TWI785092B - Liquid-crystalline compounds - Google Patents

Abstract

The invention relates to compounds of the formula I,

in which the alkyl/alkenyl radicals R¹ and R² have the meanings indicated in Claim 1, to a process for the preparation thereof, to liquid-crystalline media com­prising at least one compound of the formula I, and to electro-optical displays containing a liquid-crystalline medium of this type.

Description

liquid crystal compound

其中烷基/烯基R¹ 及R² 係如下定義， 係關於其製備方法、包含至少一種式I化合物之液晶介質及其作為液晶介質中之組分的用途。另外，本發明係關於液晶及含有本發明液晶介質之光電顯示元件。The present invention relates to compounds of formula I,

wherein the alkyl/alkenyl groups R ¹ and R ² are defined below in relation to their preparation, liquid-crystalline media comprising at least one compound of formula I and their use as components in liquid-crystalline media. Furthermore, the invention relates to liquid crystals and optoelectronic display elements comprising the liquid crystal media according to the invention.

In the past few years, the application range of liquid crystal compounds has been greatly expanded to various types of display devices, optoelectronic devices, electronic components, sensors, and the like. For this reason, many different structures have been proposed, especially in the field of nematic liquid crystals. Nematic liquid crystal mixtures have heretofore found widespread use in flat panel display devices. It has especially been used in passive TN or STN matrix displays or systems with TFT active matrices.

The liquid crystal compound of the present invention can be used as a component of liquid crystal media, especially for effects based on twisted cell principle, guest-host effect, alignment phase deformation DAP or ECB (electrically controlled birefringence), IPS (in-plane switching) effect or Display with dynamic scattering effect.

The use of liquid crystal substances containing cyclohexene rings and a total of three rings is known to those skilled in the art. Various compounds containing a cyclohexene ring and their preparation have been described for example as liquid crystals or liquid crystal raw materials in the publication Liquid Crystals, 1997, 23, 69-75 (V.S. Bezborodov et al.). One of the compounds proposed therein contains, in addition to the biphenyl unit, a cyclohexene ring and a pentyl group and a methyl group as terminal groups.

The present invention is based on the object of finding novel stable compounds suitable as components of liquid-crystalline media. Specifically, the compound should have both a relatively low viscosity and a high optical anisotropy.

In view of the extremely wide range of applications of compounds of this type with high Δn, it is desirable to obtain available further compounds, preferably with high clearing points and low viscosities, which have properties precisely adjusted for the respective application.

It was therefore an object of the present invention to find novel stable compounds which are suitable as components of liquid-crystalline media, especially for use in displays such as TN, STN, IPS, FFS and TN-TFT.

In addition, the compounds according to the invention aim to be thermally and photochemically stable under the conditions prevailing in the field of application. As a mesogen, it should promote a broad nematic phase in mixtures with liquid crystalline cocomponents and be readily miscible with nematic base mixtures, especially at low temperatures. Likewise, preference is given to substances with a low melting point and low melting enthalpy, since these parameters are in turn indicative of the above mentioned desirable properties, such as high solubility, broad liquid crystalline phases and a low tendency for spontaneous crystallization in mixtures . In particular, solubility at low temperatures while avoiding any crystallization is important for safe handling and transport of displays in vehicles and aircraft and outdoors.

Surprisingly, it has been found that the compounds according to the invention are remarkably suitable as components of liquid-crystalline media. They can be used to obtain liquid-crystalline media for displays requiring especially high optical anisotropy, especially IPS and FFS displays and TN or STN displays. The compounds of the invention are sufficiently stable and colorless. In particular, it is characterized by a neutral to slightly positive dielectric anisotropy Δε. It has good solubility for compounds with comparable properties. In addition, the compounds according to the invention have relatively high clearing points and at the same time low rotational viscosity values. Compounds have relatively low melting points. With the aid of the compounds according to the invention, it is surprisingly possible to prepare liquid-crystalline mixtures with high elastic constants and low ratios of rotational viscosity to elastic constant K ¹¹ without adversely affecting other parameters of use. This gives a medium with short response times and high contrast.

The provision of the compounds according to the invention very generally greatly broadens the range of liquid-crystalline substances which are suitable for the preparation of liquid-crystalline mixtures from the standpoint of various applications.

其中 R¹ 表示分別具有1至15個或2至15個C原子之烷基或烯基，其中另外此基團中之一或多個CH₂ 基團可各自彼此獨立地以O/S原子不會彼此直接連接之方式由-C≡C-、-CF₂ O-、-OCF₂ -、

、

、

、

、-O-、-S-、-CO-O-或-O-CO-替代，且其中，另外，一或多個H原子可由鹵素替代，或表示H， 且 R² 表示分別具有1至15個或2至15個C原子之烷基或烯基，其中另外該等基團中之一或多個CH₂ 基團可各自彼此獨立地以O/S原子不會彼此直接連接之方式由-C≡C-、-CF₂ O-、-OCF₂ -、

、

、

、

、-O-、-S-、-CO-O-或-O-CO-替代，且其中，另外，一或多個H原子可由鹵素替代，或表示H， 較佳地，具有2至15個C原子之鹵化或未經取代之烯基，其中另外該等基團中之一或多個CH₂ 基團可各自彼此獨立地以O/S原子不會彼此直接連接之方式由-C≡C-、-CF₂ O-、-OCF₂ -、

、

、

、

、-O-、-S-、-CO-O-或-O-CO-替代，且其中，另外，一或多個H原子可由鹵素替代， 其中R¹ 及R² 不同時表示具有1至15個C原子之烷基鏈，且其中R¹ 及R² 較佳包括至少一個鹵化或未經取代之烯基，其中另外該等基團中之一或多個CH₂ 基團可各自彼此獨立地以O/S原子不會彼此直接連接之方式由-C≡C-、-CF₂ O-、-OCF₂ -、

、

、

、

、-O-、-S-、-CO-O-或-O-CO-替代，且此外其中一或多個H原子可由鹵素替代。Accordingly, the present invention relates to compounds of formula I,

wherein R represents an alkyl or alkenyl group having ¹ to 15 or 2 to 15 C atoms, respectively, wherein in addition one or more _CH groups in this group can each independently of each other be separated by O/S atoms The way of direct connection with each other is from -C≡C-, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -O-, -S-, -CO-O-, or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen, or represent H, and R ² represents 1 to 15 Alkyl or alkenyl groups of one or 2 to 15 C atoms, wherein one or more _CH groups in the other groups can be formed independently of each other in such a way that the O/S atoms are not directly connected to each other by - C≡C-, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -O-, -S-, -CO-O- or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen, or represent H, preferably with 2 to 15 Halogenated or unsubstituted alkenyl at C atom, wherein one or more of the _CH2 groups in the other groups can be formed from -C≡C independently of each other in such a way that the O/S atoms are not directly connected to each other -, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -O-, -S-, -CO-O- or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen, wherein R ¹ and R ² do not simultaneously represent 1 to 15 Alkyl chain of C atoms, and wherein R ¹ and R ² preferably comprise at least one halogenated or unsubstituted alkenyl, wherein one or more CH ₂ groups in these groups can each independently of each other By -C≡C-, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -O-, -S-, -CO-O- or -O-CO-, and furthermore one or more of the H atoms may be replaced by a halogen.

The invention further relates to the use of compounds of the formula I in liquid-crystalline media.

、

、

、

、-O-、-S-、-CO-O-或-O-CO-替代，且其中，另外，一或多個H原子可由鹵素替代，或表示H， 且 R² 表示分別具有1至15個或2至15個C原子之烷基或烯基，其中另外該等基團中之一或多個CH₂ 基團可各自彼此獨立地以O/S原子不會彼此直接連接之方式由-C≡C-、-CF₂ O-、-OCF₂ -、

、

、

、

、-O-、-S-、-CO-O-或-O-CO-替代，且其中，另外，一或多個H原子可由鹵素替代，或表示H。The invention likewise relates to liquid-crystalline media having at least two liquid-crystalline components comprising at least one compound of the formula I, in which the substituents have the following meanings: R represents ¹ to 15 or 2 to 15 C Alkyl or alkenyl of atoms, wherein one or more _CH2 groups in these other groups can be formed from -C≡C-, -CF independently of each other in such a way that the O/S atoms are not directly connected to each other ₂ O-, -OCF ₂ -,

,

,

,

, -O-, -S-, -CO-O-, or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen, or represent H, and R ² represents 1 to 15 Alkyl or alkenyl groups of one or 2 to 15 C atoms, wherein one or more _CH groups in the other groups can be formed independently of each other in such a way that the O/S atoms are not directly connected to each other by - C≡C-, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -O-, -S-, -CO-O- or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen, or represent H.

Preferred liquid-crystalline media according to the invention comprise at least one compound of the formula I according to the preferred embodiments of compounds as indicated above and below.

The compounds of formula I have a wide range of applications. Depending on the choice of substituents, these compounds can be used as base materials which mainly constitute liquid-crystalline media; however, it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compounds in order, for example, to influence the type Dielectric and/or optical anisotropy of the dielectric and/or optimization of its threshold voltage and/or its viscosity.

