DE102005016985A1 - New as-indacene derivatives useful in liquid crystal media for electrooptic displays - Google Patents

Abstract

as-Indacene derivatives (I) are new. as-Indacene derivatives of formula (I) are new: B 1, B 2rings of formula (a)-(g); A 1>, A 2>1,4-phenylene with 0-2 CH groups replaced by N, optionally substituted with 1-4 of CN, halo, A and OA; or 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-cyclohexadienylene with 0-2 CH 2 groups replaced by O or S, optionally substituted with halo; A : 1-6C alkyl optionally substituted with F and/or Cl; Z 1>, Z 2>single or double bonds, CF 2O, OCF 2, CH 2CH 2, CF 2CF 2, CF 2CH 2, CH 2CF 2, CHFCHF, COO, OCO, CH 2O, OCH 2, CF=CH, CH=CF, CF=CF, CH=CH or ethynylene; R 1>, R 2>H, A', halo, CN, SCN, NCS or SF 5; A' : 1-15C alkyl, alkoxy, alkenyl or alkynyl with CH 2 groups optionally replaced by O, S, SOO 2, CO, COO, OCO or OCOO, optionally substituted with one of CN or CF 3 or one or more of halo; m, n : 0-3; X 1>, X 2>H, A", halo, CN, SCN, NCS or SF 5; A" : 1-15C alkyl, alkoxy, alkenyl or alkynyl with CH 2 groups optionally replaced by O, S, SOO 2, CO, COO, OCO or OCOO, optionally substituted with one or more of halo; provided that R 1> is not COOH when B is ring f or g and B' is ring d and m : 0 and X 2> is not H or R 2> is not COOH when B' is ring f or g and B is ring d and n= 0 and X 1> is not H; and R 1>(A 1>Z 1>) m and (Z 2>A 2>) nR 2> are not CH 3 when one of X 1> and X 2> is H and the other is H or Cl and B and B' are ring g. Independent claims are included for: (1) liquid crystal medium comprising at least two liquid crystal compounds including at least one compound (I); (2) electrooptic display element containing the liquid crystal medium. Y 2>H, A", halo, CN, SCN, NCS or SF 5; Y 1>Y 2> or (Z 3>A 3>) pR 3>; Z 3>Z 1> and Z 2>; A 3>A 1> and A 2>; R 3>R 1> and R 2>; p : m and n. [Image] [Image].

Description

The The present invention relates to as-indacene derivatives, liquid crystalline Media containing these derivatives and electro-optical display elements containing these liquid crystalline Media. In particular, the invention relates to as-indacene derivatives with negative dielectric anisotropy.

liquid Crystals have found a wide range of applications since about 30 years ago the first commercially applicable liquid crystalline compounds were found. Known application areas are in particular display displays for watches and calculators as well as big ones Scoreboards, as in train stations, Airports and sports arenas are used. Further fields of application are Displays of portable computers and navigation systems as well as video applications. Especially for The latter applications are demanding high switching times and the contrast of the pictures.

The spatial ordering of the molecules in a liquid crystal causes many of its properties to be directional. Of particular importance for use in liquid crystal displays are the anisotropies in the optical, dielectric and elasto-mechanical behavior. Depending on whether the molecules are oriented with their longitudinal axes perpendicular or parallel to the two plates of a capacitor, this has a different capacity; the dielectric constant ε of the liquid-crystalline medium is therefore different for the two orientations. Substances whose dielectric constant is greater when the molecular longitudinal axes are perpendicular to the capacitor plates than in a parallel arrangement are referred to as dielectrically positive. In other words, is the dielectric constant ε _|| parallel to the molecular _{longitudinal axes} greater than the dielectric constant ε _⊥ perpendicular to the _longitudinal molecular axes, the dielectric anisotropy Δε = ε _|| - ε _⊥ greater than zero. Most of the liquid crystals used in conventional displays fall into this group.

For the dielectric Anisotropy play both the polarizability of the molecule and permanent dipole moments play a role. When applying a voltage the longitudinal axis of the molecules aligns itself with the display that the larger of the dielectric constant becomes effective. The strength of the interaction with depends on the electric field thereby from the difference of the two constants. With small differences are higher Switching voltages required as large. By installing suitable polar groups, e.g. of nitrile groups or fluorine in which liquid crystal molecules can be realize a wide range of working voltages.

at in conventional liquid crystal displays used liquid crystalline molecules this is along the molecule's longitudinal axis oriented dipole moment greater than that is perpendicular to the molecular axis oriented dipole moment. In the most widely used TN cells (derived from English: "twisted nematic", twisted nematic) is only about 5 to 10 microns thick liquid crystalline Layer between two plane-parallel glass plates arranged on each an electrically conductive, transparent layer of tin oxide or Indium tin oxide (ITO) is deposited as an electrode. Between these Films and the liquid-crystalline layer there is also a transparent orientation layer, which usually consists of a plastic (for example polyimides). she serves in addition, by surface forces the longitudinal axes the adjacent liquid crystalline molecules to bring in a preferred direction, so that they are in the tension-free state uniform with the same orientation flat or with the same small angle of attack (English: "tilt angle") on the inside of the display surface rest. On the outside of the display are two polarizing films, which are only linearly polarized Let light in and out, applied in a specific arrangement.

With liquid crystals in which the larger dipole moment is oriented parallel to the longitudinal axis of the molecule, very powerful displays have already been developed. Mixtures of 5 to 20 components are usually used to achieve a sufficiently wide temperature range of the mesophase as well as short switching times and low threshold voltages. However, the strong viewing angle dependence in liquid crystal displays, such as those used for laptops, causes difficulties. The best image quality can be achieved if the surface of the display is perpendicular to the viewing direction of the viewer. If the display is tilted relative to the viewing direction, the image quality may deteriorate drastically. For a higher comfort, it is endeavored to make as large as possible the angle by which the display can be tilted from the viewing direction of a viewer without significantly reducing the imaging quality. More recently, attempts have been made to improve the viewing angle dependence using liquid crystalline compounds whose dipole moment is greater perpendicular to the longitudinal molecular axis than parallel to the longitudinal axis of the molecule. The dielectric anisotropy Δε is negative. In the field-free state, these molecules are oriented with their longitudinal axis perpendicular to the glass surface of the display. By applying an electric field, they orient themselves more or less parallel to the glass surfaces. By realizing multiple domains, it was possible to improve the viewing angle dependence using liquid crystal media with negative dielectric anisotropy. Also, with this technology, shorter switching times in displays and better contrasts can be achieved. Such displays are referred to as VA-TFT displays (derived from the English: "vertically aligned").

The Development in the field of liquid crystalline materials is far from complete. To improve the properties liquid-crystalline Display elements is one constantly endeavored, new Develop links that optimize such displays enable.

In the DE 25 14 389 A Among others, 7-substituted-6-oxo-6H-indeno [5,4-b] furancarboxylic acids and their use as medicaments are disclosed; neither mesogenic properties nor the use in liquid-crystalline media of these compounds are described.

In J. Heterocycl. Chem., 15 (1978) 43-48, 2,7-dimethylbenzo [1,2-b: 4,3-b '] difuran and 4-chloro-2,7-dimethylbenzo [1,2-b: 4 3-b '] difuran; neither mesogenic properties nor use in liquid crystalline Media of these compounds will be described.

In the EP 1 350 780 A1 In general, 1,7-dihydroindacene derivatives with negative dielectric anisotropy are described without specifying physical or electro-optical properties.

