaporated in a rotary evaporator. The residue is obtained by column chromatography (Si 〇 2, 162172. Doc *33- 201245421 Heptane/nonylbenzene = 9:1) Purified to give the product as an orange solid. Further purification was carried out by recrystallization from a mixture of isopropanol and ethanol/toluene. MS (El): m /e (%) = 456 (just, M+), 428 (46, [m extension B

基]+)’ 413(8, [M-丙基]+)，385(30, [M _伸乙基_丙基]+)。 Δε=+0.6 △ η=0·34 γ,= 5504 mPa-s Tg -18 C 95 N 105 I 7) 2,6-雙-(4-正丁基苯基乙炔基）苯并噻吩（7)Base]+)' 413 (8, [M-propyl]+), 385 (30, [M _extended ethyl propyl]+). Δε=+0.6 △ η=0·34 γ,= 5504 mPa-s Tg -18 C 95 N 105 I 7) 2,6-bis-(4-n-butylphenylethynyl)benzothiophene (7)

MS (El): m/e (%) = 446 (100, M+)，403 (35, [Μ-丙基]+)， 360 (22, [Μ·2丙基]+ )，180 (16, [Μ-2丙基]2+)。 △ ε=+3.1 Δη=0.5〇 7,= 1494 mPa-s C 99 Ν 224 I 混合物實例1 製備具有如在下表中表明之組成及性質的液晶介質Μ-ΐ 。化合物（2)( 第 15號）來自於合成實例2 。 162172.doc • 34· 201245421 組成物理性質化合物 Τ(Ν,Ι) =99.5 °C 編號縮寫 1 BCH-3F.F 10.8% 2 BCH-5F.F 9.00% △n(20〇C，589.3 nm) =0.135 3 ECCP-30CF3 4.50% 4 ECCP-50CF3 4.50% 5 CBC-33F 1.80% Δε(20°〇 > 1 kHz) =4.9 6 CBC-53F 1.80% 7 CBC-55F 1.80% 8 PCH-6F 7.20% 9 PCH-7F 5.40% 10 CCP-20CF3 7.20% 11 CCP-30CF3 10.8% 12 CCP-40CF3 6.30% 13 CCP-50CF3 9.90% 14 PCH-5F 9.00% 15 (2) 10.0% Σ 100.0% 該混合物用於微波範圍内之應用，特定言之用於相位陣列天線之相移器。為進行比較，不含組分（2)之介質C-1係由介質M-1之化合物第1至14號而製備，其中該類化合物第1至14號係以相同相對量存在。混合物實例2 製備具有M-1之組成之液晶介質M-2，區別在於來自合成實例7之化合物（7)用以替代化合物（2)。混合物實例1及2之結果列於下表中： 162172.doc -35- 201245421 表：在19 GHz(20t：)下之混合物M-l、M-2及CM(對照）之性質混合物 εΓ," Sr.l τ >ηδε.Γ.丨丨 tan δε.Γ.ι η __ Μ-1 2.67 232 0.131 0.0046 0.0119 11.0 Μ-2 2.67 2.31 0.135 0.0044 0.0116 11.7 C-1 2.56 2,29 0.107 ~~ ^.0049 0.0126 8.50 矻。物㈡，可調諧性τ、最大損失因子(於此為加δε"，叔材料品“分別得以顯著改進。 162172.doc •36·MS (El): m/e (%) = 446 (100, M+), 403 (35, [Μ-propyl]+), 360 (22, [Μ·2 propyl]+ ), 180 (16, [Μ-2 propyl]2+). Δ ε = +3.1 Δη = 0.5 〇 7, = 1494 mPa-s C 99 Ν 224 I Mixture Example 1 A liquid crystal medium Μ-ΐ having a composition and properties as indicated in the following table was prepared. Compound (2) (No. 15) was derived from Synthesis Example 2. 162172.doc • 34· 201245421 Composition of physical properties Τ(Ν,Ι) =99.5 °C No. 1 BCH-3F.F 10.8% 2 BCH-5F.F 9.00% △n(20〇C,589.3 nm) = 0.135 3 ECCP-30CF3 4.50% 4 ECCP-50CF3 4.50% 5 CBC-33F 1.80% Δε(20°〇> 1 kHz) =4.9 6 CBC-53F 1.80% 7 CBC-55F 1.80% 8 PCH-6F 7.20% 9 PCH-7F 5.40% 10 CCP-20CF3 7.20% 11 CCP-30CF3 10.8% 12 CCP-40CF3 6.30% 13 CCP-50CF3 9.90% 14 PCH-5F 9.00% 15 (2) 10.0% Σ 100.0% This mixture is used in the microwave range Internal applications, specifically phase shifters for phased array antennas. For comparison, the medium C-1 containing no component (2) was prepared from the compound Nos. 1 to 14 of the medium M-1, wherein the compounds Nos. 1 to 14 were present in the same relative amounts. Mixture Example 2 A liquid crystal medium M-2 having a composition of M-1 was prepared, except that the compound (7) from Synthesis Example 7 was used instead of the compound (2). The results of mixtures Examples 1 and 2 are listed in the following table: 162172.doc -35- 201245421 Table: Mixtures of properties Ml, M-2 and CM (control) at 19 GHz (20t:) εΓ," Sr .l τ >ηδε.Γ.丨丨tan δε.Γ.ι η __ Μ-1 2.67 232 0.131 0.0046 0.0119 11.0 Μ-2 2.67 2.31 0.135 0.0044 0.0116 11.7 C-1 2.56 2,29 0.107 ~~ ^.0049 0.0126 8.50 矻. (2), tunability τ, maximum loss factor (in this case, adding δ ε ", uncle materials) were significantly improved. 162172.doc •36·

