# Patent

## Title
Thiophene derivatives, and LC media comprising same

## Abstract

The present invention relates to thiophene derivatives, to processes and intermediates for the preparation thereof, to the use thereof for optical, electro-optical and electronic purposes, in particular in liquid-crystal (LC) media and LC displays, and to LC media and LC displays comprising same.

## Background
The present invention relates to thiophene derivatives, to processes and intermediates for the preparation thereof, to the use thereof for optical, electro-optical and electronic purposes, in particular in liquid-crystal (LC) media and LC displays, and to LC media and LC displays comprising same.
Liquid crystals are used principally as dielectrics in display devices, since the optical properties of such substances can be modified by an applied voltage. Electro-optical devices based on liquid crystals are extremely well known to the person skilled in the art and can be based on various effects. Examples of such devices are cells having dynamic scattering, DAP (deformation of aligned phases) cells, guest/host cells, TN cells having a twisted nematic structure, STN (supertwisted nematic) cells, SBE (super-birefringence effect) cells and OMI (optical mode interference) cells. The commonest display devices are based on the Schadt-Helfrich effect and have a twisted nematic structure. In addition, there are also cells which work with an electric field parallel to the substrate and liquid-crystal plane, such as, for example, IPS (in-plane switching) cells. In particular, TN, STN and IPS cells, especially TN, STN and IPS cells, are currently commercially interesting areas of application for the media according to the invention.
The liquid-crystal materials must have good chemical and thermal stability and good stability to electric fields and electromagnetic radiation. Furthermore, the liquid-crystal materials should have low viscosity and produce short addressing times, low threshold voltages and high contrast in the cells.
They should furthermore have a suitable mesophase, for example a nematic mesophase for the above-mentioned cells, at the usual operating temperatures, i.e. in the broadest possible range above and below room temperature. Since liquid crystals are generally used as mixtures of a plurality of components, it is important that the components are readily miscible with one another. Further properties, such as the electrical conductivity, the dielectric anisotropy and the optical anisotropy, have to satisfy various requirements depending on the cell type and area of application. For example, materials for cells having a twisted nematic structure should have positive dielectric anisotropy and low electrical conductivity.
For example, for matrix liquid-crystal displays with integrated non-linear elements for switching individual pixels (MLC displays), media having large positive dielectric anisotropy, broad nematic phases, relatively low birefringence, very high specific resistance, good UV and temperature stability and low vapour pressure are desired.
Matrix liquid-crystal displays of this type are known. Examples of non-linear elements which can be used to individually switch the individual pixels are active elements (i.e. transistors). The term “active matrix” is then used, where a distinction can be made between two types:

    1. MOS (metal oxide semiconductor) or other diodes on silicon wafers as substrate.
    2. Thin-film transistors (TFTs) on a glass plate as substrate.


The use of single-crystal silicon as substrate material restricts the display size, since even modular assembly of various part-displays results in problems at the joints.
In the case of the more promising type 2, which is preferred, the electro-optical effect used is usually the TN effect. A distinction is made between two technologies: TFTs comprising compound semiconductors, such as, for example, CdSe, or TFTs based on polycrystalline or amorphous silicon. Intensive work is being carried out worldwide on the latter technology.
The TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counterelectrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image. This technology can also be extended to fully colour-capable displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is opposite each switchable pixel.
The TFT displays usually operate as TN cells with crossed polarisers in transmission and are backlit.
The term MLC displays here encompasses any matrix display with integrated non-linear elements, i.e., besides the active matrix, also displays with passive elements, such as varistors or diodes (MIM=metal-insulator-metal).
MLC displays of this type are particularly suitable for TV applications (for example pocket televisions) or for high-information displays for computer applications (laptops) and in automobile or aircraft construction. Besides problems regarding the angle dependence of the contrast and the response times, difficulties also arise in MLC displays due to insufficiently high specific resistance of the liquid-crystal mixtures [TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, September 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, pp. 141 ff, Paris; STROMER, M., Proc. Eurodisplay 84, September 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, pp. 145 ff, Paris]. With decreasing resistance, the contrast of an MLC display deteriorates, and the problem of after-image elimination may occur. Since the specific resistance of the liquid-crystal mixture generally drops over the life of an MLC display owing to interaction with the interior surfaces of the display, a high (initial) resistance is very important in order to obtain acceptable lifetimes. In particular in the case of low-volt mixtures, it was hitherto impossible to achieve very high specific resistance values. It is furthermore important that the specific resistance exhibits the smallest possible increase with increasing temperature and after heating and/or UV exposure. The low-temperature properties of the mixtures from the prior art are also particularly disadvantageous. It is demanded that no crystallisation and/or smectic phases occur, even at low temperatures, and the temperature dependence of the viscosity is as low as possible. The MLC displays from the prior art thus do not satisfy today's requirements.
Besides liquid-crystal displays which use backlighting, i.e. are operated transmissively and if desired transflectively, reflective liquid-crystal displays are also particularly interesting. These reflective liquid-crystal displays use the ambient light for information display. They thus consume significantly less energy than backlit liquid-crystal displays having a corresponding size and resolution. Since the TN effect is characterised by very good contrast, reflective displays of this type can even be read well in bright ambient conditions. This is already known of simple reflective TN displays, as used, for example, in watches and pocket calculators. However, the principle can also be applied to high-quality, higher-resolution active matrix-addressed displays, such as, for example, TFT displays. Here, as already in the transmissive TFT-TN displays which are generally conventional, the use of liquid crystals of low birefringence (Δn) is necessary in order to achieve low optical retardation (d·Δn). This low optical retardation results in usually acceptable low viewing-angle dependence of the contrast (cf. DE 30 22 818). In reflective displays, the use of liquid crystals of low birefringence is even more important than in transmissive displays since the effective layer thickness through which the light passes is approximately twice as large in reflective displays as in transmissive displays having the same layer thickness.
For TV and video applications, MLC displays having short response times are required. Such short response times can be achieved, in particular, if liquid-crystal media having low values for the viscosity, in particular the rotational viscosity γ1, are used. However, diluting additives generally lower the clearing point and thus reduce the working-temperature range of the medium.
Thus, there continues to be a great demand for MLC displays having very high specific resistance at the same time as a large working-temperature range, short response times, even at low temperatures, and a low threshold voltage which do not exhibit these disadvantages or only do so to a lesser extent.
In the case of TN (Schadt-Helfrich) cells, media are desired which facilitate the following advantages in the cells:

    
    
        extended nematic phase range (in particular down to low temperatures)
        ability to switch at extremely low temperatures (outdoor use, automobiles, avionics)
        increased resistance to UV radiation (longer life)
        low threshold voltage.
    
    


The media available from the prior art do not enable these advantages to be achieved while simultaneously retaining the other parameters.
In the case of supertwisted (STN) cells, media are desired which facilitate greater multiplexability and/or lower threshold voltages and/or broader nematic phase ranges (in particular at low temperatures). To this end, a further widening of the available parameter latitude (clearing point, smectic-nematic transition or melting point, viscosity, dielectric parameters, elastic parameters) is urgently desired.
In the case of LC displays for TV and video applications (for example LCD TVs, monitors, PDAs, notebooks, games consoles), a significant reduction in the response times is desired. There is therefore a demand for compounds for LC media which facilitate a reduction in the response times without simultaneously impairing the other properties of the LC medium, such as, for example, the clearing point, the dielectric anisotropy Δ∈ or the birefringence Δn. Low rotational viscosities, in particular, are desirable for this purpose.
In the case of applications of LC media having positive dielectric anisotropy, fast response times are generally demanded. It is known that a reduction in the layer thickness d of the LC medium in the LC cell theoretically results in a reduction in the response times. LC media having relatively high birefringence values Δn are therefore required for this purpose in order to ensure an adequate optical retardation d·Δn. On the other hand, however, LC media having relatively high birefringence values typically also exhibit relatively high values of the rotational viscosity, which in turn results in longer response times. The shortening of the response time achieved by reducing the layer thickness is thus at least partly compensated again by the relatively high rotational viscosity of the LC medium used. There is therefore an urgent demand for LC media which simultaneously have high birefringence values and low rotational viscosities.
The invention is based on the object of providing media, in particular for MLC, TN, STN or IPS displays of this type, which have the desired properties indicated above and do not exhibit the disadvantages indicated above or only do so to a lesser extent. In particular, the LC media should have fast response times and low rotational viscosities at the same time as high dielectric anisotropy and high birefringence. In addition, the LC media should have a high clearing point, a broad nematic phase range and a low threshold voltage.
It has now been found that this object can be achieved if thiophene derivatives according to the invention are used in LC media, in particular in LC media having positive dielectric anisotropy, and in MLC, TN, STN and IPS displays. These thiophene derivatives result in LC media having the desired properties indicated above.
JP 2007-084487 A1 discloses thiophene derivatives in which a thiophene-2,5-diyl unit is linked directly or via bridges to a 2,3-difluorophenylene-1,4-diyl unit. However, these compounds have negative dielectric anisotropy and are thus unsuitable for applications in dielectrically positive LC media. Furthermore, a 2,3-difluorophenylene-1,4-diyl unit generally results in higher rotational viscosities compared with less-fluorinated phenylene units or 2,5-difluorophenylene-1,4-diyl units.
EP 0 467 260 A2 discloses compounds containing a thiophene-2,5-diyl unit which is linked directly to a 2- and/or 3-substituted phenylene-1,4-diyl unit. However, the object on which EP 0 467 260 A2 was based was the development of novel materials for use in ferroelectric LC displays. EP 0 467 260 A2 therefore also relates, in particular, to ferroelectric LC media and ferroelectric LC substances and to compounds in general which have properties which are particularly suitable for use in ferroelectric LC displays.
In particular, LC media having a chiral smectic C phase (SmC*) are suitable for use in ferroelectric LC displays. In general, mesogenic compounds having smectic phases are required for the preparation of such LC media. Smectic phases are preferably formed if the skeleton of the liquid-crystal structure is provided with particularly long alkyl or alkoxy side chains, as disclosed in the particularly preferred embodiments in EP 0 467 260 A2. Smectic phases are also stabilised if polar carbonyl functions, such as —C(O)—, are present in the side chain, as disclosed in some preferred embodiments in EP 0 467 260 A2. Chiral mesogenic compounds are required for the induction of an SmC* phase. The compounds in EP 0 467 260 A2 therefore preferably have branched alkyl chains having a centre of chirality, which can also be combined with an ester function, as, for example, in example compound I-40 on page 20 of EP 0 467 260 A2:




However, ferroelectric LC displays are of only minor importance today. Virtually exclusively nematic liquid-crystal media are used for modern display applications. However, the compounds described in EP 0 467 260 A2 are unsuitable for modern display applications of this type since virtually exclusively smectic liquid crystals are described.
As shown in the comparative examples below, the other compounds from EP 0 467 260 A2, which have no centres of chirality, carbonyl or carboxyl functions in the side chains, and have directly linked rings, likewise do not have the favourable properties which are necessary for use in LC displays according to the invention.
Thus, example compound I-1 on page 12 of EP 0 467 260 A2 is only nematic in a very limited temperature range (C 115 N 119 I):