A Object of the present invention is to provide compounds with advantageous Properties for the use in liquid crystalline Media available to deliver. In particular, they should have a negative dielectric Have anisotropy, which makes them particularly suitable for use in liquid crystalline Media for VA displays.

worin:

stehen;
A¹ und A² jeweils unabhängig voneinander 1,4-Phenylen, worin =CH- ein- oder zweimal durch =N- ersetzt sein kann und das unsubstituiert oder ein- bis viermal unabhängig voneinander mit -CN, F, Cl, Br und/oder I, unsubstituiertem oder mit Fluor und/oder Chlor ein- oder mehrfach substituiertem C₁-C₆-Alkanyl, unsubstituiertem oder mit Fluor und/oder Chlor ein- oder mehrfach substituiertem C₁-C₆-Alkoxy substituiert sein kann, 1,4-Cyclohexylen, 1,4-Cyclohexenylen oder 1,4-Cyclohexadienylen, worin -CH₂- ein- oder zweimal unabhängig voneinander durch -O- oder -S- so ersetzt sein kann, daß Heteroatome nicht direkt verknüpft sind, und die unsubstituiert oder ein- oder mehrfach durch F, Cl, Br und/oder I substituiert sein können, bedeuten;
Z¹ und Z² jeweils unabhängig voneinander eine Einfachbindung, eine Doppelbindung, -CF₂O-, -OCF₂-, -CH₂CH₂-, -CF₂CF₂-, -CF₂CH₂-, -CH₂CF₂-, -CHF-CHF-, -C(O)O-, -OC(O)-, -CH₂O-, -OCH₂-, -CF=CH-, -CH=CF-, -CF=CF-, -CH=CH- oder -C≡C- bedeuten;
R¹ und R² Wasserstoff, einen unsubstituierten, einen einfach mit -CN oder -CF₃ oder einen einfach oder mehrfach mit F, Cl, Br und/oder I substituierten Alkanyl-, Alkoxy-, Alkenyl- oder Alkinylrest mit 1 bis 15 bzw. 2 bis 15 C-Atomen, wobei in diesen Resten auch eine oder mehrere CH₂-Gruppen jeweils unabhängig voneinander durch -O-, -S-, -SO₂-, -CO-, -COO-, -OCO- oder -OCO-O- so ersetzt sein können, daß Heteroatome in der Kette nicht direkt verknüpft sind, F, Cl, Br, I, -CN, -SCN, -NCS oder -SF₅ bedeuten;
m und n unabhängig voneinander 0, 1, 2 oder 3 sind;
X¹, X² und Y² jeweils unabhängig voneinander Wasserstoff, einen unsubstituierten oder einfach oder mehrfach durch F, Cl, Br und/oder I substituierten Alkanyl-, Alkoxy-, Alkenyl- oder Alkinylrest mit 1 bis 15 bzw. 2 bis 15 C-Atomen, wobei in diesen Resten auch eine oder mehrere CH₂-Gruppen jeweils unabhängig voneinander durch -O-, -S-, -SO₂-, -CO-, -COO-, -OCO- oder -OCO-O- so ersetzt sein können, daß Heteroatome in der Kette nicht direkt verknüpft sind, F, Cl, Br, I, -CN, -SF₅, -SCN oder -NCS bedeuten;
Y¹ wie Y² definiert ist oder für -[-Z³-A³-]_p-R³ steht, wobei Z³ wie Z¹ und Z², A³ wie A¹ und A², R³ wie R¹ und R² sowie p wie n und m definiert sind;
wobei
A¹, A², A³; Z¹, Z², Z³; R¹, R², R³ jeweils die gleiche oder unterschiedliche Bedeutungen haben können, wenn m, n beziehungsweise p größer als 1 sind;
Y¹ und Y² für die Ringe B und B' jeweils die gleichen oder verschiedene Bedeutungen haben können;
und wobei

• (a) R¹ nicht für -COOH steht, wenn der Ring B für den Ring f oder g und der Ring B' für den Ring d steht sowie zugleich m null und X² nicht H sind beziehungsweise R² nicht für -COOH steht, wenn der Ring B' für den Ring f oder g und der Ring B für den Ring d steht sowie n null und X¹ nicht H sind;
• (b) R¹-[-A¹-Z¹-]_m- und -[-Z²-A²-]_n-R² nicht gleichzeitig CH₃ sind, wenn eines von X¹ und X² Wasserstoff ist und das andere von X¹ und X² Wasserstoff oder Cl ist sowie zugleich beide Ringe B und B' für den Ring g stehen.

This object is achieved by compounds of the general formula I.

wherein:

stand;
A ¹ and A ^{2 are} each independently 1,4-phenylene, wherein = CH- may be replaced once or twice by = N- and which is unsubstituted or one to four times independently of one another with -CN, F, Cl, Br and / or mono- or I, or with unsubstituted fluorine and / or chlorine mono- or polysubstituted C ₁ -C ₆ alkanyl, unsubstituted or with fluorine and / or chlorine polysubstituted C ₁ -C ₆ -alkoxy, 1, 4-cyclohexylene, 1,4-cyclohexenylene or 1,4-cyclohexadienylene, wherein -CH ₂ - may be substituted once or twice independently of one another by -O- or -S- such that heteroatoms are not directly linked, and which is unsubstituted or may be monosubstituted or polysubstituted by F, Cl, Br and / or I;
Each of Z ¹ and Z ² is independently a single bond, a double bond, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF. ₂ -, -CHF-CHF-, -C (O) O-, -OC (O) -, -CH ₂ O-, -OCH ₂ -, -CF = CH-, -CH = CF-, -CF = CF-, -CH = CH- or -C≡C-;
R ¹ and R ^{2 are} hydrogen, an unsubstituted, an alkanyl, alkoxy, alkenyl or alkynyl radical monosubstituted by -CN or -CF ₃ or a mono- or polysubstituted with F, Cl, Br and / or I with 1 to 15 or 2 to 15 C atoms, where in these radicals also one or more CH ₂ groups are each independently denoted by -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO- or - OCO-O- can be replaced so that heteroatoms in the chain are not directly linked, F, Cl, Br, I, -CN, -SCN, -NCS or -SF ₅ mean;
m and n are independently 0, 1, 2 or 3;
X ¹ , X ² and Y ^{2 are} each independently hydrogen, an unsubstituted or mono- or polysubstituted by F, Cl, Br and / or I alkanyl, alkoxy, alkenyl or alkynyl radical having 1 to 15 or 2 to 15 C. -Atomen, where in these radicals also one or more CH ₂ groups each independently by -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO- or -OCO-O- so may be replaced, that heteroatoms in the chain are not directly linked, F, Cl, Br, I, -CN, -SF ₅ , -SCN or -NCS mean;
Y ¹ is defined as Y ² or is - [- Z ³ -A ³ -] _p -R ³ , where Z ^{3 is} Z ¹ and Z ² , A ^{3 is} A ¹ and A ² , R ^{3 is} R ¹ and R ² and p are defined as n and m;
in which
A ¹ , A ² , A ³ ; Z ¹ , Z ² , Z ³ ; R ¹ , R ² , R ^{3 may} each have the same or different meanings if m, n or p are greater than 1;
Y ¹ and Y ² for the rings B and B 'may each have the same or different meanings;
and where

• (a) R ^{1 is} not -COOH if the ring B is the ring f or g and the ring B 'is the ring d and at the same time m is zero and X ^{2 is} not H or R ^{2 is} not -COOH, when ring B 'for the ring is f or g and ring B is ring d, and n is zero and X ^{1 is} not H;
• (b) R ¹ - [- A ¹ -Z ¹ -] _m - and - [Z ² -A ² -] _n -R ^{2 are} not simultaneously CH ₃ when one of X ¹ and X ^{2 is} hydrogen and the others of X ¹ and X ^{2 are} hydrogen or Cl and at the same time both rings B and B 'stand for the ring g.