Claims

201245421 七、申請專利範圍： 1. 一種式I之化合物， R1-(A1-Z1)—A2—Z2—(A3)p-Z3—A4-(Z5-A5)n-R2 其中A1·5彼此獨立地面向任一邊，且表示 a)下式之基團201245421 VII. Patent application scope: 1. A compound of formula I, R1-(A1-Z1)-A2—Z2—(A3)p-Z3—A4-(Z5-A5)n-R2 where A1·5 are independent of each other The ground is facing either side and represents a) the group of the following formula

162172.doc 201245421162172.doc 201245421

其中 X表示 Ο、s、SO、S〇2、NH、NR3 或 NO，一或兩個不相鄰_CH2-可經X取代’及R3係如Ri所定義， b) 1，4-伸苯基，其中一或多個、較佳一或兩個ch基團可經N取代， c) 下式之基團Wherein X represents Ο, s, SO, S〇2, NH, NR3 or NO, one or two non-adjacent _CH2- may be substituted by X' and R3 is as defined by Ri, b) 1,4-phenylene a group wherein one or more, preferably one or two, of the ch groups may be substituted by N, c) a group of the formula

d) 反式-1，4-伸環己基或伸環己烯基，其中，另外，一或兩個不相鄰CH2基團可經及/或_s_取代，及其中Η可經F取代，或 e) 選自1，4-二環[2.2.2]伸辛基、環丁烷丨少二基、螺 [3.3]庚烷_2,6-二基、噻吩_2,5_二基、噻吩_2,4_二基、 162172.doc -2 - 201245421 呋喃-2,5-二基、呋喃-2,4-二基之群之基團，及其中’在a)、b)、c)、d)及e)之群中，一或多個Η原子亦可經Br、ci、F、CN、-NCS、-SCN、 SFS、（：,-(：〗〇烷基、（：「(：10烧氧基、（：3-C6環烷基或單或多氟化CrCiG烧基或烧氧基取代，及其中至少一個來自A2、A3及A4之基團表示根據a)之基團， R1及R2 各自彼此獨立地表示具有1至15個碳原子之鹵化或未經取代之烷基，另外其中，此類基團中之一或多個CH2基團分別可彼此獨立地以使0或S原子彼此不直接相連之方式經_CsC_ 、-CH=CH-、_CF=CF-、-CF=CH-、-CH=CF-、-(CO)O-、-〇(CO)-、-(CO)-、-0或-S-所取代， F、C卜 Br、CN、CF3、OCF3、SCN、NCS或 SF, > —c=c— Z2、z3 Y1、Y: Z1、z5 P l2 彼此獨立地表示-cs〇或 y ，彼此獨立地表示Η、F、Cl、C〗-Ci〇烧基，彼此獨立地表示單鍵、-C = C-、-CH=CH-、 -CH20- ' -(CO)O- ' -CF20- ' -CF2CF2- > -ch2cf2-、-CH2CH2-、-(CH2)4-、-CH=CF_ 或 _CF=CF-，其中不對稱橋可向兩邊定向’ 表示1或2，及 162172.doc 201245421 或獨立地視需要表示 m ' Ω 彼此獨立地表示ο、1或2， R -(Α^Ζ^-Α2-或-A1 2-(z5_A5)n_R2亦可下式之基團d) trans-1,4-cyclohexylene or cyclohexenyl, wherein, in addition, one or two non-adjacent CH2 groups may be substituted by and/or _s_, and the hydrazine may be substituted by F , or e) selected from the group consisting of 1,4-bicyclo[2.2.2] octyl, cyclobutane oxime, spiro[3.3]heptane-2,6-diyl, thiophene-2,5_2 a group of thiophene-2,4-diyl, 162172.doc -2 - 201245421 furan-2,5-diyl, furan-2,4-diyl group, and its 'in a), b) In groups of c, d) and e), one or more of the deuterium atoms may also be Br, ci, F, CN, -NCS, -SCN, SFS, (:, -(: 〇〇 alkyl, ( : "(: 10 alkoxy, (: 3-C6 cycloalkyl or mono or polyfluorinated CrCiG alkyl or alkoxy substituted, and