In addition, this compound exhibits poor values for the clearing point (145° C.) and the rotational viscosity (196 mPa·s), which can be explained by the molecular structure, which is angled overall owing to the central thiophene unit.
Example compound I-134 on page 38 of EP 0 467 260 A2




has a broad range of smectic phases (C 44 Sm (6) SmB (38) SmC 68 SmA 75 N 93.5 I).
Example compound I-136 on page 39 of EP 0 467 260 A2




likewise has a broad range of smectic phases (C 66 SmE 89 SmC 131 SmA 144 N 146.4 I) and an unfavourable rotational viscosity to clearing point ratio (cl.p.: 179° C., γ1: 262 mPa·s).
Further example compounds in EP 0 467 260 A2 are unsuitable for use in modern MLC displays, for example owing to the presence of keto and/or ester functions, since these functional groups result in poor reliability, in particular a poor voltage holding ratio (VHR). In addition, branches, for example within an alkyl side chain, as are necessary for chiral smectic liquid crystals, are generally undesired for nematic liquid crystals since this results in higher rotational viscosity and thus poor response times.
A. S. Matharu et al., Liquid Crystals 2007, 34, 489-506, describes laterally fluorinated liquid crystals containing 2,2′-bithiophene units, including compounds of the following formulae:




where substances where n=6-10 have been synthesised and investigated. Owing to the length of the alkyl and alkoxy side chains and the central thiophene unit, the substances have poor phase properties. Thus, only narrow monotropic smectic A phases are formed with low clearing points (for example for n=6: C 30.1 SmA (24.8) I).
EP 0 499 252 A1 and a number of similar publications EP 0 459 406 A1, EP 0 476 567 A1, EP 0 500 072 A1, JP 06-025668 A describe thiophene derivatives of the following formula:




where Z1 denotes COO, CH2O or CH═C(CN), and Y1 and Y2 may also denote F besides other meanings. Specific examples described are the following compounds (see, for example, EP 0 499 252 A1, compounds I-110 on page 32 and I-130 on page 35):




These documents are also directed at the development of novel materials for use in ferroelectric LC displays. The compounds described therein thus also have the above-mentioned disadvantages (for example smectic phases, poor VHR due to ester groups) in relation to their use in modern, nematic liquid-crystal media.
GB 2 388 841 A describes specific polymerisable mesogens of the following formula:




where P denotes a polymerisable group, X denotes a single bond, and Sp denotes a spacer group or a single bond, and -A1-Z1— may also denote, inter alia, the following group:




in which L denotes, inter alia, F, and r denotes 0, 1, 2, 3 or 4. However, specific compounds containing thiophene rings are not described. Furthermore, the possibility of use of these materials in liquid-crystal mixtures for displays (active matrix displays, TN, STN, IPS, VA, etc.) is mentioned. However, the use of monoreactive mesogens in liquid-crystal media in modern displays tends to be subordinate.
GB 2 229 179 A describes alkylthiophenes of the type of the formula




where R1, R2 can denote, inter alia, alkyl radicals having up to 16 carbon atoms or CN or F, Z denotes a COO, OCO, CH2CH2 or CH2O bridge, A can be, inter alia, a fluorinated phenyl radical, and n can denote 1 or 2. However, the object of the invention described therein was to obtain compounds of moderate or low birefringence. To this end, the conjugation between the thiophene unit and aromatic units A was intentionally interrupted by the introduction of bridging units which are not capable of conjugation. However, modern TN-TFT display applications preferably require components which combine relatively high birefringence with a good rotational viscosity to clearing point ratio.
As already explained above, the ester groups which are particularly preferred here furthermore have an adverse effect on the reliability of liquid crystals. Examples of components containing ethylene bridges or CH2O groups between a thiophene unit and a further aromatic ring element are not disclosed. Furthermore, the fluorination pattern of an aromatic ring system bridged by the thiophene unit is not discussed.
WO 2004/029697 A1 and WO 02/093244 A2 describe liquid-crystal mixtures comprising compounds of the formula




where the ring elements A11, A12 and A13 can denote, independently of one another, for example, 1,4-phenylene, 3,5-difluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene, and A12 can denote thiophene-2,5-diyl. X1 is a polar group F, OCF3, OCF2H, Cl, CN, C≡C—CN, NCS, preferably CN, C≡C—CN, NCS. However, this document is directed, in particular, to the use of highly polar individual compounds in liquid-crystal mixtures which are particularly suitable for the older STN technology. A specific example mentioned is the following compound (see WO 2004/029697 A1, page 47 or 58, formula I-2c-16 where n=4):




However, both the preferred polar groups and also the ester group are unsuitable for obtaining materials having adequate reliability. In addition, the clearing point described for this compound (Tg-54 X1-35 X2-7 I, X is a liquid-crystalline phase which is not defined further) is extremely low.
WO 2001/064814 A1 describes on page 29 (formula IB4) compounds of the following formula:




again for use in STN mixtures.
On the basis of the prior art, the person skilled in the art would therefore not have expected that the use of thiophene derivatives according to the invention in achiral nematic LC media having an inherently untwisted phase, in particular in LC media having positive dielectric anisotropy, and in MLC, TN, STN and IPS displays, can result in an improvement in the properties, in particular in fast response times and low rotational viscosities at the same time as high dielectric anisotropy, high birefringence and high specific resistance.
The present invention thus relates to compounds of the formula I




in which the individual radicals have the following meanings:

    R1 and R2 denote H, F, Cl, Br, —CN, —SCN, —NCS, SF5 or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more non-adjacent CH2 groups may each be replaced, independently of one another, by —CH═CH—, —C≡C—, —O—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a way that O atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl or Br, or P-Sp-,
    P denotes a polymerisable group,
    Sp denotes a spacer group or a single bond,
    A0 denotes






    A1 and A2 each, independently of one another, denote phenylene-1,4-diyl, in which, in addition, one or two CH groups may be replaced by N and one or more H atoms may be replaced by halogen, CN, CH3, CHF2, CH2F, OCH3, OCHF2 or OCF3, cyclohexane-1,4-diyl, in which, in addition, one or two non-adjacent CH2 groups may be replaced, independently of one another, by O and/or S, and one or more H atoms may be replaced by F, cyclohexene-1,4-diyl, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl,
    Z1 and Z2 each, independently of one another, denote —CF2O—, —OCF2—, —CH2O—, —OCH2—, —CO—O—, —O—CO—, —C2H4—, —C2F4—, —CF2CH2—, —CH2CF2—, —CFHCFH—, —CFHCH2—, —CH2CFH—, —CF2CFH—, —CFHCF2—, —CH═CH—, —CF═CH—, —CH═CF—, —CF═CF—, —C≡C— or a single bond,
    m and n each, independently of one another, denote 0, 1, 2 or 3.


The invention furthermore relates to an LC medium, preferably an LC medium which has a nematic phase, preferably an achiral nematic phase, at room temperature, comprising one or more compounds of the formula I.
The invention furthermore relates to novel processes for the preparation of compounds of the formula I and to intermediates obtained or used therein.
The invention furthermore relates to the use of compounds of the formula I and LC media according to the invention in electro-optical displays, in particular LC displays.
The invention furthermore relates to an LC display containing one or more compounds of the formula I or an LC medium according to the invention, in particular an MLC, TN, STN or IPS display.
LC media which have an achiral LC phase without the presence of chiral dopants, and compounds of the formula I in which the radicals Z1,2, A1,2, R1,2 do not have a centre of chirality are generally preferred.
Particular preference is given to compounds of the formula I in which
A0 denotes




Preference is furthermore given to compounds of the formula I in which m and n denote 0, 1 or 2, particularly preferably 0 or 1. Particular preference is given to compounds of the formula I in which n denotes 0. Preference is furthermore given to compounds of the formula I in which m denotes 0, 1 or 2, preferably 1 or 2, very particularly preferably 1.
A1 and A2 in formula I particularly preferably denote phenylene-1,4-diyl, which may also be mono- or polysubstituted by F, furthermore cyclohexane-1,4-diyl, tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl.
Z1 and Z2 in formula I particularly preferably denote CF2O or a single bond, in particular a single bond.
A1 and A2 in formula I particularly preferably denote




preferably unsubstituted 1,4-phenylene,
in which L denotes halogen, CF3 or CN, preferably F.
Preference is furthermore given to compounds of the formula I in which R1 and R2 each, independently of one another, denote H, F, Cl, Br, —CN, —SCN, —NCS, SF5, P-Sp-, halogen, or alkyl, alkenyl or alkynyl having 1 to 8, preferably 1 to 5, C atoms, each of which is optionally substituted by halogen, in particular by F.
Particularly preferred radicals R1 and R2 denote H, halogen, or alkyl, alkenyl, alkynyl or alkoxy having 1 to 12, preferably 1 to 8, C atoms, each of which is optionally substituted by halogen, in particular by F, particularly preferably H, F, alkyl, alkenyl or alkynyl having 1 to 8 C atoms. R1 is very particularly preferably equal to alkyl. R2 is furthermore preferably H, alkyl or fluorine. Very particularly preferably, R1 is alkyl and R2 is H or alkyl. R1, R2 each, independently of one another, very particularly preferably denote unbranched alkyl having 1-5 C atoms. If R1 and R2 denote substituted alkyl, alkoxy, alkenyl or alkynyl, the total number of C atoms in the two groups R1 and R2 is preferably less than 10.
Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.
Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl and pentenyl.
Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl and octynyl.
Preferred alkoxy groups are, for example, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy.
Halogen preferably denotes F or Cl.
The polymerisable group P is a group which is suitable for a polymerisation reaction, such as, for example, free-radical or ionic chain polymerisation, polyaddition or polycondensation, or for a polymer-analogous reaction, for example addition or condensation onto a main polymer chain. Particular preference is given to groups for chain polymerisation, in particular those containing a C═C double bond or C≡C triple bond, and groups which are suitable for polymerisation with ring opening, such as, for example, oxetane or epoxide groups.
Preferred groups P are selected from CH2═CW1—COO—, CH2═CW1—CO—,




CH2═CW2—(O)k3—, CH3—CH═CH—O—, (CH2═CH)2CH—OCO—, (CH2═CH—CH2)2CH—OCO—, (CH2═CH)2CH—O—, (CH2═CH—CH2)2N—, (CH2═CH—CH2)2N—CO—, HO—CW2W3—, HS—CW2W3—, HW2N—, HO—CW2W3—NH—, CH2═CW1—CO—NH—, CH2═CH—(COO)k1-Phe-(O)k2—, CH2═CH—(CO)k1-Phe-(O)k2—, Phe-CH═CH—, HOOC—, OCN— and W4W5W6Si—, in which W1 denotes H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3, W2 and W3 each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W4, W5 and W6 each, independently of one another, denote Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W7 and W8 each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1,4-phenylene, which is optionally substituted by one or more radicals L as defined above, k1, k2 and k3 each, independently of one another, denote 0 or 1, and k3 preferably denotes 1.