The compounds have a negative Δε and are therefore particularly suitable for use in VA TFT displays. Preferably, the compounds of the invention have a Δε <-2 and especially preferably a Δε <-5. They show a very good compatibility with the usual substances used in liquid crystal mixtures for displays.

Further have the compounds of the invention of the formula I in particular for the use in VA TFT displays suitable values of the optical Anisotropy Δn on. The compounds according to the invention preferably have a Δn of greater than 0.02 and less than 0.25.

Also the other physical, physicochemical or electro-optical Parameters of the compounds of the invention are for the use of the compounds in liquid-crystalline media of advantage. In particular, the compounds have a sufficient width nematic phase and good low-temperature and long-term stability as well sufficiently high clearing points and good viscosities and switching times.

It is preferred that at least one of X ¹ and X ² on the central aromatic six-membered ring of the compound of formula I is not hydrogen.

Further it is preferred that at least one of the rings B and B 'at least an electronegative radical (e.g., -F, -Cl, or = O or with halogen substituted alkyl radicals). Particularly preferred are both Rings B and B 'electronegative Leftovers on.

By the radicals X ¹ and X ^2, preferably -CF _3, -OCF _3, fluorine and / or chlorine substituents, in particular fluorine substituents, aromatic at the central six-membered ring and preferably electronegative radicals on the ring B or B 'is a dipole moment perpendicular generated to the molecular longitudinal axis , which may optionally be further enhanced by suitable substituents in the wing units - (Z ¹ -A ¹ -) _m -R ¹ and - (Z ² -A ² -) _n -R ² . In the field-free state, the compounds of the formula I align with their molecular longitudinal axis perpendicular to the treated or coated glass surface of the display.

definiert sind. Dabei ist es besonders bevorzugt, daß die Ringe B und B' gleich sind, wobei der Rest Y¹ in beiden Ringen die gleiche oder unterschiedliche Bedeutungen und der Rest Y² in beiden Ringen gleiche oder unterschiedliche Bedeutungen haben können.Preferred compounds of the formula I according to the invention are those in which the rings B and B 'are each selected independently of one another

are defined. It is particularly preferred that the rings B and B 'are the same, wherein the radical Y ¹ in both rings the same or different meanings and the radical Y ² in both rings may have the same or different meanings.

Y ¹ and Y ² are particularly preferably, independently of one another, F, Cl or a (per) fluorinated alkanyl or alkoxy radical having up to 6 carbon atoms, in particular -CF ₃ or -OCF ₃ . Furthermore, Y ^{1 is} particularly preferably also - [- Z ³ -A ³ -] _p -R ³ . Y ¹ and Y ² are very particularly preferably in at least one of the rings B and B 'F, in particular in both rings.

wobei
X¹, X², R¹, R², A¹, A², Z¹, Z², m und n wie in Anspruch 1 und wie für Formel I oben definiert sind;
Y¹¹ und Y¹² wie Y¹ in Anspruch 1 und wie für Formel I oben definiert sind und die gleiche oder verschiedene Bedeutungen haben können; und
Y²¹ und Y²² wie Y² in Anspruch 1 und wie für Formel I oben definiert sind und die gleiche oder verschiedene Bedeutungen haben können.It is further preferred that the compounds of the formula I according to the invention are selected from the group of compounds of the following formulas:

in which
X ¹ , X ² , R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , m and n are as defined in claim 1 and as defined for formula I above;
Y ¹¹ and Y ^{12 are} as Y ¹ in claim 1 and as defined for formula I above and may have the same or different meanings; and
Y ²¹ and Y ^{22 are} as Y ² in claim 1 and as defined for formula I above and may have the same or different meanings.

Y ¹¹ , Y ¹² , Y ²¹ and Y ²² are particularly preferably independently of one another H, F, Cl or a (per) fluorinated alkanyl or alkoxy radical having up to 6 carbon atoms, in particular -CF ₃ or -OCF ₃ . Furthermore, Y ¹¹ and Y ^{12 are} particularly preferably also - [- Z ³ -A ³ -] _p -R ³ . Most preferably Y ¹¹ and Y ²¹ or Y ¹² and Y ^{22 are the} same and in particular fluorine. In particular, Y ¹¹ , Y ²¹ , Y ¹² and Y ^{22 are} all fluorine at the same time.

Especially Preference is given to compounds of the formulas Iaa, Ibb, Iee, Iff and Igg.

In the compounds of the general formula I according to the invention and the formulas Iaa, Iaf, Iag, Ibb, Ibf, Ibg, Icc, Idd, Iee, Iff and Igg, Z ¹ and Z ² and, if present, Z ^{3 are} preferably each independently one Single bond, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH = CH-, -CF = CH-, -CH = CF- or -CF = CF-, particularly preferred for a single bond, -CF ₂ O- or -OCF ₂ -, in particular a single bond.

In the compounds of the formula I according to the invention and the formulas Iaa, Iaf, Iag, Ibb, Ibf, Ibg, Icc, Idd, Iee, Iff and Igg, A ¹ , A ² and, if present, A ^{3 are} preferably independently of one another optionally substituted 1 , 4-phenylene, optionally substituted 1,4-cyclohexylene, wherein -CH ₂ - may be replaced once or twice by -O-, or optionally substituted 1,4-cyclohexenylene. When m> 1, the rings A ¹ can assume the same or different meanings. When n> 1, the rings A ² can assume the same or different meanings. When p> 1, the rings A ³ can assume the same or different meanings.

Particularly preferred are A ¹ , A ² and - if present - A ^{3 are} independent of one another

Very particular preference is given to A ¹ , A ² and, if present, A ³ 1,4-cyclohexylene rings and / or optionally fluorine-substituted 1,4-phenylene rings.

R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I can each independently be an alkanyl radical and / or an alkoxy radical (alkyloxy radical) having 1 to 15 C atoms which is straight-chain or branched is. Preferably, it is straight-chain, has 1, 2, 3, 4, 5, 6 or 7 carbon atoms and is therefore preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, Hexoxy or heptoxy.

R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I can each independently be oxaalkyl - ie one of the nonterminal CH ₂ groups of the alkanyl radical is replaced by -O- -, preferably straight-chain 2-oxapropyl (= methoxymethyl), 2- (= ethoxymethyl) or 3-oxabutyl (= methoxyethyl), 2-, 3- or 4-oxapen tyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl. In a corresponding manner, R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I can also be independently thioalkanyl or Sulfonalkanylreste, ie alkanyl radicals in which a CH ₂ group by -S - or -SO ₂ - is replaced.

R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I can furthermore each independently be an alkenyl radical having 2 to 15 C atoms which is straight-chain or branched and at least one C-C double bond having. It is preferably straight-chain and has 2 to 7 carbon atoms. It is therefore preferably vinyl, prop-1 or prop-2-enyl, but-1, 2- or but-3-enyl, pent-1, 2-, 3- or pent-4-enyl, hexyl 1-, 2-, 3-, 4- or hex-5-enyl, hept-1-2, 3-, 4-, 5- or hept-6-enyl. If the two carbon atoms of the CC double bond are substituted, the alkenyl radical can be present as an E and / or Z isomer (trans / cis). In general, the respective E isomers are preferred.

R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I can independently of one another also be an alkynyl radical having 2 to 15 C atoms which is straight-chain or branched and has at least one C-C triple bond ,

R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I may each independently be an alkanyl radical having 1 to 15 carbon atoms, in which a CH ₂ group by -O- and one is replaced by -CO-, these being preferably adjacent. Thus, this includes an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. Preferably, this radical is straight-chain and has 2 to 6 carbon atoms. The following of these radicals are preferred: acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxy-methyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-acetyloxypropyl, 3-propionyloxypropyl, 4- Acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3 (Ethoxycarbonyl) propyl or 4- (methoxycarbonyl) butyl. Furthermore, an alkanyl radical may also have an -O-CO-O moiety. Also, the replacement of a CH ₂ group by only one -CO-group (carbonyl function) is possible.