In the pure state, the compounds of the formula I are colorless and form liquid-crystalline mesophases by themselves or in mixtures in a temperature range which is advantageously located for optoelectronic applications. The compounds of the invention enable the achievement of a broad nematic phase range. In liquid-crystalline mixtures, the substances according to the invention significantly increase the optical anisotropy and/or lead to improved storage stability at low temperatures compared to comparable mixtures with high dielectric anisotropy. At the same time, the compounds are distinguished by good UV stability.

The radical R ¹ in formula I and its subformulas preferably represents an alkyl or alkenyl group having up to 8 carbon atoms. R ¹ particularly preferably represents an unbranched alkenyl group having 2 to 8 C atoms, especially an unbranched alkenyl group having 2 to 7 C atoms.

The radical R ² in formula I preferably represents an alkyl or alkenyl group having up to 8 carbon atoms. R ² particularly preferably represents straight-chain alkyl having 1 to 7 C atoms or unbranched alkenyl having 2 to 8 C atoms, especially unbranched alkyl having 1 to 5 C atoms.

Especially preferably, one of the groups R ¹ and R ² is alkenyl and the other is alkyl. Thus, R is especially preferably ^an alkenyl group having up to ⁸ carbon atoms and R is an alkyl group having up to 8 carbon atoms, or R is ^an alkyl group having up to 8 carbon atoms and R is an alkyl group having up to ⁸ carbon atoms. Alkenyl of carbon atoms.

Compounds of the ^formula I containing branched or substituted wing ^- like groups R1 and/or R2 may sometimes be of importance due to better solubility in customary liquid crystal base materials. The group R ¹ is preferably a straight chain.

The group R ¹ is especially preferably selected from the moieties: -CH=CH ₂ -CH=CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH=CH ₂ -CH ₂ -CH ₂ -CH=CH-CH ₃ wherein alkenyl The chain preferably has an E configuration.

其中烯基獨立地代表具有2-8個C原子之烯基或上文所指示含義中之一者。在式I-1至I-6之化合物中，式I-1、I-2、I-5及I-6較佳、尤其式I-1及I-5之化合物。Particularly preferred compounds of formula I are compounds of formulas I-1 to I-6:

Wherein alkenyl independently represents alkenyl having 2-8 C atoms or one of the meanings indicated above. Among the compounds of formulas I-1 to I-6, formulas I-1, I-2, I-5 and I-6 are preferred, especially compounds of formulas I-1 and I-5.

式I化合物係藉由本身已知之方法製備，如文獻中所述(例如在權威著作中，例如Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart)，確切而言在已知且適於該等反應之反應條件下進行。此處亦可使用其本身已知之各種變化形式，此處未更詳細地提及變化形式。Excellent compounds are indicated below:

The compounds of formula I are prepared by methods known per se, as described in the literature (for example in authoritative works, e.g. Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), exactly The reaction is carried out under known and suitable reaction conditions for such reactions. Various variants known per se can also be used here, which are not mentioned here in more detail.

方案 1. 用於製備式I化合物之合成方案。Bn表示苄基。R² 表示如式I中所定義之基團R² 。Compounds of formula I can advantageously be prepared as shown in the following illustrative syntheses and examples (Schemes 1 and 2):

Scheme 1. Synthetic scheme for the preparation of compounds of formula I. Bn represents benzyl. R ² represents a group R ² as defined in formula I.

方案 2. 式I化合物之一般合成方案。基團R¹ 及R² 如式I中所定義。From this a more general synthetic scheme follows (Scheme 2).

Scheme 2. General synthetic scheme for compounds of formula I. The groups R ¹ and R ² are as defined in formula I.

The corresponding starting materials can generally be readily prepared by a person skilled in the art by synthetic methods known from the literature.

Instead of the listed Grignard compounds for the addition of biphenyl groups to cyclohexanone, aryllithium compounds can also be used, which can advantageously be carried out by halogen- Obtained by metal exchange (see eg US 4,940,822).

其中R² 如針對式I所定義，且 M 表示Li、MgBr或MgCl， 與式III之環己酮化合物反應

其中 R¹ 如針對式I所定義， 且，在涉及消除先前反應步驟中所形成之OH官能基之其他反應步驟中， 轉化為式I化合物：

其中基團如上所定義。Accordingly, the present invention also relates to a process for the preparation of compounds of formula I, comprising the following process steps: wherein the aryl-metal compound of formula II

Wherein R ² is as defined for formula I, and M represents Li, MgBr or MgCl, reacts with the cyclohexanone compound of formula III

wherein R is as defined for formula ^I , and, in a further reaction step involving elimination of the OH function formed in a previous reaction step, is converted into a compound of formula I:

wherein the groups are as defined above.

The reaction methods and reagents used are known in principle from the literature. Other reaction conditions are revealed by the working examples.

Other preferred process variations not mentioned above are disclosed by examples or claims.

The processing and subsequent processing of the reaction mixture can basically be carried out in batch reactions or in a continuous reaction procedure. Continuous reaction procedures encompass, for example, reactions in continuous stirred tank reactors, stirred tank reactor cascades, loop or cross flow reactors, flow tubes or microreactors. By solid phase filtration, chromatography, separation between immiscible phases (eg extraction), adsorption onto a solid support, removal of solvents and/or azeotropes by distillation, selective distillation, sublimation, crystallization, The reaction mixtures are optionally processed for co-crystallization or by nanofiltration on membranes.

The invention also relates to liquid-crystalline media comprising one or more of the compounds of formula I, preferred compounds of the invention and preferred subformulas thereof, as defined above. Liquid-crystalline media comprise at least two components. It is preferably obtained by mixing components such as mesogens or liquid crystalline compounds with each other. Accordingly, the present invention also relates to liquid-crystalline media comprising at least two mesogen compounds, characterized in that they comprise at least one compound of the formula I. The process according to the invention for the preparation of liquid-crystalline media is therefore characterized in that at least one compound of the formula I is mixed with at least one further mesogen compound and optionally additives are added.

The achievable combination of clearing point, viscosity at low temperature, thermal/UV stability, dielectric anisotropy, reaction time and contrast is far superior to previous materials from the prior art.

The liquid-crystalline media according to the invention preferably comprise, in addition to one or more compounds according to the invention, 2 to 40, particularly preferably 4 to 30, components as further constituents. In particular, such media comprise 7 to 25 components in addition to one or more compounds of the invention. These other constituents are preferably selected from nematic or nematogenic (monomorphic or isotropic) substances, in particular substances from the following classes: oxazobenzenes, benzylidene anilines, biphenyls , terphenyl, phenyl benzoate or cyclohexyl benzoate, phenyl or cyclohexyl cyclohexanecarboxylate, phenyl or cyclohexyl cyclohexylbenzoate, cyclohexylcyclohexanecarboxylic acid Phenyl esters or cyclohexyl esters; cyclohexylphenyl esters of benzoic acid, cyclohexanecarboxylic acid, or cyclohexylcyclohexanecarboxylic acid; phenylcyclohexane, cyclohexylbiphenyl, phenylcyclohexylcyclohexane, cyclohexyl Cyclohexane, cyclohexylcyclohexylcyclohexene, 1,4-bicyclohexylbenzene, 4,4'-bicyclohexylbiphenyl, phenylpyrimidine or cyclohexylpyrimidine, phenylpyridine or cyclohexylpyridine, phenyldioxin alkane or cyclohexyldioxane, phenyl-1,3-dithiathanol or cyclohexyl-1,3-dithiathanolane, 1,2-diphenylethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2-(4-phenylcyclohexyl)ethane, 1-cyclohexyl-2-biphenylethane, 1-phenyl-2-cyclo Hexylphenylethane, optionally halogenated stilbenes, benzylphenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene groups in these compounds may also be fluorinated.

The most important compounds suitable as other components in the medium of the invention can be characterized by the formulas 1, 2, 3, 4 and 5: R'-LER" 1 R'-L-COO-ER" 2 R'-L-CF ₂ OER" 3 R'-L-CH ₂ CH ₂ -ER" 4 R'-L-CºC-ER" 5 In formulas 1, 2, 3, 4 and 5, L and E may be the same or different, and each Independently represented from the structural elements -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -Py-, -G-Phe- , -G-Cyc- and the divalent group of the group formed by its mirror image, wherein Phe represents unsubstituted or fluorine-substituted 1,4-phenylene, Cyc represents trans-1,4-cyclohexyl , Pyr means pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio means 1,3-dioxane-2,5-diyl, Py means tetrahydropyran-2,5-di and G represents 2-(trans-1,4-cyclohexyl)ethyl.