Particularly preferred groups P are CH2═CW1—COO—, in particular CH2═CH—COO—, CH2═C(CH3)—COO— and CH2═CF—COO—, furthermore CH2═CH—O—, (CH2═CH)2CH—OCO—, (CH2═CH)2CH—O—,




Very particularly preferred groups P are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide.
The term “spacer group”, also referred to as “Sp” above and below, is known to the person skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 73(5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. Unless indicated otherwise, the term “spacer group” or “spacer” above and below denotes a flexible group which connects the mesogenic group and the polymerisable group(s) to one another in a polymerisable liquid-crystalline or mesogenic compound.
Preferred spacer groups Sp are selected from the formula Sp′-X′, so that the radical P-Sp- corresponds to the formula P-Sp′-X—, where

    Sp′ denotes alkylene having 1 to 20, preferably 1 to 12, C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, and in which, in addition, one or more non-adjacent CH2 groups may each be replaced, independently of one another, by —O—, —S—, —NH—, —NR0—, —SiR00R000—, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —NR00—CO—O—, —O—CO—NR00—, —NR00—CO—NR00—, —CH═CH— or —C≡C— in such a way that O and/or S atoms are not linked directly to one another,
    X′ denotes —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR00—, —NR00—CO—, —NR00—CO—NR00—, —OCH2—, —CH2O—, —SCH2—, —CH2S—, —CF2O—, —OCF2—, —CF2S—, —SCF2—, —CF2CH2—, —CH2CF2—, —CF2CF2—, —CH═N—, —N═CH—, —N═N—, —CH═CR0—, —CY2═CY3—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,
    R00 and R000 each, independently of one another, denote H or alkyl having 1 to 12 C atoms, and
    Y2 and Y3 each, independently of one another, denote H, F, Cl or CN.
    X is preferably —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR0—, —NR0—CO—, —NR0—CO—NR0— or a single bond.


Typical spacer groups Sp′ are, for example, —(CH2)p1—, —(CH2CH2O)q1—CH2CH2—, —CH2CH2—S—CH2CH2—, —CH2CH2—NH—CH2CH2— or —(SiR00R000—O)p1—, in which p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R00 and R000 have the meanings indicated above.
Particularly preferred groups —X′-Sp′- are —(CH2)p1—, —O—(CH2)p1—, —OCO—(CH2)p1—, —OCOO—(CH2)p1—.
Particularly preferred groups Sp′ are, for example, in each case straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.
Particularly preferred compounds of the formula I are those selected from the following sub-formulae:













in which R1 and R2 have the meanings indicated above and below. R1 and R2 therein preferably denote optionally fluorinated alkyl, alkenyl, alkynyl or alkoxy having 1 to 12 C atoms, particularly preferably optionally fluorinated alkyl, alkenyl or alkynyl having 1 to 5 C atoms. The compounds of the formula I3 are very particularly preferred.
The compounds of the formula I can be prepared analogously to processes known to the person skilled in the art and described in standard works of organic chemistry, such as, for example, in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart.
Particularly preferred processes for the preparation of compounds of the formula I are described below. The individual radicals R1,2, A0,1,1, Z1,2, m and n here have the meanings indicated in formula I.
The compounds of the formula I are preferably synthesised, as shown by way of example in Scheme 1 below, starting from correspondingly substituted bromothiophenes 2. These are reacted with corresponding boronic acids 1 or boronic acid esters in a palladium-promoted Suzuki cross-coupling to give the compounds of the formula I.




The bromothiophenes 2 are synthesised by bromination of thiophenes 3. This can be carried out by direct bromination using bromine or NBS (for example methods A and B in Scheme 2) or by bromination of a lithiothiophene intermediate (method C).




If bromothiophene 2a (2 where n=0 and R2═H) is used for the above Suzuki coupling, compounds Ib (I where n=0 and R2═H) are obtained, which can be further functionalised, as shown by way of example in Scheme 3. This functionalisation can be carried out, for example, via a lithiated intermediate. This can be reacted with numerous electrophiles.
Reaction with bromine or iodine gives compounds Ic (I where n=0 and R2═Br or I), which can be further functionalised by cross-coupling reactions (for example Suzuki, Kumada or Sonogashira couplings).




Access to the particularly preferred compounds I in which R2 denotes an alkyl radical consists in the alkylation of the lithiated compound 4 obtained from Ib using, for example, alkyl halides or alkyl sulfates, as shown by way of example in Scheme 4.




In some cases, however, these alkylations proceed with unreacted starting materials Ib remaining, the separation of which may be difficult. The intermediates 6 are therefore preferred materials for obtaining the preferred compounds of the formula I containing alkenyl and alkyl substituents. The thiophenecarbaldehydes 6 are, as shown by way of example in Scheme 5, obtained by reaction of compounds 4 with DMF or N-formylmorpholine. The aldehydes can then be converted into alkenyl-substituted thiophenes 7 in a Wittig reaction. The latter compounds can be hydrogenated to alkylthiophene derivatives 8.




For the synthesis of compounds I in which R2[A2Z2]— is equal to alkyl or alkenyl, 5-bromothiophene-2-carbaldehyde 9 is also a preferred starting material, as shown by way of example in Scheme 6.




Furthermore, the roles of electrophile and nucleophile can be exchanged in the cross-couplings from Scheme 1 by reacting compounds of type 10 with thiopheneboronic acids or thiophenehydroxyboronic acid salts 11, as shown by way of example in Scheme 7. The latter compounds can be synthesised and isolated particularly simply [A. N. Cammidge, V. H. M. Goddard, H. Gopee, N. L. Harrison, D. L. Hughes, C. J. Schubert, B. M. Sutton, G. L. Watts, A. J. Whitehead, Org. Lett. 2006, 8, 4071-4074].




Preference is furthermore given to compounds in which n=0 and R2 preferably represents an alkoxy substituent. Their synthesis requires 5-bromothiophen-2-yl ethers 2c (2 where n=0 and R2═OR22, where R22 may adopt the same meanings and the same preferred meanings as defined under formula I, where O atoms should not be linked directly to one another, and R22 preferably denotes alkyl). These are prepared starting from bromothiophene 2a (2 where n=0 and R2═Br), as shown by way of example in Scheme 8. Firstly, the alkoxy group is introduced by reaction with an alkoxide in the presence of copper(I) bromide [M. A. Keegstra, T. H. A. Peters, L. Brandsma, Tetrahedron 1992, 48, 3633-3652]. The thiophenes 12 obtained in this way are then brominated to give the compounds 2c (2 where n=0 and R2═OR22, where R22 may adopt the same meanings and the same preferred meanings as defined under formula I, where O atoms should not be linked directly to one another, and R22 preferably denotes alkyl) and reacted further as shown in Scheme 1.




Preference is furthermore given to compounds of type I in which —[Z2-A2]n- R2 denotes fluorine (=Id). These are advantageously prepared from compounds Ib (I where n=0 and R2═H), as shown by way of example in Scheme 9. To this end, the lithiated intermediate 4 formed initially is scavenged using N-fluorobenzenesulfonamide.




The present invention furthermore relates to the processes described above and below and to the novel intermediates produced or used therein, and to the use thereof for the preparation of compounds of the formula I according to the invention.
Particularly preferred LC media according to the invention are mentioned below:

    
    
        LC medium which additionally comprises one or more compounds of the formulae II and/or III:
    
    






    
    
        in which
        
            A denotes 1,4-phenylene or trans-1,4-cyclohexylene,
            a is 0 or 1,
            R3 denotes alkenyl having 2 to 9 C atoms, and
            R4 denotes alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO— in such a way that O atoms are not linked directly to one another, and preferably denotes alkyl having 1 to 12 C atoms or alkenyl having 2 to 9 C atoms.
        
        
        The compounds of the formula II are preferably selected from the group consisting of the following formulae:
    
    






    
    
        in which R3a and R4a each, independently of one another, denote H, CH3, C2H5 or C3H7, and “alkyl” denotes a straight-chain alkyl group having 1 to 8, preferably 1, 2, 3, 4 or 5, C atoms. Particular preference is given to compounds of the formulae IIa and IIf, in particular in which R3a denotes H or CH3, preferably H, and compounds of the formula IIc, in particular in which R3a and R4a denote H, CH3 or C2H5.
        The compounds of the formula III are preferably selected from the group consisting of the following formulae:
    
    






    
    
        in which “alkyl” and R3a have the meanings indicated above, and R3a preferably denotes H or CH3. Particular preference is given to compounds of the formula IIIb;
        LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:
    
    






    
    
        in which
        
            R0 denotes an alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH2 groups in these radicals may each be replaced, independently of one another, by —C≡C—, —CF2O—, —CH═CH—,
        
        
    
    






—O—, —CO—O— or —O—CO— in such a way that O atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by halogen,

    
    
        
        
            X0 denotes F, Cl, CN, SF5, SCN, NCS, a halogenated alkyl radical, halogenated alkenyl radical, halogenated alkoxy radical or halogenated alkenyloxy radical, each having up to 6 C atoms,
            Y1-6 each, independently of one another, denote H or F,
            Z0 denotes —C2H4—, —(CH2)4—, —CH═CH—, —CF═CF—, —C2F4—, —CH2CF2—, —CF2CH2—, —CH2O—, —OCH2—, —COO—, —CF2O— or —OCF2—, in the formulae V and VI also a single bond, and
        
        
        b and c each, independently of one another, denote 0 or 1.
        In the compounds of the formulae IV to VIII, X0 preferably denotes F or OCF3, furthermore OCHF2, CF3, CF2H, Cl, OCH═CF2. R0 is preferably straight-chain alkyl or alkenyl, each having up to 6 C atoms.
        The compounds of the formula IV are preferably selected from the group consisting of the following formulae:
    
    






    
    
        in which R0 and X0 have the meanings indicated above.
        Preferably, R0 in formula IV denotes alkyl having 1 to 8 C atoms and X0 denotes F, Cl, OCHF2 or OCF3, furthermore OCH═CF2. In the compound of the formula IVb, R0 preferably denotes alkyl or alkenyl. In the compound of the formula IVd, X0 preferably denotes Cl, furthermore F.
        The compounds of the formula V are preferably selected from the group consisting of the following formulae:
    
    






    
    
        in which R0 and X0 have the meanings indicated above. Preferably, R0 in formula V denotes alkyl having 1 to 8 C atoms and X0 denotes F;
        LC medium which comprises one or more compounds of the formula VI-1.
    