R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I may each independently be an alkenyl radical having 2 to 15 carbon atoms in which a CH ₂ group is adjacent to an unsubstituted one or substituted -C = C unit, a CH ₂ group is replaced by -CO- or -CO-O- or -O-CO-, which radical may be straight-chain or branched. Preferably, the radical is straight-chain and has 4 to 13 carbon atoms. Particularly preferred are acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl or 8-methacryloyloxyoctyl. Similarly, in an alkynyl radical adjacent to a substituted -C≡C moiety, a CH ₂ group may be replaced by -CO-, -CO-O-, -O-CO- or -O-CO-O-.

R ¹ , R ² and R ³ in formula I can each independently be an alkanyl radical having 1 to 15 C atoms or alkenyl radical having 2 to 15 C atoms which is monosubstituted by -CN or -CF _3, these radicals preferably being straight-chain. The substitution by -CN or -CF ₃ is possible in any position.

R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I can each independently be an alkanyl radical in which two or more CH ₂ groups are substituted by -O- and / or -CO- O- are replaced, which may be straight-chain or branched. Preferably, it is branched and has 3 to 12 carbon atoms.

R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I can each independently be a mono- or polysubstituted with F, Cl, Br and / or I alkanyl radical having 1 to 15 carbon atoms or alkenyl radical having 2 to 15 carbon atoms, where these radicals are preferably straight-chain and halogen is preferably -F and / or -Cl. In the case of multiple substitution, halogen is preferably -F. The resulting radicals also include perfluorinated radicals such as -CF ₃ . In the case of monosubstitution, the fluorine or chlorine substituent may be in any position, preferably in the ω position.

R ¹ , R ² , R ³ , X ¹ , X ² , Y ¹ and Y ² in formula I can also each independently of one another denote -F, -Cl, -Br, -I, -CN, -SCN, -NCS or - Be SF ₅ .

Particular preference is given to R ¹ , R ² and R ³ independently of one another in the general formula I being an alkanyl radical, alkoxy radical or alkenyl radical having 1 to 7 or 2 to 7 C atoms.

X ¹ and X ² independently of one another in the general formula I are preferably hydrogen, an alkanyl radical which is at least monosubstituted by halogen, alkoxy radical or alkenyl radical having 1 to 7 or 2 to 7 C atoms or a halogen. It is particularly preferred that at least one of X ¹ and X ^{2 is} -CF ₃ , -OCF ₃ , F or Cl. Most preferably, both radicals, X ¹ and X ² -CF ₃ , -OCF ₃ , fluorine or chlorine, and in particular both fluorine.

Preferred compounds of general formula I have no total, one, two or three wing units -Z ¹ -A ¹ - and -Z ² -A ² -, that is n + m = 0, 1, 2 or 3 with n and m in each case 0, 1, 2 or 3. If two or three wing units are present, they can be bound to only one side of the molecule, ie either to ring B or to ring B ', or else to both sides of the molecule. Particularly preferred is n + m = 0 or 1.

halogen in the context of the present invention means fluorine, chlorine, Bromine and iodine.

In the context of the present invention, the term "alkyl", unless otherwise defined in this specification or claims, means a straight or branched chain aliphatic hydrocarbon radical of 1 to 15 (ie 1, 2, 3, 4, 5 , 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15) carbon atoms; this radical is unsubstituted or monosubstituted or polysubstituted by fluorine, chlorine, bromine, iodine, carboxy, nitro, -NH ₂ , -N (alkanyl) ₂ and / or cyano, wherein the multiple substitution can take place with the same or different substituents. If this alkyl radical is a saturated radical, it is also referred to as "alkanyl". Furthermore, the term "alkyl" also includes unsubstituted or correspondingly in particular with F, Cl, Br, I and / or -CN mono- or polysubstituted or differently substituted hydrocarbon radicals in which one or more CH ₂ groups are substituted by -O- ( "Alkoxy", "oxaalkyl"), -S - ("thioalkyl"), -SO ₂ -, -CH = CH- ("alkenyl"), C≡C- ("alkynyl"), -CO-, -CO -O-, -O-CO- or -O-CO-O- may be replaced, that heteroatoms (O, S) are not directly linked in the chain. Preferably, alkyl is a straight-chain or branched, unsubstituted or substituted alkanyl, alkenyl or alkoxy radical having 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms.

Since one or more CH ₂ groups in an alkyl radical may be replaced by -O-, the term "alkyl" also includes "alkoxy" or "oxaalkyl" radicals. By alkoxy in the context of the present invention, unless the term is otherwise defined elsewhere in the specification or in the claims, is meant an O-alkyl radical in which the oxygen atom is directly linked to the group substituted by the alkoxy radical or the substituted ring and alkyl is as defined above; preferably, alkyl is then alkanyl or alkenyl. Preferred alkoxy radicals are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy and octoxy, where any of these radicals can also be substituted, preferably with one or more fluorine atoms. Particularly preferred is alkoxy-OCH ₃ , -OC ₂ H ₅ , -OnC ₃ H ₇ , -OnC ₄ H ₉ , -OtC ₄ H ₉ , -OCF ₃ , -OCHF ₂ , -OCHF or -OCHFCHF ₂ . In the context of the present invention, unless the term is otherwise defined elsewhere in the specification or in the claims, the term "oxaalkyl" means alkyl radicals in which at least one non-terminal CH ₂ group is represented by -O- replaced, that no adjacent heteroatoms (O, S) are present. Preferably, oxaalkyl includes straight chain radicals of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.

In the context of the present invention, the term "alkenyl", unless otherwise defined in the claims or elsewhere in this specification, means an alkyl radical as defined above in which one or more -CH = CH groups are present. If two -CH = CH groups are present in the radical, this may also be referred to as "alkadienyl". An alkenyl radical may contain 2 to 15 (ie 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15) carbon atoms and is branched chain or preferably straight chain. The rest is unsubstituted or monosubstituted or polysubstituted or differently substituted in particular with F, Cl, Br, I and / or CN. In addition, one or more CH ₂ groups can each independently be represented by -O-, -S-, -C≡C-, -CO-, -CO-O-, -O-CO-, -O-CO-O- be replaced so that heteroatoms (O, S) are not directly connected. If the CH = CH group on each carbon atom carries a radical other than hydrogen, for example, if it is a nonterminal group, the CH = CH group can exist in two configurations, namely as the E isomer and as the Z isomer. In general, the E-isomer (trans) is preferred. Preferably, the alkenyl radical contains 2, 3, 4, 5, 6 or 7 carbon atoms and is vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 2-propenyl, 2E-butenyl, 2E- Pentenyl, 2E-hexenyl, 2E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl and 6-heptenyl.

If one or more CH ₂ groups in an alkyl radical have been replaced by -C≡C-, an alkynyl radical is present. The replacement of one or more CH ₂ groups by -CO-O- or -O-CO- is possible. The following of these radicals are preferred: acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, Acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl or 4- (methoxycarbonyl) butyl.

If in an alkyl radical a CH ₂ group is replaced by unsubstituted or substituted -CH = CH- and an adjacent CH ₂ group by CO, CO-O or O-CO-, this radical may be straight-chain or branched. It is preferably straight-chain and has 4 to 12 C atoms. It therefore particularly preferably means acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4 Methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl or 8-methacryloyloxyoctyl.