One of the groups L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. The medium of the present invention preferably comprises one or more components selected from compounds of formulas 1, 2, 3, 4 and 5, wherein L and E are selected from the group consisting of Cyc, Phe and Pyr; and simultaneously one or more selected from Components of compounds of formulas 1, 2, 3, 4 and 5, wherein one of the groups L and E is selected from the group consisting of Cyc, Phe, Py and Pyr and the other group is selected from the group consisting of -Phe- The group consisting of Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-; and optionally one or more compounds selected from formulas 1, 2, 3, 4 and 5 Components, wherein the groups L and E are selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and -G-Cyc-.

R' and/or R" each independently represent an alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkyloxy group having up to 8 C atoms, -F, -Cl , -CN, -NCS or -(O) _i CH _3-k F _k , wherein i is 0 or 1 and k is 1, 2 or 3.

In smaller subgroups of compounds of formulas 1, 2, 3, 4 and 5, R' and R'' each independently represent an alkyl, alkenyl, alkoxy, alkoxy group having up to 8 C atoms ylalkyl, alkenyloxy or alkyloxy. This smaller subgroup is hereinafter referred to as Group A, and the compounds are referred to by subformulas 1a, 2a, 3a, 4a and 5a. In most of these compounds, R' and R'' are different from each other, and one of these groups is usually an alkyl, alkenyl, alkoxy or alkoxyalkyl group.

In another smaller subgroup of compounds of formulas 1, 2, 3, 4 and 5 (which is referred to as group B), R" represents -F, -Cl, -NCS or -(O) _i CH _3-k F _k , where i is 0 or 1 and k is 1, 2 or 3. Compounds in which R" has this meaning are mentioned by the subformulas 1b, 2b, 3b, 4b and 5b. Especially preferred are those compounds of the subformulas 1b, 2b, 3b, 4b and 5b in which R" has the meaning -F, -Cl, -NCS, _-CF3 , _-OCHF2 or _-OCF3 .

In the compounds of the sub-formulas 1b, 2b, 3b, 4b and 5b, R' has the meaning indicated in the case of the compounds of the sub-formulas 1a to 5a and is preferably alkyl, alkenyl, alkoxy or alkoxy base alkyl.

In other smaller subgroups of compounds of formulas 1, 2, 3, 4 and 5, R" represents -CN. This subgroup is hereinafter referred to as group C, and the compounds of this subgroup are correspondingly represented by sub-formulas 1c, 2c , 3c, 4c and 5c are described. In the compound of sub-formula 1c, 2c, 3c, 4c and 5c, R' has the meaning indicated in the case of the compound of sub-formula 1a to 5a and is preferably alkyl, alkane oxy or alkenyl.

Besides the preferred compounds of groups A, B and C, other compounds of formulas 1, 2, 3, 4 and 5 with other variations of the proposed substituents are also common. All these substances can be obtained by methods known from the literature or by methods analogous thereto.

In addition to the compounds of formula I of the present invention, the medium of the present invention preferably comprises one or more compounds selected from groups A, B and/or C. The weight ratio of compounds from these groups in the medium of the present invention is: Group A: 0 to 90%, preferably 20 to 90%, especially 30 to 90%; Group B: 0 to 80%, preferably 10 to 90% 80%, preferably 10 to 65%; Group C: 0 to 80%, preferably 0 to 80%, especially preferably 0 to 50%; wherein the group A, B and/or C compounds present in the individual media of the present invention The sum of the weight ratios is preferably from 5 to 90% and particularly preferably from 10 to 90%.

The medium of the invention preferably comprises from 1% to 40%, especially preferably from 3% to 30%, of the compound of the invention.

The liquid crystal mixtures of the present invention are prepared in a manner customary per se. In general, the desired amount of the lesser component is dissolved in the component constituting the main component, preferably at elevated temperature. It is also possible to mix solutions of the components in organic solvents, for example in acetone, chloroform or methanol, and to remove the solvent by, for example, distillation after thorough mixing. Furthermore, mixtures can be prepared in other customary ways, for example using premixes (eg homogeneous mixtures) or using so-called "multi-bottle" systems.

The dielectric may also contain other additives known to those skilled in the art and described in the literature. For example, 0 to 15%, preferably 0 to 10%, of pleochroic dyes, chiral dopants, stabilizers or nanoparticles may be added. The individual compounds added are employed in concentrations of 0.01 to 6%, preferably 0.1 to 3%. However, the concentration data of other components (ie, liquid crystals or mesogen compounds) in the liquid crystal mixture are given here without taking into account the concentration of these additives. The liquid crystal mixtures of the invention significantly broaden the range of available parameters.

The invention also relates to optoelectronic displays containing media of this type (in particular TFT displays with two plane-parallel outer plates forming a unit together with the frame, integrated nonlinear elements on the outer plates for switching individual pixels and located on the Nematic liquid crystal mixtures with positive dielectric anisotropy and high specific resistance in the cell) and relate to the use of these media for optoelectronic purposes.

The expression "alkyl" covers unbranched and branched alkyl groups having 1 to 15 carbon atoms, especially the unbranched groups methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and n-heptyl. Groups having 2 to 5 carbon atoms are generally preferred.

The expression "alkenyl" covers unbranched and branched alkenyl groups having up to 15 carbon atoms, especially unbranched groups. Particularly preferred alkenyl groups are C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -3E-alkenyl, C ₅ -C ₇ -4-alkenyl, C ₆ -C ₇ -5-alkenyl and C ₇ -6-alkenyl, especially C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -3E-alkenyl and C ₅ -C ₇ -4-alkenyl. Examples of preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl , 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4E-hexenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.

The expression "halogenated alkyl" preferably covers mono- or polyfluorinated and/or chlorinated groups. Includes perhalogenated groups. Especially preferred are _fluorinated alkyl groups, especially _CF3 , _CH2CF3 , _CH2CHF2 , _CHF2 , _CH2F , _{CHFCF3 and CF2CHFCF3 .} The expression "halogenated alkenyl" and related expressions are to be interpreted accordingly.

The total amount of compounds of formula I in the mixtures according to the invention is not critical. Accordingly, such mixtures may contain one or more additional components for the purpose of optimizing various properties.

The construction of the matrix display of the invention from polarizers, electrode substrates and surface-treated electrodes corresponds to the general design of this type of display. The term common design has a broad meaning here and also covers all derivatives and improvements of matrix displays, in particular also matrix display elements based on multi-Si TFTs.

However, a significant difference between the display according to the invention and hitherto conventional displays based on twisted nematic cells lies in the choice of the liquid crystal parameters of the liquid crystal layer.

The following examples illustrate the invention and are not intended to limit the invention. Those skilled in the art will be able to deduce from these examples working details not given in detail in the general description, generalize them according to general professional knowledge, and apply them to specific problems.

In this context, percentage data represent percentages by weight. All temperatures are indicated in degrees Celsius. Furthermore, C = crystalline state, N = nematic phase, Sm = smectic phase (more specifically, SmA, SmB, etc.), Tg = glass transition temperature and I = isotropic phase. The data between these symbols represent the transition temperature. Δn denotes optical anisotropy (589 nm, 20°C), Δε denotes dielectric anisotropy (1 kHz, 20°C) and γ1 _denotes rotational viscosity (20°C; unit is mPa×s).

The physical, physicochemical or optoelectronic parameters are determined by well-known methods, as described in the inter alia brochure "Merck Liquid Crystals - Licristal® - Physical Properties of Liquid Crystals - Description of the Measurement Methods", 1998, Merck KGaA, Darmstadt.

The dielectric anisotropy Δε of individual substances was measured at 20°C and 1 kHz. For this purpose, 5-10% by weight of the substances to be studied were measured, dissolved in the dielectrically positive mixture ZLI-4792 (Merck KGaA), and the measured values were extrapolated to a 100% concentration. The optical anisotropy Δn was measured at 20°C and a wavelength of 589.3 nm, and the rotational viscosity γ1 was measured at ₂₀ °C, both by linear extrapolation.

In this application, unless expressly indicated otherwise, plural forms of terms mean both singular and plural forms and vice versa. Further combinations of embodiments and variants of the invention according to the description also result from the accompanying technical solutions and combinations of a plurality of these technical solutions.

In this context, the abbreviations have the following meanings: DBB 4,4'-di-tert-butylbiphenyl EA ethyl acetate n-BuLi n-butyllithium, solution in hexane MTB ether methyl tert-butyl ether PCC pyridinium chlorochromate THF tetrahydrofuran LiDBB di-tert-butylbiphenyl lithium RT room temperature sat. saturated dist. distillation

Examples The invention is illustrated in detail by the following non-limiting examples.