    






    
    
        particularly preferably those selected from the group consisting of the following formulae:
    
    






    
    
        in which R0 and X0 have the meanings indicated above. Preferably, R0 in formula VI denotes alkyl having 1 to 8 C atoms and X0 denotes F, furthermore OCF3.
        LC medium which comprises one or more compounds of the formula VI-2:
    
    






    
    
        particularly preferably those selected from the group consisting of the following formulae:
    
    






    
    
        in which R0 and X0 have the meanings indicated above.
        Preferably, R0 in formula VI denotes alkyl having 1 to 8 C atoms and X0 denotes F;
        LC medium which preferably comprises one or more compounds of the formula VII in which Z0 denotes —CF2O—, —CH2CH2— or —COO—, particularly preferably those selected from the group consisting of the following formulae:
    
    






    
    
        in which R0 and X0 have the meanings indicated above. Preferably, R0 in formula VII denotes alkyl having 1 to 8 C atoms and X0 denotes F, furthermore OCF3.
        The compounds of the formula VIII are preferably selected from the group consisting of the following formulae:
    
    






    
    
        in which R0 and X0 have the meanings indicated above. R0 preferably denotes a straight-chain alkyl radical having 1 to 8 C atoms. X0 preferably denotes F.
        LC medium which additionally comprises one or more compounds of the following formula:
    
    






    
    
        in which R0, X0, Y1 and Y2 have the meanings indicated above, and
    
    






each, independently of one another, denote





where the rings A and B do not both simultaneously denote cyclohexylene.

    
    
        The compounds of the formula IX are preferably selected from the group consisting of the following formulae:
    
    






    
    
        in which R0 and X0 have the meanings indicated above. Preferably, R0 denotes alkyl having 1 to 8 C atoms and X0 denotes F. Particular preference is given to compounds of the formula IXa;
        LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:
    
    






    
    
        in which R0, X0 and Y1-4 have the meanings indicated above, and
    
    






each, independently of one another, denote





    
    
        The compounds of the formulae X and XI are preferably selected from the group consisting of the following formulae:
    
    






    
    
        in which R0 and X0 have the meanings indicated above. Preferably, R0 denotes alkyl having 1 to 8 C atoms and X0 denotes F. Particularly preferred compounds are those in which Y1 denotes F and Y2 denotes H or F, preferably F;
        LC medium which additionally comprises one or more compounds of the following formula:
    
    






    
    
        in which R5 and R6 each, independently of one another, denote n-alkyl, alkoxy, oxaalkyl, fluoroalkyl or alkenyl, each having up to 9 C atoms, and preferably each, independently of one another, denote alkyl having 1 to 8 C atoms. Y1 denotes H or F.
        Preferred compounds of the formula XII are those selected from the group consisting of the following formulae:
    
    






    
    
        in which
        
            alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 to 6 C atoms, and
            alkenyl and
            alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2 to 6 C atoms.
        
        
        Very particular preference is given to compounds of the following formula:
    
    






    
    
        in which alkyl has the meaning indicated above, and R6a denotes H or CH3.
        LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:
    
    






    
    
        in which R0, X0, Y1 and Y2 have the meanings indicated above. Preferably, R0 denotes alkyl having 1 to 8 C atoms and X0 denotes F or Cl.
        The compounds of the formulae XIII and XIV are preferably selected from the group consisting of the following formulae:
    
    






    
    
        in which R0 and X0 have the meanings indicated above. R0 preferably denotes alkyl having 1 to 8 C atoms. In the compounds of the formula XIII, X0 preferably denotes F or Cl.
        LC medium which additionally comprises one or more compounds of the formulae D1 and/or D2:
    
    






    
    
        in which Y1, Y2, R0 and X0 have the meanings indicated above. Preferably, R0 denotes alkyl having 1 to 8 C atoms and X0 denotes F. Particular preference is given to compounds of the following formulae:
    
    






    
    
        in which R0 has the meanings indicated above and preferably denotes straight-chain alkyl having 1 to 6 C atoms, in particular C2H5, n-C3H7 or n-C5H11.
        LC medium which additionally comprises one or more compounds of the following formula:
    
    






    
    
        in which Y1, R1 and R2 have the meanings indicated above. R1 and R2 preferably each, independently of one another, denote alkyl having 1 to 8 C atoms;
        LC medium which additionally comprises one or more compounds of the following formula:
    
    






    
    
        in which X0, Y1 and Y2 have the meanings indicated above, and “alkenyl” denotes C2-7-alkenyl. Particular preference is given to compounds of the following formula:
    
    






    
    
        in which R3a has the meaning indicated above and preferably denotes H;
        LC medium which additionally comprises one or more tetracyclic compounds selected from the group consisting of the formulae XIX to XXV:
    
    






    
    
        in which Y1-4, R0 and X0 each, independently of one another, have one of the meanings indicated above. X0 is preferably F, Cl, CF3, OCF3 or OCHF2. R0 preferably denotes alkyl, alkoxy, oxaalkyl, fluoroalkyl or alkenyl, each having up to 8 C atoms.
        LC medium which additionally comprises one or more compounds of the following formula:
    
    






    
    
        in which R0, X0 and Y1-4 have the meanings indicated above. Particular preference is given to compounds of the following formula:
    
    






    
    
        LC medium which additionally comprises one or more compounds of the following formula:
    
    






    
    
        in which R0 and Y1-3 have the meanings indicated above. Particular preference is given to compounds of the following formulae:
    
    






    
    
        in which R0 has the meaning indicated above and preferably denotes alkyl, alkoxy, oxaalkyl, fluoroalkyl or alkenyl, each having up to 8 C atoms.
        LC medium which additionally comprises one or more compounds of the following formula:
    
    






    
    
        in which R0 has the meaning indicated above and is preferably straight-chain alkyl having 2-5 C atoms, and d denotes 0 or 1, preferably 1. Preferred mixtures comprise 3-30% by weight, in particular 5-20% by weight, of this (these) compound(s).
        LC medium which additionally comprises one or more compounds of the following formula:
    
    






    
    
        in which Y1, R1 and R2 have the meanings indicated above. R1 and R2 preferably each, independently of one another, denote alkyl having 1 to 8 C atoms. Y1 preferably denotes F. Preferred mixtures comprise 1-15% by weight, in particular 1-10% by weight, of these compounds.
    
    






is preferably





    
    
        R0 is preferably straight-chain alkyl or alkenyl having 2 to 7 C atoms;
        X0 is preferably F, furthermore OCF3, Cl or CF3;
        the medium preferably comprises one, two or three compounds of the formula I;
        the medium preferably comprises one or more compounds selected from the group of the compounds of the formulae I, II, III, VI-2, XI, XII, XIII, XIV, XXIV, XXV, XXVI, XXVII and XXIX;
        the medium preferably comprises in each case one or more compounds of the formulae VI-2, XI and XXVI;
        the medium preferably comprises 1-25% by weight, preferably 1-20% by weight, of compounds of the formula I;
        the proportion of compounds of the formulae II-XXVIII in the mixture as a whole is preferably 20 to 99% by weight;
        the medium preferably comprises 25-80% by weight, particularly preferably 30-70% by weight, of compounds of the formulae II and/or III;
        the medium preferably comprises 20-70% by weight, particularly preferably 25-60% by weight, of compounds of the formula IIa, in particular in which R3a denotes H;
        the medium preferably comprises 2-20% by weight, particularly preferably 3-15% by weight, of compounds of the formula VI-2;
        the medium comprises 2-20% by weight, particularly preferably 3-15% by weight, of compounds of the formula XI;
        the medium preferably comprises 1-20% by weight, particularly preferably 2-15% by weight, of compounds of the formula XXIV;
        the medium preferably comprises 1-25% by weight, particularly preferably 2-20% by weight, of compounds of the formula XXVI;
        the medium preferably comprises 1-35% by weight, particularly preferably 5-30% by weight, of compounds of the formula XXVII;
        the medium preferably comprises one or more compounds selected from the group of the compounds of the formulae VI-2, VII-1a, VII-1b, IX, X, XI and XXV (CF2O-bridged compounds).
    
    