Provided Radicals or substituents of the compounds of the invention or the compounds of the invention even as optically active or stereoisomeric radicals, substituents or compounds may be present because they, for example have an asymmetric center, so these are from the present Invention comprises. It goes without saying that the Compounds of the invention of the general formula I in isomerically pure form, for example as pure enantiomers, diastereomers, E or Z isomers, trans or cis isomers, or as a mixture of several isomers in any ratio, for example as a racemate, E / Z isomer mixture or as a cis / trans isomer mixture, may be present.

The Compounds of general formula I are known per se Methods presented in the literature (for example in the standard works like Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart) are described under reaction conditions, the for the said reactions are known and suitable. It can one makes use of known per se, not mentioned here variants.

The Starting materials can optionally also be formed in situ, such that they are not isolated from the reaction mixture, but immediately on to the compounds of general formula I are reacted.

The Syntheses of Various Multiply Substituted Phenyl Derivatives, The for the construction of the as-indacene derivatives according to the invention with the finned five-rings B and B 'used are described in the examples by way of example. The starting substances are generally accessible Literature regulations or commercially available to obtain. The reactions described are also known from the literature to watch.

A exemplary synthesis for the construction of the as-Indacengerüsts is shown below. The synthesis can be done by choosing appropriate Starting materials to the particular desired compounds of the general Formula I are adjusted.

Starting from the 1,2-Dibromphenolderivat A, the compound C is obtained by reaction with the α, β-unsaturated aldehyde B 'in the presence of lithium diisopropylamide (LDA). By repeating this reaction with the aldehyde B ² , D is obtained. D reacts under palladium catalysis in the presence of triethylamine to form diketone E (= compound Icc). From the diketone E and 1,2-ethanedithiol, the corresponding bis-dithiane F is obtained in the presence of BF ₃ diethyl ether. This is reacted with 1,3-dibromo-5,5-dimethylhydantoin (DBH) and HF in pyridine to give G. Elimination of HBr in the presence of diazabicycloundecene (DBU) gives the as-indacene derivative H (= compound Ibb with Y ¹¹ = Y ¹² = Y ²¹ = Y ²² = F). The as-indacene derivative H is hydrogenated on palladium / carbon catalyst in hydrogen atmosphere to the as-indacene derivative J (= compound Iaa with Y ¹¹ = Y ¹² = Y ²¹ = Y ²² = F).

The alcohol K is first obtainable from the diketone E by reduction, for example with LiAlH ₄ , from which, on the one hand, by subsequent elimination with acid, the as-indacene derivative L (= compound Iee with Y ¹¹ = Y ²¹ = H) and, on the other hand, with DAST ( Diamino sulfur trifluoride, see M. Hudlicky, Organic Reactions, 35, 1988, 513) the as-indacene derivative M (= compound Iaa with Y ¹¹ = Y ¹² = F and Y ²¹ = Y ²² = H) analogous to that described in DE 44 34 975 A1 described method is accessible.

From the diketone E is also analogous to that in DE 44 34 975 A1 disclosed the as-indacene derivative N (= compound Iee with Y ¹ = Y ² = F) by reaction with DAST.

The introduction of chlorine atoms (instead of Fuoratomen) is possible starting from diketone E with phosphoryl chloride under heating in dimethylformamide. The introduction of trifluoromethyl radicals is analogous to that in DE 10135499 A1 disclosed methods starting from diketone E.

A further exemplary synthesis of compounds of the formula I according to the invention shows the following scheme:

Starting from O, a trimethylsilyl group can be introduced on the phenyl ring with n-butyllithium and trimethylsilyl chloride; subsequent reaction with the acid chloride shown under Lewis acid catalysis gives P. Depending on the importance of the radical - [- Z ³ -A ³ -] _p -R ³ is carried out its introduction to form Q by Wittig reaction and subsequent catalytic hydrogenation ( p = 0, R ³ = alkyl) or by reaction with a suitable organometallic compound containing - [- Z ³ -A ³ -] _p -R ³ as a structural element, followed by elimination of the OH group formed and subsequent catalytic reduction. The cyclization to R occurs after saponification of the ester function and conversion into an acid chloride under Lewis acid catalysis. The formed keto function of R can be reduced by Wolff-Kishner reduction, followed by silylation with trimethylsilyl chloride and reaction with the acid chloride shown to form S. The cyclization to T occurs under acid catalysis. Starting from T, further compounds of the formula I according to the invention are then accessible in the manner set forth above.

Compounds according to the invention having one or two oxygen-containing five-membered rings can be prepared according to the following scheme or with adaptation of these and the syntheses described for the formation of the carbocyclic five-membered rings:

Aromat U is converted into the diiodinated aromatic compounds V after diazotization and introduction of the second OH group with iodine / potassium carbonate. Under catalysis with Bistriphenylphosphinpalladium (II) chloride and copper (I) iodide with the alkyne R ¹ - [- A ¹ -Z ¹ -] _m -≡ or R ² - [- A ² -Z ² -] _n -≡ get the benzodifuran W, from which by means of catalytic hydrogenation and X is accessible.

The The following synthesis sequence illustrates the preparation of compounds of the invention with an oxygen-containing five-membered ring, being for the individual synthesis steps to those explained for the above schemes Manufacturing methods used can be.

The Reactions shown are only to be considered as exemplary. The person skilled in the art can make appropriate variations of the syntheses presented as well as other suitable synthetic routes, to obtain compounds of formula I.

As already mentioned, can the compounds of the general formula I are used in liquid-crystalline media become.

object The present invention is therefore also a liquid-crystalline medium with at least two liquid-crystalline ones Compounds containing at least one compound of the general Formula I.

The present invention also liquid-crystalline media containing in addition to a or more compounds of the formula I according to the invention as further constituents 2 to 40, preferably 4 to 30 components. With particular preference, these media contain, in addition to one or more compounds according to the invention, 7 to 25 components. These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, 1,3-dioxanes, 2,5-tetrahydropyrane-, phenyl- or cyclohexylbenzoates, cyclohexanecarboxylic acid phenyl or cyclohexyl esters, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid or of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes, 1,4-biscyclohexylbenzenes, 4 ' , 4'-bis-cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- or cyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithiane, 1,2-diphenylethane, 1,2-dicyclohexylethane, 1-phenyl- 2-cyclohexylethane, 1-cyclohexyl-2-one ( 4-phenylcyclohexyl) ethane, 1-cyclohexyl-2-biphenylethane, 1-phenyl-2-cyclohexylphenylethane, optionally halogenated stilbenes, benzylphenyl ethers, tolans and substituted cinnamic acids. The 1,4-phenylene groups in these compounds may also be mono- or polyfluorinated.

The most important compounds which may be used as further constituents of media according to the invention can be characterized by the formulas (II), (III), (IV), (V) and (VI): R'-LE-R '' (II) R'-L-COO-E-R '' (III) R'-L-OOC-E-R "(IV) R'-L-CH ₂ CH ₂ -E-R '' (V) R'-L-CF ₂ OE-R "(VI)

In In the formulas (II), (III), (IV), (V) and (VI), L and E, denote may be the same or different, respectively independently each other is a bivalent radical from the group consisting of -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc, -Cyc-Cyc, -Pyr-, -Dio, -Thp-, -G-Phe- and -G-Cyc- and whose mirror images formed a group, with Phe unsubstituted or fluorine-substituted 1,4-phenylene, Cyc trans-1,4-cyclohexylene or 1,4-cyclohexylene, Pyr pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio 1,3-dioxane-2,5-diyl, Thp tetrahydropyran-2,5-diyl and G 2- (trans-1,4-cyclohexyl) -ethyl, Pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl mean.