Example 1 : 4'-Ethyl-4-(4-propylcyclohex-1-enyl)biphenyl

在-55℃下將n -BuLi (145 ml於正己烷中之15%溶液, 231 mmol)添加至1,4-二溴苯1 (50 g, 212 mmol)於二乙醚(950 ml)中之溶液中。1 h後，在-50℃下逐滴添加4-丙基環己酮2 (30 g, 214 mmol)於二乙醚(50 ml)中之溶液。再1 h後，使批料升溫至RT，添加蒸餾水，並使用鹽酸(25%)將批料調整至pH 2。將水相分離並用MTB醚萃取。用飽和氯化鈉溶液洗滌合併之有機層，經硫酸鈉乾燥，過濾並在真空中濃縮。殘餘物給出呈澄清黃色油狀物之1-(4-溴苯基)-4-丙基環己醇3 。 Step 1.1 : 1-(4-bromophenyl)-4-propylcyclohexanol

Add n -BuLi (145 ml of a 15% solution in n-hexane, 231 mmol) to 1,4-dibromobenzene 1 (50 g, 212 mmol) in diethyl ether (950 ml) at -55°C in solution. After 1 h, a solution of 4-propylcyclohexanone 2 (30 g, 214 mmol) in diethyl ether (50 ml) was added dropwise at -50 °C. After another 1 h, the batch was allowed to warm to RT, distilled water was added, and the batch was adjusted to pH 2 using hydrochloric acid (25%). The aqueous phase was separated and extracted with MTB ether. The combined organic layers were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated in vacuo. The residue gave 1-(4-bromophenyl)-4-propylcyclohexanol 3 as a clear yellow oil.

將甲苯-4-磺酸一水合物(2.0 g, 11.6 mmol)添加至1-(4-溴苯基)-4-丙基環己醇3 (67.7 g, 212 mmol)於甲苯(300 ml)中之溶液中，並將混合物在水分離器上回流3 h。將反應混合物冷卻至RT，並添加蒸餾水及2N NaOH (15 ml)。將水相分離並用甲苯萃取。將合併之有機層經硫酸鈉乾燥，過濾並蒸發。將殘餘物在矽膠上層析(庚烷/氯丁烷1:1)。粗產物之結晶(正庚烷)給出呈無色固體之1-溴-4-(4-丙基環己-1-烯基)苯4 。 Step 1.2 : 1-bromo-4-(4-propylcyclohex-1-enyl)benzene

Toluene-4-sulfonic acid monohydrate (2.0 g, 11.6 mmol) was added to 1-(4-bromophenyl)-4-propylcyclohexanol 3 (67.7 g, 212 mmol) in toluene (300 ml) In the solution, the mixture was refluxed on the water separator for 3 h. The reaction mixture was cooled to RT, and distilled water and 2 N NaOH (15 ml) were added. The aqueous phase was separated and extracted with toluene. The combined organic layers were dried over sodium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (heptane/chlorobutane 1:1). Crystallization (n-heptane) of the crude product gave 1-bromo-4-(4-propylcyclohex-1-enyl)benzene 4 as a colorless solid.

初始將1-溴-4-(4-丙基環己-1-烯基)苯4 (30 g, 107mmol)及4-乙基苯基

酸5 (17 g, 113 mmol)併入至丙酮(250 ml)中，並在50℃下添加雙(二亞苄基丙酮)鈀(0) (70 mg, 0.12 mmol)及參(鄰甲苯基)膦(210 mg, 0.69 mmol)。隨後在回流下逐滴添加2N NaOH (107 ml, 215 mmol)。反應混合物在回流下沸騰3 h，冷卻至RT，於蒸餾水(500 ml)中攪拌並使用2N HCl酸化。將沈澱出之產物利用抽吸濾出並藉由在矽膠上層析(庚烷/甲苯1:1)來純化。結晶(正庚烷)之後，分離出呈無色晶體形式之4’-乙基-4-(4-丙基環己-1-烯基)聯苯6 。 Step 1.3 : 4'-Ethyl-4-(4-propylcyclohex-1-enyl)biphenyl

Initially 1-bromo-4-(4-propylcyclohex-1-enyl)benzene 4 (30 g, 107 mmol) and 4-ethylphenyl

Acid 5 (17 g, 113 mmol) was incorporated into acetone (250 ml), and bis(dibenzylideneacetone)palladium(0) (70 mg, 0.12 mmol) and ginseng (o-tolyl ) Phosphine (210 mg, 0.69 mmol). Then 2 N NaOH (107 ml, 215 mmol) was added dropwise at reflux. The reaction mixture was boiled at reflux for 3 h, cooled to RT, stirred in distilled water (500 ml) and acidified with 2 N HCl. The precipitated product was filtered off with suction and purified by chromatography on silica gel (heptane/toluene 1:1). After crystallization (n-heptane), 4'-ethyl-4-(4-propylcyclohex-1-enyl)biphenyl 6 is isolated in the form of colorless crystals.

Compound 6 exhibits the following phase behavior: C 126 SmB 160 SmA 170 N 179 I Δε = 3.1 Δn = 0.24 γ ₁ = 195 mPa·s

Example 2 : 4'-methyl-4-(4-vinylcyclohex-1-enyl)biphenyl

在氮氣氛下將碳酸鈉(74 g, 13 mmol)、蒸餾水(310 ml)及在約70℃之四(三苯基膦)鈀(0) (12 g, 10 mmol)添加至1-溴-4-碘苯8 (100 g, 346 mmol)於甲苯(550 ml)中之溶液中，並隨後將混合物加熱至沸騰。快速添加對-甲苯

酸7 (47 g, 346 mmol)於乙醇(100 ml)中之溶液。將反應混合物在回流下加熱過而已，且冷卻後添加蒸餾水及甲苯。用甲苯萃取水相。將合併之有機層經硫酸鈉乾燥，過濾並蒸發。將殘餘物在矽膠上層析(庚烷/ MTB醚9:1)。分離出呈黃色、微晶固體之4-溴-4’-甲基聯苯9 。 Step 2.1 : 4-Bromo-4'-methylbiphenyl

Sodium carbonate (74 g, 13 mmol), distilled water (310 ml) and tetrakis(triphenylphosphine)palladium(0) (12 g, 10 mmol) at about 70°C were added to 1-bromo- 4-Iodobenzene 8 (100 g, 346 mmol) was dissolved in toluene (550 ml), and the mixture was then heated to boiling. Rapid addition of p-toluene

A solution of acid 7 (47 g, 346 mmol) in ethanol (100 ml). The reaction mixture was heated only under reflux, and after cooling, distilled water and toluene were added. The aqueous phase was extracted with toluene. The combined organic layers were dried over sodium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (heptane/MTB ether 9:1). 4-Bromo-4'-methylbiphenyl 9 was isolated as a yellow, microcrystalline solid.

初始將4-苄基氧基環己酮10 (50 g, 239 mmol)及甲氧基甲基三苯基氯化鏻(100 g, 292 mmol)併入THF (600 ml)中。將第三丁醇鉀(41 g, 367 mmol)分數份併入，並將反應混合物在RT下攪拌10 h。混合物隨後用正庚烷稀釋，用蒸餾水及飽和氯化鈉溶液洗滌並經硫酸鈉乾燥。將粗產物在矽膠上層析(庚烷/MTB醚8:2)，獲得呈黃色油狀物之(4-甲氧基亞甲基環己基氧基甲基)苯11 。 Step 2.2 : (4-methoxymethylenecyclohexyloxymethyl)benzene

4-Benzyloxycyclohexanone 10 (50 g, 239 mmol) and methoxymethyltriphenylphosphonium chloride (100 g, 292 mmol) were initially incorporated into THF (600 ml). Potassium tert-butoxide (41 g, 367 mmol) was incorporated in portions and the reaction mixture was stirred at RT for 10 h. The mixture was then diluted with n-heptane, washed with distilled water and saturated sodium chloride solution and dried over sodium sulfate. The crude product was chromatographed on silica gel (heptane/MTB ether 8:2) to obtain (4-methoxymethylenecyclohexyloxymethyl)benzene 11 as a yellow oil.

將(4-甲氧基亞甲基環己基氧基甲基)苯11 (53 g, 201 mmol)及甲酸(170 ml)於甲苯(600 ml)中之混合物於RT下攪拌24 h。相分離後，有機相用飽和碳酸氫鈉溶液(2x)洗滌，經硫酸鈉乾燥，過濾並在真空中蒸發。分離出呈黃色油狀物之4-苄基氧基環己烷甲醛12 。 Step 2.3 : 4-Benzyloxycyclohexanecarbaldehyde

A mixture of (4-methoxymethylenecyclohexyloxymethyl)benzene 11 (53 g, 201 mmol) and formic acid (170 ml) in toluene (600 ml) was stirred at RT for 24 h. After phase separation, the organic phase was washed with saturated sodium bicarbonate solution (2x), dried over sodium sulfate, filtered and evaporated in vacuo. 4-Benzyloxycyclohexanecarbaldehyde 12 was isolated as a yellow oil.