It has been found that even a relatively small proportion of compounds of the formula I mixed with conventional liquid-crystal materials, but in particular with one or more compounds of the formulae II to XXIX, results in a significant increase in the light stability and in low birefringence values, with broad nematic phases having low smectic-nematic transition temperatures being observed at the same time, improving the storage stability. The mixtures simultaneously exhibit very low threshold voltages and very good values for the VHR on exposure to UV.
The term “alkyl” or “alkyl*” in this application encompasses straight-chain and branched alkyl groups having 1-7 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 1-6 carbon atoms are generally preferred.
The term “alkenyl” or “alkenyl*” in this application encompasses straight-chain and branched alkenyl groups having 2-7 carbon atoms, in particular the straight-chain groups. Preferred alkenyl groups are C2-C7-1E-alkenyl, C4-C7-3E-alkenyl, C5-C7-4-alkenyl, C6-C7-5-alkenyl and C7-6-alkenyl, in particular C2-C7-1E-alkenyl, C4-C7-3E-alkenyl and C5-C7-4-alkenyl. Examples of particularly 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, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.
The term “fluoroalkyl” in this application encompasses straight-chain groups containing at least one fluorine atom, preferably a terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.
The term “oxaalkyl” or “alkoxy” in this application encompasses straight-chain radicals of the formula CnH2n+1—O—(CH2)m, in which n and m each, independently of one another, denote 1 to 6. m may also denote 0. Preferably, n=1 and m=1-6 or m=0 and n=1-3.
The term “halogenated alkyl radical” preferably encompasses mono- or polyfluorinated and/or -chlorinated radicals. Perhalogenated radicals are included. Particular preference is given to fluorinated alkyl radicals, in particular CF3, CH2CF3, CH2CHF2, CHF2, CH2F, CHFCF3 and CF2CHFCF3.
If R0 in the formulae above and below denotes an alkyl radical and/or an alkoxy radical, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.
Oxaalkyl preferably denotes straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.
If R0 denotes an alkyl radical in which a CH2 group has been replaced by —CH═CH—, this may be straight-chain or branched. It is preferably straight-chain and has 2 to 10 C atoms. Accordingly, it denotes, in particular, vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl. These radicals may also be mono- or polyhalogenated.
If R0 denotes an alkyl or alkenyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain, and halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resultant radicals also include perfluorinated radicals. In the case of mono-substitution, the fluorine or chlorine substituent may be in any desired position, but is preferably in the ω-position.
In the formulae above and below, X0 is preferably F, Cl or a mono- or polyfluorinated alkyl or alkoxy radical having 1, 2 or 3 C atoms or a mono- or polyfluorinated alkenyl radical having 2 or 3 C atoms. X0 is particularly preferably F, Cl, CF3, CHF2, OCF3, OCHF2, OCFHCF3, OCFHCHF2, OCFHCHF2, OCF2CH3, OCF2CHF2, OCF2CHF2, OCF2CF2CHF2, OCF2CF2CH2F, OCFHCF2CF3, OCFHCF2CHF2, OCH═CF2, OCF═CF2, OCF2CHFCF3, OCF2CF2CF3, OCF2CF2CClF2, OCClFCF2CF3, CF═CF2, CF═CHF or CH═CF2, very particularly preferably F or OCF3.
Through a suitable choice of the meanings of R0 and X0, the addressing times, the threshold voltage, the steepness of the transmission characteristic lines, etc., can be modified in the desired manner. For example, 1E-alkenyl radicals, 3E-alkenyl radicals, 2E-alkenyloxy radicals and the like generally result in shorter addressing times, improved nematic tendencies and a higher ratio between the elastic constants k33 (bend) and k11 (splay) compared with alkyl and alkoxy radicals. 4-Alkenyl radicals, 3-alkenyl radicals and the like generally give lower threshold voltages and lower values of k33/k11 compared with alkyl and alkoxy radicals. The mixtures according to the invention are distinguished, in particular, by high K1 values and thus have significantly faster response times than the mixtures from the prior art.
The optimum mixing ratio of the compounds of the above-mentioned formulae depends substantially on the desired properties, on the choice of the components of the above-mentioned formulae and on the choice of any further components that may be present.
Suitable mixing ratios within the range indicated above can easily be determined from case to case.
The total amount of compounds of the above-mentioned formulae in the mixtures according to the invention is not crucial. The mixtures can therefore comprise one or more further components for the purposes of optimisation of various properties. However, the observed effect on the desired improvement in the properties of the mixture is generally greater, the higher the total concentration of compounds of the above-mentioned formulae.
In a particularly preferred embodiment, the media according to the invention comprise compounds of the formulae IV to VIII in which X0 denotes F, OCF3, OCHF2, OCH═CF2, OCF═CF2 or OCF2—CF2H. A favourable synergistic action with the compounds of the formula I results in particularly advantageous properties. In particular, mixtures comprising compounds of the formulae I, VI and XI are distinguished by their low threshold voltages.
The individual compounds of the above-mentioned formulae and the sub-formulae thereof which can be used in the media according to the invention are either known or can be prepared analogously to the known compounds.
The invention also relates to electro-optical displays, such as, for example, TN, STN, TFT, OCB, IPS, FFS or MLC displays, having two plane-parallel outer plates, which, together with a frame, form a cell, integrated non-linear elements for switching individual pixels on the outer plates, and a nematic liquid-crystal mixture having positive dielectric anisotropy and high specific resistance located in the cell, which contain media of this type, and to the use of these media for electro-optical purposes.
The liquid-crystal mixtures according to the invention enable a significant broadening of the available parameter latitude. The achievable combinations of clearing point, viscosity at low temperature, thermal and UV stability and high optical anisotropy are far superior to previous materials from the prior art.
The mixtures according to the invention are particularly suitable for mobile applications and high-An TFT applications, such as, for example, PDAs, notebooks, LCD TVs and monitors.
The liquid-crystal mixtures according to the invention, with retention of the nematic phase down to −20° C. and preferably down to −30° C., particularly preferably down to −40° C., and of the clearing point ≧70° C., preferably ≧75° C., simultaneously enable rotational viscosities γ1 of ≦100 mPa·s, particularly preferably ≦70 mPa·s, to be achieved, enabling excellent MLC displays having fast response times to be obtained.
The dielectric anisotropy Δ∈ of the liquid-crystal mixtures according to the invention is preferably ≧+5, particularly preferably ≧+10. In addition, the mixtures are characterised by low operating voltages. The threshold voltage of the liquid-crystal mixtures according to the invention is preferably ≦1.5 V, in particular ≦1.2 V.
The birefringence Δn of the liquid-crystal mixtures according to the invention is preferably ≧0.10, particularly preferably ≧0.11.
The nematic phase range of the liquid-crystal mixtures according to the invention preferably has a width of at least 90°, in particular at least 100°. This range preferably extends at least from −25° C. to +70° C.
It goes without saying that, through a suitable choice of the components of the mixtures according to the invention, it is also possible for higher clearing points (for example above 100° C.) to be achieved at higher threshold voltages or lower clearing points to be achieved at lower threshold voltages with retention of the other advantageous properties. At viscosities correspondingly increased only slightly, it is likewise possible to obtain mixtures having higher Δ∈ and thus low thresholds. The MLC displays according to the invention preferably operate at the first Gooch and Tarry transmission minimum [C. H. Gooch and H. A. Tarry, Electron. Lett. 10, 2-4, 1974; C. H. Gooch and H. A. Tarry, Appl. Phys., Vol. 8, 1575-1584, 1975], where, besides particularly favourable electro-optical properties, such as, for example, high steepness of the characteristic line and low angle dependence of the contrast (German patent 30 22 818), lower dielectric anisotropy is sufficient at the same threshold voltage as in an analogous display at the second minimum. This enables significantly higher specific resistance values to be achieved using the mixtures according to the invention at the first minimum than in the case of mixtures comprising cyano compounds. Through a suitable choice of the individual components and their proportions by weight, the person skilled in the art is able to set the birefringence necessary for a pre-specified layer thickness of the MLC display using simple routine methods.
Measurements of the voltage holding ratio (HR) [S. Matsumoto et al., Liquid Crystals 5, 1320 (1989); K. Niwa et al., Proc. SID Conference, San Francisco, June 1984, p. 304 (1984); G. Weber et al., Liquid Crystals 5, 1381 (1989)] have shown that mixtures according to the invention comprising compounds of the formula I exhibit a significantly smaller decrease in the HR on UV exposure than analogous mixtures comprising cyanophenylcyclohexanes of the formula




or esters of the formula





instead of the compounds of the formula I. The LC media are preferably 99% by weight, particularly preferably 100% by weight, free from benzonitrile derivatives.

The light stability and UV stability of the mixtures according to the invention are considerably better, i.e. they exhibit a significantly smaller decrease in the HR on exposure to light or UV. Even low concentrations of the compounds (<10% by weight) of the formula I in the mixtures increase the HR by 6% or more compared with mixtures from the prior art.
The LC media may also comprise further additives known to the person skilled in the art and described in the literature, such as, for example, UV stabilisers, such as Tinuvin® from Ciba, antioxidants, free-radical scavengers, nanoparticles, etc. For example, 0-15% of pleochroic dyes or chiral dopants can be added. Suitable stabilisers and dopants are mentioned below in Tables C and D.
The individual components of the above-mentioned preferred embodiments of the LC media according to the invention are either known or their preparation methods can readily be derived from the prior art by the person skilled in the relevant art since they are based on standard methods described in the literature.
It goes without saying to the person skilled in the art that the LC media according to the invention may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.
The liquid-crystal mixtures which can be used in accordance with the invention are prepared in a manner conventional per se, for example by mixing one or more compounds of the formula I with one or more compounds of the formulae II-XXVIII or with further liquid-crystalline compounds and/or additives. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after thorough mixing. The invention furthermore relates to the process for the preparation of the LC media according to the invention.
The construction of the MLC display according to the invention from polarisers, electrode base plates and surface-treated electrodes corresponds to the usual design for displays of this type. The term usual design is broadly drawn here and also encompasses all derivatives and modifications of the MLC display, in particular including matrix display elements based on poly-Si TFTs or MIM.
A significant difference between the displays according to the invention and the hitherto conventional displays based on the twisted nematic cell consists, however, in the choice of the liquid-crystal parameters of the liquid-crystal layer.
The following examples explain the present invention without limiting it. However, they show the person skilled in the art preferred mixture concepts with compounds preferably to be employed and the respective concentrations thereof and combinations thereof with one another. In addition, the examples illustrate which properties and property combinations are accessible.
In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by means of acronyms, with the transformation into chemical formulae taking place in accordance with Tables A and B below. All radicals CnH2n+1 and CmH2m+1 are straight-chain alkyl radicals having n and m C atoms respectively; n, m and k are integers and preferably denote 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. The coding in Table B is self-evident. In Table A, only the acronym for the parent structure is indicated. In individual cases, the acronym for the parent structure is followed, separated by a dash, by a code for the substituents R1*, R2*, L1* and L2*:














Code for R1*,






R2*, L1*, L2*, L3*
R1*
R2*
L1*
L2*







nm
CnH2n+1
CmH2m+1
H
H


nOm
CnH2n+1
OCmH2m+1
H
H


nO.m
OCnH2n+1
CmH2m+1
H
H


n
CnH2n+1
CN
H
H


nN.F
CnH2n+1
CN
F
H


nN.F.F
CnH2n+1
CN
F
F


nF
CnH2n+1
F
H
H


nCl
CnH2n+1
Cl
H
H


nOF
OCnH2n+1
F
H
H


nF.F
CnH2n+1
F
F
H


nF.F.F
CnH2n+1
F
F
F


nOCF3
CnH2n+1
OCF3
H
H


nOCF3.F
CnH2n+1
OCF3
F
H


n-Vm
CnH2n+1
—CH═CH—CmH2m+1
H
H


nV-Vm
CnH2n+1—CH═CH—
—CH═CH—CmH2m+1
H
H









Preferred mixture components are found in Tables A and B.







TABLE A













 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 






















TABLE B













 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 















In a preferred embodiment of the present invention, the LC media according to the invention comprise one or more compounds selected from the group consisting of compounds from Tables A and B.







TABLE C





Table C indicates possible dopants which can be added to the LC media


according to the invention.













 








 








 








 








 








 








 








 








 








 








 








 















The LC media preferably comprise 0 to 10% by weight, in particular 0.01 to 5% by weight and particularly preferably 0.1 to 3% by weight, of dopants. The LC media preferably comprise one or more dopants selected from the group consisting of compounds from Table C.







TABLE D





Table D indicates possible stabilisers which can be added to the LC media


according to the invention.


(n here denotes an integer from 1 to 12)













 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 








 















The LC media preferably comprise 0 to 10% by weight, in particular 0.01 to 5% by weight and particularly preferably 0.1 to 3% by weight, of stabilisers. The LC media preferably comprise one or more stabilisers selected from the group consisting of compounds from Table D.
In addition, the following abbreviations and symbols are used:

    V0 threshold voltage, capacitive [V] at 20° C.,
    V10 optical threshold for 10% relative contrast [V] at 20° C.,
    ne extraordinary refractive index at 20° C. and 589 nm,
    no ordinary refractive index at 20° C. and 589 nm,
    Δn optical anisotropy at 20° C. and 589 nm,
    ∈⊥ dielectric susceptibility perpendicular to the director at 20° C. and 1 kHz,
    ∈∥ dielectric susceptibility parallel to the director at 20° C. and 1 kHz,
    Δ∈ dielectric anisotropy at 20° C. and 1 kHz,
    cl.p., T(N,I) clearing point [° C.],
    γ1 rotational viscosity at 20° C. [mPa·s],
    K1 elastic constant, “splay” deformation at 20° C. [pN],
    K2 elastic constant, “twist” deformation at 20° C. [pN],
    K3 elastic constant, “bend” deformation at 20° C. [pN],
    LTS low-temperature stability (phase), determined in test cells,
    HR20 voltage holding ratio at 20° C. [%] and
    HR100 voltage holding ratio at 100° C. [%].