Preferably one of the radicals L and E is cyc or phe. E is preferably Cyc, Phe or Phe-Cyc. Preferably, the media of the invention contain one or more components selected from the compounds of Formulas (II), (III), (IV), (V) and (VI) wherein L and E are selected from the group Cyc and Phe and at the same time one or more components selected from the compounds of the formulas (II), (III), (IV), (V) and (VI), wherein one of the radicals L and E is selected from the group Cyc and Phe and the other radical is selected from the group -Phe-Phe-, -Phe-Cyc, -Cyc-Cyc, -G-Phe and -G-Cyc-, and optionally one or multiple components selected from the compounds of the formulas (II), (III), (IV), (V) and (VI), wherein the radicals L and E are selected are from the group -Phe-Cyc, -Cyc-Cyc, -G-Phe and -G-Cyc-.

R 'and R' 'are in a smaller subgroup the compounds of formulas (II), (III), (IV), (V) and (VI), respectively independently alkyl, alkenyl, alkoxy, alkoxyalkyl (oxaalkyl), alkenyloxy or alkanoyloxy with up to 8 C atoms. The following will be this smaller subgroup called group A and the compounds become with sub-formulas (IIa), (IIIa), (IVa), (Va) and (VIa). For most of these compounds R 'and R "are from each other different, one of these radicals usually alkyl, alkenyl, alkoxy or alkoxyalkyl (oxaalkyl).

In a smaller subgroup of the compounds of formulas (II), (III), (IV), (V) and (VI) other than group B, E denotes

In the compounds of group B which have the sub-formulas (IIb), (IIIb), (IVb), (Vb) and (VIb), R 'and R' 'have the in the compounds of the sub-formulas (IIa) to (VIa) specified Meaning and are preferably alkyl, alkenyl, alkoxy or alkoxyalkyl (Oxaalkyl).

In another smaller subgroup of the compounds of the formulas (II), (III), (IV), (V) and (VI) represents R "-CN; this subgroup is referred to below as group C and the compounds of this subgroup are correspondingly sub-formulas (IIc), (IIIc), (IVc), (Vc) and (VIc). In the connections of sub-formulas (IIc), (IIIc), (IVc), (Vc) and (VIc) R 'has the compounds of sub-formulas (IIa) to (VIa) and is preferably Alkyl, alkenyl, alkoxy or alkoxyalkyl (oxaalkyl).

Next the preferred compounds of groups A, B and C are also others Compounds of formulas (II), (III), (IV), (V) and (VI) with others Variants of the proposed substituents in use. All these substances are available by literature methods or in analogy thereto.

In addition to the compounds of the general formula I according to the invention, the media according to the invention preferably contain one or more compounds from groups A, B and / or C. The mass fractions of the compounds from these groups on the media according to the invention are as follows:
Group A: 0 to 90%, preferably 20 to 90%, in particular 30 to 90%
Group B: 0 to 80%, preferably 10 to 80%, in particular 10 to 70%
Group C: 0 to 80%, preferably 5 to 80%, in particular 5 to 50%.

The inventive media preferably contain 1 to 40%, more preferably 5 to 30% the compounds of the invention of formula I. Further preferred are media containing more than 40%, in particular 45 to 90% of compounds of the formulas according to the invention I, II, III, IV and / or V. The media preferably contain one, two, three, four or five compounds of the invention the formula I.

mit R^a, R^b unabhängig voneinander -C_nH_2n+1 oder -OC_nH_2n+1 und n = 1, 2, 3, 4, 5, 6, 7, 8 sowie L¹, L² unabhängig voneinander -H oder -F,

mit m, n unabhängig voneinander 1, 2, 3, 4, 5, 6, 7, 8.Examples of the compounds of the formulas (II), (III), (IV), (V) and (VI) are the compounds listed below:

with R ^a , R ^b independently of one another -C _n H _{2n + 1} or -OC _n H _{2n + 1} and n = 1, 2, 3, 4, 5, 6, 7, 8 and L ¹ , L ² independently of one another - H or -F,

with m, n independently 1, 2, 3, 4, 5, 6, 7, 8.

The preparation of the media according to the invention is carried out in a conventional manner. In general, the components are dissolved in each other, useful at elevated temperature. By means of suitable additives, the liquid-crystalline phases of the present invention can be modified so that they can be used in all types of liquid-crystal display elements known hitherto. Such additives are Known to the skilled worker and described in detail in the literature (H. Kelker / R. Hatz, Handbook of Liquid Crystals, Verlag Chemie, Weinheim, 1980). For example, pleochroic dyes can be added to produce colored guest-host systems or to modify the dielectric anisotropy, viscosity and / or orientation of the nematic phases.

The Compounds of formula I are particularly suitable because of their negative Δε for one Use in VA TFT displays.

object The present invention therefore also provides electro-optical liquid crystal display elements, containing a liquid crystalline according to the invention Medium.

The Invention will be explained in more detail below with reference to embodiments, without but limited to become.

The Starting substances can after generally accessible Literature regulations or commercially available to be obtained. The reactions described are known from the literature.

The determination of physical, physicochemical and electro-optical parameters are determined by generally known processes, as described inter alia, in the brochure "Merck Liquid Crystals - Licristal ^® - Physical Properties of Liquid Crystals - Description of the Measurements Methods", 1998, Merck KGaA, Darmstadt ,

Example A

Be at -75 ° C 27.0 ml of one diluted with 100 ml solution of 2N lithium diisopropylamide (LDA) in cyclohexane / ethylbenzene / THF (54.0 mmol) with a solution of 13.5 g (50.0 mmol) of 1,2-dibromo-4,5-difluorobenzene 2 in 10 ml of THF. After 2 hours at the low temperature, 4.6 g (47.0 mmol) of the aldehyde 1 in 10 ml of THF. After 30 minutes, the cooling removed, and the batch at 20 ° C with 100 ml of 1 N HCl. After extraction of the aqueous phase, Drying of the organic phase, concentration and chromatography are obtained Allyl alcohol 3.

By Repeating this reaction starting from 3, the bis-allyl alcohol 4 is obtained.

35.0 g (74.8 mmol) of bis-allyl alcohol 4, 5.5 g of bis (tri-o-tolylphosphine) palladium dichloride and 50 ml of triethylamine are dissolved in 390 ml of acetonitrile and until to the full Reaction of allyl alcohol heated to 90 ° C. The cold approach becomes given to water. After extraction, drying, concentration and chromatography receives the diketone 5

Example B

10.0 g (32.6 mmol) of the diketone 5 and 7.0 ml (69.9 mmol) of propanedithiol are dissolved in 50 ml of dichloromethane and at 6 to 7 ° C with 7.0 ml of boron trifluoride-diethyl ether complex and then overnight stirred at room temperature. The batch is saturated to 10 ml Sodium bicarbonate solution given and stirred until completion of gas evolution. After extraction of the aqueous Phase, drying of the organic phase, concentration and filtration over silica gel becomes the residue obtained without further purification in the next Step used.

10.0 g of crude thioketal 6, dissolved in 30 ml of dichloromethane are slowly added at -75 ° C in a mixture of 45.8 g (160 mmol) 1,3-dibromo-5,5-dimethylhydantoin (DBH), 80 ml of a 65% solution of hydrogen fluoride in pyridine and 50 ml of dichloromethane. Subsequently the approach is over Stirred at room temperature overnight. The reaction mixture is placed in ice-cooled hydrogen sulfite solution and with more saturated Sodium bicarbonate solution and caustic soda deacidified. After extraction, drying, concentration, washing again with water, Chromatography and crystallization from hexane to obtain the as-indole derivative 7.

6.0 g (11.8 mmol) of the as-indacene derivative 7 are dissolved in 50 ml of dichloromethane solved, with 4.5 ml (30.0 mmol) of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and stirred at room temperature until the starting material is completely reacted is. The batch is washed with water and saturated sodium chloride solution, concentrated and Chromatograph. The as-indole derivative 8 is isolated.