初始將4-苄基氧基環己烷甲醛12 (32 g, 110 mmol)及甲基三苯基溴化鏻(47 g, 132 mmol)併入THF (230 ml)中。將第三丁醇鉀(19 g, 166 mmol)分數份併入，並將反應混合物於RT下攪拌18 h。將混合物隨後用正庚烷稀釋，用蒸餾水及飽和氯化鈉溶液洗滌並經硫酸鈉乾燥。粗產物藉由矽膠上層析(庚烷/MTB醚9:1)來純化，給出呈淺黃色油狀物之(4-乙烯基環己基氧基甲基)苯13 。 Step 2.4 : (4-vinylcyclohexyloxymethyl)benzene

4-Benzyloxycyclohexanecarbaldehyde 12 (32 g, 110 mmol) and methyltriphenylphosphonium bromide (47 g, 132 mmol) were initially incorporated into THF (230 ml). Potassium tert-butoxide (19 g, 166 mmol) was incorporated in portions and the reaction mixture was stirred at RT for 18 h. The mixture was then diluted with n-heptane, washed with distilled water and saturated sodium chloride solution and dried over sodium sulfate. The crude product was purified by chromatography on silica gel (heptane/MTB ether 9:1) to give (4-vinylcyclohexyloxymethyl)benzene 13 as a pale yellow oil.

在第一步驟中，將DBB (80 g, 299 mmol)及鋰顆粒(2.1 g, 300 mmol)於THF (400 ml)中之混合物在氬下攪拌4 h。在第二步驟中，在冷卻的同時將溴化鎂合二乙醚(98 g, 373 mmol)添加至(4-乙烯基環己基氧基甲基)苯13 (18 g, 75 mmol)於THF (700 ml)中之溶液中。隨後在-75℃下逐滴添加第一步驟中製得之LiDBB溶液。將反應混合物攪拌1 h並升溫至0℃，並在冰水冷卻的同時添加碳酸氫鹽溶液及MTB醚。將水相分離並用MTB醚萃取。合併之有機相用氯化鈉溶液洗滌，經硫酸鈉乾燥，過濾並在真空中蒸發。殘餘物藉由在矽膠上層析(二氯甲烷/EA)來純化。分離呈淡黃色油狀物形式之4-乙烯基環己醇14 。 Step 2.5 : 4-Vinylcyclohexanol

In the first step, a mixture of DBB (80 g, 299 mmol) and lithium particles (2.1 g, 300 mmol) in THF (400 ml) was stirred under argon for 4 h. In a second step, magnesium bromide diethyl ether (98 g, 373 mmol) was added to (4-vinylcyclohexyloxymethyl)benzene 13 (18 g, 75 mmol) in THF ( 700 ml) in the solution. The LiDBB solution prepared in the first step was then added dropwise at -75°C. The reaction mixture was stirred for 1 h and warmed to 0 °C, and bicarbonate solution and MTB ether were added while cooling in ice water. The aqueous phase was separated and extracted with MTB ether. The combined organic phases are washed with sodium chloride solution, dried over sodium sulfate, filtered and evaporated i.vac. The residue was purified by chromatography on silica gel (dichloromethane/EA). 4-Vinylcyclohexanol 14 was isolated as a pale yellow oil.

在平緩冷卻的同時將4-乙烯基環己醇14 (9.4 g, 72 mmol)於二氯甲烷(85 ml)中之溶液添加至PCC (15.6 g, 72 mmol)及矽藻土(15.6 g)於二氯甲烷(85 ml)中之混合物中，並將混合物於RT下攪拌10 h。反應混合物藉助矽膠過濾，用二氯甲烷洗滌並在真空中蒸發，給出作為殘餘物之呈淡黃色油狀物形式之4-乙烯基環己酮15 。 Step 2.6 : 4-Vinylcyclohexanone

A solution of 4-vinylcyclohexanol 14 (9.4 g, 72 mmol) in dichloromethane (85 ml) was added to PCC (15.6 g, 72 mmol) and Celite (15.6 g) with gentle cooling in dichloromethane (85 ml) and the mixture was stirred at RT for 10 h. The reaction mixture is filtered through silica gel, washed with dichloromethane and evaporated in vacuo to give 4-vinylcyclohexanone 15 as a residue in the form of a pale yellow oil.

在-70℃下將n -BuLi (20 ml於正己烷中之15%溶液, 32 mmol)添加至4-溴-4’-甲基聯苯9 (8.9 g, 31 mmol)於THF (150 ml)中之溶液，並將混合物攪拌1 h。隨後在-60℃下逐滴添加4-乙烯基環己酮15 (4.0 g, 31 mmol)於THF (40 ml)中之溶液。再1 h後，使批料升溫至RT，添加蒸餾水，並使用鹽酸(25%)將pH調整至2。將水相分離並用MTB醚萃取。合併之有機相用氯化鈉溶液洗滌，經硫酸鈉乾燥，過濾並蒸發。分離出呈褐色油狀物之1-(4’-甲基聯苯-4-基)-4-乙烯基環己醇16 。 Step 2.7 : 1-(4'-Methylbiphenyl-4-yl)-4-vinylcyclohexanol

Add n -BuLi (20 ml of a 15% solution in n-hexane, 32 mmol) to 4-bromo-4'-methylbiphenyl 9 (8.9 g, 31 mmol) in THF (150 ml ), and the mixture was stirred for 1 h. A solution of 4-vinylcyclohexanone 15 (4.0 g, 31 mmol) in THF (40 ml) was then added dropwise at -60 °C. After another 1 h, the batch was allowed to warm to RT, distilled water was added, and the pH was adjusted to 2 using hydrochloric acid (25%). The aqueous phase was separated and extracted with MTB ether. The combined organic phases are washed with sodium chloride solution, dried over sodium sulfate, filtered and evaporated. 1-(4'-Methylbiphenyl-4-yl)-4-vinylcyclohexanol 16 was isolated as a brown oil.

在0℃下將三乙胺(5.6 ml, 40 mmol)及甲磺醯氯(1.4 ml, 17 mmol)添加至1-(4’-甲基聯苯-4-基)-4-乙烯基環己醇16 (10.2 g, 13 mmol)於二氯甲烷(50 ml)中之溶液中，並將混合物於RT下攪拌18 h。混合物隨後用正庚烷及蒸餾水稀釋，並分離水相。將有機相在矽膠上層析(正庚烷)。殘餘物之結晶(異丙醇/丙酮)及製備型HPLC (乙腈/水95/5)給出呈無色晶體之4’-甲基-4-(4-乙烯基環己-1-烯基)聯苯17 。 Step 2.9 : 4'-Methyl-4-(4-vinylcyclohex-1-enyl)biphenyl

Add triethylamine (5.6 ml, 40 mmol) and methanesulfonyl chloride (1.4 ml, 17 mmol) to 1-(4'-methylbiphenyl-4-yl)-4-vinyl ring at 0 °C Hexanol 16 (10.2 g, 13 mmol) was dissolved in dichloromethane (50 ml) and the mixture was stirred at RT for 18 h. The mixture is then diluted with n-heptane and distilled water, and the aqueous phase is separated. The organic phase was chromatographed on silica gel (n-heptane). Crystallization (isopropanol/acetone) and preparative HPLC (acetonitrile/water 95/5) of the residue gave 4'-methyl-4-(4-vinylcyclohex-1-enyl) as colorless crystals Biphenyl 17 .

Compound 17 exhibited the following phase behavior: C 177 (SmA 171 ) N 180 I Δε = 3.69 Δn = 0.26. γ ₁ = 189 mPa s

Example 3 : 4'-methyl-4-[(4-prop-(1 E )-enyl)cyclohex-1-enyl]biphenyl

在第一步驟中，在-60℃下將第三丁醇鉀(9.7 g, 86 mmol)於THF (90 ml)中之溶液添加至1-第三丁基-5-乙基磺醯基四唑(16.4 g, 75 mmol)於乙二醇二甲醚(100 ml)中之溶液中，並將混合物攪拌30 min。在單獨的設備中，在-70℃下將在第一步驟中製備之溶液逐滴添加至4-側氧基環己烷甲醛18 (10 g, 75 mmol)於乙二醇二甲醚(170 ml)中之溶液中，並將混合物攪拌1 h。使反應混合物升溫至0℃並用蒸餾水及MTB醚稀釋。相分離後，有機相用蒸餾水及飽和氯化鈉溶液洗滌並經硫酸鈉乾燥。粗產物藉由矽膠上層析(1. 二氯甲烷，2. 戊烷/MTB醚8:2)來純化，獲得呈黃色油狀物之4-丙-(1E )-烯基環己酮19 。 Step 3.1 : 4-prop-(1E) -enylcyclohexanone

In the first step, a solution of potassium tert-butoxide (9.7 g, 86 mmol) in THF (90 ml) was added to 1-tert-butyl-5-ethylsulfonyl tetra azole (16.4 g, 75 mmol) in a solution of ethylene glycol dimethyl ether (100 ml), and the mixture was stirred for 30 min. In a separate apparatus, the solution prepared in the first step was added dropwise to 4-oxocyclohexanecarbaldehyde 18 (10 g, 75 mmol) in ethylene glycol dimethyl ether (170 ml), and the mixture was stirred for 1 h. The reaction mixture was warmed to 0 °C and diluted with distilled water and MTB ether. After phase separation, the organic phase is washed with distilled water and saturated sodium chloride solution and dried over sodium sulfate. The crude product was purified by chromatography on silica gel (1. dichloromethane, 2. pentane/MTB ether 8:2) to obtain 4-prop-(1E) -enylcyclohexanone as a yellow oil 19 .