at least one of the groups from A2, A3 and A4 is represented by a) a group, R1 and R2 each independently represent a halogenated or unsubstituted alkyl group having 1 to 15 carbon atoms, and wherein one or more of the CH2 groups of such a group may be independently of each other _CsC_, -CH=CH-, _CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -〇(CO) in such a way that the 0 or S atoms are not directly connected to each other. - , -(CO)-, -0 or -S-, F, C, Br, CN, CF3, OCF3, SCN, NCS or SF, > -c=c - Z2, z3 Y1, Y: Z1 Z5 P l2 independently of each other represents -cs〇 or y, and independently of each other represents Η, F, Cl, C--Ci 〇, independently of each other, represents a single bond, -C = C-, -CH=CH-, -CH20- ' -(CO)O- ' -CF20- ' -CF2CF2- > -ch2cf2-, -CH2CH2-, -(CH2)4-, -CH=CF_ or _CF=CF-, where asymmetric bridge Can be directed to either side to indicate 1 or 2, and 162172.doc 201245421 or independently as needed to indicate that m ' Ω independently of each other represents ο, 1 or 2, R -(Α^Ζ^-Α2- or -A1 2-( z5_A5) n_R2 can also be a group of the formula

2.如睛求項1之化合物，其中彳I之兮| _ a 3 士具中式亥基團A3表示根據定義 a)之基團。找2. A compound according to claim 1, wherein 彳I is 兮| _ a 3 士 has a Chinese group A3 represents a group according to definition a). Find

其:：包括心、表示阳，均表 5.如凊求項】至4中任一表不CF3。示視需要經取代之M-伸苯基環化。物，其中該等環心表 162172.docIt:: including the heart, indicating the yang, the average table 5. If the request item is to any of the 4, the table is not CF3. The display requires a substituted M-phenylene cyclization. Object, of which the centroids 162172.doc

1 -如請求項1或2之化合物，其中p為1。 2 4.如請求項⑴中任一項之化合物物， T具為下式之化合 201245421 6_如請求項1至5中任一項之化合物，其中m及η表示〇。 7· 一種液晶介質’其特徵在於：其包括一或多種如請求項 1至6中任一項之式I之化合物。 8.如請求項7之液晶介質，其中其另外包括一或多種選自式II化合物之化合物：1 - A compound of claim 1 or 2 wherein p is 1. The compound of any one of claims 1 to 5, wherein the compound of any one of claims 1 to 5, wherein m and η represent hydrazine. A liquid crystal medium' characterized in that it comprises one or more compounds of the formula I according to any one of claims 1 to 6. 8. The liquid crystal medium of claim 7, which additionally comprises one or more compounds selected from the group consisting of compounds of formula II:

II L11 L丨2 R11 及 R12 X11 及 X1 p' q z11 至 z13 表示R11或X11，表示R12或χυ，彼此獨立地表示具有1至17個碳原子之非氟化燒基或非氟化烷氧基，或具有2至15個碳原子之非氟化烯基、非氟化炔基、非氟化烯氧基或非氟化烷氧基烷基，彼此獨立地表示F、（：卜Br、-CN、-NCS、-SCN 、-SFs、具有1至7個碳原子之氟化烷基或氟化烷氧基或具有2至7個碳原子之氟化烯基、氟化烯氧基或氟化烷氧基烷基，獨立地表示〇或1，彼此獨立地表示反式-CH=CH-、反式-CF=CF- 、-C=C-或單鍵’及II L11 L丨2 R11 and R12 X11 and X1 p' q z11 to z13 represent R11 or X11, represent R12 or χυ, independently of each other, represent a non-fluorinated or non-fluorinated alkoxy group having 1 to 17 carbon atoms. a group, or a non-fluorinated alkenyl group having 2 to 15 carbon atoms, a non-fluorinated alkynyl group, a non-fluorinated alkenyloxy group or a non-fluorinated alkoxyalkyl group, independently of each other, F, (: Br, -CN, -NCS, -SCN, -SFs, a fluorinated alkyl group having 1 to 7 carbon atoms or a fluorinated alkoxy group or a fluorinated alkenyl group having 2 to 7 carbon atoms, a fluorinated alkenyloxy group or Fluorinated alkoxyalkyl, independently denotes 〇 or 1, independently of each other, represents trans-CH=CH-, trans-CF=CF-, -C=C- or a single bond' and

162172.doc 201245421 彼此獨立地表示 L162172.doc 201245421 Representing each other independently L

其中L獨立地表示具有1至12個碳原子之支鏈或非支鏈烷基、烯基或炔基，其中，一或多個「-CH2·」基團亦可彼此獨立地經〇所取代’或表示CVC6環烷基、C3-C6環烯基、氟化烧基或烯基、氟化烷氧基或烯氧基、F、 CM、Br、CN、NCS、SCN或 SF5 〇 9. 如請求項7或8之液晶介質，其中該介質中式j化合物之濃度係於總計5%至95%之範圍内。 10. —種以如請求項1至6中任一項之式I化合物用於液晶介質中之用途。 11. 一種以如請求項1至6中任一項之式I化合物用於高頻技術之構件中之用途。 12. —種製備如請求項7至9中任一項之液晶介質之方法，其 162172.doc 201245421 13. 14. 15. 16. 特徵在於將一或多種幻之化合物與一或多種其他化合物及視需要與一或多種添加劑混合。一種用於高頻技術之構件，其特徵在於其包含如請求項 7至9中任一項之液晶介質。、如請求項13之構件，其中其包括一相移器。或多個功能上連接之一種以如請求項7至9中住一項之液晶介質之構件之用途。用於高頻技術一種「相位陣列」天線，請求項13或14之構件。其特徵在於其包括一或多個如 162172.doc 201245421 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明：五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 162172.docWherein L independently represents a branched or unbranched alkyl, alkenyl or alkynyl group having 1 to 12 carbon atoms, wherein one or more "-CH2." groups may also be substituted independently of each other by hydrazine. 'or denotes CVC6 cycloalkyl, C3-C6 cycloalkenyl, fluoroalkyl or alkenyl, fluorinated alkoxy or alkenyloxy, F, CM, Br, CN, NCS, SCN or SF5 〇9. The liquid crystal medium of claim 7 or 8, wherein the concentration of the compound of formula j in the medium is in the range of from 5% to 95% by total. 10. Use of a compound of formula I according to any one of claims 1 to 6 for use in a liquid crystal medium. 11. Use of a compound of formula I according to any one of claims 1 to 6 for use in a component of a high frequency technique. 12. A method of preparing a liquid-crystalline medium according to any one of claims 7 to 9, which is 162172.doc 201245421 13. 14. 15. 16. characterized by one or more compounds of the phantom and one or more other compounds and Mix with one or more additives as needed. A member for a high frequency technique, characterized in that it comprises the liquid crystal medium according to any one of claims 7 to 9. The component of claim 13 wherein it includes a phase shifter. Or a plurality of functionally connected ones of the components of the liquid crystal medium as claimed in claim 7 to 9. For high frequency technology A "phase array" antenna, the component of claim 13 or 14. It is characterized in that it includes one or more such as 162172.doc 201245421 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If the case has a chemical formula Please reveal the chemical formula that best shows the characteristics of the invention: (none) 162172.doc