Unless explicitly noted otherwise, all concentrations in the present application are indicated in percent by weight and relate to the corresponding mixture as a whole without solvents.
Unless explicitly noted otherwise, all temperature values indicated in the present application, such as, for example, the melting point T(C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I), are indicated in degrees Celsius (° C.). M.p. denotes melting point, cl.p.=clearing point. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between these symbols represent the transition temperatures.
All physical properties are and have been determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, Status November 1997, Merck KGaA, Darmstadt, Germany, and apply to a temperature of 20° C., and Δn is determined at 589 nm and Δ∈ at 1 kHz, unless explicitly indicated otherwise in each case.
The liquid-crystalline properties of the individual compounds are, unless indicated otherwise, determined in the nematic host mixture ZLI-4792 (commercially available from Merck KGaA, Darmstadt) at a concentration of 10%.
“Room temperature” means 20° C., unless indicated otherwise.
The term “threshold voltage” for the present invention relates to the capacitive threshold (V0), also called the Freedericks threshold, unless explicitly indicated otherwise. In the examples, as generally usual, the optical threshold for 10% relative contrast (V10) may also be indicated.
The test cells used for measurement of the capacitive threshold voltage V0 and for V10 are constructed from substrates consisting of soda-lime glass coated with polyimide alignment layers (Durimid 32 with diluent (70% of NMP+30% of xylene) in the ratio 1:4) from Arch Chemicals, which are rubbed antiparallel to one another and have a surface tilt of quasi 0 degrees. The area of the transparent, virtually square ITO electrodes is 1 cm2. The capacitive threshold voltage is determined using a standard commercial high-resolution LCR meter (for example Hewlett Packard 4284A LCR meter).


EXAMPLE 1
2-(3,5-Difluoro-4′-propylbiphenyl-4-yl)-5-methylthiophene (PUS-3-1)
The compound 2-(3,5-difluoro-4′-propylbiphenyl-4-yl)-5-methylthiophene (PUS-3-1) according to the invention is prepared as described below:




A mixture of 5.50 g (31.0 mmol) of 2-bromo-5-methylthiophene, 9.0 g (32.6 mmol) of 4′-propyl-3,5-difluoro-4-biphenylboronic acid, 1.83 g (1.58 mmol) of tetrakis(triphenylphosphine)palladium(0) and 36 ml of 2 N sodium carbonate soln. in 90 ml of toluene/ethanol (1:2) is heated under reflux for 16 h. After cooling, the organic phase is separated off, and the aqueous phase is extracted a number of times with toluene. The combined organic phases are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to completion. The residue is purified by column chromatography (SiO2, n-heptane:toluene=9:1). Further purification is carried out by recrystallisation from ethanol and n-heptane; 2-(3,5-difluoro-4′-propylbiphenyl-4-yl)-5-methylthiophene (PUS-3-1) is obtained as a colourless solid (m.p. 75° C.).
1H-NMR (300 MHz, CHCl3): δ=7.49 (d, 2H, J=8.4 Hz, Harom.), 7.39 (d, 1H, J=3.6 Hz, Harom.), 7.28-7.16 (m, 4H, Harom.), 6.82-6.80 (m, 1H, Harom.), 2.63 (t, 2H, J=7.5 Hz, H3CCH2CH2—), 2.54 (d, 3H, J=0.6 Hz, CH3), 1.74-1.61 (m, 2H, H3CCH2CH2—), 0.97 (t, 3H, J=7.5 Hz, H3CCH2CH2—).
19F-NMR (376 MHz, CHCl3): δ=−110.5 (d, 2F, J=10.9 Hz).
MS (EI): m/e (%)=328 (100, M+), 299 (79, [M-C2H5]+)
Δ∈=+3.1
Δn=0.3055
γ1=102 mPa·s
C 75 N 107 I
EXAMPLE 2
2-(3,5-Difluoro-4′-propylbiphenyl-4-yl)-5-ethylthiophene (PUS-3-2)
The compound 2-(3,5-difluoro-4′-propylbiphenyl-4-yl)-5-ethylthiophene (PUS-3-2) according to the invention is prepared as described below:




17.0 g (54.6 mmol) of 4-bromo-3,5-difluoro-4′-propylbiphenyl, 16.1 g (82.1 mmol) of 2-ethylthiophene-5-hydroxyboronic acid sodium salt and 9.2 g (0.11 mol) of sodium hydrogencarbonate are refluxed together with 700 mg (1.37 mmol) of bis(tri-tert-butylphosphine)palladium(0) in 250 ml of THF/water mixture (2:1). After 22 h, the mixture is diluted with MTBE, and the organic phase is separated off. The aqueous phase is extracted a number of times with MTBE, and the combined organic phases are washed with water and saturated sodium chloride solution. The solution is dried using sodium sulfate and concentrated to completion. The crude product is purified by column chromatography (SiO2, n-heptane). The further purification is carried out by recrystallisation from ethanol and n-heptane. 2-(3,5-Difluoro-4′-propylbiphenyl-4-yl)-5-ethylthiophene (PUS-3-2) is obtained as a colourless solid (m.p. 45° C.).
1H-NMR (400 MHz, CHCl3): δ=7.49 (d, 2H, J=8.4 Hz, Harom.), 7.41 (d, 1H, J=3.6 Hz, Harom.), 7.28-7.17 (m, 4H, Harom.), 6.85-6.83 (m, 1H, Harom.), 2.90 (q, 2H, J=7.5 Hz, CH2CH3), 2.63 (t, 2H, J=7.6 Hz, H3CCH2CH2—), 1.74-1.61 (m, 2H, H3CCH2CH2—), 1.36 (t, 3H, J=7.5 Hz, CH2CH3), 0.97 (t, 3H, J=7.6 Hz, H3CCH2CH2—).
19F-NMR (376 MHz, CHCl3): δ=−110.5 (d, 2F, J=11.0 Hz).
MS (EI): m/e (%)=342 (100, M+), 327 (80, [M-CH3]+).
Δ∈=+3.8
Δn=0.2939
γ1=76 mPa·s
C 45 N 90 I
EXAMPLE 3
2-(3,5-Difluoro-4′-propylbiphenyl-4-yl)-5-propylthiophene (PUS-3-3)
The compound 2-(3,5-difluoro-4′-propylbiphenyl-4-yl)-5-propylthiophene (PUS-3-3) according to the invention is prepared as described below:




5.0 g (24.4 mmol) of 2-bromo-5-propylthiophene, 7.40 g (26.8 mmol) of 4′-propyl-3,5-difluoro-4-biphenylboronic acid and 2.82 g (2.44 mmol) of tetrakis(triphenylphosphine)palladium(0) are initially introduced in 160 ml of toluene. A solution of 5.85 g (48.8 mmol) of sodium dihydrogenphosphate and 13.8 g (97.5 mmol) of disodium hydrogenphosphate dodecahydrate in 50 ml of water is added, and the mixture is heated under reflux for 19 h. After cooling, the organic phase is separated off, and the aqueous phase is extracted a number of times with toluene. The combined organic phases are washed with water and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to completion. The residue is purified by column chromatography (SiO2, n-heptane). Further purification is carried out by recrystallisation from ethanol and n-heptane; 2-(3,5-difluoro-4′-propylbiphenyl-4-yl)-5-propylthiophene (PUS-3-3) is obtained as a colourless solid (m.p. 64° C.).
1H-NMR (400 MHz, CHCl3): δ=7.49 (d, 2H, J=8.1 Hz, Harom.), 7.42 (d, 1H, J=3.6 Hz, Harom.), 7.28-7.17 (m, 4H, Harom.), 6.85-6.83 (m, 1H, Harom.), 2.84 (t, 2H, J=7.6 Hz, —CH2CH2CH3), 2.63 (t, 2H, J=7.6 Hz, H3CCH2CH2—), 1.81-1.63 (m, 4H, H3CCH2CH2—, —CH2CH2CH3), 1.01 (t, 3H, J=7.6 Hz, —CH2CH2CH3), 0.97 (t, 3H, J=7.6 Hz, H3CCH2CH2—).
19F-NMR (376 MHz, CHCl3): δ=−110.5 (d, 2F, J=10.9 Hz).
MS (EI): m/e (%)=358 (67, M+), 327 (100, [M-C2H5]+).
Δ∈=+4.2
Δn=0.2831
γ1=67 mPa·s
C 64 N 86 I
EXAMPLE 4
2-(3,5-Difluoro-4′-ethylbiphenyl-4-yl)-5-ethylthiophene (PUS-2-2)




The compound 2-(3,5-difluoro-4′-ethylbiphenyl-4-yl)-5-ethylthiophene (PUS-2-2) according to the invention is prepared analogously to Example 3 from 4′-ethyl-3,5-difluoro-4-biphenylboronic acid and 2-bromo-5-ethyl-thiophene.
1H-NMR (400 MHz, CHCl3): δ=7.49 (d, 2H, J=8.1 Hz, Harom.), 7.42 (d, 1H, J=3.6 Hz, Harom.), 7.28-7.17 (m, 4H, Harom.), 6.85-6.83 (m, 1H, Harom.), 2.90 (q, 2H, J=7.4 Hz, —CH2CH3), 2.69 (q, 2H, J=7.4 Hz, H3CCH2—), 1.36 (t, 3H, J=7.6 Hz, —CH2CH3), 1.28 (t, 3H, J=7.6 Hz, H3CCH2—).
19F-NMR (376 MHz, CHCl3): δ=−110.5 (d, 2F, J=10.9 Hz).
MS (EI): m/e (%)=328 (98, M+), 313 (100, [M-CH3]+).
Δ∈=+5.4
Δn=0.2969
γ1=58 mPa·s
C 48 N 62 I
EXAMPLE 5
2-(3,5-Difluoro-4′-ethylbiphenyl-4-yl)-5-propylthiophene (PUS-2-3)