將4-溴-4’-甲基聯苯9 (4.0 g, 16 mmol)於THF (7 ml)中之溶液小心地計量於鎂屑(0.4 g, 16 mmol)於THF (3 ml)中之懸浮液中。使反應混合物在回流下沸騰1 h且然後緩慢冷卻至30℃，添加4-丙-(1E )-烯基環己酮19 (4.6 g, 16 mmol)，並將混合物於RT下再攪拌18 h。 Step 3.2 : 1-(4'-methylbiphenyl-4-yl)-4-prop-(1E) -enyl )cyclohexanol

A solution of 4-bromo-4'-methylbiphenyl 9 (4.0 g, 16 mmol) in THF (7 ml) was carefully dosed to magnesium turnings (0.4 g, 16 mmol) in THF (3 ml). in suspension. The reaction mixture was boiled at reflux for 1 h and then cooled slowly to 30 °C, 4-prop-(1E) -enylcyclohexanone 19 (4.6 g, 16 mmol) was added and the mixture was stirred at RT for a further 18 h. h.

For work-up, distilled water was added and the mixture was acidified to pH 2 by addition of hydrochloric acid (25%). The aqueous phase was separated and extracted with MTB ether. The combined organic phases were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. 1-(4'- Methylbiphenyl -4-yl)-4-prop-(1E)-enylcyclohexanol 20 was isolated as a yellow oil.

在0℃下將三乙胺(5.0 ml, 36 mmol)及甲磺醯氯(1.2 ml, 15 mmol)添加至1-(4‘-甲基聯苯-4-基)-4-丙-(1E )-烯基環己醇20 (6.6 g, 12 mmol)於二氯甲烷(50 ml)中之溶液中。將反應混合物於RT下攪拌18 h且隨後用庚烷及蒸餾水稀釋。將水相分離，且有機相藉助矽膠過濾(庚烷)。粗產物藉由結晶(1. 異丙醇/丙酮，2. 庚烷/活性碳)來純化，獲得呈無色閃光晶體之4’-甲基-4-[(4-丙-(1E )-烯基)環己-1-烯基]聯苯21 。 Step 3.3 : 4'-Methyl-4-[(4-prop-(1E) -enyl )cyclohex-1-enyl]biphenyl

Triethylamine (5.0 ml, 36 mmol) and methanesulfonyl chloride (1.2 ml, 15 mmol) were added to 1-(4'-methylbiphenyl-4-yl)-4-propan-( 1 E )-Alkenylcyclohexanol 20 (6.6 g, 12 mmol) in a solution in dichloromethane (50 ml). The reaction mixture was stirred at RT for 18 h and then diluted with heptane and distilled water. The aqueous phase was separated and the organic phase was filtered through silica gel (heptane). The crude product was purified by crystallization (1. isopropanol/acetone, 2. heptane/activated carbon) to obtain 4'-methyl-4-[(4-propan-(1 E )- alkenyl)cyclohex-1-enyl]biphenyl 21 .

Compound 21 exhibits the following phase behavior: C 161 (Sm·160) SmA 180 N 209 I

Example 4 : 4-(4-but-3-enylcyclohex-1-enyl)-4'-methylbiphenyl

初始將4-苄基氧基環己烷甲醛12 (41.2 g, 183 mmol)及甲氧基甲基三苯基氯化鏻(69.0 g, 200 mmol)併入THF (450 ml)中，並在RT下分數份添加第三丁醇鉀(25.6 g, 228 mmol)。將反應混合物攪拌18 h gerührt且隨後用庚烷稀釋，用蒸餾水及飽和氯化鈉溶液洗滌並經硫酸鈉乾燥。粗產物藉由矽膠上層析(庚烷/MTB醚9:1)來純化，獲得呈淺黃色油狀物之[4-(2-甲氧基乙烯基)環己基氧基甲基]苯22 。 Step 4.1 : [4-(2-Methoxyvinyl)cyclohexyloxymethyl]benzene

4-Benzyloxycyclohexanecarbaldehyde 12 (41.2 g, 183 mmol) and methoxymethyltriphenylphosphonium chloride (69.0 g, 200 mmol) were initially incorporated into THF (450 ml) and dissolved in Potassium tert-butoxide (25.6 g, 228 mmol) was added in portions at RT. The reaction mixture was stirred for 18 h gerührt and then diluted with heptane, washed with distilled water and saturated sodium chloride solution and dried over sodium sulfate. The crude product was purified by chromatography on silica gel (heptane/MTB ether 9:1) to obtain [4-(2-methoxyvinyl)cyclohexyloxymethyl]benzene 22 as a pale yellow oil .

將[4-(2-甲氧基乙烯基)環己基氧基甲基]苯22 (30.0 g, 108 mmol)及甲酸(82 ml, 2.2 mol)於甲苯(300 ml)中之混合物於RT下攪拌24 h。相分離後，有機相用飽和碳酸氫鈉溶液洗滌，經硫酸鈉乾燥，過濾並在真空中蒸發。分離出呈黃色油狀物之(4-苄基氧基環己基)乙醛23 。 Step 4.2 : (4-Benzyloxycyclohexyl)acetaldehyde

A mixture of [4-(2-methoxyvinyl)cyclohexyloxymethyl]benzene 22 (30.0 g, 108 mmol) and formic acid (82 ml, 2.2 mol) in toluene (300 ml) was stirred at RT Stir for 24 h. After phase separation, the organic phase was washed with saturated sodium bicarbonate solution, dried over sodium sulfate, filtered and evaporated i.vac. (4-Benzyloxycyclohexyl)acetaldehyde 23 was isolated as a yellow oil.

類似於步驟4.1，使(4-苄基氧基環己基)乙醛23 與甲氧基甲基三苯基氯化鏻在威悌(Wittig)反應中反應，以獲得[4-(3-甲氧基烯丙基)環己基氧基甲基]苯24 ，其分離為淺黃色油狀物。 Step 4.3 : [4-(3-methoxyallyl)cyclohexyloxymethyl]benzene

Similar to step 4.1, (4-benzyloxycyclohexyl)acetaldehyde 23 was reacted with methoxymethyltriphenylphosphonium chloride in a Wittig reaction to obtain [4-(3-methyl oxyallyl)cyclohexyloxymethyl]benzene 24 , which was isolated as a pale yellow oil.

類似於步驟4.2，[4-(3-甲氧基烯丙基)環己基氧基甲基]苯24 使用甲酸藉由烯醇醚裂解轉化為3-(4-苄基氧基環己基)丙醛25 ，其分離為黃色油狀物。 Step 4.4 : 3-(4-Benzyloxycyclohexyl)propanal

Similar to step 4.2, [4-(3-methoxyallyl)cyclohexyloxymethyl]benzene 24 was converted to 3-(4-benzyloxycyclohexyl)propane by enol ether cleavage using formic acid Aldehyde 25 , which was isolated as a yellow oil.

在RT下將第三丁醇鉀(10.0 g, 89 mmol)分數份添加至3-(4-苄基氧基環己基)丙醛25 (21.3 g, 74 mmol)及甲基三苯基氯化鏻(29.2 g, 82 mmol)於THF (180 ml)中之混合物，並將混合物攪拌18 h。隨後藉由添加蒸餾水使混合物水解，使用2N 鹽酸酸化並用庚烷稀釋。有機相用蒸餾水及飽和氯化鈉溶液洗滌並經硫酸鈉乾燥。粗產物藉由矽膠上層析(庚烷/MTB醚 8:2)來純化，獲得呈淺黃色油狀物之(4-丁-3-烯基環己基氧基甲基)苯26 。 Step 4.5 : (4-but-3-enylcyclohexyloxymethyl)benzene

Potassium tert-butoxide (10.0 g, 89 mmol) was added in portions at RT to 3-(4-benzyloxycyclohexyl)propanal 25 (21.3 g, 74 mmol) and methyltriphenyl chloride A mixture of phosphonium (29.2 g, 82 mmol) in THF (180 ml), and the mixture was stirred for 18 h. The mixture was then hydrolyzed by addition of distilled water, acidified with 2 N hydrochloric acid and diluted with heptane. The organic phase is washed with distilled water and saturated sodium chloride solution and dried over sodium sulfate. The crude product was purified by chromatography on silica gel (heptane/MTB ether 8:2) to obtain (4-but-3-enylcyclohexyloxymethyl)benzene 26 as a pale yellow oil.