Example C

4.0 g (11.6 mmol) of the as-Indacenderivats 8 are dissolved in 50 ml of THF and at Room temperature and normal pressure hydrogenated on palladium catalyst. After concentration, chromatography on silica gel and crystallization receives the as-indole derivative 9.

Example D

Under Nitrogen becomes 116.5 g (1.00 mol) of 1,2-difluorobenzene (10) in 600 ml of tetrahydrofuran dissolved and at -70 ° C with 656 ml of a 15% solution of butyllithium in n-hexane (1.05 mol). After 1 h at this Temperature becomes a solution of 132.6 ml (1.05 mol) of trimethylsilyl chloride (11) in 100 ml of tetrahydrofuran slowly added to the reaction mixture. The approach thaws overnight on and gesges to 1.5 l. Ammonium chloride solution given. The organic Phase is over Dried sodium sulfate and concentrated: The residue obtained is distilled at 8 mbar. This gives 152 g (81%, bp 88 ° C) of the silyl compound 12th

Under Nitrogen, 37.6 g (250 mmol) of the acid chloride 13 in 200 ml of cyclohexane solved. At 0-2 ° C 46.6 g (250 mmol) of silyl compound 12 are added to the solution. Subsequently 37.3 g (280 mmol) of aluminum chloride are added in portions to the reaction mixture given, the temperature between -2 ° C and 2 ° C is maintained. After 1 h at low temperature is the cooling away. The approach heats rises to room temperature and is placed on ice. The aqueous phase is extracted with methyl tert-butyl ether, the organic phase will over Dried sodium sulfate and concentrated. The residue is purified on silica gel. You get 31.4 g (55%) of the ketoester 14.

Under Nitrogen, 51.1 g (150 mmol) of the Wittigsalzes 15 in 200 ml THF suspended and at 5-10 ° C with a solution of 15.7 g (140 mmol) of potassium tert-butoxide in 75 ml of THF. After one hour, the ketoester 14 is added dissolved in 75 ml of THF. Subsequently, will the cooling away. After 20 h at room temp. the approach is mixed with water. The aqueous phase is extracted with MTB ether. The organic phase is washed with sat. Sodium chloride solution washed over Dried sodium sulfate and concentrated. The residue is over silica gel given (MTB ether / n-hexane 1:10). 29.4 g (88%) of the ester 16 are obtained.

29.0 g (21.6 mmol) of the ester 16 are dissolved in 500 ml of tetrahydrofuran and the Hydrogenated palladium catalyst. The hydrogenation solution is concentrated and the Residue chromatographed on silica gel. This gives 27.8 g (95%) of the substance 17th

27.0 g (105 mmol) of the ester 17 are 5h in ethanolic potassium hydroxide under Reflux heated. Subsequently the alcohol is distilled off, the residue is taken up with water, with hydrochloric acid acidified and extracted with MTB ether. The organic phase is over sodium sulfate dried and concentrated. The residue obtained is mixed with 50 ml of thionyl chloride and a drop of DMF and until the end of gas evolution under reflux heated. Excess thionyl chloride is distilled off. The residue (25 g) is used without further purification in the next stage.

A solution of 25 g (about 105 mmol) of the crude acid chloride 18 in 120 ml of dichloromethane under nitrogen and at -20 to -15 ° C in a suspension of 16.4 g (119 mmol) of aluminum chloride in 80 ml of dichloromethane. To 4.5 h, the reaction is terminated by the addition of ice and with Hydrochloric acid acidified. The aqueous phase is extracted with methylene chloride. The organic phase is over sodium sulfate dried and concentrated. The residue is chromatographed on silica gel (MTB / n-heptane 1: 5). You get 18.5 g (84%) of indanone 19.

23.9 g (361 mmol) of potassium hydroxide are dissolved in 90 ml of diethylene glycol. The solution is charged with 13.0 ml (268 mmol) of hydrazinium hydroxide and 18.0 g (85.6 mmol) of indanone 19 and heated under reflux for 2 h. Subsequently, will the temperature of the heating bath is increased to 200 ° C and until the end of gas evolution held. The cooled Reaction mixture is poured into water and acidified. The aqueous phase is extracted with n-pentane. The organic phase is over sodium sulfate dried and concentrated. The residue is purified by chromatography on silica gel (n-pentane). you receives 11.4 g (68%) of indane 20.

The Silylation of indane 20 is carried out according to the above procedure. The Purification is via Chromatography on silica gel (n-pentane). Obtained from 11.0 g (56.5 mmol) of indan 20 12.6 g (84%) of the silyl compound 21.

The Acylation of the silyl compound 21 is carried out according to the above procedure. You get from 12.0 g (44.7 mmol) of 21 6.8 g (52%) of the ketone 23.

Under ice cooling and stirring 6.5 g (22.2 mmol) of the ketone 23 are introduced into 30 l of trifluoromethanesulfonic acid. After 24 h, the mixture is poured on ice and extracted with MTB ether. The organic phase is washed with sat. Sodium bicarbonate solution washed over sodium sulfate dried and concentrated. The residue is on silica gel (MTB ether / n-heptane 1: 8). You get 2.6 g (40%) of indacene 24.

The Further derivatization of 24 is carried out analogously to Examples B and C.

Example E

25.0 g (172 mmol) of the aromatic 1 are half-concentrated in 10 ml. Dissolved hydrochloric acid and at a temperature of less than 5 ° C with 11.9 g (172 mmol) of sodium nitrite in 70 ml of water. To Upon completion of addition of nitrite, the batch is diluted with 100 ml of water and heated to boiling. After the evolution of nitrogen (bubble counter) subsided is, the approach is still another hour under reflux heated. The cooled reaction solution is extracted with MTB ether. The organic phase is over sodium sulfate dried and concentrated. 13.7 g (54%) of the diol 26 are obtained.

13.0 g (90.0 mmol) of phenol 26 and 48 g (348 mmol) of potassium carbonate are dissolved in 160 ml of water and at 5 ° C added in portions with 50 g (200 mmol) of iodine. The approach will be overnight touched. The reaction solution is decanted from the resulting precipitate and acidified with hydrochloric acid. The aqueous phase is extracted with MTB ether, with sat. Sodium chloride solution, washed over sodium sulfate dried and concentrated. The residue will over Silica gel (MTB ether / heptane 2: 1). 20.1 g are obtained (57%) of the diiodinated aromatic 27.

Under Nitrogen, 20.0 g (50.3 mmol) of phenol 27 in 120 ml of dimethylformamide and 28 ml triethylamine dissolved and with 1.0 g of bistriphenylphosphinepalladium (II) chloride and 580 mg Copper (I) iodide is added. Subsequently, a solution of 10.3 ml (105 mmol) of 1-pentyne in 30 ml of dimethylformamide slowly in given the approach. The approach will take until full turnover (DC) at room temp. touched. The reaction mixture is mixed with water and with MTB ether extracted. The organic phase is dried over sodium sulfate and concentrated. After chromatography on silica gel, 6.5 g (46%) of benzodifuran 28.