The compound 2-(3,5-difluoro-4′-ethylbiphenyl-4-yl)-5-propylthiophene (PUS-2-3) according to the invention is prepared analogously to Example 3 from 4′-ethyl-3,5-difluoro-4-biphenylboronic acid and 2-bromo-5-propyl-thiophene.
1H-NMR (400 MHz, CHCl3): δ=7.49 (d, 2H, J=8.1 Hz, Harom.), 7.42 (d, 1H, J=3.6 Hz, Harom.), 7.28-7.17 (m, 4H, Harom.), 6.85-6.83 (m, 1H, Harom.) 2.84 (t, 2H, J=7.5 Hz, —CH2CH2CH3), 2.70 (q, 2H, J=7.4 Hz, H3CCH2—), 1.81-1.71 (m, 2H, —CH2CH2CH3), 1.27 (t, 3H, J=7.5 Hz, —CH2CH2CH3), 1.01 (t, 3H, J=7.4 Hz, H3CCH2—).
19F-NMR (376 MHz, CHCl3): δ=−110.5 (d, 2F, J=10.9 Hz).
MS (EI): m/e (%)=342 (58, M+), 313 (100, [M-C2H5]+).
Δ∈=+3.3
Δn=0.2829
γ1=61 mPa·s
C 50 N 61 I
EXAMPLE 6
2-(4′-Ethyl-2,6-difluorobiphenyl-4-yl)-5-propylthiophene (SUP-3-2)




The compound 2-(4′-ethyl-2,6-difluorobiphenyl-4-yl)-5-propylthiophene (SUP-3-2) according to the invention is prepared analogously to Example 1 from 4′-ethyl-2,6-difluoro-4-biphenylboronic acid and 2-bromo-5-propyl-thiophene.
1H-NMR (400 MHz, CHCl3): δ=7.41 (d, 2H, J=8.2 Hz, Harom.), 7.29 (d, 2H, J=8.2 Hz, Harom.), 7.19-7.12 (m, 3H, Harom.), 6.76 (d, 1H, J=3.4 Hz, Harom.), 2.80 (t, 2H, J=7.6 Hz, —CH2CH2CH3), 2.70 (q, 2H, J=7.6 Hz, H3CCH2—), 1.78-1.69 (m, 2H, —CH2CH2CH3), 1.28 (t, 3H, J=7.6 Hz, —CH2CH2CH3), 1.00 (t, 3H, J=7.6 Hz, H3CCH2—).
19F-NMR (376 MHz, CHCl3): δ=−114.5 (d, 2F, J=8.3 Hz).
MS (EI): m/e (%)=342 (61, M+), 313 (100, [M-C2H5]+).
Δ∈=+5.5
Δn=0.2332
γ1=110 mPa·s
C 80 I
EXAMPLE 7
2-(4′-Ethyl-2,6-difluorobiphenyl-4-yl)-5-ethylthiophene (SUP-2-2)




The compound 2-(4′-ethyl-2,6-difluorobiphenyl-4-yl)-5-ethylthiophene (SUP-2-2) according to the invention is prepared analogously to Example 1 from 4′-ethyl-2,6-difluoro-4-biphenylboronic acid and 2-bromo-5-ethyl-thiophene.
1H-NMR (400 MHz, CHCl3): δ=7.41 (d, 2H, J=8.1 Hz, Harom.), 7.29 (d, 2H, J=8.1 Hz, Harom.), 7.19-7.13 (m, 3H, Harom.), 6.77 (d, 1H, J=3.4 Hz, Harom.), 2.87 (q, 2H, J=7.5 Hz, —CH2CH3), 2.71 (q, 2H, J=7.5 Hz, H3CCH2—), 1.34 (t, 3H, J=7.5 Hz, —CH2CH3), 1.28 (t, 3H, J=7.6 Hz, —CH2CH3).
19F-NMR (376 MHz, CHCl3): δ=−114.5 (d, 2F, J=8.3 Hz).
MS (EI): m/e (%)=328 (100, M+), 313 (89, [M-CH3]+).
Δ∈=+6.4
Δn=0.3021
γ1=106 mPa·s
C 106 I
EXAMPLE 8
2-[2,6-Difluoro-4-(4-propylcyclohexyl)phenyl]-5-ethylthiophene (CUS-3-2)




The compound 2-[2,6-difluoro-4-(4-propylcyclohexyl)phenyl]-5-ethylthiophene (“CUT-3-2”) according to the invention is prepared analogously to Example 3 from 2,5-difluoro-4-(4-propylcyclohexyl)benzeneboronic acid and 2-bromo-5-ethylthiophene.
1H-NMR (400 MHz, CHCl3): δ=7.31 (d, 1H, J=3.6 Hz, Harom.), 6.84-6.79 (m, 3H, Harom.), 2.88 (dq, 2H, J=7.5 Hz, J=0.8 Hz, —CH2CH3), 2.48-2.40 (m, 1H, Haliphat.), 1.93-1.84 (m, 4H, Haliphat.), 1.46-1.18 (m, 10H, Haliphat.), 1.10-0.98 (m, 2H, Haliphat.), 0.90 (t, 3H, J=7.5 Hz, —CH2CH3).
19F-NMR (376 MHz, CHCl3): δ=−111.5 (d, 2F, J=10.0 Hz).
MS (EI): m/e (%)=348 (100, M+), 333 (67, [M-CH3]+).
Δ∈=+3.0
Δn=0.1719
γ1=107 mPa·s
C 34 N 97 I
EXAMPLE 9
2-(3,5-Difluoro-4′-propylbiphenyl-4-yl)-5-vinylthiophene (PUS-3-V)




The compound 2-(3,5-difluoro-4′-propylbiphenyl-4-yl)-5-vinylthiophene (PUS-2-V) according to the invention is prepared analogously to Example 3 from 4′-propyl-3,5-difluoro-4-biphenylboronic acid and 2-bromo-5-vinyl-thiophene.
Δ∈=+6.5
Δn=0.349
γ1=163 mPa·s
C 69 N 111 I
COMPARATIVE EXAMPLE 1
2-(2-Fluoro-4′-pentylbiphenyl-4-yl)-5-hexylthiophene




A mixture of 3.30 g (13.1 mmol) of 5-hexylthiophen-2-ylhydroxyboronic acid sodium salt, 4.20 g (13.1 mmol) of 4-bromo-2-fluoro-4′-pentylbiphenyl, 2.2 g (26.2 mmol) of sodium hydrogencarbonate and 0.70 g (0.61 mmol) of tetrakis(triphenylphosphine)palladium(0) in THF/water (1:1) is heated under reflux for 6 h. The mixture is diluted with MTBE, and the organic phase is separated off. The aqueous phase is extracted with MTBE. The combined organic phases are washed with sat. sodium chloride soln. and dried using sodium sulfate. The solution is concentrated to completion, and the residue is purified by column chromatography (SiO2, n-heptane). The further purification is carried out by recrystallisation from methanol/pentane (5:1). 2-(2-Fluoro-4′-pentylbiphenyl-4-yl)-5-hexylthiophene is obtained as a colourless solid having an m.p. of 44° C.
1H-NMR (400 MHz, CHCl3): δ=7.47 (dd, 2H, J=8.6 Hz, J=1.7 Hz, Harom.), 7.42-7.35 (m, 2H, Harom.), 7.31-7.30 (d, 1H, J=12.0 Hz, Harom.), 7.26 (d, 2H, J=8.4 Hz, Harom.), 7.17 (d, 1H, J=3.3 Hz, Harom.), 6.76 (d, 1H, J=3.3 Hz, Harom.), 2.82 (t, 2H, J=7.6 Hz, —CH2(CH2)4CH3), 2.68 (t, 2H, J=7.8 Hz, H3C(CH2)3CH2—), 1.75-1.60 (m, 4H, —(CH2)—), 1.44-1.27 (m, 10H, —(CH2)—), 0.94-0.86 (m, 6H, H3C(CH2)3CH2—, —CH2(CH2)4CH3).
19F-NMR (282 MHz, CHCl3): δ=118.0 (dd, 1F, J=12.0 Hz, J=7.6 Hz).
MS (EI): m/e (%)=408 (100, M+), 337 (77, [M-pent]+), 280 (21, [M-pent-Bu]+).
Δ∈=+3.2
Δn=0.2311
γ1=153 mPa·s
C 44 Sm (6) SmB (38) SmC 68 SmA 75 N 94 I
COMPARATIVE EXAMPLE 2
2-Butyl-5-(3-fluoro-4′-hexyloxybiphenyl-4-yl)thiophene




A mixture of 4.48 g (20.0 mmol) of 5-butylthiophen-2-ylhydroxyboronic acid sodium salt, 7.0 g (19.9 mmol) of 4-bromo-3-fluoro-4′-hexyloxybiphenyl, 3.36 g (40.0 mmol) of sodium hydrogencarbonate and 1.1 g (0.95 mmol) of tetrakis(triphenylphosphine)palladium(0) in 90 ml of THF/water (2:1) is heated under reflux for 19 h. The mixture is diluted with MTBE, and the organic phase is separated off. The aqueous phase is extracted with MTBE. The combined organic phases are washed with sat. sodium chloride soln. and dried using sodium sulfate. The solution is concentrated to completion, and the residue is purified by column chromatography (SiO2, n-heptane:toluene=9:1). The further purification is carried out by recrystallisation from ethanol. 2-Butyl-5-(3-fluoro-4′-hexyloxybiphenyl-4-yl)thiophene is obtained as a colourless wax having an m.p. of 66° C.
1H-NMR (300 MHz, CHCl3): δ=7.62-7.57 (m, 1H, Harom.), 7.52 (d, 2H, J=8.2 Hz, Harom.), 7.35-7.28 (m, 3H, Harom.), 7.96 (d, 2H, J=8.2 Hz, Harom.), 6.80-6.78 (m, 1H, Harom.), 3.99 (t, 2H, J=6.1 Hz, OCH2(CH2)4CH3), 2.85 (t, 2H, J=7.2 Hz, CH2(CH2)2CH3), 1.85-1.65 (m, 4H, Haliph.), 1.54-1.31 (8H, Haliph.), 0.99-0.89 (m, 6H, 2×CH3).
19F-NMR (282 MHz, CHCl3): δ=114.2 (dd, 1F, J=12.7 Hz, J=8.2 Hz).
MS (EI): m/e (%)=410 (100, M+), 367 (31, [M-propyl]+), 283 (51, [M-propyl-hexyl]+).
Δ∈=+8.9
Δn=0.2749
γ1=262 mPa·s
C 66 SmE 89 SmC 131 SmA 144 N 146 I
COMPARATIVE EXAMPLE 3
2-(3-Fluoro-4-pentylphenyl)-5-p-tolylthiophene
Synthesis of 2-(3-fluoro-4-pentylphenyl)thiophene




A mixture of 40.0 g (0.31 mol) of thiophen-2-ylboronic acid, 80.0 g (0.32 mol) of 4-bromo-2-fluoro-1-pentylbenzene, 18.0 g (15.6 mmol) of tetrakis(triphenylphosphine)palladium(0) and 400 ml of 2 M sodium hydrogencarbonate soln. in 1000 ml of ethanol/toluene=3:2 is heated at 80° C. for 19 h. Toluene and water are added to the mixture, and the organic phase is separated off. The aqueous phase is extracted with toluene, and the combined organic phases are washed with sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to completion. The residue is purified by column chromatography (SiO2, n-heptane). 2-(3-Fluoro-4-pentylphenyl)thiophene is obtained as a colourless liquid.
Synthesis of 2-bromo-5-(3-fluoro-4-pentylphenyl)thiophene