在第一步驟中，將DBB (38.0 g, 141 mmol)及鋰顆粒(1.0 g, 144 mmol)於THF (200 ml)中之混合物在氬下攪拌4 h。在第二步驟中，在冷卻的同時將溴化鎂合二乙醚(46.5 g, 176 mmol)添加至(4-丁-3-烯基環己基氧基甲基)苯26 (11.6 g, 35 mmol)於THF (300 ml)中之溶液中。隨後在-75℃下逐滴添加在第一步驟中製得之LiDBB溶液。將反應混合物攪拌1 h並升溫至0℃，並在冰水冷卻的同時添加碳酸氫鹽溶液及MTB醚。將水相分離並用MTB醚萃取。合併之有機相用氯化鈉溶液洗滌，經硫酸鈉乾燥，過濾並在真空中蒸發。殘餘物藉由在矽膠上層析(二氯甲烷/EA)來純化。分離呈淡黃色油狀物形式之4-丁-3-烯基環己醇27 。 Step 4.6 : 4-but-3-enylcyclohexanol

In the first step, a mixture of DBB (38.0 g, 141 mmol) and lithium particles (1.0 g, 144 mmol) in THF (200 ml) was stirred under argon for 4 h. In a second step, magnesium bromide diethyl ether (46.5 g, 176 mmol) was added to (4-but-3-enylcyclohexyloxymethyl)benzene 26 (11.6 g, 35 mmol) while cooling. ) in a solution in THF (300 ml). The LiDBB solution prepared in the first step was then added dropwise at -75°C. The reaction mixture was stirred for 1 h and warmed to 0 °C, and bicarbonate solution and MTB ether were added while cooling in ice water. The aqueous phase was separated and extracted with MTB ether. The combined organic phases are washed with sodium chloride solution, dried over sodium sulfate, filtered and evaporated i.vac. The residue was purified by chromatography on silica gel (dichloromethane/EA). 4-But-3-enylcyclohexanol 27 was isolated as a pale yellow oil.

在平緩冷卻的同時將4-丁-3-烯基環己醇27 (4.8 g, 29 mmol)於二氯甲烷(30 ml)中之溶液添加至PCC (6.3 g, 29 mmol)及矽藻土(6.3 g)於二氯甲烷(35 ml)中之混合物,，並將混合物於RT下攪拌10 h。反應混合物藉助矽膠過濾，用二氯甲烷洗滌並在真空中蒸發，獲得呈淡黃色油狀物形式之丁-3-烯基環己酮28 。 Step 4.7 : But-3-enylcyclohexanone

A solution of 4-but-3-enylcyclohexanol 27 (4.8 g, 29 mmol) in dichloromethane (30 ml) was added to PCC (6.3 g, 29 mmol) and Celite with gentle cooling (6.3 g) in dichloromethane (35 ml), and the mixture was stirred at RT for 10 h. The reaction mixture was filtered through silica gel, washed with dichloromethane and evaporated in vacuo to afford but-3-enylcyclohexanone 28 as a pale yellow oil.

將4-溴-4’-甲基聯苯9 (4.4 g, 18 mmol)於THF (15 ml)中之溶液小心地計量於鎂屑(0.4 g, 18 mmol)於THF (2 ml)中之懸浮液中。使反應混合物在回流下沸騰1 h且然後緩慢冷卻至30℃，添加丁-3-烯基環己酮28 (2.8 g, 18 mmol)於THF (7 ml)中之溶液，並將混合物於RT下再攪拌18 h。 Step 4.8 : 4-but-3-enyl-1-(4'-methylbiphenyl-4-yl)cyclohexanol

A solution of 4-bromo-4'-methylbiphenyl 9 (4.4 g, 18 mmol) in THF (15 ml) was carefully dosed to magnesium turnings (0.4 g, 18 mmol) in THF (2 ml). in suspension. The reaction mixture was boiled at reflux for 1 h and then cooled slowly to 30 °C, a solution of but-3-enylcyclohexanone 28 (2.8 g, 18 mmol) in THF (7 ml) was added, and the mixture was incubated at RT Stir for another 18 h.

For work-up, distilled water was added and the mixture was acidified to pH 2 by addition of hydrochloric acid (25%). The aqueous phase was separated and extracted with MTB ether. The combined organic phases were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. 4-But-3-enyl-1-(4'-methylbiphenyl-4-yl)cyclohexanol was isolated as a yellow-green oil 29 .

在0℃下將三乙胺(3.7 ml, 27 mmol)及甲磺醯氯(1.0 ml, 13 mmol)添加至4-丁-3-烯基-1-(4’-甲基聯苯-4-基)環己醇29 (4.4 g, 9 mmol)於二氯甲烷(30 ml)中之溶液中。將反應混合物於RT下攪拌18 h且隨後用庚烷及蒸餾水稀釋。將水相分離，且有機相藉助矽膠(庚烷)過濾。粗產物藉由結晶(1. 異丙醇/丙酮，2. 庚烷/丙酮)來純化，獲得呈無色閃光晶體之4-(4-丁-3-烯基環己-1-烯基)-4’-甲基聯苯30 。 Step 4.9 : 4-(4-but-3-enylcyclohex-1-enyl)-4'-methylbiphenyl

Triethylamine (3.7 ml, 27 mmol) and methanesulfonyl chloride (1.0 ml, 13 mmol) were added to 4-but-3-enyl-1-(4'-methylbiphenyl-4 at 0°C -yl) cyclohexanol 29 (4.4 g, 9 mmol) in a solution in dichloromethane (30 ml). The reaction mixture was stirred at RT for 18 h and then diluted with heptane and distilled water. The aqueous phase was separated and the organic phase was filtered through silica gel (heptane). The crude product was purified by crystallization (1. isopropanol/acetone, 2. heptane/acetone) to obtain 4-(4-but-3-enylcyclohex-1-enyl)- 4'-methylbiphenyl 30 .

Compound 30 exhibits the following phase behavior: C 99 SmE 133 SmB 159 SmA 181 N 192 I

在-60℃下將第三丁醇鉀(11.7 g, 105 mmol)於THF (115 ml)中之溶液添加至1-第三丁基-5-乙基磺醯基四唑(21.8 g, 100 mmol)於乙二醇二甲醚(100 ml)中之溶液中，並將混合物攪拌30 min。隨後在-70℃下逐滴添加3-(4-苄基氧基環己基)丙醛25 (27.8 g, 95 mmol)於乙二醇二甲醚(200 ml)中之溶液，並將混合物攪拌1 h。將反應混合物升溫至0℃並用蒸餾水及MTB醚稀釋。相分離後，有機相用蒸餾水及飽和氯化鈉溶液洗滌並經硫酸鈉乾燥。粗產物藉由矽膠上層析(庚烷/MTB醚9:1)來純化，獲得呈澄清黃色油狀物之[(4-戊-(3E )-烯基)環己基氧基甲基]苯31 。 Example 5 : 4'-Methyl-4-[(4-pent-( 3E )-enyl)cyclohex-1-enyl]biphenyl Step 5.1 : [(4-pent-( 3E )-ene base) cyclohexyloxymethyl] benzene

A solution of potassium tert-butoxide (11.7 g, 105 mmol) in THF (115 ml) was added to 1-tert-butyl-5-ethylsulfonyl tetrazole (21.8 g, 100 mmol) in ethylene glycol dimethyl ether (100 ml), and the mixture was stirred for 30 min. A solution of 3-(4-benzyloxycyclohexyl)propionaldehyde 25 (27.8 g, 95 mmol) in ethylene glycol dimethyl ether (200 ml) was then added dropwise at -70 °C, and the mixture was stirred 1 h. The reaction mixture was warmed to 0 °C and diluted with distilled water and MTB ether. After phase separation, the organic phase is washed with distilled water and saturated sodium chloride solution and dried over sodium sulfate. The crude product was purified by chromatography on silica gel (heptane/MTB ether 9:1) to obtain [(4-pent-( 3E )-enyl)cyclohexyloxymethyl] as a clear yellow oil Benzene 31 .

在第一步驟中，將DBB (84 g, 312 mmol)及鋰顆粒(2.2 g, 312 mmol)於THF (400 ml)中之混合物在氬下攪拌4 h。在第二步驟中，在冷卻的同時將溴化鎂合二乙醚(103 g, 391 mmol)添加至[(4-戊-(3E )-烯基)環己基氧基甲基]苯31 (22 g, 78 mmol)於THF (600 ml)中之溶液中。隨後在-75℃下逐滴添加在第一步驟中製得之LiDBB溶液。將反應混合物攪拌1 h並升溫至0℃，並在冰水冷卻的同時添加碳酸氫鹽溶液及MTB醚。將水相分離並用MTB醚萃取。合併之有機相用氯化鈉溶液洗滌，經硫酸鈉乾燥，過濾並在真空中蒸發。殘餘物藉由於矽膠上層析(二氯甲烷/EA)來純化。分離呈淡黃色油狀物形式之4-戊-(3E )-烯基環己醇32 。 Step 5.2 : 4-Pent-( 3E )-enylcyclohexanol

In the first step, a mixture of DBB (84 g, 312 mmol) and lithium particles (2.2 g, 312 mmol) in THF (400 ml) was stirred under argon for 4 h. In a second step, magnesium bromide diethyl ether (103 g, 391 mmol) was added to [(4-pent-( 3E )-enyl)cyclohexyloxymethyl]benzene with cooling 31 ( 22 g, 78 mmol) in THF (600 ml). The LiDBB solution prepared in the first step was then added dropwise at -75°C. The reaction mixture was stirred for 1 h and warmed to 0 °C, and bicarbonate solution and MTB ether were added while cooling in ice water. The aqueous phase was separated and extracted with MTB ether. The combined organic phases are washed with sodium chloride solution, dried over sodium sulfate, filtered and evaporated i.vac. The residue was purified by chromatography on silica gel (dichloromethane/EA). 4-Pent-( 3E )-enylcyclohexanol 32 was isolated as a pale yellow oil.