6.0 g (21.6 mmol) of benzodifuran 28 are dissolved in 100 ml of tetrahydrofuran solved and hydrogenated on the palladium catalyst. The hydrogenation solution is concentrated and the residue chromatographed on silica gel. This gives 5.5 g (90%) of the substance 29th

Beispiele 260-518

Beispiele 519-777

Beispiele 778-840

Beispiele 841-903

Beispiele 904-966

Beispiele 967-1029

Beispiele 1030-1142

Beispiele 1143-1255

Beispiele 1256-1368

Beispiele 1369-1481

Beispiele 1482-1594

Beispiele 1595-1707

Beispiele 1708-1820

Beispiele 1821-1933

Beispiele 1934-1958

Beispiele 1959-1983

Beispiele 1984-2008

Beispiele 2009-2033

Beispiele 2034-2058

Beispiele 2059-2083

Beispiele 2084-2108

Beispiele 2109-2133

Beispiele 2134-2189

Beispiele 2190-2245

Beispiele 2246-2301

Beispiele 2302-2357

Beispiele 2358-2621

Beispiele 2622-2885

Beispiele 2886-2949

Beispiele 2950-3013

Beispiele 3014-3077

Beispiele 3078-3141

Beispiele 3142-3205

Beispiele 3206-3269

Beispiele 3270-3333

Beispiele 3334-3397

Beispiele 3398-3461

Beispiele 3462-3525

Beispiele 3526-3589

Beispiele 3590-3653

Beispiele 3654-3912

Tabelle 1 Δε- und Δn-Werte für Substanzen einzelner Beispiele

The following compounds were prepared according to or analogously to Examples A to E. It says "Bdg." for a single bond: Examples 1-259

Examples 260-518

Examples 519-777

Examples 778-840

Examples 841-903

Examples 904-966

Examples 967-1029

Examples 1030-1142

Examples 1143-1255

Examples 1256-1368

Examples 1369-1481

Examples 1482-1594

Examples 1595-1707

Examples 1708-1820

Examples 1821-1933

Examples 1934-1958

Examples 1959-1983

Examples 1984-2008

Examples 2009-2033

Examples 2034-2058

Examples 2059-2083

Examples 2084-2108

Examples 2109-2133

Examples 2134-2189

Examples 2190-2245

Examples 2246-2301

Examples 2302-2357

Examples 2358-2621

Examples 2622-2885

Examples 2886-2949

Examples 2950-3013

Examples 3014-3077

Examples 3078-3141

Examples 3142-3205

Examples 3206-3269

Examples 3270-3333

Examples 3334-3397

Examples 3398-3461

Examples 3462-3525

Examples 3526-3589

Examples 3590-3653

Examples 3654-3912

Table 1 Δε and Δn values for substances of individual examples

Claims (14)

Compound of the general formula I:

wherein:

A ¹ and A ^{2 are} each independently 1,4-phenylene, wherein = CH- may be replaced once or twice by = N- and which is unsubstituted or one to four times independently of one another with -CN, F, Cl, Br and / or mono- or I, or with unsubstituted fluorine and / or chlorine mono- or polysubstituted C ₁ -C ₆ alkanyl, unsubstituted or with fluorine and / or chlorine polysubstituted C ₁ -C ₆ -alkoxy, 1, 4-cyclohexylene, 1,4-cyclohexenylene or 1,4-cyclohexadienylene, wherein -CH ₂ - may be substituted once or twice independently of one another by -O- or -S- such that heteroatoms are not directly linked, and which is unsubstituted or may be monosubstituted or polysubstituted by F, Cl, Br and / or I; Each of Z ¹ and Z ² is independently a single bond, a double bond, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF. ₂ -, -CHF-CHF-, -C (O) O-, -OC (O) -, -CH ₂ O-, -OCH ₂ -, -CF = CH-, -CH = CF-, -CF = CF-, -CH = CH- or -C≡C-; R ¹ and R ^{2 are} hydrogen, an unsubstituted, an alkanyl, alkoxy, alkenyl or alkynyl radical monosubstituted by -CN or -CF ₃ or a mono- or polysubstituted with F, Cl, Br and / or I with 1 to 15 or 2 to 15 C atoms, where in these radicals also one or more CH ₂ groups are each independently denoted by -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO- or - OCO-O- can be replaced so that heteroatoms in the chain are not directly linked, F, Cl, Br, I, -CN, -SCN, -NCS or -SF ₅ mean; m and n are independently 0, 1, 2 or 3; X ¹ , X ² and Y ^{2 are} each independently hydrogen, an unsubstituted or mono- or polysubstituted by F, Cl, Br and / or I alkanyl, alkoxy, alkenyl or alkynyl radical having 1 to 15 or 2 to 15 C. -Atomen, where in these radicals also one or more CH ₂ groups each independently by -O-, -S-, -SO ₂ -, -CO-, -COO-, -OCO- or -OCO-O- so may be replaced, that heteroatoms in the chain are not directly linked, F, Cl, Br, I, -CN, -SF ₅ , -SCN or -NCS mean; Y ¹ is defined as Y ² or is - [- Z ³ -A ³ -] _p -R ³ , where Z ^{3 is} Z ¹ and Z ² , A ^{3 is} A ¹ and A ² , R ^{3 is} R ¹ and R ² and p are defined as n and m; wherein A ¹ , A ² , A ³ ; Z ¹ , Z ² , Z ³ ; R ¹ , R ² , R ^{3 may} each have the same or different meanings if m, n or p are greater than 1; Y ¹ and Y ² for the rings B and B 'may each have the same or different meanings; and wherein (a) R ¹ does not stand for -COOH, if the ring B for the ring f or g and the ring B 'is the ring d and at the same time m is zero and X ^{2 is} not H or R ^{2 is} not -COOH when ring B 'is f or g ring and ring B is ring d, and n is zero and X ^{1 is} not H; (b) R ¹ - [- A ¹ -Z ¹ -] _m - and - [Z ² -A ² -] _n -R ^{2 are} not simultaneously CH ₃ when one of X ¹ and X ^{2 is} hydrogen and the others of X ¹ and X ^{2 are} hydrogen or Cl and at the same time both rings B and B 'stand for the ring g. A compound according to the preceding claim, characterized in that the rings B and B 'each independently

A compound according to at least one of the preceding claims, characterized in that the rings B and B 'are the same, wherein the radical Y ¹ in both rings may have the same or different meanings and the radical Y ² in both rings may have the same or different meanings. A compound according to at least one of the preceding claims, characterized in that the compound of the formula I is selected from the group consisting of compounds of the formulas Iaa, Ibb, Iee, Iff, Igg:

wherein X ¹ , X ² , R ¹ , R ² , A ¹ , A ² , Z ¹ , Z ² , m and n are as defined in claim 1; Y ¹¹ and Y ^{12 are defined} as Y ¹ in claim 1 and may have the same or different meanings; and Y ²¹ and Y ^{22 are defined} as Y ² in claim 1 and may have the same or different meanings. A compound according to at least one of the preceding claims, characterized in that Y ¹ and Y ² or Y ¹¹ , Y ¹² , Y ²¹ and Y ^{22 are} simultaneously F. Compound according to at least one of the preceding claims, characterized in that Z ¹ and Z ² and Z ³ independently of one another are a single bond, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH = CH-, - CF = CH-, -CH = CF- or -CF = CF-. Compound according to at least one of the preceding claims, characterized in that A ¹ and A ² and A ^{3 are} independent of one another

A compound according to at least one of the preceding claims, characterized in that R ¹ and R ² and R ³ are each independently an alkanyl radical, alkoxy radical or alkenyl radical having 1 to 7 or 2 to 7 carbon atoms. Compound according to at least one of the preceding claims, characterized in that m 0, 1 or 2; n is 0, 1 or 2; m + n 0, 1, 2 or 3 is; and p is 0. Compound according to at least one of the preceding claims, characterized in that at least one of X ¹ and X ^{2 is} F, Cl, CF ₃ or OCF ₃ . Compound according to at least one of the preceding claims, characterized in that X ¹ and X ^{2 are} F. Use of a compound according to at least one of the preceding claims in liquid crystalline Media. liquid-crystalline Medium with at least two liquid-crystalline Compounds, characterized in that there is at least one compound at least one of the claims 1 to 11 contains. Electro-optical display element, containing a liquid crystalline Medium according to claim 13th