20.0 g (80.5 mmol) of 2-(3-fluoro-4-pentylphenyl)thiophene are initially introduced in 200 ml of THF, and 50.0 ml of n-BuLi (79.6 mmol, 15% soln. in hexane) are added dropwise to the solution at a temperature in the range 0-5° C. After 1 h at 0° C., the batch is cooled to −70° C., and 4.1 ml (80.0 mmol) of bromine are metered in. When the addition is complete, the mixture is stirred at 0° C. for 1 h. The batch is diluted with MTBE and washed successively with 2 N HCl, 10% sodium hydrogensulfite soln., sat. sodium hydrogencarbonate soln. and sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to completion. The crude product is purified by column chromatography (SiO2, n-heptane). 2-Bromo-5-(3-fluoro-4-pentylphenyl)thiophene is obtained as a yellowish liquid.
Synthesis of 2-(3-fluoro-4-pentylphenyl)-5-p-tolylthiophene




A mixture of 3.54 g (26.0 mmol) of p-tolylboronic acid, 8.50 g (26.0 mmol) of 2-bromo-5-(3-fluoro-4-pentylphenyl)thiophene, 1.50 g (1.30 mmol) of tetrakis(triphenylphosphine)palladium(0) and 33 ml of 2 M sodium hydrogencarbonate soln. in 80 ml of ethanol/toluene=3:2 is heated at 80° C. for 20 h. Toluene and water are added to the mixture, and the organic phase is separated off. The aqueous phase is extracted with toluene, and the combined organic phases are washed with sat. sodium chloride soln. The solution is dried using sodium sulfate and concentrated to completion. The residue is purified by column chromatography (SiO2, toluene). The further purification is carried out by recrystallisation from ethanol and n-heptane. 2-(3-Fluoro-4-pentylphenyl)-5-p-tolylthiophene is obtained as a solid having an m.p. of 115° C.
1H-NMR (300 MHz, CHCl3): δ=7.53-7.49 (m, 2H, Harom.), 7.32-7.37 (m, 2H, Harom.), 7.24-7.13 (m, 5H, Harom.), 2.63 (t, 2H, J=7.7 Hz, —CH2(CH2)3CH3), 2.36 (s, 3H, Me), 1.67-1.56 (m, 2H, Haliph.), 1.39-1.29 (m, 4H, Haliph.), 0.90 (t, 3H, J=6.9 Hz, —CH2(CH2)3CH3).
19F-NMR (282 MHz, CHCl3): δ=118.6 (dd, 1F, J=11.0 Hz, J=8.2 Hz).
MS (EI): m/e (%)=338 (92, M+), 281 (100, [M-butyl]+).
Δ∈=+3.7
Δn=0.1877
γ1=196 mPa·s
C 115 N 119 I
MIXTURE EXAMPLES
Comparative Example M1
A nematic LC mixture is formulated as follows:



















PUQU-3-F
5.0%
cl.p.
+75.5°
C.












PGUQU-3-F
7.0%
Δn
0.1036



APUQU-2-F
8.0%
Δε
+7.4



APUQU-3-F
8.0%
ε∥
10.6



CC-3-V
47.0%
K3/K1
1.10













CC-3-V1
6.0%
γ1
57
mPa · s












CCP-V-1
10.0%
V0 [V]
1.36



PGP-2-3
4.0%



PGP-2-4
5.0%










Mixture Example 1
A nematic LC mixture according to the invention is formulated as follows:



















PUQU-3-F
5.0%
cl.p.
+74.5°
C.












PGUQU-3-F
7.0%
Δn
0.1026



APUQU-2-F
8.0%
Δε
+7.6



APUQU-3-F
8.0%
ε∥
10.7



CC-3-V
47.0%
K3/K1
1.07













CC-3-V1
7.0%
γ1
55
mPa · s












CCP-V-1
11.0%
V0 [V]
1.36












PUS-2-2
7.0%










The mixture has lower rotational viscosity than Comparative Mixture M1, with virtually unchanged values of the clearing point, dielectric anisotropy, birefringence and threshold voltage.
Mixture Example 2
A nematic LC mixture according to the invention is formulated as follows:


















PUQU-3-F
6.0%
cl.p. [° C.]
+74.0



PGUQU-3-F
6.0%
Δn
0.1001



APUQU-2-F
8.0%
Δε
+7.3



APUQU-3-F
8.0%
ε∥
10.5



CC-3-V
48.0%
K3/K1
1.08



CC-3-V1
6.0%
γ1 [mPa · s ]
53



CCP-V-1
12.0%
V0 [V]
1.36



PUS-2-2
6.0%










The mixture has lower rotational viscosity than Comparative Mixture M1, with virtually unchanged values of the clearing point, dielectric anisotropy, birefringence and threshold voltage.
Comparative Example M2
A nematic LC mixture is formulated as follows:


















PUQU-3-F
9.0%
cl.p. [° C.]
+75.5



CPGU-3-OT
9.0%
Δn
0.1351



PUQU-2-F
14.0%
Δε
+8.0



CC-3-V
41.5%
ε∥
11.3



CCP-V-1
4.5%
γ1 [mPa · s ]
63



PP-1-2V1
5.0%
V0 [V]
1.53



PGP-2-2V
17.0%










Mixture Example 3
A nematic LC mixture according to the invention is formulated as follows:


















PUQU-3-F
9.0%
cl.p. [° C.]
+74.0



CPGU-3-OT
9.0%
Δn
0.132



PUQU-2-F
14.0%
Δε
+7.9



CC-3-V
43.5%
ε∥
11.2



CCP-V-1
4.5%
γ1 [mPa · s ]
61



PP-1-2V1
3.0%
V0 [V]
1.50



PGP-2-2V
11.0%



PUS-3-2
6.0%










The mixture has lower rotational viscosity and threshold voltage than Comparative Mixture M1, with virtually unchanged values of the clearing point, dielectric anisotropy and birefringence.
Mixture Example 4
A nematic LC mixture according to the invention is formulated as follows:


















PUQU-3-F
8.0%
cl.p. [° C.]
+74.0



CPGU-3-OT
5.5%
Δn
0.132



PUQU-2-F
15.0%
Δε
+7.2



CC-3-V
44.0%
ε∥
10.4



CCP-V-1
7.0%
γ1 [mPa · s ]
58



PGP-2-2V
3.0%
V0 [V]
1.56



CPGP-4-3
1.5%



PUS-3-2
16.0%










The mixture has lower rotational viscosity than Comparative Mixture M2, with virtually unchanged values of the clearing point, dielectric anisotropy, birefringence and threshold voltage.
Further combinations of the embodiments and variations of the invention arise from the following patent claims.

## Claims

1. Compounds of the formula I



in which the individual radicals have the following meanings:
R1 and R2 denote H, F, Cl, Br, —CN, —SCN, —NCS, SF5 or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more non-adjacent CH2 groups may each be replaced, independently of one another, by —CH═CH—, —C≡C—, —O—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a way that O atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl or Br, or P-Sp-,
P denotes a polymerisable group,
Sp denotes a spacer group or a single bond,
A0 denotes




A1 and A2 each, independently of one another, denote phenylene-1,4-diyl, in which, in addition, one or two CH groups may be replaced by N and one or more H atoms may be replaced by halogen, CN, CH3, CHF2, CH2F, OCH3, OCHF2 or OCF3, cyclohexane-1,4-diyl, in which, in addition, one or two non-adjacent CH2 groups may be replaced, independently of one another, by O and/or S, and one or more H atoms may be replaced by F, cyclohexene-1,4-diyl, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl,
Z1 and Z2 each, independently of one another, denote —CF2O—, —OCF2—, —CH2O—, —OCH2—, —CO—O—, —O—CO—, —C2H4—, —C2F4—, —CF2CH2—, —CH2CF2—, —CFHCFH—, —CFHCH2—, —CH2CFH—, —CF2CFH—, —CFHCF2—, —CH═CH—, —CF═CH—, —CH═CF—, —CF=CF—, —C≡C— or a single bond,
m and n each, independently of one another, denote 0, 1, 2 or 3.

2. Compounds according to claim 1, characterised in that they are selected from the group consisting of the following formulae:












in which R1 and R2 have the meanings indicated in claim 1.

3. Compounds according to claim 1, characterised in that, in formula I, n denotes 0, m denotes 0 or 1, and Z1 denotes a single bond.

4. LC medium which has a nematic phase at room temperature, comprising one or more compounds according to claim 1.

5. LC medium according to claim 4, characterised in that it additionally comprises one or more compounds of the formulae II and/or III:



in which
A denotes 1,4-phenylene or trans-1,4-cyclohexylene,

a is 0 or 1,
R3 denotes alkenyl having 2 to 9 C atoms, and
R4 denotes alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO— in such a way that O atoms are not linked directly to one another, and preferably denotes alkyl having 1 to 12 C atoms or alkenyl having 2 to 9 C atoms.

6. LC medium according to claim 4, characterised in that it additionally comprises one or more compounds selected from the group consisting of the following formulae:



in which
R0 denotes an alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH2 groups in these radicals may each be replaced, independently of one another, by —C≡C—, —CF2O—, —CH═CH—,





—O—, —CO—O— or —O—CO— in such a way that O atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by halogen,
X0 denotes F, Cl, CN, SF5, SCN, NCS, a halogenated alkyl radical, halogenated alkenyl radical, halogenated alkoxy radical or halogenated alkenyloxy radical, each having up to 6 C atoms,
Y1-6 each, independently of one another, denote H or F,
Z0 denotes —C2H4—, —(CH2)4—, —CH═CH—, —CF═CF—, —CH2CF2—, —CF2CH2—, —CH2O—, —OCH2—, —COO—, —CF2O— or —OCF2—, in the formulae V and VI also a single bond, and
b and c each, independently of one another, denote 0 or 1.

7. LC medium according to claim 4, characterised in that it additionally comprises one or more compounds selected from the group consisting of the following formulae:



in which R0, X0 and Y1-4 have the meanings indicated in claim 4, and





each, independently of one another, denotes

8. LC medium according to claim 4, characterised in that it additionally comprises one or more compounds of the following formula:



in which R0, X0 and Y1-4 have the meanings indicated in claim 4.

9. Process for the preparation of compounds of the formula I according to claim 1, characterised in that, in a palladium-promoted Suzuki cross-coupling, a substituted bromothiophene 2



is reacted with a boronic acid 1




or a corresponding boronic acid ester,
or a compound of type 10




is reacted with a thiopheneboronic acid or a corresponding thiophene-hydroxyboronic acid salt 11




where R1,2, A0,1,2, Z1,2, m and n have the meanings indicated in claim 1, and
X denotes Br or I.

10. LC display containing an LC medium comprising one or more compounds according to claim 1.

11. LC display according to claim 10, characterised in that it is an MLC, TN, STN or IPS display.