在平緩冷卻的同時將4-戊-(3E )-烯基環己醇32 (16.0 g, 94 mmol)於二氯甲烷(120 ml)中之溶液添加至PCC (22.2 g, 103 mmol)及矽藻土(22.5 g)於二氯甲烷(120 ml)中之混合物，並將混合物於RT下攪拌10 h。反應混合物藉助矽膠過濾，用二氯甲烷洗滌並在真空中蒸發，獲得作為殘餘物之呈黃色油狀物形式之4-戊-(3E )-烯基環己酮33 。 Step 5.3 : 4-Pent-( 3E )-enylcyclohexanone

A solution of 4-pent-( 3E )-enylcyclohexanol 32 (16.0 g, 94 mmol) in dichloromethane (120 ml) was added to PCC (22.2 g, 103 mmol) with gentle cooling and A mixture of Celite (22.5 g) in dichloromethane (120 ml) was stirred at RT for 10 h. The reaction mixture is filtered through silica gel, washed with dichloromethane and evaporated in vacuo to give 4-pent-( 3E )-enylcyclohexanone 33 as a residue in the form of a yellow oil.

將4-溴-4’-甲基聯苯9 (5.3g, 20 mmol)於THF (20 ml)中之溶液小心地計量至鎂屑(0.5 g, 21 mmol)於THF (2 ml)中之懸浮液中。將反應混合物在回流下加熱1 h且然後緩慢冷卻至30℃，添加4-戊-(3E )-烯基環己酮33 (3.6 g, 21 mmol)於THF (8 ml)中之溶液，並將混合物於RT下再攪拌18 h。為進行後處理，添加蒸餾水並藉由添加鹽酸(25%)將混合物酸化至pH 2。將水相分離並用MTB醚萃取。合併之有機相用飽和氯化鈉溶液洗滌，經硫酸鈉乾燥，過濾並蒸發。分離呈黃綠色油狀物之1-(4‘-甲基聯苯-4-基)-4-戊-(3E )-烯基環己醇34 。 Step 5.4 : 1-(4'-Methylbiphenyl-4-yl)-4-penta-( 3E )-enylcyclohexanol

A solution of 4-bromo-4'-methylbiphenyl 9 (5.3 g, 20 mmol) in THF (20 ml) was carefully metered into magnesium turnings (0.5 g, 21 mmol) in THF (2 ml). in suspension. The reaction mixture was heated at reflux for 1 h and then cooled slowly to 30 °C, a solution of 4-pent-( 3E )-enylcyclohexanone 33 (3.6 g, 21 mmol) in THF (8 ml) was added, And the mixture was stirred for another 18 h at RT. For work-up, distilled water was added and the mixture was acidified to pH 2 by addition of hydrochloric acid (25%). The aqueous phase was separated and extracted with MTB ether. The combined organic phases were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. 1-(4'-Methylbiphenyl-4-yl)-4-penta-( 3E )-enylcyclohexanol 34 was isolated as a yellow-green oil.

在0℃下將三乙胺(8.3 ml, 60 mmol)及甲磺醯氯(2.3 ml, 30 mmol)添加至1-(4‘-甲基聯苯-4-基)-4-戊-(3E )-烯基環己醇34 (6.7 g, 20 mmol)於二氯甲烷(60 ml)中之溶液中。將反應混合物於RT下攪拌18 h且隨後用庚烷及蒸餾水稀釋。將水相分離，且有機相藉助矽膠(庚烷)過濾。粗產物藉由結晶(1. 異丙醇/丙酮, 2. 庚烷)來純化，獲得呈無色閃光晶體之4‘-甲基-4-[(4-戊-(3E )-烯基)環己-1-烯基]聯苯35 。 Step 5.5 : 4'-Methyl-4-[(4-pent-( 3E )-enyl)cyclohex-1-enyl]biphenyl

Triethylamine (8.3 ml, 60 mmol) and methanesulfonyl chloride (2.3 ml, 30 mmol) were added to 1-(4'-methylbiphenyl-4-yl)-4-penta-( 3E )-Alkenylcyclohexanol 34 (6.7 g, 20 mmol) in a solution in dichloromethane (60 ml). The reaction mixture was stirred at RT for 18 h and then diluted with heptane and distilled water. The aqueous phase was separated and the organic phase was filtered through silica gel (heptane). The crude product was purified by crystallization (1. isopropanol/acetone, 2. heptane) to obtain 4'-methyl-4-[(4-pent-( 3E )-enyl) as colorless flashing crystals Cyclohex-1-enyl]biphenyl 35 .

Compound 35 exhibits the following phase behavior: C 120 Sm 154 SmA 180 N 197 I Δε = 3.48 Δn = 0.25 γ ₁ = 709 mPa·s

C 127 Sm 140 SmE 153 SmA 170 N 189.9 I Δε = 4.10 Δn = 0.25

C 104 Sm 173 SmA 193 IThe following compounds were prepared in a similar manner:

C 127 Sm 140 SmE 153 SmA 170 N 189.9 I Δε = 4.10 Δn = 0.25

C 104 Sm 173 SmA 193 I

Claims (13)

A compound of formula I,

wherein R represents an alkyl group having ¹ to 15 C atoms or an alkenyl group having 2 to 15 C atoms, wherein one or more _CH groups in these groups can each be independently of each other with O and The way that S atoms are not directly connected to each other is defined by -C≡C-, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -O-, -S-, -CO-O- or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen, or represent H, and R ² represents 1 to 15 An alkyl group of 2 to 15 C atoms or an alkenyl group of 2 to 15 C atoms, wherein in addition one or more _CH groups in this group can be formed independently of each other in such a way that the O and S atoms are not directly connected to each other -O-, -S-, -C≡C-, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -CO-O- or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen, or represent H, wherein R ¹ and R ² do not simultaneously represent a compound having 1 to 15 C atoms Alkyl chain. The compound of claim ¹ , wherein R represents a halogenated or unsubstituted alkenyl group with 2 to 15 C atoms, wherein one or more _CH groups in these groups can each be independently represented by each other The way that O and S atoms are not directly connected to each other is defined by -C≡C-, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -O-, -S-, -CO-O- or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by a halogen. The compound as claimed in item 1, wherein R ² represents an alkyl or alkenyl group having up to 8 carbon atoms. The compound according to any one of claims 1 to 3, wherein R ¹ represents an unbranched alkenyl group with 2 to 7 C atoms. The compound according to any one of claims 1 to 3, wherein R ² represents an unbranched alkyl group with 1 to 5 C atoms. The compound according to any one of claims 1 to 3, wherein R ² represents CH ₃ or CH ₂ CH ₃ . The compound according to any one of claims 1 to 3, wherein R ² represents an unbranched alkenyl group with 2 to 8 C atoms. The compound according to any one of claims 1 to 3, which is selected from the following formulae:

Wherein alkenyl represents an alkenyl group having 2 to 10 C atoms. A method for preparing a compound of formula I as any one of claims 1 to 8, comprising the following method steps: wherein the aryl-metal compound of formula II

Wherein R ² is as defined for formula I, and M represents Li, MgBr or MgCl, reacts with the cyclohexanone compound of formula III

wherein R is as defined for formula ^I and, in a further reaction step involving elimination of the OH function formed in a previous reaction step, is converted to a compound of formula I

Wherein the groups R ¹ and R ² are as defined in Claim 1. Use of one or more compounds of formula I according to any one of claims 1 to 8 as a component in a liquid crystal medium. A liquid-crystalline medium comprising at least two mesogen compounds, characterized in that at least one compound of formula I

wherein R represents an alkyl group having ¹ to 15 C atoms or an alkenyl group having 2 to 15 C atoms, wherein one or more _CH groups in these groups can each be independently of each other with O and The way that S atoms are not directly connected to each other is defined by -C≡C-, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -O-, -S-, -CO-O- or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen, or represent H, and R ² represents 1 to 15 An alkyl group of 2 to 15 C atoms or an alkenyl group of 2 to 15 C atoms, wherein in addition one or more _CH groups in this group can be formed independently of each other in such a way that the O and S atoms are not directly connected to each other -O-, -S-, -C≡C-, -CF ₂ O-, -OCF ₂ -,

,

,

,

, -CO-O- or -O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen, or represent H. A use of the liquid crystal medium according to claim 11 for optoelectronic purposes. An optoelectronic liquid crystal display, which contains the liquid crystal medium as claimed in claim 11.